JP6941960B2 - Manufacturing method of adhesive tape and electronic parts - Google Patents

Description

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

Adhesive tapes are used in the manufacturing or processing process of precision parts, optical parts, or electronic parts for the purpose of protecting the parts and masking the supporting members of the parts. In Patent Document 1, it is said that a base material made of a polyimide resin is preferable as a base material of the masking adhesive tape. In Patent Document 2, a silicone pressure-sensitive adhesive composition having excellent adhesiveness and heat resistance and having no adhesive residue in a predetermined adhesive residue test is studied.
Japanese Unexamined Patent Publication No. 2016-222863 Japanese Unexamined Patent Publication No. 2015-193803

As the conventional heat-resistant adhesive tape, a combination of a base material formed of a polyimide resin and an adhesive layer formed of a silicone adhesive is often used. However, since the base material formed of the polyimide resin is manufactured by the solvent casting method, the obtained base material often contains a residual solvent. If the base material contains a residual solvent, the residual solvent may volatilize and gas may be generated when the adhesive tape is heat-treated at a high temperature. Further, when the pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer formed of the silicone pressure-sensitive adhesive is heat-treated at a high temperature, siloxane gas derived from the silicone pressure-sensitive adhesive may be generated. As described above, the conventional adhesive tape in which the base material using the polyimide resin and the adhesive layer using the silicone adhesive is combined with each other produces organic gas when heat-treated at a high temperature, so that the outgassing property is remarkably poor. When such a conventional adhesive tape is used, for example, as a masking tape when vacuum-depositing a part, the generated organic gas causes the vapor-deposited film formed on the surface of the part to be colored or deposits inside the chamber. May precipitate and the quality may deteriorate.

An object of the present invention is to provide an adhesive tape capable of suppressing the generation of organic gas even when heat-treated, and a method for manufacturing an electronic component using the adhesive tape.

The adhesive tape according to the present invention has an adhesive layer on one surface of the base film, the base film contains a polyether sulfone, and the adhesive layer is a (meth) acrylic acid ester copolymer (A). The (meth) acrylic acid ester copolymer (A) containing an isocyanate-based curing agent (B) contains a hydroxyl group and has a hydroxyl value of more than 0 and 90 mgKOH / g or less.

In the present invention, the weight average molecular weight of the (meth) acrylic acid ester copolymer (A) is preferably 300,000 or more and 2.2 million or less. Further, the content of the isocyanate-based curing agent (B) is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). Further, the (meth) acrylic acid ester copolymer (A) can be configured to contain 1% by mass or more and 15% by mass or less of the (meth) acrylic acid ester having a hydroxyl group.

In the present invention, the mass loss rate after heating at 250 ° C. for 1 hour is preferably less than 4% by mass. Further, it can be configured to have an adhesive layer on the other surface of the base film.

The method for manufacturing an electronic component according to the present invention includes a step of attaching an adhesive tape to a support plate, a step of fixing the electronic component on the adhesive tape, and a step of heating the electronic component. In the process of heating an electronic component, a film can be formed on the surface of the electronic component.

According to the present invention, it is possible to provide an adhesive tape capable of suppressing the generation of organic gas even when heat-treated, and a method for manufacturing an electronic component using the adhesive tape.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. In the present specification, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth) acrylate" is a general term for acrylate and methacrylate.

[Adhesive tape]
The adhesive tape of the present embodiment has an adhesive layer on one surface of the base film.
(Base film)
The base film contains a polyether sulfone. The polyether sulfone has heat resistance and can form a film by an extrusion molding method, so that the film formed by a solvent casting method does not contain a residual solvent. Therefore, the generation of organic gas can be suppressed even when the adhesive tape is heat-treated at a high temperature of 200 ° C. or higher. In addition to the polyether sulfone, a general thermoplastic resin can be used, although not particularly limited. As the thermoplastic resin, polyetheretherketone, polyarylate and the like are preferable from the viewpoint of heat resistance.

