JPWO2019221065A1 - Manufacturing method of adhesive tape and electronic parts - Google Patents

Abstract

INDUSTRIAL APPLICABILITY The present invention can be attached to an adherend and a support plate with sufficient adhesive strength even after long-term storage, exhibits high heat resistance and adhesive residue suppressing performance, and can also be used on a support plate that does not transmit light. It is an object of the present invention to provide an adhesive tape that can be used and a method for manufacturing an electronic component using the adhesive tape. The present invention is an adhesive tape having an ultraviolet curable pressure-sensitive adhesive layer and a non-ultraviolet curable pressure-sensitive adhesive layer laminated on the UV-curable pressure-sensitive adhesive layer, wherein the UV-curable pressure-sensitive adhesive layer is a silicone compound. The non-ultraviolet curable pressure-sensitive adhesive layer contains a base polymer having an epoxy group-reactive functional group, a compound having an epoxy group, and a silica filler, and the non-ultraviolet curable pressure-sensitive adhesive layer is further grade 3. An adhesive tape containing a compound having an amino group, or having at least one of the base polymer or the compound having an epoxy group having a tertiary amino group.

Description

The present invention relates to an adhesive tape and a method for manufacturing an electronic component using the adhesive tape.

In the semiconductor chip manufacturing process, adhesive tape is used to facilitate handling of wafers and semiconductor chips during processing and to prevent damage. For example, when a thick film wafer cut out from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin film wafer, grinding is performed after attaching an adhesive tape to the thick film wafer.

The adhesive composition used for such an adhesive tape has high adhesiveness enough to firmly fix an adherend such as a wafer or a semiconductor chip during the processing process, and is covered with the wafer or the semiconductor chip after the process is completed. It is required that the wafer can be peeled off without damaging it (hereinafter, also referred to as "high adhesive easy peeling").
As an adhesive composition that achieves high adhesiveness and easy peeling, Patent Document 1 discloses an adhesive tape using a photocurable adhesive that cures by irradiating light such as ultraviolet rays to reduce the adhesive strength. .. By using a photocurable pressure-sensitive adhesive as the pressure-sensitive adhesive, the adherend can be reliably fixed during the processing process, and can be easily peeled off by irradiating with ultraviolet rays or the like.

Japanese Unexamined Patent Publication No. 5-32946

In recent years, due to the thinning and miniaturization of semiconductor products, the substrate has also been thinned to 100 μm or less (hereinafter, the thinned substrate is referred to as a thin substrate) in order to prevent warpage and damage in the manufacture of the substrate. Adhesive tape is used. In the production of such a thin substrate, a base material such as a polyimide film, which is the base of the substrate, is fixed to the support plate via a non-support type adhesive tape, and then wiring or the like is performed. However, the support plate used for manufacturing a thin substrate is often an opaque material such as copper, aluminum, or glass epoxy from the viewpoint of cost and handleability, and such an opaque support plate is a conventional photocurable adhesive. There is a problem that the adhesive tape using the agent cannot be cured.

Further, since a high temperature treatment of applying heat of 150 ° C. or higher is performed in the manufacturing process of a thin substrate, the adhesive tape used is required to have heat resistance and an adhesive resistance that does not increase even at a high temperature. The adhesive tape used in the conventional manufacturing process involving high-temperature treatment contains a silicone bleeding agent in order to suppress the promotion of adhesion. However, when a silicone bleeding agent is mixed with a non-support type adhesive tape, the silicone bleeding agent bleeds out at the interface between the adhesive tape and the support plate, although the adhesion between the base material and the adhesive tape can be suppressed. , The adhesive strength between the support plate and the adhesive tape may decrease. Further, since the adhesive tape used for manufacturing electronic parts such as thin substrates and semiconductor devices is often stored for a certain period of time before being used, bleed-out easily proceeds during storage.

INDUSTRIAL APPLICABILITY The present invention can be attached to an adherend and a support plate with sufficient adhesive strength even after long-term storage, exhibits high heat resistance and adhesive residue suppressing performance, and can also be used on a support plate that does not transmit light. It is an object of the present invention to provide an adhesive tape that can be used and a method for manufacturing an electronic component using the adhesive tape.

The present invention is an adhesive tape having an ultraviolet curable pressure-sensitive adhesive layer and a non-ultraviolet curable pressure-sensitive adhesive layer laminated on the UV-curable pressure-sensitive adhesive layer, wherein the UV-curable pressure-sensitive adhesive layer is a silicone compound. The non-ultraviolet curable pressure-sensitive adhesive layer contains a base polymer having an epoxy group-reactive functional group, a compound having an epoxy group, and a silica filler, and the non-ultraviolet curable pressure-sensitive adhesive layer is further grade 3. An adhesive tape containing a compound having an amino group, or having at least one of the base polymer or the compound having an epoxy group having a tertiary amino group.
The present invention will be described in detail below.

The adhesive tape according to one embodiment of the present invention has an ultraviolet curable pressure-sensitive adhesive layer.
Since the adhesive tape has an ultraviolet curable adhesive layer, it can be attached to the adherend with sufficient adhesive strength to protect the adherend, and it is protected by curing the ultraviolet curable adhesive layer after application. The adhesive tape can be easily peeled off without damaging the adherend. From the viewpoint of simplifying the manufacturing process, the ultraviolet curable pressure-sensitive adhesive layer may be cured by irradiating ultraviolet rays immediately after the adhesive tape is attached to the adherend.

Examples of the UV-curable pressure-sensitive adhesive component constituting the UV-curable pressure-sensitive adhesive layer include a UV-curable pressure-sensitive adhesive containing a polymerizable polymer as a main component and a UV polymerization initiator as a polymerization initiator. For the polymerizable polymer, for example, a (meth) acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth) acrylic polymer) is synthesized in advance and reacted with the functional group in the molecule. It can be obtained by reacting a functional group to be subjected to a compound having a radically polymerizable unsaturated bond (hereinafter, referred to as a functional group-containing unsaturated compound).

The functional group-containing (meth) acrylic polymer mainly contains an acrylic acid alkyl ester and / or a methacrylate alkyl ester in which the number of carbon atoms of the alkyl group is usually in the range of 2 to 18, and the functional group-containing monomer and the functional group-containing monomer are used. Further, if necessary, it is obtained by copolymerizing these with another copolymerizable monomer for modification by a conventional method. The alkyl group of the acrylic acid alkyl ester and / or methacrylic acid alkyl ester preferably has 3 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. The weight average molecular weight of the functional group-containing (meth) acrylic polymer is usually about 200,000 to 2,000,000. In the present specification, the weight average molecular weight can be usually determined by the GPC method, and specifically, the method shown in Examples can be used.

Examples of the functional group-containing monomer include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, an isocyanate group-containing monomer, and an amino group-containing monomer. Examples of the carboxy group-containing monomer include acrylic acid and methacrylic acid. Examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate and hydroxyethyl methacrylate. Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate. Examples of the isocyanate group-containing monomer include ethyl isocyanate, ethyl methacrylate, and the like. Examples of the amino group-containing monomer include aminoethyl acrylate and aminoethyl methacrylate.

