TW202033704A - Adhesive tape - Google Patents

Abstract

The purpose of the present invention is to provide an adhesive tape which is capable of protecting an adherend even if used in a process that involves a high temperature treatment reaching 260 DEG C, and which is able to be removed without leaving adhesive residue. The present invention is an adhesive tape which comprises a base material film and an ultraviolet curable adhesive layer that is superposed on one surface of the base material film, and which is configured such that: the gel fraction of the ultraviolet curable adhesive layer after having the base material-side surface of the adhesive tape irradiated with 3,000 mJ/cm2 of ultraviolet light at 405 nm is 90% or more; and if Et(X) is the tensile elastic modulus of the adhesive tape at X DEG C after having the base material film-side surface of the adhesive tape irradiated with 3,000 mJ/cm2 of ultraviolet light at 405 nm, the value of Et(270) is 1.0 * 107 Pa or more.

Description

Adhesive tape

The present invention relates to an adhesive tape.

In the manufacturing steps of semiconductor wafers, in order to facilitate the processing of wafers or semiconductor wafers and prevent damage, adhesive tapes are used. For example, when a thick film wafer cut from a high-purity silicon single crystal is polished to a specific thickness to make a thin film wafer, the adhesive tape is attached to the thick film wafer and then polished.

For the adhesive composition used for this kind of adhesive tape, it is required to have a high degree of adhesiveness that can firmly fix the adherend such as a wafer or a semiconductor chip during the processing step, and it can be peeled off after the step is finished. Damage to adherends such as wafers or semiconductor chips (hereinafter also referred to as "high adhesion and easy peeling"). As an adhesive composition that achieves high adhesion and easy peeling, Patent Document 1 discloses an adhesive tape using a photocurable adhesive that is cured by irradiating light such as ultraviolet rays to reduce the adhesive force. By using a light-curing adhesive as the adhesive, the adherend can be securely fixed during the processing steps, and it can be easily peeled off by irradiating ultraviolet rays or the like. Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 5-32946

[The problem to be solved by the invention]

In recent years, due to the thinning and miniaturization of semiconductor products, semiconductor devices with multiple semiconductor chips stacked on a wafer have begun to be manufactured. In the manufacture of such a semiconductor device with a plurality of semiconductor chips stacked, the semiconductor chip is fixed on the wafer or the semiconductor chip by a thermocompression bonding step while the wafer or the semiconductor chip is protected by an adhesive tape. The inventors of the present invention found that the high temperature of the conventional high-temperature treatment exceeding 260℃ is applied in the thermocompression bonding, so even the conventional adhesive tape using a hardening type adhesive cannot withstand the heat of the high-temperature treatment. The base material of the adhesive tape The film shrinks, and the adhesive layer is stretched due to the shrinkage, causing the adhesive tape to peel off. In addition, pressure is applied in addition to high temperature during thermocompression bonding, so the adhesive is likely to be excessively bonded, and paste residue is likely to occur. Furthermore, most of the wafers that have undergone the thermocompression bonding process will have large bumps on the sticking surface of the adhesive tape. If the adhesive enters the deep part of the bumps, it will be broken during peeling and become paste residue. .

The object of the present invention is to provide an adhesive tape that can protect the adherend even when used in a step accompanied by high-temperature treatment up to 260°C, and can be peeled off without any paste residue. [Technical means to solve the problem]

The present invention is an adhesive tape having a substrate film and an ultraviolet-curing adhesive layer laminated on one side of the substrate film, and the surface of the substrate film side of the adhesive tape is irradiated with 3000 mJ/cm ² of 405 nm The gel fraction of the ultraviolet-curable adhesive layer after ultraviolet rays is 90% or more. The adhesive tape is irradiated with 3000 mJ/cm ² of the ultraviolet rays of 405 nm on the surface of the substrate film side of the adhesive tape. When the tensile modulus of elasticity at X°C is set to Et(X), the value of Et(270) is 1.0×10 ⁷ Pa or more. The present invention will be described in detail below.

The adhesive tape of the present invention has an ultraviolet-curable adhesive layer laminated on one side of the base film. The adhesive tape has an ultraviolet-curing adhesive layer, which can be attached to the adherend with sufficient adhesive force to protect the adherend, and by hardening the ultraviolet-curing adhesive layer after attachment, It can also protect the adherend during high temperature processing. In addition, after no protection is required, the adhesive tape can be easily peeled off without any paste remaining.

In the adhesive tape of the present invention, the gel fraction of the ultraviolet curable adhesive layer after irradiating 3000 mJ/cm ² of 405 nm ultraviolet rays to the surface of the substrate film side of the adhesive tape is 90% or more. The gel fraction of the UV-curable adhesive layer after UV irradiation is 90% or more, so that it is difficult to continue the bonding even at high temperatures. Therefore, the adhesive tape can be peeled off without any paste residue after protection is not required. . In addition, the chemical resistance of the adhesive tape can also be improved. Furthermore, if ultraviolet rays can be irradiated to the surface of the base film side to harden the ultraviolet-curable adhesive layer, the ultraviolet-curable adhesive layer can be hardened after bonding the adhesive tape and the adherend. From the viewpoint of further improving the inhibition of excessive adhesion and chemical resistance of the adhesive tape, the gel fraction of the ultraviolet-curable adhesive layer after ultraviolet irradiation is preferably 93% or more, more preferably 95% or more , More preferably 97% or more. Furthermore, the gel fraction of the ultraviolet curable adhesive layer after ultraviolet irradiation is usually 100% or less. Furthermore, when the adhesive tape of the present invention has a structure in which other layers such as an adhesive layer are also laminated on the other side of the base film, the above-mentioned base film side means that the base film is laminated with an ultraviolet-curing adhesive The face on the opposite side of the layer.

For the adhesive tape of the present invention, the tensile elastic modulus of the adhesive tape at X°C after irradiating 3000 mJ/cm ² of the 405 nm ultraviolet rays on the surface of the substrate film side of the adhesive tape is Et (X ), the value of Et (270) is 1.0×10 ⁷ Pa or more. By making the UV-irradiated adhesive tape have a tensile elastic modulus in the above range at 270°C, an adhesive tape with excellent heat resistance can be made. Even if the high temperature treatment reaches 260°C, the adhesive tape is difficult to soften and shrink. Can prevent accidental peeling of the adhesive tape. The lower limit of the above-mentioned Et(270) is preferably 3.0×10 ⁷ Pa, the lower limit is more preferably 5.0×10 ⁷ Pa, and the lower limit is still more preferably 1.0×10 ⁸ Pa. The upper limit of Et(270) is not particularly limited, but from the viewpoint of the operability of the adhesive tape, it is preferably 1.0×10 ⁹ Pa. Furthermore, the tensile modulus of elasticity of the adhesive tape can be measured by the following method. The ultraviolet curable adhesive layer is irradiated with 405 nm ultraviolet rays from the surface of the base film side so that the cumulative intensity becomes 3000 mJ/cm ² to harden the ultraviolet curable adhesive layer. Secondly, press with a punching blade in such a way that the long side is consistent with the direction of travel when the belt is manufactured, thereby making a test piece of 5 mm×35 mm. The obtained test piece was immersed in liquid nitrogen and cooled to -50°C. After that, a viscoelastic spectrometer (DVA-200, IT Meter. and Control, Inc., or its equivalent) was used to raise the temperature at a constant rate Raise the temperature to 300°C under the conditions of 10°C/min and 10 Hz in the tensile mode, and measure the tensile elastic modulus. Set the value of the tensile modulus (E') at the temperature X°C at this time as Et(X). That is, the value of the tensile modulus (E') at a temperature of 270°C is Et(270).

