JP2014015580A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive tape that is easily releasable from an adherend without an adhesive residue upon being irradiated with rays of light even after undergoing high-temperature processing.SOLUTION: An adhesive tape includes an adhesive layer comprising an adhesive composition containing a photocurable adhesive component and a photoinitiator on at least one face of a base material. On the surface of the base material on the side in contact with the adhesive layer, an anchor agent layer with a storage elastic modulus of 1.0×10Pa or more at 260°C is formed.

Description

The present invention relates to a pressure-sensitive adhesive tape that can be easily peeled off from an adherend without leaving adhesive residue even after a high temperature processing process.

In the manufacture of semiconductors, a semiconductor processing tape is applied to facilitate handling of the semiconductor during processing and prevent damage. For example, when a thick film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to form a thin film wafer, a double-sided adhesive tape is used to bond and reinforce the thick film wafer to a support plate. Used. An adhesive tape called a dicing tape is also used when dicing a thin film wafer ground to a predetermined thickness into individual IC chips.

The tape for semiconductor processing is required to have high adhesiveness capable of firmly fixing the semiconductor during the processing step and to be able to be peeled off after the step without damaging the semiconductor. On the other hand, Patent Document 1 discloses a pressure-sensitive adhesive tape using a photo-curing pressure-sensitive adhesive that is cured by irradiating light such as ultraviolet rays to reduce adhesive strength. Such an adhesive tape can reliably fix the semiconductor during the processing step and can be easily peeled off by irradiating with ultraviolet rays or the like.
Even if it is an adhesive tape using such a photocurable adhesive, when it is used at the time of processing a semiconductor having a heating process, it is exposed to ultraviolet rays or the like to reduce the adhesive force and peel off. There was a problem that adhesive residue was generated on the body.
In recent years, an increasing number of semiconductor processing requires a high-temperature processing process exceeding 200 ° C. such as a CVD process and a solder reflow process. After such a high temperature processing process, even if it is the photocurable adhesive described in Patent Document 1, the adhesive remains on the adherend after peeling. Such a problem of adhesive residue was particularly remarkable when irregularities such as circuits were formed on the non-attached surface.

JP-A-5-32946

An object of this invention is to provide the adhesive tape which can be easily peeled off from a to-be-adhered body without leaving an adhesive residue by irradiating light, even after passing through a high temperature processing process.

The present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a photocurable pressure-sensitive adhesive component and a photopolymerization initiator on at least one surface of a substrate, wherein the pressure-sensitive adhesive layer Is an adhesive tape in which an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more is formed on the surface of the substrate in contact with the substrate.
The present invention is described in detail below.

The present inventor attempted to solve the problem of adhesive residue by applying a treatment for improving the adhesive force between the base material and the adhesive, such as a corona treatment or an anchor agent treatment, to the base material of the adhesive tape. It was. However, in the conventional processing method, the anchor agent and the pressure-sensitive adhesive sometimes peel off during the high-temperature processing process, and it has not been possible to prevent adhesive residue.

As a result of intensive studies, the inventor formed an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more on the surface of the base material, so that the anchor agent layer It has been found that peeling from the pressure-sensitive adhesive layer can be prevented and adhesive residue can be reliably prevented, and the present invention has been completed.
The cause of the adhesive residue on the adherend when peeled after being subjected to a high temperature processing process is the result of the adhesive force of the adhesive being increased by heating, even after the adhesive force has been reduced by light irradiation, It was thought that the adhesive force between the adherend and the adhesive exceeded the adhesive force between the substrate and the adhesive at least partially. Also in the conventional adhesive tape, for the purpose of improving the adhesive force between the substrate and the adhesive layer, the surface of the substrate is subjected to corona treatment, anchor agent treatment or the like. However, the effect of improving the adhesive strength by the corona treatment was slight, and practically it was not useful for preventing adhesive residue. On the other hand, the conventional anchor agent can exhibit a relatively high adhesive force improving effect in a temperature range from room temperature to about 200 ° C. However, when the temperature exceeds 200 ° C., particularly above 230 ° C., the effect of improving the adhesive strength is abruptly reduced, so that the anchor agent and the adhesive are peeled off during the high-temperature processing process, thereby preventing adhesive residue. I could not.