Examples of the other copolymerizable monomer for modification include various monomers used in general (meth) acrylic polymers such as vinyl acetate, acrylonitrile, and styrene.

As the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth) acrylic polymer, the same one as the above-mentioned functional group-containing monomer is used depending on 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. 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. When the functional group is an amino group, an epoxy group-containing monomer is used.

Examples of the ultraviolet polymerization initiator include those that are activated by irradiating with ultraviolet rays having a wavelength of 200 to 410 nm. Examples of such an ultraviolet polymerization initiator include acetophenone derivative compounds, benzophenone ether compounds, ketal derivative compounds, phosphine oxide derivative compounds, bis (η5-cyclopentadienyl) titanosen derivative compounds, benzophenone, Michler ketone, and chloro. Examples thereof include thioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane and the like. Examples of the acetophenone derivative compound include methoxyacetophenone and the like. Examples of the benzoin ether compound include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivative compound include benzyldimethyl ketal and acetophenone diethyl ketal. These ultraviolet polymerization initiators may be used alone or in combination of two or more.

In the ultraviolet curable pressure-sensitive adhesive layer, the content of the polymerization initiator is preferably 0.1 part by weight or more, more preferably 0.3 parts by weight or more, and further preferably 0. It is 5 parts by weight or more, preferably 5 parts by weight or less, more preferably 4 parts by weight or less, and further preferably 3 parts by weight or less.

The UV curable pressure-sensitive adhesive layer preferably contains a radically polymerizable polyfunctional oligomer or monomer. When the ultraviolet curable pressure-sensitive adhesive layer contains a radically polymerizable polyfunctional oligomer or monomer, the ultraviolet curability is improved.
The polyfunctional oligomer or monomer preferably has a weight average molecular weight of 10,000 or less, and more preferably the weight average thereof so that the ultraviolet curable pressure-sensitive adhesive layer can be efficiently reticulated by irradiation with ultraviolet rays. The molecular weight is 5000 or less and the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20. The weight average molecular weight can be determined by using, for example, a GPC measurement method, and specifically, the method shown in Examples can be used.

The polyfunctional oligomer or monomer is, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or the same methacrylate as above. Kind and the like. Other examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and the same methacrylates as described above. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.

The UV curable pressure-sensitive adhesive layer contains a silicone compound.
By containing the silicone compound, the silicone compound bleeds out at the interface between the ultraviolet curable pressure-sensitive adhesive layer and the adherend, so that the adhesive tape can be easily peeled off after the treatment is completed. Further, since the silicone compound is excellent in heat resistance, it is possible to suppress scorching of the ultraviolet curable pressure-sensitive adhesive layer and suppress adhesive residue even when the treatment is accompanied by heating at 150 ° C. or higher.

The silicone compound preferably has a functional group that can be crosslinked with the ultraviolet curable pressure-sensitive adhesive component.
Since the silicone compound has a functional group that can be crosslinked with the UV-curable pressure-sensitive adhesive component, the silicone compound chemically reacts with the UV-curable pressure-sensitive adhesive component by UV irradiation and is incorporated into the UV-curable pressure-sensitive adhesive component. Contamination due to the adhesion of the silicone compound to the adherend is suppressed. The functional value of the silicone compound is, for example, 2 to 6 valent, preferably 2 to 4 valent, and more preferably divalent. The functional group is appropriately determined by the functional group contained in the ultraviolet curable pressure-sensitive adhesive component. For example, the UV-curable pressure-sensitive adhesive component is photocurable containing a (meth) acrylic acid alkyl ester-based polymerizable polymer as a main component. In the case of a type pressure-sensitive adhesive, a functional group that can be crosslinked with a (meth) acrylic group is selected.
The functional group crosslinkable with the (meth) acrylic group is a functional group having an unsaturated double bond, and specifically contains, for example, a vinyl group, a (meth) acrylic group, an allyl group, a maleimide group and the like. Select a silicone compound.

The silicone compound preferably has a weight average molecular weight of 300 to 50,000. When the weight average molecular weight of the silicone compound is 300 or more, bleeding out to the non-ultraviolet curable pressure-sensitive adhesive layer can be further suppressed depending on the size of the molecular size. When the weight average molecular weight is 50,000 or less, it is possible to bleed out at the interface between the ultraviolet curable pressure-sensitive adhesive layer and the adherend, and further suppress the adhesion enhancement. The more preferable lower limit of the weight average molecular weight of the silicone compound is 400, the more preferable lower limit is 500, the more preferable upper limit is 10,000, and the further preferable upper limit is 5000. In the present invention, the weight average molecular weight of the silicone compound can be determined by GPC analysis, and specifically, the method shown in Examples can be used.

Examples of the silicone compound having the functional group and the weight average molecular weight include silicon monoacrylate, silicon diacrylate, silicon triacrylate, silicon tetra acrylate, silicon penta acrylate, and silicon hexa acrylate. Of these, silicon diacrylate, silicon triacrylate, silicon tetraacrylate, silicon pentaacrylate, and silicon hexaacrylate are preferable, and silicon diacrylate is more preferable, from the viewpoint of further improving heat resistance and peelability. When silicon diacrylate is used, heat resistance and peelability are further improved.

The content of the silicone compound is such that the preferable lower limit is 1 part by weight, the more preferable lower limit is 5 parts by weight, the further preferable lower limit is 10 parts by weight, and the particularly preferable lower limit is 15 parts by weight with respect to 100 parts by weight of the polymerizable polymer. is there. Further, a preferable upper limit is 50 parts by weight, a more preferable upper limit is 40 parts by weight, a further preferable upper limit is 30 parts by weight, and a particularly preferable upper limit is 25 parts by weight. When the content of the silicone compound is within the above range, the adherend can be protected with sufficient adhesive strength, and the adhesive tape can be more easily peeled off after the protection is completed.

The ultraviolet curable pressure-sensitive adhesive layer may contain a known additive such as an inorganic filler such as fumed silica, a plasticizer, a resin, a surfactant, a wax, and a fine particle filler.

The thickness of the ultraviolet curable pressure-sensitive adhesive layer is not particularly limited, but the lower limit is preferably 5 μm and the upper limit is preferably 100 μm. When the thickness of the ultraviolet curable pressure-sensitive adhesive layer is within the above range, the adherend can be protected with sufficient adhesive strength, and adhesive residue during peeling can be suppressed. From the viewpoint of further improving the adhesive strength and further suppressing the adhesive residue at the time of peeling, the more preferable lower limit of the thickness of the ultraviolet curable pressure-sensitive adhesive layer is 10 μm, the more preferable lower limit is 20 μm, and the particularly preferable lower limit is 25 μm. A more preferred upper limit is 80 μm, a more preferred upper limit is 60 μm, and a particularly preferred upper limit is 50 μm.