As the polyether sulfone, generally, any one used for molding and film may be used, and one having a hydroxyl group instead of chlorine as a terminal group is preferable. The glass transition temperature of the polyether sulfone is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and even more preferably 225 ° C. or higher. When the glass transition temperature is 220 ° C. or higher, it is possible to suppress an increase in the heat shrinkage rate. Examples of the polyether sulphon having a glass transition temperature of 200 ° C. or higher include polyphenyl sulphon (glass transition temperature 220 ° C.) and polyether sulphon (glass transition temperature 225 ° C.). The glass transition temperature conforms to JIS K7121 and is measured by DSC from room temperature to 380 ° C at a heating rate of 10 ° C / min under a nitrogen atmosphere using a differential thermogravimetric analyzer. The intermediate value of the curved point temperature.

The polyether sulfone is a polymer having a chemical structure of the formulas (1) to (10). The polyether sulphon constituting the base material layer (A) is not particularly limited, but a polyether phenyl sulphon having a repeating unit represented by the formula (1) is preferable, and a polyether phenyl sulphon having a repeating unit represented by the formula (1) is more preferable. Examples thereof include polyether sulfone having a repeating unit to be used. One or more types of polyether sulfone can be selected and used.

The polyphenyl sulfone may be a homopolymer having only the chemical structure of the formula (1), or may have a chemical structure other than the formula (1). However, the ratio of the chemical structure of the formula (1) in the polyphenyl sulfone is preferably 50 mol% or more, preferably 80 mol% or more, based on 100 mol% of the polyphenyl sulfone, because it is excellent in film strength, heat resistance, and molding processability. % Or more is more preferable.

When the polyphenyl sulfone has a chemical structure other than the formula (1) and is a copolymer, it may be any of a block copolymer, a random copolymer, and an alternating copolymer. Further, it may be a modified product having another chemical structure only at the end of the chemical structure of the formula (1). Specific examples of the polyphenyl sulfone include a trade name of Solvay Specialty Polymers, Inc.: Radel R series, and a trade name of BASF, Inc.: Ultrazone P series.

The polyether sulfone may be a homopolymer having only the chemical structure of the formula (2), or may have a chemical structure other than the formula (2). However, the ratio of the chemical structure of the formula (2) in the polyether sulfone is preferably 50 mol% or more, preferably 80% or more, based on 100 mol% of the polyether sulfone because it is excellent in film strength, heat resistance, and molding processability. More preferably, mol% or more.

When the polyether sulphon has a chemical structure other than the formula (2) and is a copolymer, it may be any of a block copolymer, a random copolymer, and an alternating copolymer. Further, it may be a modified product having another chemical structure only at the end of the chemical structure of the formula (2). Specific examples of the polyether sulfone include Sumika Excel PES series manufactured by Sumitomo Chemical Co., Ltd. and Ultrazone E series manufactured by BASF.

The base film may contain additives such as a plasticizer and a stabilizer, if necessary. The plasticizer is not particularly limited, and for example, a phthalate ester-based plasticizer such as dioctyl phthalate, an epoxy-based plasticizer such as epoxidized soybean oil, and a polyester-based plasticizer such as phthalate polyethylene glycol diester can be used. The stabilizer is not particularly limited, and is, for example, an epoxy-based stabilizer, a barium-based stabilizer, a calcium-based stabilizer, a tin-based stabilizer, a zinc-based stabilizer, a calcium-zinc-based (Ca-Zn-based) or barium-zinc stabilizer. Complex stabilizers such as system (Ba-Zn system), metal soaps such as fatty acid calcium, fatty acid zinc, fatty acid barium, hydrotalcite, β-diketone compounds and copolymers of glycidyl methacrylate and methyl methacrylate, etc. Be done. These stabilizers may be used alone or in combination of two or more.

In order to improve the slipperiness of the film, the base film contains organic or inorganic fine particles having an average particle size of about 0.01 to 20 μm as a lubricant, for example, in a blending ratio of 0.005 to 20% by mass. Can be contained. The average particle size is the average particle size of the primary particles (average primary particle size), and the maximum diameter of several tens to 100 particles is actually measured using a transmission electron microscope (TEM). It is a value obtained by calculating the average value.

Specific examples of the fine particles include calcium carbonate, calcium oxide, amylnium oxide, titanium oxide, graphite, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, acrylic resin particles, crosslinked polystyrene resin particles, and melamine resin particles. , Silicone resin particles and the like can be preferably mentioned.