As a result of investigation by the present inventor, it has been found that the conventional anchor agent softens when the temperature exceeds 230 ° C., and the shear storage elastic modulus suddenly decreases, thereby losing the effect of improving the adhesive strength.
In the pressure-sensitive adhesive tape of the present invention, by forming an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more on the surface of the base material, even after a high temperature processing process exceeding 200 ° C. The anchor agent layer and the pressure-sensitive adhesive layer can be prevented from peeling off during the high-temperature processing process, and the adhesive force between the substrate and the pressure-sensitive adhesive layer can be maintained, so that adhesive residue can be reliably prevented.
In this specification, the shear storage modulus is the storage elasticity when measured in the measurement mode in dynamic viscoelasticity measurement: shear, temperature rising rate: 5 ° C./min, frequency: 10 Hz, strain: 0.5%. Means rate.

The pressure-sensitive adhesive tape of the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on at least one surface of a substrate.
The base material is, for example, a sheet made of a transparent resin such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, or a network structure. And a sheet having a hole and the like.

In the base material, an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more is formed on the surface in contact with the pressure-sensitive adhesive layer. By having such an anchor agent layer, the pressure-sensitive adhesive tape of the present invention can be easily peeled off from the adherend without being left behind by irradiation with light even after undergoing a high-temperature processing process. The preferable lower limit of the storage elastic modulus at 260 ° C. of the anchor agent layer is 5.0 × 10 ⁵ Pa, and the more preferable lower limit is 1.0 × 10 ⁶ Pa. The upper limit of the storage elastic modulus at 260 ° C. of the anchor agent layer is not particularly limited.

As a method for forming an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more, for example, an anchor agent containing a cross-linking agent is applied to the surface of the substrate, and the degree of cross-linking is The method of hardening so that it may become 90% or more is mentioned. Furthermore, when an anchor agent contains an inorganic filler or a metal oxide, the storage elastic modulus at 260 ° C. of the anchor agent layer can be more easily adjusted to 1.0 × 10 ⁵ Pa or more.
The degree of cross-linking of the anchor agent layer can be measured by gel fraction measurement. The gel fraction of the anchor agent can be measured by dispersing the anchor agent in an organic solvent such as ethyl acetate, stirring with a shaker for 8 hours or more, and then measuring the dry weight of the undissolved portion.

Although it does not specifically limit as an inorganic filler or a metal oxide mix | blended with the said anchor agent, For example, a silica nano filler, an alumina nano filler, a zirconia filler, a carbon nano filler, a glass filler, a titania filler, a zinc oxide filler etc. are mentioned.
Although the compounding quantity of the inorganic filler or metal oxide mix | blended with the said anchor agent is not specifically limited, The preferable upper limit of the compounding quantity of the inorganic filler or metal oxide with respect to a total of 100 weight part of the main ingredient of an anchor agent, a crosslinking agent, and a catalyst is 40. The upper limit is more preferably 30 parts by weight.

The preferable lower limit of the thickness of the anchor agent layer is 0.1 μm, and the preferable upper limit is 3 μm. If the thickness of the anchor agent layer is less than 0.1 μm, the adhesive force between the adhesive layer and the substrate cannot be sufficiently improved, and the adherend is not left behind after a high-temperature processing process. In some cases, it is difficult to peel off the film, and even if an anchor agent layer having a thickness of more than 3 μm is formed, there is no further effect. The more preferable lower limit of the thickness of the anchor agent layer is 0.5 μm, and the more preferable upper limit is 1.5 μm.

The pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition containing a photocurable pressure-sensitive adhesive component and a photopolymerization initiator. When such a pressure-sensitive adhesive layer is irradiated with light, the pressure-sensitive adhesive tape is peeled off from the adherend because it is cured and the adhesive strength is reduced.
The photocurable pressure-sensitive adhesive component (hereinafter also simply referred to as “pressure-sensitive adhesive component”) is not particularly limited, and a conventionally known one can be used. Specifically, for example, a photo-curable pressure-sensitive adhesive mainly composed of a (meth) acrylic acid alkyl ester-based polymerizable polymer having a radical polymerizable unsaturated bond in the molecule can be used.
Such a photocurable pressure-sensitive adhesive is uniformly and quickly polymerized and cross-linked by light irradiation, so that the elastic modulus is remarkably increased due to polymerization and curing, and the adhesive strength is greatly reduced.

The polymerizable polymer is prepared by, for example, previously synthesizing a (meth) acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth) acrylic polymer) and reacting with the functional group in the molecule. It can obtain by making it react with the compound (henceforth a functional group containing unsaturated compound) which has a functional group to perform and a radically polymerizable unsaturated bond.