The value of Et(270)/Et(200) of the adhesive tape of the present invention is preferably 0.1 or more. By making the difference between the tensile elastic modulus at 270°C and 200°C of the adhesive tape after ultraviolet irradiation smaller, an adhesive tape with better heat resistance can be made, which can further inhibit adhesion Accidental peeling of the tape. From the viewpoint of further suppressing the peeling, the value of Et(270)/Et(200) is more preferably 0.2 or more, still more preferably 0.3 or more, and particularly preferably 0.5 or more. The upper limit of the value of Et(270)/Et(200) is not particularly limited. The closer to 1, the better, and it is usually less than 1, and preferably less than 0.8.

5 mm之圓狀，製作測定樣本。測定所獲得之測定樣本之重量，使用示差熱熱重量同時測定裝置（TG-DTA；STA7200，日立高新技術科技股份有限公司製造，或其同等品）進行測定。將升溫速度設為5℃/min，自25℃升溫至280℃，測定於280℃之狀態下保持10分鐘之後之測定樣本之重量。能夠根據加熱前後之重量算出重量減少率。The adhesive tape of the present invention is irradiated with 3000 mJ/cm ² of 405 nm ultraviolet rays on the surface of the substrate film side of the adhesive tape, and then heated from 25°C to 280°C at a rate of 5°C/min. The weight loss rate when kept for 10 minutes is preferably 5% or less. The weight loss is less at a high temperature of 280°C, that is, thermal decomposition is difficult to occur at high temperatures, thereby reducing the amount of outgassing due to thermal decomposition, which can inhibit the outgassing that gathers at the interface between the adherend and the adhesive tape Become a starting point and peel off. From the viewpoint of suppressing peeling at high temperatures, the weight reduction rate is more preferably 4% or less, still more preferably 3% or less, and usually 0% or more. In addition, the above-mentioned weight reduction rate can be measured by the following method. The ultraviolet curable adhesive layer is irradiated with 405 nm ultraviolet rays from the surface of the base film side so that the cumulative intensity becomes 3000 mJ/cm ² to harden the ultraviolet curable adhesive layer. Secondly, stamp the adhesive tape into

5 mm round shape to make measurement samples. Measure the weight of the obtained measurement sample using a differential thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Technology Co., Ltd., or its equivalent). The heating rate was set to 5°C/min, the temperature was raised from 25°C to 280°C, and the weight of the measurement sample after being kept at 280°C for 10 minutes was measured. The weight reduction rate can be calculated based on the weight before and after heating.

The UV transmittance at 405 nm of the base film is preferably 1% or more. By making the ultraviolet light transmittance of 405 nm of the base film more than 1%, the ultraviolet curable adhesive layer can be cured through the base film, and it is easy to adjust the gel content of the ultraviolet curable adhesive layer after the above-mentioned ultraviolet irradiation. rate. As a result, the paste remaining on the adherend due to excessive bonding can be suppressed. The above-mentioned ultraviolet transmittance is more preferably 10% or more, still more preferably 50% or more, particularly preferably 70% or more. Since the above-mentioned ultraviolet transmittance is more than the lower limit, even if a photosensitizer is not used, the ultraviolet curable adhesive layer can be cured sufficiently. The upper limit of the ultraviolet transmittance is not particularly limited, the higher the better, and it is usually 100% or less. Furthermore, the UV transmittance can be measured using a spectrophotometer (U-3900, manufactured by Hitachi, Ltd., or its equivalent). More specifically, the measurement is performed in the region of 800-200 nm with a scanning speed of 300 nm/min and a slit interval of 4 nm, and the transmittance in 405 nm can be measured.

When the tensile elastic modulus at X°C is set to Ef(X), the value of Ef(270) of the above-mentioned base film is preferably 5.0×10 ⁷ Pa or more. Since the tensile elastic modulus of the base film at 270°C is in the above range, an adhesive tape with better heat resistance can be made, and peeling caused by the heat shrinkage or softening of the base film during high temperature processing can be suppressed . A more preferable lower limit of the above-mentioned Ef(270) is 1.0×10 ⁸ Pa, a still more preferable lower limit is 5.0×10 ⁸ Pa, and a particularly preferable lower limit is 1.0×10 ⁹ Pa. The upper limit of the Ef (270) is not particularly limited, but from the viewpoint of the operability of the adhesive tape, it is preferably 1.0×10 ¹⁰ Pa. Furthermore, the tensile modulus of the base film can be measured by the same method as the tensile modulus of the adhesive tape.

The above-mentioned base film is not particularly limited as long as the obtained adhesive tape satisfies the tensile modulus of elasticity and the gel fraction in the above-mentioned range. In terms of excellent heat resistance and strength, the above-mentioned base film is preferred. A resin containing at least one selected from the group consisting of amides, imines, ethers, and ketones in the main chain skeleton of the repeating unit. Examples of resins having at least one selected from the group consisting of amides, amides, ethers and ketones in the main chain skeleton of the repeating bonding unit include polyamides, polyimines, and polyamides. Ether, polyketone, etc. Among them, in terms of more excellent heat resistance and strength, it is preferable that the base film contains polyamide resin, and in terms of excellent ultraviolet light penetration, it is more preferable that it is contained in the repeating unit. The main chain skeleton has a long-chain alkyl group or aromatic polyamide resin having a carbon number of 4 or more and 12 or less. As the polyamide resin having a long-chain alkyl group or aromatic having a carbon number of 4 or more and 12 or less in the main chain skeleton of the repeating unit, for example, nylon 9T, nylon 6T, and the like can be cited.

The thickness of the aforementioned substrate film is not particularly limited, and the lower limit is preferably 25 μm, the lower limit is more preferably 50 μm, the upper limit is preferably 250 μm, and the upper limit is more preferably 125 μm. By making the above-mentioned base film within this range, an adhesive tape excellent in handleability can be obtained.

The adhesive constituting the above-mentioned ultraviolet-curable adhesive layer is not particularly limited as long as it is an ultraviolet-curable adhesive. For example, an ultraviolet-curable polymer containing a polymerizable polymer as a main component and an ultraviolet polymerization initiator as a polymerization initiator can be mentioned. Type adhesive. As said polymerizable polymer, (meth)acrylic acid polymer, urethane acrylate polymer, etc. are mentioned, for example. Among them, in terms of easily satisfying the above-mentioned gel fraction and the above-mentioned Et(270), a (meth)acrylic polymer is preferred, and (a) having a radically polymerizable unsaturated bond in the molecule is more preferred. Base) Polymerizable polymer of alkyl acrylate series. The above-mentioned (meth)acrylic acid alkyl ester-based polymerizable polymer can be obtained, for example, by the following method: a (meth)acrylic polymer having a functional group in the molecule is synthesized in advance, and the The above-mentioned functional group reacts with the radical polymerizable unsaturated bond compound. Furthermore, hereinafter, the polymer of "(meth)acrylic polymer having functional group in the molecule" is referred to as "functional group-containing (meth)acrylic polymer", and the "(meth)acrylic polymer having functional group in the molecule" The compound of "functional group and radically polymerizable unsaturated bond compound" is called "functional group-containing unsaturated compound".

The functional group-containing (meth)acrylic polymer is based on alkyl acrylate and/or alkyl methacrylate whose alkyl group’s carbon number is usually in the range of 2-18 as the main monomer. It is obtained by copolymerizing it with functional group-containing monomers and, if necessary, other modifying monomers that can be copolymerized. The weight average molecular weight of the functional group-containing (meth)acrylic polymer is usually about 200,000 to 2 million. Furthermore, in this specification, the weight average molecular weight can usually be determined by the GPC method. For example, THF can be used as the eluent at 40°C and HSPgel HR MB-M 6.0×150 mm (manufactured by Waters) can be used as the column. , Determined by polystyrene standards.