In addition to the above, an antistatic agent, an organic lubricant, a catalyst, a pigment, a fluorescent whitening agent, a cross-linking agent, a lubricant, an ultraviolet absorber, another resin and the like can be added to the base film as needed. ..

The content of these additives is not particularly limited and may be 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polyether sulfone.

The thickness of the base film is not particularly limited, and can be 5 μm or more and 150 μm or less, preferably 10 μm or more and 75 μm or less. Further, the base film may be a single layer or may have a multilayer structure of two or more layers.

As a method for forming the base film, an extrusion molding method, a calendar film forming method, a T-die processing method, or the like can be adopted. The surface of the base film may be subjected to a treatment for forming fine irregularities, if necessary. As a method for forming fine irregularities, (i) a method of extruding a melt-kneaded resin from a T-die and sandwiching it with a pressure-bonding roll different from the metal roll to form a film, using a metal roll having fine irregularities. Examples thereof include a method of simultaneously cooling the film and forming irregularities, and (ii) a method of forming a multilayer film and then bringing the film into close contact with a metal roll having fine irregularities to form irregularities. Of these, the method (i) is preferable from the viewpoint of simplifying the apparatus.

(Adhesive layer)
The adhesive layer (hereinafter, also referred to as “first adhesive layer”) contains a (meth) acrylic acid ester copolymer (A) and an isocyanate-based curing agent (B). Since the adhesive layer contains the (meth) acrylic acid ester copolymer (A) and the isocyanate-based curing agent (B), it has heat resistance, does not contain a residual solvent in the base material, and is siloxane gas-free. Can be achieved. As a result, it is possible to prevent the generation of organic gas even when the adhesive tape is heat-treated at a high temperature. This pressure-sensitive adhesive layer can be formed by using an acrylic pressure-sensitive adhesive composition containing the (meth) acrylic acid ester copolymer (A) and the isocyanate-based curing agent (B).

The (meth) acrylic acid ester copolymer (A) contains a hydroxyl group. Examples of the hydroxyl group-containing (meth) acrylic acid ester copolymer include a hydroxyl group-containing (meth) acrylic acid ester copolymer, a hydroxyl group-containing (meth) acrylic acid ester, and a hydroxyl group-free (meth) acrylic. Examples thereof include a copolymer with an acid ester or a copolymer obtained by copolymerizing these monomers with an unsaturated monomer (for example, vinyl acetate, styrene, acrylonitrile) that can be copolymerized.

Examples of the hydroxyl group-containing (meth) acrylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, and glycidoldi. (Meta) acrylate, dipentaerythritol pentaacrylate and the like can be mentioned, and one or more selected from these can be used.

Examples of the hydroxyl group-free (meth) acrylic acid ester monomer include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, and octyl (meth) acrylate. 2-Ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, ethyl acrylate, 2-methoxyethyl acrylate, isopropyl (meth) ) Acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate and the like. One kind or two or more kinds selected from these can be used.

The hydroxyl value of the (meth) acrylic acid ester copolymer (A) is more than 0 and 90 mgKOH / g or less, preferably 1 mgKOH / g or more and 80 mgKOH / g or less, and more preferably 3 mgKOH / g or more and 70 mgKOH. It is / g or less, or 65 mgKOH / g or less. By setting the hydroxyl value of the (meth) acrylic acid ester copolymer (A) to more than 0 and 90 mgKOH / g or less, it is possible to obtain an adhesive tape capable of suppressing the generation of organic gas even when heat-treated. can. When the hydroxyl value is 80 mgKOH / g or less, the crosslinked structure with the isocyanate-based curing agent (B) can be controlled, sufficient adhesive strength can be obtained, and peelability and adhesive residue after heating can be obtained. And mass change can be suppressed, which is preferable. The hydroxyl value can be measured by the neutralization titration method according to JIS K 0070-1992.

The weight average molecular weight (Mw) of the (meth) acrylic acid ester copolymer (A) is preferably 300,000 or more and 2.2 million or less. By setting the weight average molecular weight to 300,000 or more, it is possible to suppress the adhesive residue after the heat treatment. By setting the weight average molecular weight to 2.2 million or less, the desired adhesive strength can be enhanced. The weight average molecular weight (Mw) can be determined by a gel permeation chromatography (GPC) method.