The pressure-sensitive adhesive tape according to an embodiment of the present invention has a non-UV-curable pressure-sensitive adhesive layer laminated on the UV-curable pressure-sensitive adhesive layer.
Since the adhesive tape contains a non-ultraviolet curable adhesive layer, the ultraviolet curable adhesive layer is attached to the adherend, the ultraviolet curable adhesive layer is cured, and then the non-ultracurable adhesive layer is supported. Since it can be attached to the adhesive, the ultraviolet curable adhesive can be cured even when the support plate is opaque. In a preferred embodiment of the present invention, the non-ultraviolet curable pressure-sensitive adhesive layer is ultraviolet transmissive. Here, the ultraviolet transmittance means that the light absorption wavelength band of the ultraviolet polymerization initiator contained in the ultraviolet curable pressure-sensitive adhesive layer and the wavelength band that transmits light of the non-ultraviolet curable pressure-sensitive adhesive layer overlap. In particular, it is preferable that the light absorption wavelength band of the ultraviolet polymerization initiator and the wavelength band having an absorbance of 0.2 or less of the non-ultraviolet curable pressure-sensitive adhesive layer overlap. Since the non-ultraviolet curable pressure-sensitive adhesive layer is ultraviolet-transmissive, the ultraviolet-curable pressure-sensitive adhesive layer can be irradiated with ultraviolet rays via the non-ultraviolet-curable pressure-sensitive adhesive layer.

The non-ultraviolet curable pressure-sensitive adhesive layer contains a base polymer having an epoxy group-reactive functional group (a functional group capable of reacting with an epoxy group).
Examples of the epoxy group-reactive functional group include a carboxyl group, a hydroxyl group, a phenol group, an ester group, an amino group, a carbonyl group, a methoxy group and a sulfo group. Among them, at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a phenol group, an ester group and an amino group is preferable because of its high reactivity.

The base polymer has an epoxy group-reactive functional group and is not particularly limited as long as it is non-ultraviolet curable, and examples thereof include acrylic polymers, silicone polymers, and urethane polymers. Of these, a (meth) acrylic copolymer containing a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms and a carboxyl group-containing monomer as constituent components is preferable. By using a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group as a constituent component, a non-ultraviolet curable pressure-sensitive adhesive layer having more excellent adhesive strength (preferably having ultraviolet transparency) can be obtained. Can be done. Further, by using the carboxyl group-containing monomer as a constituent component, it is possible to enhance the cohesive force of the non-ultraviolet curable pressure-sensitive adhesive layer and impart a larger adhesive force. Further, since the carboxyl group, which is a polar group, inhibits the approach of the low-polarity silicone compound, it is possible to further suppress the silicone compound from bleeding out to the non-ultraviolet curable pressure-sensitive adhesive layer side.

Examples of the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group include butyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and isononyl (meth) acrylate. Of these, butyl acrylate is preferable because it has excellent adhesive strength.

Examples of the carboxyl group-containing monomer include acrylic acid and methacrylic acid. Of these, acrylic acid is preferable because it can impart high adhesive strength.

The (meth) acrylic copolymer contains 80 to 99% by weight of a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms of an alkyl group and 1 to 20% by weight of a carboxyl group-containing monomer. Is preferable. Further, it is more preferable to contain 85 to 98% by weight of the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms of the alkyl group and 2 to 15% by weight of the carboxyl group-containing monomer. Further, it is more preferable to contain 92 to 97% by weight of the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms of the alkyl group and 3.0 to 8.0% by weight of the carboxyl group-containing monomer.
When the content of the acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group is in the above range, an adhesive tape having more excellent adhesive strength can be obtained. When the carboxyl group-containing monomer is 3.0% by weight or more, bleeding out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer can be further suppressed. When the carboxyl group-containing monomer is 8.0% by weight or less, the acidity of the (meth) acrylic copolymer can be adjusted within an appropriate range, and the silicone compound is bleeded into the non-ultraviolet curable pressure-sensitive adhesive layer. Out can be suppressed more. From the same viewpoint, the content of the (meth) acrylic acid alkyl ester in the (meth) acrylic copolymer has a more preferable lower limit of 93% by weight, a more preferable lower limit of 94% by weight, and a more preferable upper limit of 96. By weight%. From the same viewpoint, the content of the carboxyl group-containing monomer in the (meth) acrylic copolymer has a more preferable lower limit of 4% by weight, a more preferable upper limit of 7% by weight, and a further preferable upper limit of 6% by weight. Is.

The non-ultraviolet curable pressure-sensitive adhesive layer contains a compound having an epoxy group.
The compound having an epoxy group can act as a curing agent for cross-linking the polymer having the epoxy group-reactive functional group, and plays a role of improving the chemical resistance of the non-ultraviolet curable pressure-sensitive adhesive layer. In addition, since the base polymer after cross-linking has a molecular structure in which the gel content is improved and it is difficult to move, it is possible to prevent the silicone compound from bleeding out to the non-ultraviolet curable pressure-sensitive adhesive layer and store it for a long period of time. Even if it exists, it can exert sufficient adhesive strength. Examples of the compound having an epoxy group include N, N, N', N'-tetraglycidyl-1,3-benzenedi (methaneamine), methylglycidyl ether, and 3,4-epoxycyclohexylmethyl-3,4-epoxy. Examples thereof include cyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, bisphenol A diglycidyl ether, diglycidyl ether condensate of bisphenol A, and epichlorohydrin modified product of novolak resin and cresol resin. Among them, N, N, N', N'-tetraglycidyl-1, because it has a tertiary amino group, which will be described later, and can further suppress bleeding out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer. It is preferably 3-benzenedi (methaneamine).

The content of the compound having an epoxy group in the non-ultraviolet curable pressure-sensitive adhesive layer is preferably 0.1 part by weight, more preferably 0.2 part by weight, still more preferable with respect to 100 parts by weight of the base polymer. The lower limit is 0.3 parts by weight, the preferable upper limit is 3.0 parts by weight, the more preferable upper limit is 2.0 parts by weight, and the further preferable upper limit is 1.0 part by weight. When the content of the compound having an epoxy group is within the above range, the base polymer can be sufficiently and quickly crosslinked, and the bleed-out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer can be further suppressed.

The non-ultraviolet curable pressure-sensitive adhesive layer further contains a compound having a tertiary amino group, or at least one of the base polymer and the compound having an epoxy group has a tertiary amino group.
Since the base polymer before the cross-linking reaction with the compound having an epoxy group has a low gel content and a structure in which molecules move easily, the silicone compound easily bleeds out. Therefore, if the rate of the cross-linking reaction is slow, a large amount of the silicone compound bleeds out to the non-ultraviolet curable pressure-sensitive adhesive layer. When a tertiary amino group is present in the non-ultraviolet curable pressure-sensitive adhesive layer, the tertiary amino group acts as a catalyst for the cross-linking reaction and the rate of the cross-linking reaction of the base polymer is increased, so that the reaction is completed early. .. Since the cross-linking reaction is completed early, it becomes difficult for the silicone compound to bleed out to the non-ultraviolet curable adhesive layer, so it is possible to obtain an adhesive tape with sufficient adhesive strength even when stored for a long period of time. it can. The tertiary amino group may be present in the base polymer, may be present in the compound having an epoxy group, or a compound having a tertiary amino group may be added separately. Among them, the non-ultraviolet curable pressure-sensitive adhesive layer further contains a compound having a tertiary amino group, or the compound having an epoxy group is a tertiary amino because it is superior in adhesive strength after long-term storage. It is preferable to have a group, and it is more preferable that the compound having an epoxy group has a tertiary amino group.