Examples of the functional group-containing monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, isocyanate group-containing monomers, and amine group-containing monomers. As said carboxyl group-containing monomer, acrylic acid, methacrylic acid, etc. are mentioned. As said hydroxyl-containing monomer, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. are mentioned. As said epoxy group-containing monomer, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned. Examples of the above-mentioned isocyanate group-containing monomer include isocyanatoethyl acrylate, isocyanatoethyl methacrylate, and the like. As said amine group-containing monomer, amino ethyl acrylate, amino ethyl methacrylate, etc. are mentioned.

As the aforementioned other copolymerizable monomers for modification, for example, various monomers commonly used for (meth)acrylic polymers such as vinyl acetate, acrylonitrile, and styrene can be cited.

As the functional group-containing unsaturated compound that reacts with the above-mentioned functional group-containing (meth)acrylic polymer, the same as the above-mentioned functional group-containing monomer can be used according to the functional group of the above-mentioned functional group-containing (meth)acrylic polymer By. For example, when the functional group of the functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer can be used. When the functional group is a hydroxyl group, an isocyanate group-containing monomer can be used. When the functional group is an epoxy group, an amine group-containing monomer such as a carboxyl group-containing monomer or acrylamide can be used. When the functional group is an amino group, an epoxy group-containing monomer can be used.

、十二烷基-9-氧硫

、二甲基-9-氧硫

、二乙基-9-氧硫

、α-羥基環己基苯基酮、2-羥基甲基苯基丙烷等。作為上述苯乙酮衍生物化合物，可列舉甲氧基苯乙酮等。作為上述安息香醚系化合物，可列舉安息香丙醚、安息香異丁醚等。作為上述縮酮衍生物化合物，苯偶醯二甲基縮酮、苯乙酮二乙基縮酮等。該等紫外線聚合起始劑可單獨使用，亦可併用2種以上。Examples of the above-mentioned ultraviolet polymerization initiator include those activated by irradiating ultraviolet rays with a wavelength of 200 to 410 nm. Examples of such ultraviolet polymerization initiators include acetophenone derivative compounds, benzoin ether compounds, ketal derivative compounds, phosphine oxide derivative compounds, and bis(η5-cyclopentadienyl) dicene Titanium derivative compounds, benzophenone, michelone, chloro-9-oxysulfur

, Dodecyl-9-oxysulfur

, Dimethyl-9-oxysulfur

, Diethyl-9-oxysulfur

, Α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl propane, etc. As said acetophenone derivative compound, methoxyacetophenone etc. are mentioned. As said benzoin ether type compound, benzoin propyl ether, benzoin isobutyl ether, etc. are mentioned. As the aforementioned ketal derivative compound, benzil dimethyl ketal, acetophenone diethyl ketal, and the like. These ultraviolet polymerization initiators may be used alone or in combination of two or more kinds.

The ultraviolet-curable adhesive layer preferably contains a radically polymerizable polyfunctional oligomer or monomer. The ultraviolet curable adhesive layer contains radically polymerizable polyfunctional oligomers or monomers, so that the ultraviolet curability is improved. The above-mentioned multifunctional oligomer or monomer preferably has a weight average molecular weight of 10,000 or less, and more preferably has a weight average molecular weight of 5,000 or less and the number of radically polymerizable unsaturated bonds in the molecule is 2-20. In order to efficiently complete the three-dimensional meshing of the ultraviolet-curing adhesive layer by ultraviolet irradiation. The said weight average molecular weight can be determined using GPC measurement method, for example.

The above-mentioned multifunctional oligomers or monomers include, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentyl erythritol triacrylate, neopentyl erythritol tetraacrylate, dineopentyl Tetraol monohydroxy pentaacrylate, dineopentaerythritol hexaacrylate, or the same methacrylates as above. In addition, examples include: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and the same methacrylic acid as above Esters etc. These polyfunctional oligomers or monomers may be used alone or in combination of two or more kinds.

The aforementioned ultraviolet-curable adhesive layer may also contain a crosslinking agent for the purpose of enhancing the cohesive force of the ultraviolet-curable adhesive. As said crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned, for example. Among them, in terms of further enhancing the cohesive force of the ultraviolet curable adhesive, an isocyanate-based crosslinking agent is preferred.

The crosslinking agent is preferably contained in the adhesive layer at 0.1 to 20% by weight. By keeping the cross-linking agent within the above range, the UV-curing adhesive can be appropriately cross-linked, maintaining a high adhesive force, and further improving the cohesion of the UV-curing adhesive. From the viewpoint of maintaining a higher adhesive force and further enhancing the cohesive force of the UV-curing adhesive, the lower limit of the content of the crosslinking agent is more preferably 0.5% by weight, and the lower limit is more preferably 1.0% by weight, and the upper limit is more preferably 15% by weight, and a more preferable upper limit is 10% by weight.

The ultraviolet-curable adhesive layer preferably contains silicone or fluorine compound. By making the aforementioned UV-curing adhesive layer contain silicone or fluorine compound, the silicone or fluorine compound oozes out at the interface between the UV-curing adhesive layer and the adherend, so that it can be easily and freely after the treatment. The adhesive tape is peeled off with the paste remaining. As said polysiloxane or fluorine compound, for example, polysiloxane diacrylate, a polymer having a fluoroalkyl group (for example, a (meth)acrylic copolymer having a structural unit derived from a fluoroacrylate), and the like can be cited.

The polysiloxane or fluorine compound preferably has the above-mentioned functional group capable of being crosslinked with the polymerizable polymer. By making the polysiloxane or fluorine compound have the above-mentioned functional group that can be cross-linked with the polymerizable polymer, the polysiloxane or fluorine compound can chemically react with the polymerizable polymer by cross-linking agent or ultraviolet irradiation. Polymeric polymer bonding. Thereby, the pollution caused by the adhesion of silicone or fluorine compound to the adherend can be suppressed. The functional group that can be crosslinked with the polymerizable polymer is appropriately selected according to the functional group contained in the polymerizable polymer. Examples include carboxyl groups, radically polymerizable unsaturated bonds, hydroxyl groups, and amide groups. , Isocyanate, epoxy, etc. Among them, a radically polymerizable unsaturated bond is preferred. By making the polysiloxane or fluorine compound have a radically polymerizable unsaturated bond as the functional group that can be crosslinked with the polymerizable polymer, the polysiloxane or fluorine compound can be polymerized with the polymerizable polymer by ultraviolet irradiation The substance undergoes a chemical reaction and is incorporated into the polymerizable polymer. Therefore, the contamination caused by the adhesion of silicone or fluorine compound to the adherend is further suppressed. The cross-linkable functionality in the polysiloxane or fluorine compound is, for example, 2-6, preferably 2-4, more preferably 2.

The functional group that can be cross-linked with the polymerizable polymer is appropriately determined according to the functional group contained in the polymerizable polymer. For example, the polymerizable polymer is one having radically polymerizable unsaturated bonds in the molecule ( In the case of an alkyl meth)acrylate system, it is preferable to select a functional group capable of crosslinking with an unsaturated bond. The functional group that can be crosslinked with the unsaturated bond is a functional group having an unsaturated double bond. Specifically, for example, it is selected to contain a vinyl group, a (meth)acrylic acid group, an allyl group, a maleimide group, etc. The silicone or fluorine compounds, etc.

The content of the polysiloxane or fluorine compound in the ultraviolet curable adhesive layer preferably has a lower limit of 2% by weight, more preferably a lower limit of 5% by weight, still more preferably a lower limit of 10% by weight, and a more preferred upper limit of 40 % By weight, a more preferable upper limit is 35% by weight, and a more preferable upper limit is 30% by weight. By setting the content of the polysiloxane or fluorine compound in the above range, the amount of outgassing generated from the adhesive tape can be reduced, and an adhesive tape with better heat resistance and paste resistance can be made.