The functional group-containing (meth) acrylic polymer is an acrylic having an alkyl group usually in the range of 2 to 18 as a polymer having adhesiveness at room temperature, as in the case of a general (meth) acrylic polymer. By copolymerizing an acid alkyl ester and / or methacrylic acid alkyl ester as a main monomer, a functional group-containing monomer, and, if necessary, another modifying monomer copolymerizable therewith by a conventional method It is obtained. The weight average molecular weight of the functional group-containing (meth) acrylic polymer is usually about 200,000 to 2,000,000.

Examples of the functional group-containing monomer include a carboxyl group-containing monomer such as acrylic acid and methacrylic acid; a hydroxyl group-containing monomer such as hydroxyethyl acrylate and hydroxyethyl methacrylate; and an epoxy group containing glycidyl acrylate and glycidyl methacrylate. Monomers; Isocyanate group-containing monomers such as isocyanate ethyl acrylate and isocyanate ethyl methacrylate; and amino group-containing monomers such as aminoethyl acrylate and aminoethyl methacrylate.
Examples of other modifying monomers that can be copolymerized include various monomers used in general (meth) acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.

The functional group-containing unsaturated compound to be reacted with the functional group-containing (meth) acrylic polymer is the same as the functional group-containing monomer described above according to the functional group of the functional group-containing (meth) acrylic polymer. it can. 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 is used, and when the functional group is a hydroxyl group, an isocyanate group-containing monomer is used. When the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used, and when the functional group is an amino group, an epoxy group-containing monomer is used.

The (meth) acrylic acid alkyl ester-based polymerizable polymer having a radical polymerizable unsaturated bond in the molecule may be used in combination with a polyfunctional oligomer or monomer.
The polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5, so that the three-dimensional network of the pressure-sensitive adhesive layer can be efficiently formed by heating or light irradiation. 000 or less and the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20. Examples of such more preferable polyfunctional oligomers or monomers include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate. Or the above-mentioned methacrylates etc. are mentioned. Other examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and methacrylates similar to those described above. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include those activated by irradiation with light having a wavelength of 250 to 800 nm. Examples of such a photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone. Benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether; ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal; phosphine oxide derivative compounds; bis (η5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone Chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl pro Examples thereof include photo radical polymerization initiators such as bread. These photoinitiators may be used independently and 2 or more types may be used together.

The pressure-sensitive adhesive composition preferably contains fumed silica.
By adding fumed silica, the heat resistance of the pressure-sensitive adhesive composition is improved and the tensile strength is remarkably improved, so that the pressure-sensitive adhesive is less likely to break depending on the stress at the time of peeling even after a high temperature processing process. Thus, adhesive residue can be further prevented.

The preferable lower limit of the average particle diameter of the fumed silica is 0.05 μm, and the preferable upper limit is 3 μm. When the average particle size of the fumed silica is within this range, high heat resistance that does not cause floating even when subjected to a high-temperature processing process, and high adhesive that does not remain even when peeled after undergoing a high-temperature processing process Non-glue residue can be exhibited. The more preferable lower limit of the average particle diameter of the fumed silica is 0.06 μm, the more preferable upper limit is 2 μm, the still more preferable lower limit is 0.07 μm, and the still more preferable upper limit is 1 μm.
In addition, in this specification, the average particle diameter of fumed silica is determined by using any of the laser scattering / diffraction method or the dynamic light scattering method, methyl ethyl ketone, methyl ethyl ketone / toluene (60:40) solution before blending, or the like. The particle diameter of fumed silica dispersed in the medium is measured.

As for the compounding quantity of the said fumed silica, the preferable minimum with respect to 100 weight part of said adhesive components is 10 weight part, and a preferable upper limit is 40 weight part. When the blended amount of the fumed silica is within this range, high heat resistance that does not cause floating even when subjected to a high-temperature processing process, and high non-stickiness that does not remain even when peeled after undergoing a high-temperature processing process. Adhesive residue can be exhibited. The more preferred lower limit of the amount of fumed silica blended is 15 parts by weight, the more preferred upper limit is 38 parts by weight, the still more preferred lower limit is 20 parts by weight, and the still more preferred upper limit is 35 parts by weight.