When the compound having a tertiary amino group is added separately, examples of the compound having a tertiary amino group include 2-hydroxy-1,4-diazabicyclo [2,2,2] octane, triethylenediamine, and triethylamine. Benzyldimethylamine can be mentioned. Of these, 2-hydroxy-1,4-diazabicyclo [2,2,2] octane is preferable because the reaction rate of the cross-linking reaction is further improved. The compound having a tertiary amino group may or may not have another functional group.

When the compound having an epoxy group has a tertiary amino group, the compound having an epoxy group may have one or more tertiary amino groups or two or more tertiary amino groups. .. The compound having an epoxy group usually has a tertiary amino group of 4 or less.
In a preferred embodiment of the present invention, when at least one of the compounds having an epoxy group has a tertiary amino group, the compound having an epoxy group is 1 or the compound having an epoxy group from the viewpoint of improving adhesiveness and heat resistance. It preferably has 2 tertiary amino groups.

When the compound having a tertiary amino group is added separately, the content of the compound having a tertiary amino group has a preferable lower limit of 0.1 parts by weight and a more preferable lower limit of 0 with respect to 100 parts by weight of the base polymer. .2 parts by weight, the preferred upper limit is 2 parts by weight, and the more preferred upper limit is 1 part by weight. When the content of the compound having a tertiary amino group is in the above range, the cross-linking reaction can proceed at a sufficient speed, and the bleed-out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer is further suppressed. be able to.

The non-UV curable pressure-sensitive adhesive layer contains a silica filler.
The silica filler may be a hydrophilic silica filler or a hydrophobic silica filler, but is preferably a hydrophilic silica filler from the viewpoint of suppressing bleed-out. Since the hydrophilic silica filler has high polarity, it is possible to prevent the silicone compound having low polarity from approaching by containing the hydrophilic silica filler in the non-ultraviolet curable pressure-sensitive adhesive layer. Bleed-out to the curable pressure-sensitive adhesive layer can be further suppressed.

The hydrophilic silica filler is not particularly limited, and for example, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, silica-titania composite oxide, magnesium-aluminum-silicon composite oxide, hexamethylcyclotrisiloxane. , Tetramethoxysilane, chlorosilane, monosilane and the like. Among them, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, and silica-titania composite oxide are preferable because they have physical characteristics similar to silica generally used as an inorganic filler.

When the silica filler is a hydrophilic silica filler, it is preferable that at least a part of the surface of the silica filler is hydrophobized.
By substituting at least a part of the hydrophilic groups present in the hydrophilic silica filler with hydrophobic groups, the dispersibility in the base polymer can be improved. The hydrophobic group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among them, from the viewpoint of dispersibility in the base polymer, the hydrophilic silica filler after the hydrophobization treatment preferably has a monomethylsilyl group, a dimethylsilyl group or a trimethylsilyl group. In particular, at least a part of the hydrophilic silica filler has a monomethylsilyl group because it has an excellent balance between the effect of suppressing bleeding out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer and the dispersibility in the base polymer. It is more preferable to do so. As described above, since the hydrophilic silica filler prevents the silicone compound from approaching due to its hydrophilicity, a material in which the entire surface of the hydrophilic silica filler is replaced with a hydrophobic group is effective as the hydrophilic silica filler. It is difficult to demonstrate.

When the hydrophilic silica filler has at least a monomethylsilyl group, a dimethylsilyl group or a trimethylsilyl group, the hydrophilic silica filler has the functional group of 100 m ² / g or more in terms of the raw material specific surface area. It is preferable to have 140 m ² / g or more. When the hydrophilic silica filler has the above functional groups on the surface in the above range, the dispersibility of the hydrophilic silica filler with respect to the base polymer can be further improved.

The average particle size of the silica filler is not particularly limited, but a preferable lower limit is 0.06 μm, a more preferable lower limit is 0.07 μm, a further preferable lower limit is 0.1 μm, a preferable upper limit is 2 μm, a more preferable upper limit is 1 μm, and further. The preferred upper limit is 0.8 μm. When the average particle size of the silica filler is in the above range, the dispersibility in the non-ultraviolet curable pressure-sensitive adhesive can be further improved, and the bleed-out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer is further suppressed. be able to.

The content of the silica filler is not particularly limited, but the preferable lower limit is 1 part by weight, the more preferable lower limit is 3 parts by weight, the preferable upper limit is 20 parts by weight, and the more preferable upper limit is 18 parts by weight with respect to 100 parts by weight of the base polymer. Is.
When the content of the silica filler is 3 parts by weight or more, bleeding out of the silicone compound to the non-ultraviolet curable pressure-sensitive adhesive layer can be sufficiently suppressed. When the content of the silica filler is 18 parts by weight or less, an adhesive tape having sufficient adhesive strength can be obtained. From the same viewpoint, the content of the silica filler with respect to 100 parts by weight of the base polymer has a further preferable lower limit of 6 parts by weight, a further preferable lower limit of 8 parts by weight, a further preferable upper limit of 15 parts by weight, and a further preferable upper limit. 13 parts by weight.

The non-ultraviolet curable pressure-sensitive adhesive layer may contain known additives such as plasticizers, resins, surfactants, waxes, and fine particle fillers. One or two or more of the above additives may be used.

The thickness of the non-ultraviolet curable pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 5 μm, a more preferable lower limit is 10 μm, a further preferable lower limit is 20 μm, a further preferable lower limit is 25 μm, and a preferable upper limit is 100 μm, more preferable. The upper limit is preferably 80 μm, the more preferred upper limit is 60 μm, and the even more preferred upper limit is 50 μm. When the thickness of the non-ultraviolet curable adhesive layer is within the above range, it adheres to the support plate with sufficient adhesive force, and the adherend can be reliably fixed.

The adhesive tape according to one embodiment of the present invention is preferably a non-support type double-sided adhesive tape having no base material. In the case of the support type having a base material, the silicone compound does not bleed out to the interface on the support plate side, but the cost is inferior to that of the non-support type.

The adhesive tape according to one embodiment of the present invention is released on the surface of the non-ultraviolet curable adhesive layer opposite to the surface on which the ultraviolet curable adhesive layer is laminated (preferably UV permeable). It is preferable that the films are laminated.
By having the release film on the non-ultraviolet curable adhesive layer, the non-ultraviolet curable adhesive layer can be protected until it is attached to the adherend, and the handleability of the adhesive tape can be improved. When the release film is ultraviolet-transparent, the curing step described later can be performed while protecting the non-ultraviolet curable pressure-sensitive adhesive layer.

The release film is not particularly limited, and for example, polyethylene naphthalate (PEN), polyimide (PI), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT). ), Polyhexamethylene terephthalate, polybutylene terephthalate, butanediol terephthalate polytetramethylene glycol copolymer, butanedium terephthalate polycaprolactone copolymer and the like. Of these, polyethylene terephthalate (PET) is preferable.

The adhesive tape according to one embodiment of the present invention has an ultraviolet curable pressure-sensitive adhesive layer as long as the ultraviolet curable pressure-sensitive adhesive layer and the non-ultraviolet curable pressure-sensitive adhesive layer are located on the outermost layer (the layer in contact with the adherend). Another layer may be provided between the surface and the non-ultraviolet curable pressure-sensitive adhesive layer.