The ultraviolet curable adhesive layer preferably contains urethane acrylate. By making the ultraviolet curable adhesive layer contain urethane acrylate, the flexibility of the adhesive tape can be improved, and the obtained adhesive tape is not easily broken.

The upper limit of the content of the urethane acrylate in the ultraviolet curable adhesive layer is preferably 20% by weight, more preferably 15% by weight, and still more preferably 10% by weight. By making the content of the above amine acrylate within the above range, it is possible to produce an adhesive tape with more excellent heat resistance and paste residue suppression performance. The lower limit of the content of the above amine acrylate is not particularly limited, but from the viewpoint of further preventing the adhesive tape from being broken and suppressing the residue of the paste, it is preferably 1% by weight.

The total content of the polysiloxane or fluorine compound and the urethane acrylate in the ultraviolet curable adhesive layer is preferably 50% by weight or less. By making the total content of the polysiloxane or fluorine compound and the urethane acrylate within the above range, the amount of outgassing due to the thermal decomposition of these components can be suppressed, so the heat resistance can be improved, and the occurrence of outgassing can be suppressed. Caused accidental peeling. From the viewpoint of further suppressing the peeling, a more preferable upper limit of the total content of the polysiloxane or fluorine compound and the urethane acrylate is 40% by weight, and a more preferable upper limit is 25% by weight.

The ultraviolet curable adhesive layer preferably contains a filler. The above-mentioned ultraviolet-curable adhesive layer contains a filler to increase the modulus of elasticity, so that the heat resistance of the adhesive tape can be improved. Examples of the material of the above-mentioned filler include silica, alumina, carbon black, calcium, boron, magnesium, and zirconia. Among them, in terms of further improving heat resistance, silicon dioxide is preferred.

The average particle diameter of the aforementioned filler is not particularly limited, and the lower limit is preferably 0.06 μm, the lower limit is more preferably 0.07 μm, the upper limit is preferably 2 μm, and the upper limit is more preferably 1 μm. By making the average particle diameter of the filler within the above-mentioned range, the dispersibility to the ultraviolet curable adhesive can be further improved.

The lower limit of the content of the filler in the ultraviolet curable adhesive layer is preferably 1% by weight, the lower limit is more preferably 3% by weight, the upper limit is preferably 18% by weight, and the upper limit is more preferably 12% by weight. By setting the content of the filler within the above range, an adhesive tape with more excellent heat resistance can be produced.

The ultraviolet-curable adhesive layer preferably contains a gas generating agent that generates gas by stimulation. By making the above-mentioned ultraviolet curable adhesive layer contain a gas generating agent, it is stimulated to generate gas after the step is completed, thereby generating a gap due to gas between the adherend and the adhesive tape, so that it can be peeled more easily Adhesive tape. The above-mentioned gas generating agent is not particularly limited, and it is preferably a gas generating agent that generates gas by light in terms of being usable in a high-temperature processing step. Among them, in terms of excellent resistance to treatment accompanied by heating, carboxylic acid compounds such as phenylacetic acid, diphenylacetic acid, and triphenylacetic acid or salts thereof, or 1H-tetrazole, 5-phenyl-1H- Tetrazole, 5,5-azobis-1H-tetrazole and other tetrazole compounds or their salts. On the one hand, this gas generating agent generates gas by irradiating light such as ultraviolet rays, and on the other hand, it has high heat resistance that does not decompose even at a high temperature of about 260°C.

等9-氧硫

系化合物、或二丁基蒽、二丙基蒽等蒽系化合物等。又，亦可列舉2,2-二甲氧基-1,2-二苯乙烷-1-酮、二苯甲酮、2,4-二氯二苯甲酮、o-苯甲醯苯甲酸甲酯、4,4'-雙(二甲胺基)二苯甲酮、4-苯甲醯基-4'甲基二苯硫醚等。該等光敏劑可單獨使用，亦可組合2種以上使用。再者，上述光敏劑於高溫下熱分解而產生脫氣，使紫外線硬化型黏著劑層發泡，故而若大量使用，則存在導致糊劑殘留或意外剝離之情況。因此，較佳為儘可能減少上述光敏劑之使用量。The ultraviolet curable adhesive layer may contain a photosensitizer. By containing the above-mentioned photosensitizer, even when the ultraviolet light transmittance of 405 nm of the above-mentioned base film is low, the ultraviolet-curable adhesive layer can be sufficiently hardened. In addition, since the photosensitizer has the effect of amplifying the stimulation of the light on the gas generating agent, it can release gas by irradiating less light. In addition, gas can be released by light of a wider wavelength range. As the aforementioned photosensitizer, for example, 2,4-diethyl-9-oxysulfur

9-oxysulfur

-Based compounds, or anthracene-based compounds such as dibutylanthracene and dipropylanthracene. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, o-benzoic acid Methyl ester, 4,4'-bis(dimethylamino)benzophenone, 4-benzyl-4'methyl diphenyl sulfide, etc. These photosensitizers may be used alone or in combination of two or more kinds. Furthermore, the above-mentioned photosensitizer is thermally decomposed at a high temperature to generate outgassing and foam the ultraviolet-curing adhesive layer. Therefore, if it is used in large amounts, it may cause the paste to remain or accidentally peel off. Therefore, it is preferable to reduce the usage amount of the aforementioned photosensitizer as much as possible.

The aforementioned ultraviolet-curable adhesive layer may also contain well-known additives such as plasticizers, resins, surfactants, and waxes. These additives can be used alone or in combination of multiple.

The storage elastic modulus G'of the above-mentioned ultraviolet curable adhesive layer before ultraviolet irradiation is not particularly limited. Preferably, the storage elastic modulus G'at 23°C is 5.0×10 ³ Pa or more, 1.0×10 ⁵ Pa the following. By making the storage elastic modulus G'of the ultraviolet curable adhesive layer before ultraviolet irradiation at 23° C. within the above range, the adherend can be protected with sufficient adhesive force. The storage elastic modulus G'of the UV-curing adhesive layer at 23°C before UV irradiation can be adjusted according to the type of adhesive constituting the UV-curing adhesive layer and the type and amount of filler. The storage elastic modulus G'of the above-mentioned UV-curing adhesive layer before UV irradiation at 23°C can use a viscoelastic spectrometer (such as DVA-200, manufactured by IT Meter. and Control, Inc.) and increase the temperature at a constant rate. It is determined by measuring the storage elastic modulus under the conditions of shear mode, heating rate 10°C/min, and frequency 10 Hz.

The thickness of the ultraviolet-curable adhesive layer is not particularly limited, but the lower limit is preferably 5 μm and the upper limit is 100 μm. If the thickness of the ultraviolet-curable adhesive layer is within the above-mentioned range, the adherend can be protected with sufficient adhesive force, and the paste residue during peeling can also be suppressed. From the viewpoint of further improving the adhesive force and further suppressing the paste residue during peeling, the lower limit of the thickness of the ultraviolet curable adhesive layer is more preferably 10 μm, and the upper limit is more preferably 60 μm.

The adhesive tape of the present invention preferably has an adhesive layer on the surface opposite to the surface on which the ultraviolet-curable adhesive layer is laminated on the base film. By making the adhesive tape of the present invention a double-sided adhesive tape with an ultraviolet-curable adhesive layer on one side of the base film and an adhesive layer on the other side, it is possible to bond a support such as glass to a substrate through the double-sided adhesive tape. Adhesive, so it can be used in the manufacturing process of the semiconductor device with the support.