Examples of the (meth) acrylic acid ester copolymer (A) include a (meth) acrylic acid ester copolymer containing 1% by mass or more and 15% by mass or less of a (meth) acrylic acid ester having a hydroxyl group. .. For example, the (meth) acrylic acid ester copolymer (A) containing 1% by mass or more and 15% by mass or less of a (meth) acrylic acid ester having a hydroxyl group and having a weight average molecular weight (Mw) of 300,000 or more and 2.2 million or less. By doing so, the hydroxyl value can be easily adjusted within the above range, sufficient adhesive strength can be achieved, and adhesive residue after heat treatment can be suppressed.

The glass transition temperature of the (meth) acrylic acid ester copolymer (A) is preferably −50 ° C. or higher and −30 ° C. or lower as the theoretical glass transition temperature determined by the FOX formula described later. By setting this range, it is possible to impart step followability when the support member has irregularities.

The content of the (meth) acrylic acid ester copolymer (A) is preferably 50% by mass or more, more preferably 60% by mass or more, or 80% by mass or more in the pressure-sensitive adhesive layer. By setting the content of the (meth) acrylic acid ester copolymer (A) to 50% by mass or more, a sufficient hydroxyl value can be achieved and sufficient heat resistance can be imparted to the adhesive tape. ..

As the isocyanate-based curing agent (B), it is preferable to use a polyfunctional isocyanate curing agent. Examples of the polyfunctional isocyanate curing agent include an aromatic polyisocyanate curing agent, an aliphatic polyisocyanate curing agent, and an alicyclic polyisocyanate curing agent, and a trimer thereof or an adduct with trimethylolpropane may be used. can.

The aromatic polyisocyanate curing agent is not particularly limited, and is, for example, 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate. Isocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4'-triphenylmethane triisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1 , 4-Diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

The aliphatic polyisocyanate curing agent is not particularly limited, and is, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

The alicyclic polyisocyanate curing agent is not particularly limited, and is, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexane. Diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, and 1,4-bis (isocyanate) Methyl) cyclohexane and the like can be mentioned.

The adduct body with a trimer or trimethylolpropane is not particularly limited, and an adduct body containing 2,4-tolylene diisocyanate and trimethylolpropane is preferably used.

The content of the isocyanate-based curing agent (B) is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). It is a mass part to 15 parts by mass. By setting the content of the curing agent within the above range, it becomes possible to control the crosslinked structure with the (meth) acrylic acid ester copolymer (A), and it is possible to obtain sufficient adhesive strength and also to obtain sufficient adhesive strength. It is possible to suppress peelability, adhesive residue and mass change after heating.

The adhesive layer can contain a tackifier, if necessary. Examples of the tackifier include completely or partially hydrogenated terpene phenol resin, terpene phenol resin, alicyclic saturated hydrocarbon resin, rosin ester, rosin, styrene resin, aliphatic hydrocarbon resin, acrylic acid ester and the like. Can be mentioned. The content of the tackifier can be 0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).

(Other additives, etc.)
Various additives such as a softening agent, an antiaging agent, a filler, a conductive agent, an ultraviolet absorber, and a light stabilizer may be added to the pressure-sensitive adhesive composition. The content of the other additives is not particularly limited, and may be 0 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).

The thickness of the adhesive layer is preferably 5 μm to 40 μm. By setting the thickness of the pressure-sensitive adhesive layer to 5 μm or more, sufficient adhesiveness can be ensured, and it is possible to prevent deterioration of thickness accuracy, adhesive strength, step followability, and the like. By setting the thickness of the pressure-sensitive adhesive layer to 40 μm or less, the pressure-sensitive adhesive layer can be easily formed, and it is possible to prevent adhesive residue after heating, cost increase, productivity decrease, etc. that may occur when the thickness is increased. can.