In the adhesive tape according to one embodiment of the present invention, the gel content of the non-UV curable pressure-sensitive adhesive layer is 60% or more, and the gel content of the UV-curable pressure-sensitive adhesive layer is 80% or more after UV curing. Is preferable.
When the gel fraction of the non-ultraviolet curable adhesive layer and the ultraviolet curable adhesive layer is equal to or higher than the above lower limit, the chemical resistance of the adhesive tape can be further improved, and the non-ultraviolet color of the silicone compound over time can be improved. Bleed-out to the curable pressure-sensitive adhesive layer can be further suppressed. A more preferable lower limit of the gel fraction of the non-ultraviolet curable pressure-sensitive adhesive layer is 80%, a further preferable lower limit is 85%, a further preferable lower limit is 90%, and a particularly preferable lower limit is 95%. The upper limit of the gel fraction of the non-ultraviolet curable pressure-sensitive adhesive layer is not particularly limited, but is preferably 99%. The more preferable lower limit of the gel fraction of the ultraviolet curable pressure-sensitive adhesive layer is 85%, and the more preferable lower limit is 90%. The upper limit of the gel fraction of the ultraviolet curable pressure-sensitive adhesive layer is not particularly limited, but is preferably 99%. When the adhesive tape has a layer other than the ultraviolet curable pressure-sensitive adhesive layer and the non-ultraviolet curable pressure-sensitive adhesive layer, it is preferable that the layer also satisfies the gel fraction.

The method for producing the adhesive tape according to the embodiment of the present invention is not particularly limited, and a conventionally known method can be used. For example, a solution of the above-mentioned UV-curable pressure-sensitive adhesive component is applied onto a film that has been subjected to a mold release treatment and dried to form a UV-curable pressure-sensitive adhesive layer, and the same is applied on a film that has been subjected to another mold release treatment. It can be produced by forming a non-UV curable pressure-sensitive adhesive layer by the method and then laminating the UV-curable pressure-sensitive adhesive layer and the non-UV-curable pressure-sensitive adhesive layer.

The use of the adhesive tape according to one embodiment of the present invention is not particularly limited, but is particularly limited as a protective tape in the manufacture of electronic components such as electronic substrates and semiconductor chips, which uses an opaque support plate and has a manufacturing process involving high temperature treatment. It can be preferably used.

A substrate sticking step of attaching an adhesive tape according to an embodiment of the present invention to a substrate from an ultraviolet curable pressure-sensitive adhesive layer, a curing step of irradiating ultraviolet rays to cure the ultraviolet-curable pressure-sensitive adhesive layer, and non-ultraviolet curing. An electronic component including a support plate sticking step of sticking a support plate on a mold pressure-sensitive adhesive layer, a heat treatment step of treating the substrate at a high temperature of 150 ° C. or higher, and a peeling step of peeling the substrate from the adhesive tape. The manufacturing method is also one of the present inventions.

In the method for manufacturing an electronic component according to an embodiment of the present invention, first, the pressure-sensitive adhesive tape having a UV-curable pressure-sensitive adhesive layer and a non-UV-curable pressure-sensitive adhesive layer is applied from the UV-curable pressure-sensitive adhesive layer side. Perform the board sticking process to stick to the board.
Examples of the substrate include a silicon wafer, a base material that is a basis for manufacturing an electronic substrate, a material for electronic components, and the like. Examples of the base material include a polyimide film and a glass epoxy substrate.

In the method for manufacturing an electronic component according to an embodiment of the present invention, a curing step of irradiating ultraviolet rays to cure the ultraviolet curable pressure-sensitive adhesive layer is then performed.
By curing the ultraviolet curable pressure-sensitive adhesive layer, the pressure-sensitive adhesive tape can be easily peeled off from the substrate after the treatment while suppressing adhesive residue. In the above method for manufacturing electronic parts, the ultraviolet curable adhesive layer is cured before the adhesive tape is attached to the support plate. Therefore, even if the support plate is a material that does not transmit light, the photocurable adhesive is cured. Can be done. Further, when the non-ultraviolet curable adhesive layer of the adhesive tape is ultraviolet transmissive, even if the ultraviolet curable adhesive layer is irradiated with ultraviolet rays from the non-ultraviolet curable adhesive layer side, the ultraviolet curable adhesive can be sufficiently applied. Can be cured. Since the UV-curable pressure-sensitive adhesive layer is cured after being attached to the substrate, even if the UV-curable pressure-sensitive adhesive layer is cured before the substrate is processed, the adhesive tape is released from the substrate. It does not peel off immediately.

The light irradiation conditions for curing the ultraviolet curable pressure-sensitive adhesive layer can be appropriately adjusted by the combination of the polymerizable polymer used and the ultraviolet polymerization initiator. For example, when a polymerizable polymer having an unsaturated double bond such as a vinyl group in the side chain and an ultraviolet polymerization initiator activated at a wavelength of 200 to 410 nm are used, by irradiating light with a wavelength of 365 nm or more, The ultraviolet curable pressure-sensitive adhesive layer can be crosslinked and cured.
For such an ultraviolet curable pressure-sensitive adhesive layer, for example, it is preferable to irradiate light having a wavelength of 365 nm with an illuminance of 5 mW or more, more preferably with an illuminance of 10 mW or more, and irradiate with an illuminance of 20 mW or more. It is more preferable to irradiate with an illuminance of 50 mW or more. Further, it is preferable to irradiate light having a wavelength of 365 nm with an integrated illuminance of 300 mJ or more, more preferably with an integrated illuminance of 500 mJ or more and 10,000 mJ or less, and further preferably with an integrated illuminance of 500 mJ or more and 7500 mJ or less. It is particularly preferable to irradiate with an integrated illuminance of 1000 mJ or more and 5000 mJ or less.

In the method for manufacturing the electronic component, the support plate sticking step of sticking the support plate on the non-ultraviolet curable pressure-sensitive adhesive layer is then performed.
In the present invention, since the adhesive layer of the adhesive tape is divided into an ultraviolet curable adhesive layer and a non-ultracurable adhesive layer, non-ultracurable even when a curing step is performed before attaching the support plate. The mold adhesive layer does not cure. Therefore, the adhesive tape can be attached to the support plate with sufficient adhesive strength. When the adhesive tape has the ultraviolet-transmissive release film, the release film is peeled off from the end of the curing step to the front of the support plate attaching step.

In the method for manufacturing electronic components, a heat treatment step of treating the substrate at a high temperature of 150 ° C. or higher is then performed.
Examples of the heat treatment step include a substrate manufacturing step and a chip mounting step. In the substrate manufacturing process, heat treatment of 150 ° C. or higher is usually performed, and in the chip mounting step, heat treatment of 200 ° C. or higher is usually performed. In the above method for manufacturing electronic components, the ultraviolet curable pressure-sensitive adhesive layer is cured before the heat treatment step, so that even when a treatment involving a high temperature of 150 ° C. or higher is performed in the heat treatment step, the enhancement of adhesion is suppressed. The substrate can be easily peeled off after the processing is completed. Further, since the ultraviolet curable pressure-sensitive adhesive layer contains a silicone compound, it is possible to further suppress the enhancement of adhesion.