The pressure-sensitive adhesive composition of the present invention preferably further contains a silicone compound having a functional group capable of crosslinking with the photocurable pressure-sensitive adhesive component (hereinafter also simply referred to as “silicone compound A”).
Since the silicone compound is excellent in heat resistance, the adhesive is prevented from being burnt even after a high-temperature processing process, and at the time of peeling, it bleeds out to the adherend interface to facilitate peeling. Since the silicone compound has a functional group capable of cross-linking with the pressure-sensitive adhesive component, it is incorporated into the pressure-sensitive adhesive component by chemically reacting with the pressure-sensitive adhesive component by light irradiation at the time of peeling. The compound will not adhere and contaminate.

The silicone skeleton of the silicone compound A is not particularly limited, and may be either D-form or DT-form.
The silicone compound A preferably has the functional group at the side chain or terminal of the silicone skeleton.
In particular, the use of a silicone compound having a D-form silicone skeleton and having a functional group capable of crosslinking with the above-mentioned pressure-sensitive adhesive component at the end achieves both high initial adhesive strength and peeling strength after a high-temperature processing process. It is preferable because it is easy.

As the functional group of the silicone compound A, an appropriate one is selected and used according to the pressure-sensitive adhesive component. For example, when the pressure-sensitive adhesive component is a photocurable pressure-sensitive adhesive mainly composed of a (meth) acrylic acid alkyl ester-based polymerizable polymer having a radical polymerizable unsaturated bond in the molecule, (meth) A functional group capable of crosslinking with an acrylic group is selected.
The functional group capable of crosslinking with the (meth) acryl group is a functional group having an unsaturated double bond, and specific examples include a vinyl group, a (meth) acryl group, an allyl group, and a maleimide group. .

The functional group equivalent of the silicone compound A is not particularly limited, but the preferred lower limit is 1, and the preferred upper limit is 20. When the functional group equivalent is less than 1, the silicone compound A is not sufficiently taken into the pressure-sensitive adhesive component when the resulting pressure-sensitive adhesive composition is cured, and the adherend is contaminated or exhibits sufficient peelability. If it exceeds 20, sufficient adhesive strength may not be obtained. A more preferred upper limit of the functional group equivalent is 10, a more preferred lower limit is 2, and a more preferred upper limit is 6.

The molecular weight of the silicone compound A is not particularly limited, but a preferred lower limit is 300 and a preferred upper limit is 50000. If the molecular weight is less than 300, the resulting pressure-sensitive adhesive composition may have insufficient heat resistance, and if it exceeds 50,000, mixing with the pressure-sensitive adhesive component may be difficult. The more preferable lower limit of the molecular weight is 400, the more preferable upper limit is 10,000, the still more preferable lower limit is 500, and the more preferable upper limit is 5000.

The method of synthesizing the silicone compound A is not particularly limited. For example, by reacting a silicone resin having a SiH group and a vinyl compound having a functional group capable of crosslinking with the pressure-sensitive adhesive component, by a hydrosilylation reaction, Examples thereof include a method of introducing a functional group capable of crosslinking with the pressure-sensitive adhesive component into the silicone resin, and a method of causing a condensation reaction between the siloxane compound and a siloxane compound having a functional group capable of crosslinking with the pressure-sensitive adhesive component.

Examples of commercially available silicone compounds A include X-22-164, X-22-164AS, X-22-164A, X-22-164B, and X-22-164C manufactured by Shin-Etsu Chemical Co., Ltd. , A silicone compound having methacrylic groups at both ends such as X-22-164E, and a methacrylic group at one end such as X-22-174DX, X-22-2426, X-22-2475 manufactured by Shin-Etsu Chemical Co., Ltd. Silicone compounds having acrylic groups such as EBECRYL350 and EBECRYL1360 manufactured by Daicel Cytec, silicone compounds having acrylic groups such as AC-SQ TA-100 and AC-SQ SI-20 manufactured by Toagosei Co., Ltd. MAC-SQ TM-100, MAC-SQ SI-20, MAC-S manufactured by Toagosei Co., Ltd. Silicone compounds having a methacryl group such as HDM and the like.

Among these, the silicone compound A has particularly high heat resistance and high polarity, so that bleeding out from the pressure-sensitive adhesive composition is easy. Therefore, the following general formula (I), general formula (II), and general formula A silicone compound represented by (III) having a (meth) acryl group in the siloxane skeleton is preferred.