As a method for forming the pressure-sensitive adhesive layer, a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester copolymer (A), an isocyanate-based curing agent (B), a pressure-sensitive adhesive used as necessary, and the like is placed on a substrate. It can be a coating method. The method includes a method of directly applying the pressure-sensitive adhesive composition on the base film with a coater such as a gravure coater, a comma coater, a bar coater, a knife coater or a roll coater, or a method of applying the pressure-sensitive adhesive composition to a release film. There is a method of sticking to the base film after drying. The pressure-sensitive adhesive composition may be printed on the base film by convex plate printing, concave plate printing, flat plate printing, flexographic printing, offset printing, screen printing, or the like.

(Second adhesive layer)
The adhesive tape according to the present embodiment further has an adhesive layer (hereinafter, also referred to as "second adhesive layer") on the other surface of the base film (the surface opposite to the surface having the adhesive layer). May be. The second adhesive layer includes the same resin as the (meth) acrylic acid ester copolymer (A) or a different (meth) acrylic acid ester copolymer resin, an isocyanate-based curing agent, and an epoxy-based curing agent, depending on the intended use. It can be formed by using a pressure-sensitive adhesive composition containing an agent or a metal chelate-based curing agent. Since the same resin as the (meth) acrylic acid ester copolymer (A) and the isocyanate-based curing agent are the same as above, the description thereof is omitted here.

Examples of the (meth) acrylic acid ester copolymer resin different from the (meth) acrylic acid ester copolymer (A) include a (meth) acrylic acid ester copolymer resin containing no hydroxyl group. Examples of the hydroxyl group-free (meth) acrylic acid ester copolymer resin include the above-mentioned copolymers of hydroxyl group-free (meth) acrylic acid ester monomers and unsaturated monomers copolymerizable with those monomers (for example). , Vinyl acetate, styrene, acrylonitrile) and copolymers.

As the epoxy-based curing agent, a polyfunctional epoxy curing agent can be used. The polyfunctional epoxy curing agent mainly refers to a compound having 2 or more epoxy groups and 1 or more tertiary nitrogen atoms, and refers to N, N-glycidylaniline, N, N-glycidyltoluidine, m-N, N-glycidylamino. Phenylglycidyl ether, p-N, N-glycidylaminophenylglycidyl ether, triglycidyl isocyanurate, N, N, N', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N'-tetraglycidyl-m -Xylylene diamine, N, N, N', N', N "-pentaglycidyldiethylenetriamine and the like can be mentioned. The method of forming the second adhesive layer is the same as that of the first adhesive layer.

(Adhesive tape)
The adhesive tape according to this embodiment can prevent the generation of organic gas even when heat-treated at a high temperature. Therefore, even when this adhesive tape is used as a masking tape or the like when manufacturing electronic parts or the like, it is possible to prevent the electronic parts or devices from being contaminated or colored by organic gas or deposits from being deposited. .. Further, since it is possible to suppress an excessive increase in adhesiveness after the heat treatment, it is possible to prevent the occurrence of adhesive residue.

The adhesive tape has a mass loss rate of less than 4% by mass after heating at 250 ° C. for 1 hour. When the mass reduction rate is less than 4% by mass, it is shown that it is possible to suppress the generation of organic gas even when the adhesive tape is heated at a high temperature. The mass reduction rate is a value calculated by the following formula I by measuring the mass of the adhesive tape before and after heating.
Mass reduction rate = [(mass before heating-mass after heating) / (mass before heating)] x 100 (mass%)
... I

The adhesive tape preferably has an adhesive strength of 0.4 N / 20 mm or more and less than 10 N / 20 mm at a width of 20 mm after being heated at 100 ° C. By setting the adhesive strength after heating within this range, it is possible to suppress the adhesive residue after the heat treatment. The adhesive strength is a value measured according to JIS Z 0237.

(Use)
The adhesive tape of this embodiment can be used for various purposes. For example, it can be used for manufacturing and transporting electronic components, for fixing a substrate in a chip size package mounting process, for a film-like substrate production process, and the like. Since the adhesive tape can suppress the generation of organic gas even when heat-treated, it is used for fixing electronic parts in the process of heating electronic parts at high temperature and for protecting electronic parts and / or support plates. It can also be used for transporting electronic components in subsequent processes. For example, a step of forming a vapor-deposited film on the surface of an electronic component, a step of thinning a material in the manufacture of a wafer level package (WLP), an organic EL, and an LED, an electrode forming step, a thin film circuit forming step, and a resin sealing step. It can be used as a masking tape that can consistently support transport. Further, it can be used as a masking tape for a support when surface-treating a semiconductor wafer, an electronic component, glass or the like.