The method for manufacturing an electronic component then includes a peeling step of peeling the substrate from the adhesive tape. Since the ultraviolet curable pressure-sensitive adhesive layer is crosslinked and cured in the above curing step, the substrate can be easily peeled off from the pressure-sensitive adhesive tape while suppressing adhesive residue. Moreover, since the time required for peeling is shortened, the production efficiency can be improved.

In another embodiment of the invention, the use of the adhesive tape in the manufacture of the electronic components is also provided. The production of the electronic component includes the substrate sticking step, the curing step, the support plate sticking step, the heat treatment step, and the peeling step.

According to the present invention, it can be attached to an adherend and a support plate with sufficient adhesive strength even after long-term storage, exhibiting high heat resistance and adhesive residue suppressing performance, and a support plate that does not transmit light. It is also possible to provide an adhesive tape that can also be used in the above and a method for manufacturing an electronic component using the adhesive tape.

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

(Example 1)
(Manufacturing of non-UV curable adhesive)
97 parts by weight of butyl acrylate as (meth) acrylic acid alkyl ester, 3 parts by weight of acrylic acid and 120 parts by weight of ethyl acetate as carboxyl group-containing monomer were added to a reactor equipped with a thermometer, a stirrer, and a cooling tube, and nitrogen substitution was performed. After that, the reactor was heated and reflux was started. Subsequently, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator into the reactor. The mixture was refluxed at 70 ° C. for 5 hours to obtain a solution of the (meth) acrylic copolymer. The weight average molecular weight of the obtained (meth) acrylic copolymer was 800,000 as a result of using "2690 Separations Model" manufactured by Water Co., Ltd. as a column and ethyl acetate as a solvent by the GPC method and measuring the weight average molecular weight by a polystyrene standard. It was.
Epoxy-based curing agent A was added in a solid content ratio of 0.3 parts by weight to 100 parts by weight of the solid content of the (meth) acrylic copolymer contained in the obtained (meth) acrylic copolymer solution. 3 parts by weight of the silica filler was added, and the mixture was stirred to obtain an ethyl acetate solution of a non-ultraviolet curable pressure-sensitive adhesive. The epoxy curing agent A and the silica filler used were as follows.

Epoxy curing agent A: Mitsubishi Gas Chemical Company, TETRAD-X, tertiary amino group-containing epoxy curing agent (number of amino groups: 2)
Silica filler: Leoloseal MT-10 manufactured by Tokuyama Corporation (average particle size: 15 nm)

(Manufacturing of UV curable adhesive)
A reactor equipped with a thermometer, a stirrer, and a cooling tube is prepared, and 94 parts by weight of 2-ethylhexyl acrylate as the (meth) acrylic acid alkyl ester and 6 parts by weight of hydroxyethyl methacrylate as the functional group-containing monomer are prepared in the reactor. , 0.01 part by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate were added, and then the reactor was heated to start reflux. Subsequently, 0.01 part by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added as a polymerization initiator into the reactor, and the polymerization was started under reflux. It was. Next, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added 1 hour and 2 hours after the start of the polymerization, and further, the polymerization was started. After 4 hours from the above, 0.05 parts by weight of t-hexyl peroxypivalate was added to continue the polymerization reaction. Then, 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth) acrylic polymer having 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 obtained ethyl acetate solution containing a functional group-containing (meth) acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate was added as a functional group-containing unsaturated compound to react. The mixture was allowed to obtain a polymerizable polymer. Then, with respect to 100 parts by weight of the resin solid content of the ethyl acetate solution of the obtained polymerizable polymer, 20 parts by weight of silicon diacrylate, 3 parts by weight of silica filler, 30 parts by weight of urethane acrylate, and 0 isocyanate-based cross-linking agent as silicone compounds. .7 parts by weight and 1 part by weight of the photopolymerization initiator were mixed to obtain an ethyl acetate solution of an ultraviolet curable pressure-sensitive adhesive. The following silicon diacrylate, silica filler, urethane acrylate, isocyanate-based cross-linking agent, and photopolymerization initiator were used.

Silicon diacrylate: EBECRYL 350, manufactured by Daicel Ornex, weight average molecular weight 1000
Silica filler: Leoloseal MT-10, Tokuyama urethane acrylate: UN-5500, Negami Kogyo's isocyanate-based cross-linking agent: Coronate L, Nippon Urethane Kogyo's photopolymerization initiator: Esacure One, Nippon Sibel Hegner's

(Manufacturing of adhesive tape)
The obtained UV-curable pressure-sensitive adhesive solution was applied on a 50 μm polyethylene terephthalate (PET) film having a mold release treatment on one side with a doctor knife so that the thickness of the dry film was 40 μm. The coating solution was dried by heating for 5 minutes to obtain an ultraviolet curable pressure-sensitive adhesive layer.
The obtained non-ultraviolet curable adhesive solution was applied on a transparent PET film having a thickness of 50 μm, which had been released on one side, with a doctor knife so that the thickness of the dry film was 40 μm, and the temperature was 110 ° C. The coating solution was dried by heating for 5 minutes to obtain a non-ultraviolet curable pressure-sensitive adhesive layer.
Adhesive tapes were obtained by laminating the surfaces of the obtained UV-curable pressure-sensitive adhesive layer and non-UV-curable pressure-sensitive adhesive layer on which the PET films were not laminated.

(Measurement of gel fraction)
Only 0.1 g of the non-UV curable adhesive layer of the obtained adhesive tape was scraped off, immersed in 50 ml of ethyl acetate, and shaken with a shaker at a temperature of 23 ° C. and 200 rpm for 24 hours (hereinafter, The scraped non-UV curable adhesive layer is called an adhesive composition). After shaking, a metal mesh (opening # 200 mesh) was used to separate the swelling pressure-sensitive adhesive composition by absorbing ethyl acetate and ethyl acetate. The adhesive composition after separation was dried under the condition of 110 ° C. for 1 hour. The weight of the pressure-sensitive adhesive composition containing the metal mesh after drying was measured, and the gel fraction of the non-ultraviolet curable pressure-sensitive adhesive layer was calculated using the following formula. The results are shown in Table 1.
Gel fraction (% by weight) = 100 x (W _1- W ₂ ) / W ₀
(W ₀ : Weight of initial pressure-sensitive adhesive composition, W ₁ : Weight of pressure-sensitive adhesive composition including dried metal mesh, W ₂ : Initial weight of metal mesh)

The gel fraction (initial gel fraction) was measured in the same manner for the ultraviolet curable pressure-sensitive adhesive layer of the obtained adhesive tape.
Further, using a high-pressure mercury ultraviolet ray irradiator, the surface is irradiated with ultraviolet rays of 365 nm ^{for 30 seconds by adjusting the illuminance so that the irradiation intensity on the surface becomes 100 mW / cm 2,} and after cross-linking and curing, the ultraviolet curable adhesive The gel fraction of the agent layer (gel fraction after UV curing) was also measured.