The adhesive constituting the adhesive layer is not particularly limited, and examples thereof include acrylic adhesives, silicone adhesives, and urethane adhesives. Among them, in terms of excellent heat resistance, acrylic or silicone adhesives are preferred. In addition, as the adhesive constituting the adhesive layer, the ultraviolet curable adhesive as described above can also be used. By using the above-mentioned ultraviolet-curable adhesive, the support can be held with sufficient adhesive force. When the support is a transparent support, the adhesive layer composed of the above-mentioned ultraviolet-curable adhesive is cured after sticking. Therefore, even in the case of high-temperature treatment, the support can be maintained. In addition, after the support is unnecessary, the support can be easily removed.

The adhesive layer preferably contains a gas generating agent that generates gas by stimulation. By making the above-mentioned adhesive layer contain a gas generating agent, after the step is completed, a stimulus is applied to generate gas, whereby the support and the adhesive tape can be easily peeled off. The gas generating agent may be the same as the gas generating agent of the ultraviolet curable adhesive layer.

The thickness of the adhesive layer is not particularly limited, but the lower limit is preferably 5 μm and the upper limit is 30 μm. If the thickness of the adhesive layer is within the above range, it can be adhered to the support with sufficient adhesive force. From the viewpoint of further improving the adhesion to the support, the lower limit of the thickness of the adhesive layer is more preferably 10 μm, and the upper limit is more preferably 20 μm.

The adhesive layer may also contain well-known additives such as photosensitizers, plasticizers, resins, surfactants, waxes, and microparticle fillers. These additives can be used alone or in combination of multiple.

The adhesive tape of the present invention may also have an anchor layer between the base film and the ultraviolet curable adhesive layer. If there is an anchor layer between the base film and the ultraviolet-curable adhesive layer, when the ultraviolet-curable adhesive layer contains polysiloxane or fluorine compound, it can suppress the polysiloxane or fluorine compound The material film side oozes and the ultraviolet-curable adhesive layer is peeled from the base film.

Examples of the anchor layer include acrylic adhesives, urethane adhesives, and the like. Among them, an acrylic adhesive is preferred in terms of excellent anchoring performance.

If necessary, the anchor layer may contain well-known additives such as inorganic fillers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, waxes, and the like. These additives can be used alone or in combination of multiple.

The thickness of the anchor layer is not particularly limited, and the preferred lower limit is 1 μm, and the preferred upper limit is 30 μm. If the thickness of the anchor layer is within this range, the anchor force between the ultraviolet curable adhesive layer and the base film can be further improved. From the viewpoint of further improving the anchoring force between the ultraviolet curable adhesive layer and the substrate film, the lower limit of the thickness of the anchor layer is more preferably 3 μm, and the upper limit is more preferably 10 μm.

The method of manufacturing the adhesive tape of the present invention is not particularly limited, and conventionally known methods can be used. For example, it can manufacture by apply|coating the solution of the said ultraviolet-curable adhesive component on the film which performed a mold release process, and drying to form an ultraviolet-curable adhesive layer, and bonding it with a base film. In addition, when the adhesive tape of the present invention has the adhesive layer, the adhesive layer can be formed by using a solution of the adhesive constituting the adhesive layer by the same method as the ultraviolet curable adhesive layer, and It is manufactured by bonding this to the surface of the base film on the opposite side to the surface to which the ultraviolet-curable adhesive layer is bonded.

The application of the adhesive tape of the present invention is not particularly limited. Even when used in a harsh environment such as high temperature and pressure, it can protect the adherend and peel off without paste residue, so it is used in the manufacture of electronic parts , Can be particularly suitable as a protective tape for protecting wafers or semiconductor chips. As a method of manufacturing such electronic components, for example, the following manufacturing methods of electronic components can be cited. It is a method including the following steps in sequence: a substrate attaching step, which attaches the adhesive tape of the present invention from an ultraviolet-curable adhesive layer to the substrate; a curing step, which irradiates ultraviolet rays to harden the aforementioned ultraviolet-curable adhesive layer; A heat treatment step, which processes the above-mentioned substrate at a high temperature above 260°C; and a peeling step, which peels the above-mentioned substrate from the adhesive tape of the present invention. In addition, the following manufacturing method of electronic parts can also be cited. The manufacturing method of the electronic parts uses the surface opposite to the surface on which the ultraviolet-curable adhesive layer is laminated on the base film as one embodiment of the present invention Adhesive tape with adhesive layer. It is a method that sequentially includes the following steps: a substrate attaching step, which attaches the adhesive tape from the ultraviolet-curing adhesive layer to the substrate; a support attaching step, which attaches the support to the adhesive layer; hardening step , Which irradiates ultraviolet rays to harden the ultraviolet-curable adhesive layer; a heat treatment step, which treats the substrate at a high temperature above 260° C.; and a peeling step, which peels the substrate from the adhesive tape. In addition, it is a method that sequentially includes the following steps: a substrate attaching step, which attaches the adhesive tape from an ultraviolet-curable adhesive layer to the substrate; a curing step, which irradiates ultraviolet rays to harden the ultraviolet-curable adhesive layer; support body attaching The attaching step, which attaches the support to the adhesive layer; the heat treatment step, which processes the substrate at a high temperature above 260°C; and the peeling step, which peels the substrate from the adhesive tape.

The above-mentioned substrate is not particularly limited, and examples thereof include silicon wafers, semiconductor wafers, and semiconductor wafers. The said support is not specifically limited, For example, glass, a polyimide film, a glass epoxy substrate, etc. are mentioned. The upper limit of the temperature of the heat treatment step of performing the treatment at a high temperature of 260°C or higher is not particularly limited, for example, 400°C, preferably 300°C. The above-mentioned heat treatment step for processing at a high temperature of 260° C. or higher is not particularly limited, and examples thereof include a substrate manufacturing step, a wafer mounting step, a thermocompression bonding step, and a reflow step. More specifically, for example, a thermocompression bonding step or a reflow step in which the adhesive tape is heated to 260°C or higher in about tens of seconds to 1 minute. [Effects of Invention]

According to the present invention, there is provided an adhesive tape that can protect an adherend and can be peeled off without a paste residue even when it is used in a step accompanied by a high-temperature treatment up to 260°C.

The following examples are given to further describe the aspects of the present invention in detail, but the present invention is not limited to these examples.

(Example 1) (Manufacturing of ultraviolet curing adhesive A) Prepare a reactor equipped with a thermometer, a stirrer, and a cooling tube, and add 94 parts by weight of 2-ethylhexyl acrylate as an alkyl (meth)acrylate and methacrylic acid as a functional group-containing monomer to the reactor After 6 parts by weight of hydroxyethyl, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator was added to the above-mentioned reactor, and polymerization was started under reflux. Next, after 1 hour and 2 hours from the start of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane were also added, and further, After 4 hours from the start of polymerization, 0.05 parts by weight of tertiary hexyl peroxide pivalate was added to continue the polymerization reaction. And 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained. To 100 parts by weight of the resin solid content of the ethyl acetate solution containing a functional group-containing (meth)acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound were added The reaction proceeds to obtain a polymerizable polymer (acrylic polymer) A. Thereafter, 100 parts by weight of the resin solid content of the ethyl acetate solution of the acrylic polymer A obtained were mixed with 20 parts by weight of a release agent (polysiloxane), 3 parts by weight of filler, 10 parts by weight of urethane acrylate, and 0.2 parts by weight of the coupling agent and 1 part by weight of the photopolymerization initiator were used to obtain an ethyl acetate solution of the ultraviolet-curing adhesive A. In addition, the following types were used for mold release agents (polysiloxane), fillers, urethane acrylates, crosslinking agents, and photopolymerization initiators. Release agent (polysiloxane): Polysiloxane diacrylate, EBECRYL 350, manufactured by DAICEL-ALLNEX, weight average molecular weight 1000 Filler: Silica filler, Reolosil MT-10, manufactured by Tokuyama Chemical Company Amino acrylate: UN-5500, manufactured by Negami Industry Co., Ltd. Crosslinking agent: isocyanate-based crosslinking agent, Coronate L, manufactured by Japan Polyurethane Company Photopolymerization initiator: Esacure ONE, manufactured by SiberHegner, Japan