[Manufacturing method of electronic parts]
The method for manufacturing an electronic component according to the present embodiment includes a step of attaching the above-mentioned adhesive tape to a support plate, a step of fixing the electronic component on the adhesive tape, and a step of heating the electronic component in this order. ..

(Pasting process)
In the sticking process, the adhesive tape is stuck on the support plate. The support plate is a plate for fixing electronic components, and the material thereof is not particularly limited, but may be metal, alloy, glass, or plastic. Metals, alloys and glass are preferred in terms of heat resistance. The shape and size of the support plate can be appropriately selected according to the application. The adhesive layer (first adhesive layer) of the adhesive tape is brought into close contact with one side of the support plate, and the adhesive tape is attached to the support plate. The place where the adhesive tape is attached may be only the place on the support plate immediately below the electronic component and the periphery thereof, or may be the entire surface of the support plate. By attaching the adhesive tape to the entire surface of the support plate, the adhesive tape acts as a masking tape for the support plate, and the support plate can be protected from deposits and the like.

(Fixing process of electronic parts)
In the fixing process, the electronic component is fixed on the adhesive tape. The electronic component is a component used in an electronic device, and examples thereof include a component made of a glass plate, an epoxy resin, a plastic film, a metal, an alloy, and the like. When the adhesive tape has a second adhesive layer, the electronic component is brought into close contact with the surface of the second adhesive layer and fixed. When the adhesive tape does not have a second adhesive layer, the electronic component is fixed on the surface of the base film opposite to the surface on which the first adhesive layer is formed by using a known double-sided tape or the like. do.

(Heating process)
In the heating step, the electronic components fixed on the adhesive tape are heat-treated. In the heating step, a film may be formed on the surface of the electronic component. In this case, the heating step is to form a thin-film deposition film on the surface of electronic parts by heating and evaporating metal oxides such as _{SiO 2} and TiO _{2, and metal nitrides such as SiN and TiN under vacuum.} It can be a process. The heating temperature can be appropriately selected depending on the application, and can be, for example, 200 ° C. or higher, or 250 ° C. or higher. Since the adhesive tape of the present embodiment has heat resistance, it is possible to suppress the generation of organic gas even when it is heated at a high temperature of 200 ° C. or higher, and it is possible to prevent the adhesiveness from being excessively increased and the adhesive residue. Can be suppressed. The heating time can be, for example, 1 minute or more, or 300 minutes or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the interpretation of the present invention is not limited by these Examples.
[material]
In the examples and comparative examples, the following materials were used.
(Base film)
PES: Polyester sulfone resin film, "Sumika Excel PES4800G" manufactured by Sumitomo Chemical Co., Ltd., Tg 225 ° C.
PAR: Polyarylate resin film, "U Polymer U-100" manufactured by Unitika Ltd., Tg 193 ° C.
PI: Polyimide resin film (thermoplastic polyimide), "Auram PL450C" manufactured by Mitsui Chemicals, Tg 250 ° C.

(Adhesive layer)
HEMA: 2-hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.), homopolymer Tg 55 ° C., molecular weight 130, hydroxyl value 431 mgKOH / g
EA: Ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), homopolymer Tg-22 ° C, molecular weight 100
BA: Butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), homopolymer Tg-54 ° C, molecular weight 128
AN: Acrylonitrile (manufactured by Mitsubishi Rayon), homopolymer Tg 100 ° C, molecular weight 53
MMA: Methyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Inc.), homopolymer Tg 105 ° C, molecular weight 100
Isocyanate-based curing agent: TDI-TMP adduct, "Coronate L-45E" manufactured by Tosoh Corporation