(Measurement of adhesive strength)
The adhesive tape was cut into strips having a width of 5 mm to prepare test pieces. After placing the test piece on the stainless plate so that the non-UV curable adhesive layer faces the stainless plate (SUS304, manufactured by Taiyu Kikai Co., Ltd.), a 2 kg rubber roller is placed on the test piece at a speed of 300 mm / min. The test piece and the stainless steel plate were bonded to each other by reciprocating once, and then allowed to stand at 23 ° C. for 24 hours to prepare a test sample. The obtained test sample was subjected to a tensile test in the 180 ° direction at a peeling speed of 300 mm / min according to JIS Z0237, and the initial 180 ° peeling adhesive strength (N / 5 mm) was measured. Next, the adhesive strength of the adhesive tape stored at 40 ° C. for 1 month was measured by peeling off the adhesive tape at 180 ° over time by the above method. The results are shown in Table 1.

Further, the adhesive tape was cut into strips having a width of 5 mm to prepare test pieces. After placing the test piece on the stainless plate so that the ultraviolet curable adhesive layer faces the stainless plate (SUS304, manufactured by Tayu Kikai Co., Ltd.), place a 2 kg rubber roller on the test piece at a speed of 300 mm / min. The test piece and the stainless steel plate were bonded to each other by reciprocating, and then allowed to stand at 23 ° C. for 24 hours to prepare a test sample. The obtained test sample was subjected to a tensile test in the 180 ° direction at a peeling speed of 300 mm / min according to JIS Z0237, and the initial 180 ° peeling adhesive strength (N / 5 mm) was measured. Next, the adhesive strength of the adhesive tape stored at 40 ° C. for 1 month was measured by peeling off the adhesive tape at 180 ° over time by the above method. The results are shown in Table 1.

(Examples 2 to 6, Comparative Examples 1 to 3)
An adhesive tape was produced in the same manner as in Example 1 except that the amounts of butyl acrylate, acrylic acid, and silica filler in the non-ultraviolet curable adhesive layer were as shown in Tables 1, 2, and 5, and the adhesive layer gel was produced. The fraction and adhesive strength were measured. As the epoxy-based cross-linking agent A, E-5XM manufactured by Soken Chemical Co., Ltd. was used.

(Examples 7 to 9)
In the production of the non-ultraviolet curable adhesive, the adhesive tape was produced in the same manner as in Example 4 except that the epoxy-based curing agent A'was added in a solid content ratio of 0.3, 0.1 and 0.2 parts by weight. , The gel fraction and the adhesive strength of the pressure-sensitive adhesive layer were measured. The following epoxy curing agents A'were used.

Epoxy curing agent A': manufactured by Mitsubishi Chemical Corporation, jer cure, epoxy curing agent containing tertiary amino groups (number of amino groups: 1)

(Examples 10 to 12)
In the production of the non-ultraviolet curable pressure-sensitive adhesive, except that the epoxy-based curing agent B was added in an solid content ratio of 0.3, 0.1 and 0.2 parts by weight, and a compound having a tertiary amino group was added in 5 parts by weight. An adhesive tape was produced in the same manner as in Example 4, and the gel fraction and adhesive strength of the adhesive layer were measured. The following compounds were used as the epoxy curing agent B and the compound having a tertiary amino group.

Epoxy curing agent B: DIC Corporation, EXA-4710, naphthalene skeleton type epoxy curing agent (number of amino groups: 0)
Compound having a tertiary amino group: RZETA manufactured by Tosoh Corporation

(Example 13)
(Manufacturing of non-UV curable adhesive)
97 parts by weight of 2-ethylhexyl acrylate as a (meth) acrylic acid alkyl ester, 3 parts by weight of acrylic acid and 120 parts by weight of ethyl acetate as a carboxyl group-containing monomer were added to a reactor equipped with a thermometer, a stirrer, and a cooling tube. After substitution with nitrogen, the reactor was heated to initiate reflux. Subsequently, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator into the reactor. The mixture was refluxed at 70 ° C. for 5 hours to obtain a solution of the (meth) acrylic copolymer. The weight average molecular weight of the obtained (meth) acrylic copolymer was measured by the GPC method using Water's "2690 Separations Model" as a column and ethyl acetate as a solvent, and the weight average molecular weight was measured by a polystyrene standard. It was.
Epoxy-based curing agent A was added in a solid content ratio of 0.3 parts by weight to 100 parts by weight of the solid content of the (meth) acrylic copolymer contained in the obtained (meth) acrylic copolymer solution. 6 parts by weight of the silica filler was added and stirred to obtain an ethyl acetate solution of a non-ultraviolet curable pressure-sensitive adhesive.

An adhesive tape was produced in the same manner as in Example 1 except that the obtained non-ultraviolet curable adhesive was used, and the gel fraction and adhesive strength of the adhesive layer were measured.

(Example 14)
An adhesive tape was produced in the same manner as in Example 13 except that the amounts of 2-ethylhexyl acrylate, acrylic acid, and silica filler in the non-ultraviolet curable pressure-sensitive adhesive layer were as shown in Table 3, and the gel fraction of the pressure-sensitive adhesive layer was produced. And the adhesive strength was measured.

(Comparative Examples 4 and 5)
An adhesive tape was produced in the same manner as in Example 5 except that the non-ultraviolet curable pressure-sensitive adhesive was blended as shown in Table 5, and the gel fraction and the adhesive strength of the pressure-sensitive adhesive layer were measured.

(Example 15)
(Manufacturing of non-UV curable adhesive)
To a reactor equipped with a thermometer, a stirrer, and a cooling tube, 94 parts by weight of butyl acrylate as a (meth) acrylic acid alkyl ester and 6 parts by weight of acrylic acid and 120 parts by weight of ethyl acetate as a carboxyl group-containing monomer were added to replace nitrogen. After that, the reactor was heated and reflux was started. Subsequently, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator into the reactor. The mixture was refluxed at 70 ° C. for 5 hours to obtain a solution of the (meth) acrylic copolymer. The weight average molecular weight of the obtained (meth) acrylic copolymer was 800,000 as a result of using "2690 Separations Model" manufactured by Water Co., Ltd. as a column and ethyl acetate as a solvent by the GPC method and measuring the weight average molecular weight by a polystyrene standard. It was.
Epoxy-based curing agent A was added in a solid content ratio of 0.3 parts by weight to 100 parts by weight of the solid content of the (meth) acrylic copolymer contained in the obtained (meth) acrylic copolymer solution. 15 parts by weight of the silica filler was added, and the mixture was stirred to obtain an ethyl acetate solution of a non-ultraviolet curable pressure-sensitive adhesive. The epoxy curing agent A and the silica filler used were as follows.