In the formula, X and Y represent an integer of 0 to 1200 (except when X and Y are both 0), and R represents a functional group having an unsaturated double bond.

Of the silicone compounds having a (meth) acryl group in the siloxane skeleton represented by the above general formula (I), general formula (II), or general formula (III), commercially available products are, for example, manufactured by Daicel Cytec Co., Ltd. EBECRYL350, EBECRYL1360 (both of which R is an acrylic group) and the like.

Although content of the said silicone compound A is not specifically limited, A preferable minimum is 0.1 weight% and a preferable upper limit is 30 weight%. If the content of the silicone compound A is less than 0.1% by weight, it may not be peeled from the adherend, and if it exceeds 30% by weight, the initial adhesive strength may not be obtained. The more preferable lower limit of the content of the silicone compound A is 0.2% by weight, and the more preferable upper limit is 20% by weight.

The content of the silicone compound A is preferably 0.5 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive component, and 40 parts by weight with a preferred upper limit. When the content of the silicone compound A is less than 0.5 parts by weight, the adhesive strength may not be sufficiently reduced even when irradiated with light, and may not be peeled off from the adherend. May cause body contamination. The more preferable lower limit of the content of the silicone compound A is 1 part by weight, and the more preferable upper limit is 30 parts by weight.

The pressure-sensitive adhesive composition may further contain a rubber elastic oligomer.
Since the tensile strength of the cured product of the above-mentioned pressure-sensitive adhesive composition is improved by blending the rubber elastic oligomer, the pressure-sensitive adhesive is less likely to break depending on the stress at the time of peeling, even after a high temperature processing process, and more adhesive residue Can be prevented.
Examples of the rubber elastic oligomer include U-200PA, UA-4200, UA-122P manufactured by Shin-Nakamura Chemical Co., Ltd., UV-3520TL, UV-3700, UV-3000B, UV-2000B manufactured by Nippon Synthetic Chemical Co., Ltd. Examples thereof include UV-3300B, UV-3500BA, UN-5500, UN-7700, UN-6300, UN-6301, UN-952 manufactured by Negami Kogyo Co., Ltd.

The said adhesive composition may contain the gas generating agent which generate | occur | produces gas further by irradiating light. When light is applied to the pressure-sensitive adhesive composition containing such a gas generating agent, the photocurable pressure-sensitive adhesive component is cross-linked and cured to increase the elastic modulus of the entire pressure-sensitive adhesive, and in such a hard pressure-sensitive adhesive. The generated gas is released from the pressure-sensitive adhesive to the bonding interface and peels at least a part of the bonding surface, so that peeling can be facilitated.
Although the said gas generating agent is not specifically limited, For example, an azide compound, an azo compound, a ketoprofen, a tetrazole compound etc. are mentioned. Of these, ketoprofen and tetrazole compounds having excellent heat resistance are preferred.

The pressure-sensitive adhesive composition of the present invention may appropriately contain various polyfunctional compounds that are blended with general pressure-sensitive adhesives such as isocyanate compounds, melamine compounds, and epoxy compounds for the purpose of adjusting the cohesive force. Moreover, well-known additives, such as an antistatic agent, a plasticizer, resin, surfactant, and wax, can also be added. Furthermore, you may mix | blend a heat stabilizer and antioxidant in order to improve stability of an adhesive.

The method for producing the pressure-sensitive adhesive tape of the present invention is not particularly limited. For example, the pressure-sensitive adhesive composition is applied to the anchor agent layer of the base material on which the anchor agent layer is formed using a doctor knife or a spin coater. A conventionally known method such as coating can be used.

The adhesive tape of the present invention can be easily peeled off from the adherend without leaving adhesive residue by irradiating light even after a high temperature processing process exceeding 200 ° C.
Although the high temperature processing process should just be 200 degreeC or more, the minimum temperature of a preferable high temperature processing process is 220 degreeC, and the more preferable minimum temperature is 230 degreeC. The upper limit of the high temperature processing process is not particularly limited, but is 300 ° C. or less, the preferable upper limit temperature is 280 ° C., and the more preferable upper limit temperature is 260 ° C.

A support plate fixing step of fixing the wafer to the support plate via the adhesive tape of the present invention, a wafer processing step of subjecting the surface of the wafer fixed to the support plate to a treatment involving heating exceeding 200 ° C., and the post-treatment A wafer processing method comprising: irradiating the wafer with light, curing the pressure-sensitive adhesive layer, and peeling the support plate from the wafer is also one aspect of the present invention.