[Example 1]
A pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer was prepared as follows. First, a hydroxyl group-containing (meth) acrylic acid ester copolymer was synthesized as follows. In a separable flask having a capacity of 1 liter, 200 parts by mass of water containing 0.2% by mass of polyvinyl alcohol, (a) 2 parts by mass of methyl methacrylate (MMA), and (b) hydroxyethyl methacrylate (HEMA) 5 27 parts by mass of (c) ethyl acrylate (EA), 66 parts by mass of (d) butyl acrylate (BA), 0.1 parts by mass of benzoyl peroxide as a polymerization initiator, and a chain transfer agent for adjusting the molecular weight. The uniform mixed solution containing the above was charged.
The mixture was heated to 70 ° C. with stirring under a nitrogen atmosphere and suspended and polymerized for 4 hours. Water was then removed from the suspension by decantation. The solid material is washed with water while suction filtration to remove water, and then vacuum dried at 60 ° C. to obtain a copolymer resin having a water content of 0.5% or less (copolymer (A) of Example 1). Obtained. The weight average molecular weight of the obtained copolymer resin was measured by a gel permeation chromatography (GPC) method and found to be about 600,000. The monomer composition and molecular weight are shown in Table 1. Further, the hydroxyl value (OH content) and the theoretical Tg of the obtained copolymer resin were determined by the following methods. The results are shown in Table 1.
The obtained copolymer resin was melt-stirred in toluene. An isocyanate-based curing agent was added thereto, and the mixture was stirred and mixed to obtain a pressure-sensitive adhesive composition (pressure-sensitive adhesive A). This pressure-sensitive adhesive composition is applied onto a PES film having a width of 300 mm, a length of 400 mm, and a thickness of 25 μm using an applicator so that the thickness after curing is 20 μm, and then the conditions are 100 ° C. and 2 minutes. It was heated in and dried. A polyester film having a width of 300 mm, a length of 400 mm, and a release-treated thickness of 38 μm was attached to the adhesive surface to obtain an adhesive tape. This was aged in an oven at 40 ° C. for 3 days to obtain an adhesive tape of Example 1 having a width of 300 mm, a length of 400 mm, and a thickness of 0.083 mm as a crosslinked adhesive layer.

[Examples 2 to 14, Comparative Examples 1 to 4]
Adhesive tapes were prepared in the same manner as in Example 1 except that the base materials shown in Table 1 and the pressure-sensitive adhesives B to K having the compositions shown in Table 1 were used. In Example 10, a 20 μm PES film and a 5 μm PAR film were prepared by a coextrusion method to form a base material layer having a two-layer structure and a thickness of 25 μm.

[Measurement and evaluation]
(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the copolymerized resin in the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer was measured by the GPC method under the following conditions. The results are shown in Table 1.
Device name: Tosoh HLC-8220GPC
Column used: Showa Denko product name Shodex GPCKF-404 4 in series Column temperature: 40 ° C
Detection method: Ultraviolet spectroscopy (254 nm)
Mobile phase: tetrahydrofuran Sample concentration: 2% by weight
Calibration curve: Standard polystyrene (manufactured by Polymer Laboratories)

(Hydroxy group value)
The hydroxyl value (OH content) of the copolymer resin in the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer was measured by a neutralization titration method according to JIS K 0070-1992. The results are shown in Table 1.

(Theoretical glass transition temperature)
The theoretical Tg of the copolymerized resin in the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer was calculated as the theoretically calculated glass transition temperature (Tg) by the following FOX formula. The results are shown in Table 1.
(FOX type)
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + ... + W _n / Tg _n
In the above FOX equation, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n kinds of monomers is Tg ₁ , Tg ₂ , ... Tg _n (K), and the mass fraction of each monomer is set. _Let W ₁ , W ₂ , ... W n. W ₁ + W ₂ ... + W _n = 1.

The adhesive tapes obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2.
(Mass change rate)
A tape having a width of 21 mm and a length of 200 mm is cut from the adhesive tapes obtained in Examples and Comparative Examples, and massed (before heating) using an electronic balance (manufactured by Shinko Denshi Co., Ltd., model: HTR-220) in an environment of 23 ° C. Mass) was measured. Then, this tape was heated in an oven at 250 ° C. for 1 hour, and the mass of the adhesive tape after heating (mass after heating) was measured with the above electronic balance. The mass change (mass reduction rate) due to heating of the adhesive tape was calculated as a ratio to the mass before heating by the following formula I.
Mass reduction rate = [(mass before heating-mass after heating) / (mass before heating)] x 100 (mass%)
... I
3: 0% by mass or more and less than 3% by mass 2: 3% by mass or more and less than 4% by mass 1: 4% by mass or more