(Manufacture of Adhesive A for Adhesive Layer) 100 parts by weight of the resin solid content of the ethyl acetate solution of the acrylic polymer A obtained in the manufacture of the ultraviolet curing adhesive A mixed with 10 parts by weight of the release agent (polysiloxane), 12 parts by weight of the filler, and acrylic amine 20 parts by weight of ester, 1.2 parts by weight of crosslinking agent, 1 part by weight of photopolymerization initiator, and 10 parts by weight of gas generating agent, to obtain an ethyl acetate solution of adhesive A for adhesive layer. Furthermore, the mold release agent (polysiloxane), filler, urethane acrylate, cross-linking agent, and photopolymerization initiator are the same types used in the manufacture of UV-curing adhesives. The gas generating agent used a salt of a bistetrazole compound represented by the following formula (A).

(Manufacture of adhesive for anchor layer) To 100 parts by weight of the resin solid content of the ethyl acetate solution of acrylic polymer, 12 parts by weight of filler and 5 parts by weight of crosslinking agent were mixed to obtain an ethyl acetate solution of the adhesive for anchor layer. In addition, the following materials were used for the acrylic polymer, filler, and crosslinking agent. Acrylic polymer: SK Dyne1604N, manufactured by Soken Chemical Co., Ltd. Filler: Silica filler, Reolosil MT-10, manufactured by Tokuyama Chemical Company Crosslinking agent: isocyanate-based crosslinking agent, Coronate L, manufactured by Japan Polyurethane Company

(Manufacture of adhesive tape) After drying, the thickness of the adhesive layer becomes 130 μm, and the obtained ethyl acetate solution of ultraviolet curable adhesive A is applied to 50 μm thick polyethylene terephthalate (PET ) After the release treatment surface of the film, dry it at 100°C for 10 minutes to form an ultraviolet-curing adhesive layer. On the other hand, the obtained adhesive layer is coated with an ethyl acetate solution of adhesive A on another 50 μm thick PET film after the release treatment so that the thickness of the adhesive layer becomes 20 μm. After the mold release treatment surface, it was dried at 110°C for 5 minutes to form an adhesive layer. Furthermore, after drying, the thickness of the adhesive layer becomes 10 μm, and the obtained ethyl acetate solution of the adhesive for the anchor layer is applied to another PET film with a thickness of 50 μm after the release treatment. After the surface, it was dried at 110°C for 5 minutes to form an anchor layer. Next, prepare a film (nylon 9T film) composed of nylon 9T (UNIAMIDE, manufactured by Unitika) with a thickness of 25 μm that has been corona treated on both sides as a base film, and the anchor layer produced is laminated on the nylon On one side of the 9T film, peel off the PET film to form an anchor layer on the base film. After that, the obtained ultraviolet-curing adhesive layer was attached to the surface of the nylon 9T film where the anchor layer was formed, and the obtained adhesive layer was attached to the surface of the nylon 9T film where the anchor layer was formed On the opposite side, an adhesive tape with a structure of ultraviolet-curing adhesive layer/anchor layer/base film/adhesive layer is obtained.

(Measurement of the UV transmittance of the base film) Using a spectrophotometer (U-3900, manufactured by Hitachi, Ltd.), measure the transmittance of ultraviolet rays at 405 nm of the substrate film.

(Determination of Ef(270)) Use a punching blade to punch the base film into a size of 5×35 mm in such a way that the long side is consistent with the direction of travel of the base film during manufacture, thereby obtaining a measurement sample. The obtained measurement sample was immersed in liquid nitrogen and cooled to -50°C. After that, a viscoelastic spectrometer (DVA-200, manufactured by IT Meter. and Control, Inc.) was used to increase the temperature in a constant-rate heating and stretching mode. The tensile modulus of elasticity was measured at a speed of 10°C/min and a frequency of 10 Hz, and the tensile modulus of elasticity of the base film at 270°C was measured.

(Measurement of storage elastic modulus G'before UV irradiation) Use a viscoelastic spectrometer (DVA-200, IT Meter. and Control, Inc.) for the UV-curing adhesive layer, and store it under the conditions of constant-rate heating shear mode, heating rate 10℃/min, and frequency 10 Hz For the measurement of elastic modulus, obtain the storage elastic modulus G'of the UV-curing adhesive layer at 23°C before UV irradiation.

(Measurement of gel fraction after ultraviolet irradiation) Using a high-pressure mercury ultraviolet irradiation machine, irradiate 405 nm ultraviolet rays on the surface of the adhesive tape from the base film side of the adhesive tape so that the cumulative intensity becomes 3000 mJ/cm ² , To cross-link and harden the UV-curing adhesive layer. Secondly, scrape only 0.1 g of the cured UV-curable adhesive layer, immerse it in 50 ml of ethyl acetate, and shake it for 24 hours at a temperature of 23 degrees and 120 rpm (below, the The ultraviolet curable adhesive layer is called an adhesive composition). After shaking, use a metal mesh (mesh#200 mesh) to separate ethyl acetate from the adhesive composition that has absorbed ethyl acetate and swelled. The separated adhesive composition is dried at 110°C for 1 hour. The weight of the adhesive composition containing the metal mesh after drying was measured, and the gel fraction after ultraviolet irradiation was calculated using the following formula. Gel fraction (%)=100×(W ₁ －W ₂ )/W ₀ (W ₀ : initial weight of adhesive composition, W ₁ : weight of adhesive composition including metal mesh after drying, W ₂ : The initial weight of the metal mesh)

(Measurement of Et(270)) Using a high-pressure mercury ultraviolet irradiation machine, irradiate 405 nm of ultraviolet rays on the surface of the adhesive tape from the base film side of the adhesive tape so that the cumulative intensity becomes 3000 mJ/cm ² to harden the ultraviolet rays Type adhesive layer is cross-linked and hardened. Secondly, press with a punching blade in such a way that the long side is consistent with the direction of travel when the adhesive tape is manufactured, thereby making a 5 mm×35 mm test piece. The obtained test piece was immersed in liquid nitrogen and cooled to -50°C. After that, a viscoelastic spectrometer (DVA-200, manufactured by IT Meter. and Control, Inc.) was used in a constant-rate heating and stretching mode, The temperature is raised to 300°C under the conditions of a heating rate of 10°C/min and a frequency of 10 Hz, and the tensile elastic modulus is measured. The value of the tensile modulus (E') at the temperature X°C at this time is set to Et(X). That is, the value of the tensile modulus (E') at a temperature of 270°C is set to Et(270).

(Calculation of Et(270)/Et(200)) Using the same method as Et (270) for the obtained adhesive tape, the tensile elastic modulus (Et (200)) of the adhesive tape at 200°C was measured. Calculate Et(270)/Et(200) based on the obtained Et(270) and Et(200) results.