The said support plate is not specifically limited, For example, a glass plate, a quartz glass plate, a stainless steel plate etc. are mentioned.
A process involving heating at 200 ° C. or higher on the surface of the wafer fixed to the support plate is not particularly limited, and examples thereof include chemical vapor deposition (CVD), reflow, and reactive ion etching (RIE).

ADVANTAGE OF THE INVENTION According to this invention, even after passing through a high temperature processing process, the adhesive tape which can be easily peeled from a to-be-adhered body can be provided, without remaining glue by irradiating light.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Formation of anchor agent layer Tokuyama Corporation as an inorganic filler with respect to 100 parts by weight of a mixture of AP2503D2 (main agent), CL2503 (crosslinking agent), and RA-1000 (catalyst) manufactured by Arakawa Chemical Industries, Ltd. An anchor agent was prepared by mixing 20 parts by weight of Leolosil MT10.
The obtained anchor agent was applied on one side of a transparent polyethylene naphthalate film having a thickness of 50 μm with a doctor knife so that the thickness of the dried film was 1 μm, and then dried at 110 ° C. for 5 minutes. Curing was performed to form an anchor agent layer.

About the obtained anchor agent layer, it was 91% when the crosslinking degree was measured by the gel fraction measuring method.
Moreover, when the shear storage elastic modulus at 260 ° C. was measured by measuring dynamic viscoelasticity (shear) of the anchor agent layer, it was 1.2 × 10 ⁶ Pa.

(2) Production of pressure-sensitive adhesive tape A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. In this reactor, 94 parts by weight of 2-ethylhexyl acrylate, 1 part by weight of acrylic acid, and 5 parts by weight of 2-hydroxyethyl acrylate Part, 0.01 part by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate were added, and the reactor was heated to start refluxing. Subsequently, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added as a polymerization initiator in the reactor, and polymerization was started under reflux. It was. Next, after 1 hour and 2 hours from the start of polymerization, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added, and the polymerization was started. 4 hours later, 0.05 part by weight of t-hexylperoxypivalate was added to continue the polymerization reaction. And 8 hours after the start of polymerization, an acrylic copolymer having a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained.

The resin solid content of 100 parts by weight of the ethyl acetate solution containing the acrylic copolymer thus obtained is reacted by adding 3.5 parts by weight of 2-isocyanatoethyl methacrylate, and further the resin of the ethyl acetate solution after the reaction. 1 part by weight of a photopolymerization initiator (Esacure One, manufactured by Nippon Shibel Hegner), 20 parts by weight of a plasticizer (UN-5500, manufactured by Negami Industrial Co., Ltd.), a polyisocyanate-based crosslinking agent (Coronate L45, 0.5 parts by weight of Nippon Polyurethane Co., Ltd. was mixed. 20 parts by weight of a fumed silica dispersion solution (manufactured by Tokuyama, Leolosil MT-10) in which fumed silica was dispersed in methyl ethyl ketone using a homogenizer in the obtained pressure-sensitive adhesive composition, and the average particle diameter was adjusted to 0.7 μm Was added to prepare an ethyl acetate solution.

Apply the ethyl acetate solution of the obtained pressure-sensitive adhesive composition on the anchor agent layer of the base material with a doctor knife so that the thickness of the dry film becomes 30 μm, and heat and apply at 110 ° C. for 5 minutes. The solution was dried. Thereafter, static curing was performed at 40 ° C. for 3 days to obtain an adhesive tape.

(Example 2)
An adhesive tape was obtained in the same manner as in Example 1 except that the main agent of the anchor agent was changed to AP2503C manufactured by Arakawa Chemical Industries.

(Example 3)
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that no inorganic filler was added to the anchor agent.

Example 4
An adhesive tape was obtained in the same manner as in Example 1 except that the main agent and the crosslinking agent of the anchor agent were changed to AP2510 and CL2500 manufactured by Arakawa Chemical Industries.

(Example 5)
An adhesive tape was obtained in the same manner as in Example 1 except that the main agent and the crosslinking agent of the anchor agent were changed to Nippon Shokubai Co., Ltd. Poliment NK-350 and JER YL980.

(Comparative Example 1)
An adhesive tape was obtained in the same manner as in Example 1 except that the anchor agent layer was not formed on the substrate and the surface treatment such as corona treatment was not performed.