Epoxy curing agent A: Mitsubishi Gas Chemical Company, TETRAD-X, tertiary amino group-containing epoxy curing agent (number of amino groups: 2)
Silica filler: Leoloseal MT-10 manufactured by Tokuyama Corporation (average particle size: 15 nm)

(Manufacturing of UV curable adhesive)
A reactor equipped with a thermometer, a stirrer, and a cooling tube is prepared, and in this reactor, 94 parts by weight of 2-ethylhexyl acrylate as a (meth) acrylic acid alkyl ester, 6 parts by weight of acrylic acid as a functional group-containing monomer, and lauryl. After adding 0.01 part by weight of mercaptan and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Subsequently, 0.01 part by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added as a polymerization initiator into the reactor, and the polymerization was started under reflux. It was. Next, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added 1 hour and 2 hours after the start of the polymerization, and further, the polymerization was started. After 4 hours from the above, 0.05 parts by weight of t-hexyl peroxypivalate was added to continue the polymerization reaction. Then, 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth) acrylic polymer having 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 obtained ethyl acetate solution containing a functional group-containing (meth) acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate was added as a functional group-containing unsaturated compound to react. The mixture was allowed to obtain a polymerizable polymer. Then, with respect to 100 parts by weight of the resin solid content of the obtained ethyl acetate solution of the polymerizable polymer, 3 parts by weight of the acrylic silicon graft polymer, 3 parts by weight of the silica filler, 30 parts by weight of the urethane acrylate, and the isocyanate-based crosslinked as the silicone compound. 0.7 parts by weight of the agent and 1 part by weight of the photopolymerization initiator were mixed to obtain an ethyl acetate solution of an ultraviolet curable pressure-sensitive adhesive. The following acrylic silicon graft polymers, silica fillers, urethane acrylates, isocyanate-based cross-linking agents, and photopolymerization initiators were used.

Acrylic Silicon Graft Polymer: Cymac, Toa Synthetic Co., Ltd., Weight Average Molecular Weight 60,000 Silica Filler: Leorosea MT-10, Tokuyama Urethane Acrylate: UN-5500, Negami Kogyo Co., Ltd. Isocyanate Crosslinker: Coronate L, Nippon Urethane Photopolymerization initiator manufactured by Kogyo Co., Ltd .: Esacure One, manufactured by Nihon Shibel Hegner Co., Ltd.

An adhesive tape was produced in the same manner as in Example 1 except that the obtained ultraviolet curable pressure-sensitive adhesive solution and non-ultraviolet curable pressure-sensitive adhesive solution were used, and the gel fraction and adhesive strength of the pressure-sensitive adhesive layer were measured.

(Examples 16 and 17)
In the production of the ultraviolet curable pressure-sensitive adhesive, a pressure-sensitive adhesive tape was produced in the same manner as in Example 15 except that the blending amount of the silicone compound was as shown in Table 4, and the gel fraction and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer were measured.

<Evaluation>
The adhesive tapes obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1-5.

(Evaluation of heat resistance)
The surface of the adhesive tape on the ultraviolet curable adhesive layer side was attached to a substrate (TPWB-S02-READCUT, manufactured by Taisho Electronics Co., Ltd.) to obtain a laminate. Next, using a high-pressure mercury ultraviolet ray irradiator, the illuminance is adjusted so that the irradiation intensity of the adhesive tape surface is 100 mW / cm ² and the ultraviolet rays of 365 nm are irradiated from the non-ultraviolet curable adhesive layer side for 30 seconds. , The UV curable adhesive layer was crosslinked and cured. Then, the non-ultraviolet curable pressure-sensitive adhesive layer of the laminated body was attached to the CCL support plate, and heat treatment at 260 ° C. for 6 minutes was performed a total of 3 times. The adhesive tape after the heat treatment was visually observed, and the heat resistance (initial) was evaluated according to the following criteria. Further, the adhesive tape stored at 40 ° C. for 1 month was also heat-treated by the same method, and the heat resistance (aging) was evaluated according to the same criteria.
〇 〇: No peeling or voids 〇: There was a very small amount of peeling but no voids, or there was a very small amount of voids but no peeling △: There was some peeling but no voids, There was some voids but no peeling, or there was a minimum amount of peeling and voids ×: There was some peeling and there was a minimum amount of voids, there was a part of voids and there was a minimum amount of peeling, or There was some peeling and voids XX: There was peeling or one or both of the voids on the entire surface

(Evaluation of adhesive residue)
The surface of the adhesive tape on the ultraviolet curable adhesive layer side was attached to a substrate (TPWB-S02-READCUT, manufactured by Taisho Electronics Co., Ltd.) to obtain a laminate. Next, using a high-pressure mercury ultraviolet ray irradiator, the illuminance is adjusted so that the irradiation intensity of the adhesive tape surface is 100 mW / cm ² and the ultraviolet rays of 365 nm are irradiated from the non-ultraviolet curable adhesive layer side for 30 seconds. , The UV curable adhesive layer was crosslinked and cured. Then, the non-ultraviolet curable pressure-sensitive adhesive layer of the laminated body was attached to the CCL support plate, and heat treatment was performed at 240 ° C. for 1 hour. After the heat treatment was completed, the adhesive tape was peeled off from the substrate. The substrate after peeling was observed with an optical microscope, and the adhesive residue (initial) was evaluated according to the following criteria. Further, the adhesive tape stored at 40 ° C. for 1 month was also heat-treated by the same method, and the adhesive residue (aging) was evaluated according to the same criteria.
〇 〇: There was no glue residue 〇: There was a very small amount of glue residue △: There was some glue residue ×: There was glue residue on the entire surface

According to the present invention, it can be attached to an adherend and a support plate with sufficient adhesive strength even after long-term storage, exhibiting high heat resistance and adhesive residue suppressing performance, and a support plate that does not transmit light. It is also possible to provide an adhesive tape that can also be used in the above and a method for manufacturing an electronic component using the adhesive tape.

Claims (7)

An adhesive tape having an ultraviolet curable adhesive layer and a non-ultraviolet curable adhesive layer laminated on the ultraviolet curable adhesive layer.
The UV curable pressure-sensitive adhesive layer contains a silicone compound and
The non-ultraviolet curable pressure-sensitive adhesive layer contains a base polymer having an epoxy group-reactive functional group, a compound having an epoxy group, and a silica filler.
The non-ultraviolet curable pressure-sensitive adhesive layer further contains a compound having a tertiary amino group, or an adhesive tape in which at least one of the base polymer and the compound having an epoxy group has a tertiary amino group. The adhesive tape according to claim 1, wherein the epoxy group-reactive functional group in the base polymer is at least one selected from the group consisting of a carboxyl group, a hydroxyl group, a phenol group, an ester group, and an amino group. The adhesive tape according to claim 1 or 2, wherein the compound having an epoxy group has a tertiary amino group. The adhesive tape according to claim 1, 2 or 3, wherein at least a part of the surface of the silica filler is hydrophobized. The adhesive tape according to claim 1, 2, 3 or 4, wherein the content of the silica filler with respect to 100 parts by weight of the base polymer is 1 part by weight or more and 20 parts by weight or less. The adhesive tape according to claim 1, 2, 3, 4 or 5, wherein the non-ultraviolet curable pressure-sensitive adhesive layer has a gel fraction of 60% or more. A substrate attaching step of attaching the adhesive tape according to claim 1, 2, 3, 4, 5 or 6 to a substrate from an ultraviolet curable pressure-sensitive adhesive layer.
A curing step of irradiating ultraviolet rays to cure the ultraviolet curable adhesive layer, and
The support plate pasting process of sticking the support plate on the non-UV curable adhesive layer,
A heat treatment step of treating the substrate at a high temperature of 150 ° C. or higher, and
A method for manufacturing an electronic component, which comprises a peeling step of peeling the substrate from the adhesive tape.