5 mm之圓狀而獲得測定樣本。測定所獲得之測定樣本之重量，使用示差熱熱重量同時測定裝置（TG-DTA；STA7200，日立高新技術科技股份有限公司製造），測定以升溫速度5℃/min自25℃升溫至280℃後保持10分鐘後之重量減少量。根據加熱前後之重量算出重量減少率。(Measurement of weight loss rate) Using a high-pressure mercury ultraviolet irradiation machine, 405 nm ultraviolet rays are irradiated to the surface of the adhesive tape from the base film side of the obtained adhesive tape so that the cumulative intensity becomes 3000 mJ/cm ^{2 to} make the ultraviolet hardening type The adhesive layer is cross-linked and hardened. Secondly, stamp the adhesive tape into

5 mm round shape to obtain a measurement sample. Measure the weight of the obtained measurement sample using a differential thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Technology Co., Ltd.), and measure the temperature from 25°C to 280°C at a heating rate of 5°C/min The weight loss after keeping for 10 minutes. Calculate the weight loss rate based on the weight before and after heating.

(Examples 2 to 10, Comparative Examples 1 to 4) Except that the material and thickness of the base film, and the composition of the ultraviolet-curing adhesive layer were changed as shown in Table 1, an adhesive tape was obtained in the same manner as in Example 1, and each measurement was performed. The details of each material are shown below. Furthermore, in Example 5, the ultraviolet curable adhesive B shown below was used. (1) Material of base film EXPEEK: Aromatic polyether ether ketone, manufactured by Kurabo Upilex: Copolymer of biphenyltetracarboxylic dianhydride and p-phenylenediamine, manufactured by Ube Industries Co., Ltd. Torcena: Special polyester, manufactured by Kurabo Kapton: Copolymer of pyromellitic dianhydride and diaminodiphenyl ether, manufactured by Toray DuPont

(2) Ultraviolet curing adhesive B (Manufacture of UV-curing adhesive B) Prepare a reactor equipped with a thermometer, a stirrer, and a cooling tube, and add 94 parts by weight of 2-ethylhexyl acrylate as an alkyl (meth)acrylate and methacrylic acid as a functional group-containing monomer to the reactor After 6 parts by weight of hydroxyethyl, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator was added to the above-mentioned reactor, and polymerization was started under reflux. Next, after 1 hour and 2 hours from the start of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane were added each, and further, After 4 hours from the start of polymerization, 0.05 parts by weight of tertiary hexyl peroxide pivalate was added to continue the polymerization reaction. And 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained. To 100 parts by weight of the resin solid content of the ethyl acetate solution containing a functional group-containing (meth)acrylic polymer, 1.0 part by weight of 2-isocyanatoethyl methacrylate was added as a functional group-containing unsaturated compound The reaction proceeds to obtain a polymerizable polymer (acrylic polymer) B. Thereafter, 100 parts by weight of the resin solid content of the ethyl acetate solution of acrylic polymer B obtained were mixed with 20 parts by weight of release agent (polysiloxane), 3 parts by weight of filler, 10 parts by weight of urethane acrylate, and 0.2 parts by weight of the coupling agent and 1 part by weight of the photopolymerization initiator were used to obtain an ethyl acetate solution of the ultraviolet-curing adhesive B. In addition, the mold release agent (polysiloxane), filler, urethane acrylate, crosslinking agent, and photopolymerization initiator are the same types of UV-curing adhesive A.

(3) Other Photosensitizer: KAYACURE DETX-S, manufactured by Nippon Kayaku

＜Evaluation＞ The adhesive tapes obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.

(Evaluation of heat resistance) The ultraviolet-curable adhesive layer side of the adhesive tape cut into a circle with a diameter of 20 cm is attached to a silicon wafer with a diameter of 20 cm and a thickness of about 750 μm. Next, attach the adhesive layer side of the adhesive tape to a glass wafer with a diameter of 20 cm and a thickness of 0.6 mm (manufactured by Tempax, SCHOTT). After attaching, irradiate the UV-curing adhesive layer with 405 nm wavelength ultraviolet light from the glass wafer surface side with the filter to cut off the wavelength below 365 nm with a cumulative intensity of 3000 mJ/cm ² , Cross-link and harden the UV-curing adhesive layer and adhesive layer. Place the obtained laminate of silicon wafer/adhesive tape/glass wafer with the silicon wafer side down on a heating plate (NINOSND-3H, manufactured by AZONE) set at 280°C, and measure until it is produced The peeling time of the adhesive tape.

(Evaluation of peelability) The UV-curable adhesive layer side of the adhesive tape was bonded to a silicon wafer with a diameter of 20 cm and a thickness of approximately 750 μm, and the adhesive layer side was attached to the adhesive tape with a diameter of 20 cm and a thickness of 0.6 mm Of the glass wafers to obtain a laminate. Secondly, use a high-pressure mercury ultraviolet irradiation machine to irradiate 405 nm ultraviolet rays from the glass wafer side for 30 seconds, adjust the illuminance so that the irradiation intensity on the adhesive tape surface of the adhesive tape becomes 100 mW/cm ² , and the ultraviolet-curing adhesive layer And the adhesive layer is cross-linked and hardened. After that, the laminate was placed on a hot plate set at 280°C with the silicon wafer side facing down, and heat-treated for 10 minutes and cooled. After cooling, the adhesive tape is peeled from the silicon wafer. The case where the adhesive tape can be easily peeled off is marked as "○", and the case where it cannot be peeled is marked as "×" to evaluate the peelability. In addition, when the adhesive tape is peeled within 10 minutes, the heat treatment is stopped during the peeling stage, and the peelability after cooling is evaluated.

(Evaluation of paste residue) In the evaluation of peelability, observe the silicon wafer after the adhesive tape has been peeled off with an optical microscope. Mark the case where the area of the paste remains less than 5% of the total silicon wafer as "◎", and the area of the paste remains as If 5% or more and less than 20% are marked as "○", if the area of paste remaining is 20% or more and less than 50% is marked as "△", if the area of paste remaining is more than 50% It is marked with "×" to evaluate the paste residue.

＝20 μm、凸塊間距離30 μm、凸塊高度45 μm）之形成有凸塊之面。其次，將黏著帶之黏著劑層側貼附於直徑20 cm、厚度0.6 mm之玻璃晶圓（Tempax、SCHOTT公司製造）。貼附後，於利用濾波器截斷365 nm以下之波長之狀態下，以累計強度成為3000 mJ/cm² 之方式自玻璃晶圓面側對紫外線硬化型黏著劑層照射405 nm之波長之紫外線光，使紫外線硬化型黏著劑層及黏著劑層交聯、硬化。利用設定為200℃之烘箱將所獲得之矽晶圓/黏著帶/玻璃晶圓之積層體以玻璃晶圓側朝下之方式靜置1小時，進行加熱處理。 加熱處理後，使用倒裝芯片接合機（FC6000，SHIBAURA MECHATRONICS CORPORATION製造），將厚度50 μm之單晶矽薄晶圓晶片積層於恢復至常溫之積層體之矽晶圓上。具體而言，於設定為80℃之SUS載置台上，以矽晶圓面朝上之方式吸附積層體，使用頭部尺寸10 mm×10 mm之陶瓷工具積層單晶矽薄晶圓晶片（附有9.8 mm×9.8 mm、厚度50 μm、表面粗糙度未達0.1 μm、厚度25 μm之接合膜）。將積層時之頭部之溫度設為280℃，壓力設為300 N，積層時間設為90秒。 積層單晶矽薄晶圓晶片之後，將黏著帶自矽晶圓剝離。將於剝離時能夠容易剝離黏著帶之情形標記為「○」，將無法剝離之情形標記為「×」，以此評價熱壓合時之剝離性。(Evaluation of peelability during thermocompression bonding) The UV-curable adhesive layer side of the adhesive tape cut into a circle with a diameter of 20 cm is attached to a bumped silicon wafer (convex) with a diameter of 20 cm and a thickness of 50 μm. Block diameter