(Comparative Example 2)
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the main agent of the anchor agent was changed to POLYMENT NK-350 manufactured by Nippon Shokubai Co., Ltd. and no crosslinking agent was blended.

(Comparative Example 3)
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1, except that the crosslinking agent and the inorganic filler were not blended in the anchor agent.

(Comparative Example 4)
A pressure-sensitive adhesive tape was obtained in the same manner as in Example 2 except that no crosslinking agent and inorganic filler were added to the anchor agent.

(Comparative Example 5)
An adhesive tape was obtained in the same manner as in Example 3 except that the crosslinking agent and the inorganic filler were not blended in the anchor agent.

(Evaluation)
About the adhesive tape obtained by the Example and the comparative example, it evaluated by the following method.
The results are shown in Table 1.

(1) Evaluation of adhesive strength between adhesive layer and substrate The adhesive tape was heated at 260 ° C. for 10 minutes. Thereafter, light having an illuminance of 254 nm and an intensity of 70 mW / cm ² was irradiated for 150 seconds from the substrate side using an ultrahigh pressure mercury lamp. About the adhesive tape after a heating and light irradiation, the base material was lined with the double-sided tape, and the peeling strength of an adhesive layer and a base material was measured by sticking and peeling the silicon tape made from Slion on an adhesive layer.

(2) Evaluation of heat resistance The adhesive tape cut into a circle having a diameter of 20 cm was attached to a silicon wafer (bare wafer) on which a circuit having a diameter of 20 cm and a thickness of about 750 μm was not formed. In this state, it was heated at 260 ° C. for 10 minutes. The adhesive surface between the heated adhesive tape and the silicon wafer was visually observed, and “◎” indicates that no lifting was observed over the entire surface, and “0.3” indicates that the lifting was less than 3% of the entire area. The case where the float was 3% or more and less than 10% of the entire area was evaluated as “Δ”, and the case where the float was 10% or more of the entire area was evaluated as “X”.
A similar evaluation was performed using a 700 μm thick silicon wafer (circuit wafer) on which a circuit having a step of about 5 μm was formed.

(3) Evaluation of adhesive residue The adhesive tape cut into a circle having a diameter of 20 cm was attached to a silicon wafer (bare wafer) on which a circuit having a diameter of 20 cm and a thickness of about 750 μm was not formed. In this state, it was heated at 260 ° C. for 10 minutes.
After heating, pasting a dicing tape on the side of the surface not adhering to the adhesive tape of the silicon wafer, adsorbed and fixed, illuminance 254nm using an extra-high pressure mercury lamp from the Tempax glass side, the light intensity 70 mW / cm ² Irradiated for 150 seconds. Thereafter, the glass was peeled off and the adhesive tape was peeled off. When the surface of the silicon wafer from which the adhesive tape has been peeled is visually observed, “◯” indicates that no adhesive residue is present, and “△” indicates that the adhesive residue is less than 5% of the total area. The case where it was 5% or more of the entire remaining area was evaluated as “x”.
A similar evaluation was performed using a 700 μm thick silicon wafer (circuit wafer) on which a circuit having a step of about 5 μm was formed.

ADVANTAGE OF THE INVENTION According to this invention, even after passing through a high temperature processing process, the adhesive tape which can be easily peeled from a to-be-adhered body can be provided, without remaining glue by irradiating light.

Claims (4)

A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing a photocurable pressure-sensitive adhesive component and a photopolymerization initiator on at least one surface of a substrate,
An adhesive tape in which an anchor agent layer having a storage elastic modulus at 260 ° C. of 1.0 × 10 ⁵ Pa or more is formed on the surface of a base material in contact with the adhesive layer. 2. The pressure-sensitive adhesive tape according to claim 1, wherein the anchor agent layer is formed by applying an anchor agent containing a crosslinking agent to the surface of the base material and curing it so that the degree of crosslinking becomes 90% or more. . The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer further contains 10 to 40 parts by weight of fumed silica having an average particle diameter of 0.05 to 3 μm with respect to 100 parts by weight of the photocurable pressure-sensitive adhesive component. The pressure-sensitive adhesive tape according to claim 1 or 2, wherein The pressure-sensitive adhesive tape according to claim 1, 2 or 3, wherein the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer further contains a photocurable adhesive component and a silicone compound having a functional group capable of crosslinking. .