= 20 μm, distance between bumps 30 μm, bump height 45 μm) on the surface where bumps are formed. Next, attach the adhesive layer side of the adhesive tape to a glass wafer with a diameter of 20 cm and a thickness of 0.6 mm (manufactured by Tempax, SCHOTT). After attaching, irradiate the UV-curing adhesive layer with 405 nm wavelength ultraviolet light from the glass wafer surface side with the filter to cut off the wavelength below 365 nm with a cumulative intensity of 3000 mJ/cm ² , Cross-link and harden the UV-curing adhesive layer and adhesive layer. In an oven set at 200°C, the obtained laminated body of silicon wafer/adhesive tape/glass wafer was allowed to stand for 1 hour with the glass wafer side facing down, and heat treatment was performed. After the heat treatment, using a flip chip bonding machine (FC6000, manufactured by SHIBAURA MECHATRONICS CORPORATION), a single crystal silicon thin wafer with a thickness of 50 μm is laminated on the laminated silicon wafer that is restored to normal temperature. Specifically, on a SUS mounting table set at 80℃, the laminated body is adsorbed with the silicon wafer facing up, and a ceramic tool with a head size of 10 mm×10 mm is used to laminate single crystal silicon thin wafers (attached There are bonding films of 9.8 mm×9.8 mm, thickness 50 μm, surface roughness less than 0.1 μm, thickness 25 μm). Set the temperature of the head during lamination to 280°C, the pressure to 300 N, and the lamination time to 90 seconds. After laminating single-crystal silicon thin wafers, the adhesive tape is peeled from the silicon wafers. The case where the adhesive tape can be easily peeled off during peeling is marked as "○", and the case where it cannot be peeled off is marked as "×" to evaluate the peelability during thermal compression bonding.

(Evaluation of paste residue during hot pressing) In the evaluation of the peelability during thermal compression bonding, an optical microscope was used to observe the silicon wafer after the adhesive tape was peeled off. Among the bumps in the 500 μm square, the bumps with paste residue below 5% are marked as "◎", the bumps with paste residue are more than 5% and less than 20% The situation is marked as "〇", the situation where there are more than 20% of the paste residue and less than 50% is marked as "△", and the situation where the paste residue is more than 50% is marked as " ×" to evaluate the paste residue during hot pressing.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Adhesive tape Base film material UNIAMIDE Transparent polyimide EXPEEK Upilex UNIAMIDE Upilex Upilex UNIAMIDE Torcena UNIAMIDE Polyethylene naphthalate Kapton no UNIAMIDE Ultraviolet penetration rate (%) 79 78 60 3 79 1 0.8 79 79 79 66 0 - 79 Ef(270)(Pa) 9.0×10 ⁷ 3.0×10 ⁹ 6.0×10 ⁹ 2.0×10 ⁹ 9.0×10 ⁷ 2.0×10 ⁹ 2.0×10 ⁹ 9.0×10 ⁷ 2.0×10 ⁷ 9.0×10 ⁷ 3.0×10 ⁴ 2.0×10 ⁸ - 9.0×10 ⁷ Thickness (μm) 25 25 25 25 25 50 75 25 25 25 25 25 - 25 UV curable adhesive layer UV-curing adhesive A A A A B A A A A A A A A A Photosensitizer (parts by weight) 0 0 0 5 0 5 5 0 0 0 0 0 0 0 Photopolymerization initiator (parts by weight) 1 1 1 1 1 1 1 0.5 1 1 1 1 1 0.05 Release agent (parts by weight) 20 20 20 20 20 20 20 20 20 40 20 20 20 20 Storage elastic modulus G'(Pa) before UV irradiation 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 2.2×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ 3.1×10 ⁴ Gel fraction after ultraviolet radiation (%) 98 97 98 93 93 90 91 95 98 98 99 50 - 85 Et(270)(Pa) 1.7×10 ⁷ 2.8×10 ⁸ 7.3×10 ⁸ 7.5×10 ⁸ 1.2×10 ⁷ 8.4×10 ⁷ 9.1×10 ⁷ 1.3×10 ⁷ 1.1×10 ⁷ 1.7×10 ⁷ 4.3×10 ⁶ 2.2×10 ⁸ 1.4×10 ⁷ 1.5×10 ⁷ Et(270)/Et(200) 0.31 0.57 0.65 0.80 0.30 0.85 0.95 0.15 0.08 0.31 0.06 1.21 0.80 0.20 Weight reduction rate (%) 4 4 4 5 5 5 5 4 4 10 4 4 4 4 Evaluation Heat resistance (280℃) 5 min 9 min 10 min 10 min 6 min 10 min 11 min 3 min 2 min 3 min ＜1 min 7 min 5 min 7 min Peelability 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 × 〇 Paste residue ◎ ◎ ◎ 〇 〇 △ △ ◎ ◎ ◎ ◎ × × × Peelability during hot pressing 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 × 〇 Paste residue during hot pressing 〇 〇 〇 △ 〇 × × ◎ ◎ ◎ ◎ × × × [Industrial availability]

According to the present invention, it is possible to provide an adhesive tape that can protect an adherend even when it is used in a step accompanied by a high-temperature treatment up to 260° C. and can be peeled off without a paste residue.

no

no

Claims (10)

An adhesive tape having a substrate film and an ultraviolet curable adhesive layer laminated on one side of the substrate film, and irradiating 3000 mJ/cm ² of 405 nm to the surface of the substrate film side of the adhesive tape The gel fraction of the ultraviolet-curable adhesive layer after ultraviolet rays is 90% or more, and the adhesive tape is irradiated with 3000 mJ/cm ² of ultraviolet rays of 405 nm on the surface of the substrate film side of the adhesive tape on X When the tensile modulus of elasticity at ℃ is set to Et(X), the value of Et(270) is 1.0×10 ⁷ Pa or more. Such as the adhesive tape of claim 1, wherein the 405 nm ultraviolet light transmittance of the above-mentioned base film is more than 1%. Such as the adhesive tape of claim 1 or 2, where the value of Et(270)/Et(200) is 0.1 or more. The adhesive tape of 2 or 3, wherein when the tensile elastic modulus of the base film at X°C is Ef(X), the value of Ef(270) is 5.0×10 ⁷ Pa or more. The adhesive tape of 2, 3 or 4, wherein the surface of the substrate film side of the adhesive tape is irradiated with 3000 mJ/cm ² of the 405 nm ultraviolet light, and the temperature is raised from 25°C to 280 at a rate of 5°C/min ℃, the weight loss rate when kept for 10 minutes after heating up is 5% or less. The adhesive tape of 2, 3, 4, or 5, wherein the base film contains a resin having at least one selected from the group consisting of amides, imines, ethers and ketones in the main chain skeleton of the repeating unit 1 kind. The adhesive tape of 2, 3, 4, 5 or 6, wherein the base film contains a polyamide resin, and the polyamide resin has a long chain with a carbon number of 4 or more and 12 or less in the main chain skeleton of the repeating unit Alkyl or aromatic. The adhesive tape of 2, 3, 4, 5, 6, or 7, wherein the above-mentioned ultraviolet-curable adhesive layer has: (Meth)acrylic acid alkyl ester polymerizable polymer having radical polymerizable unsaturated bond in the molecule, Polymerization initiator, and Polysiloxane or fluorine compound having a functional group that can be cross-linked with the above-mentioned polymerizable polymer. The adhesive tape of 2, 3, 4, 5, 6, 7, or 8, wherein the substrate film has an adhesive layer on the opposite side of the surface on which the ultraviolet-curable adhesive layer is laminated. Adhesive tapes of 2, 3, 4, 5, 6, 7, 8, or 9 are used to manufacture electronic parts.