(Initial adhesive strength)
A tape having a width of 10 mm was cut from the adhesive tapes obtained in Examples and Comparative Examples, and placed on one side of a 10 cm square, 0.5 mm thick aluminum plate (arithmetic average surface roughness Ra: 1.0 ± 0.1 μm). A 2 kg roller was reciprocated once from above, and the adhesive tape was attached to the aluminum plate. After leaving this aluminum plate with adhesive tape at 23 ° C for 30 minutes, the adhesive tape is peeled off under the conditions of a peeling angle of 180 ° and a peeling speed (pulling speed) of 300 mm / min. Adhesive strength was measured.
3: 1.0N / 20mm or more and 6N / 20mm or less 2: 0.4N / 20mm or more and less than 1.0N / 20mm, or 6N / 20mm or more and less than 10N / 20mm 1: 0.4N / 20mm or less, 10N / 20mm that's all

(Adhesive strength after heating)
A tape having a width of 10 mm was cut from the adhesive tapes obtained in Examples and Comparative Examples, and bonded to the aluminum plate described above in the same manner as described above. The aluminum plate with the adhesive tape was heated in an oven at 250 ° C. for 1 hour, then cooled at 23 ° C. for 2 hours, and the adhesive strength was measured by the same method as described above.
3: 1.0N / 20mm or more and 6N / 20mm or less 2: 0.4N / 20mm or more and less than 1.0N / 20mm, or 6N / 20mm or more and less than 10N / 20mm 1: 0.4N / 20mm or less, 10N / 20mm that's all

(Remaining adhesiveness)
After the initial adhesive strength measurement and after the adhesive strength measurement after heating, each adhesive tape was peeled off from the aluminum plate. The area of 10 mm × 40 mm on the surface of the aluminum plate to which the adhesive tape was attached was observed with a microscope at a magnification of 100 times and evaluated according to the following criteria.
3: No glue residue 2: 1 or more and less than 10 glue residue 1: 10 or more glue residue

Claims (9)

It has an adhesive layer on one side of the base film and has an adhesive layer.
The base film contains a polyether sulfone and contains
The adhesive layer contains a (meth) acrylic acid ester copolymer (A) and an isocyanate-based curing agent (B).
The (meth) acrylic acid ester copolymer (A), hydroxyl value containing a hydroxyl group is Ri der 90 mgKOH / g or less than 0,
Adhesive tape for fixing and / or protecting electronic components and / or for protecting support plates. It has an adhesive layer on one side of a single-layer or two-layer base film, and has an adhesive layer.
The base film contains a polyether sulfone and contains
The adhesive layer contains a (meth) acrylic acid ester copolymer (A) and an isocyanate-based curing agent (B).
An adhesive tape in which the (meth) acrylic acid ester copolymer (A) contains a hydroxyl group and has a hydroxyl value of more than 0 and 90 mgKOH / g or less. The adhesive tape according to claim 1 or 2 , wherein the (meth) acrylic acid ester copolymer (A) has a weight average molecular weight of 300,000 or more and 2.2 million or less. Claims 1 to 3 in which the content of the isocyanate-based curing agent (B) is 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (A). The adhesive tape according to any one of the above. The adhesive tape according to any one of claims 1 to 4 , wherein the (meth) acrylic acid ester copolymer (A) contains 1% by mass or more and 15% by mass or less of the (meth) acrylic acid ester having a hydroxyl group. .. The adhesive tape according to any one of claims 1 to 5 , wherein the mass loss rate after heating at 250 ° C. for 1 hour is less than 4% by mass. The adhesive tape according to any one of claims 1 to 6 , further comprising an adhesive layer on the other surface of the base film. The step of attaching the adhesive tape according to any one of claims 1 to 7 to the support plate, and
The process of fixing electronic components on the adhesive tape and
A method for manufacturing an electronic component, comprising a step of heating the electronic component. The method for manufacturing an electronic component according to claim 8 , wherein a film is formed on the surface of the electronic component in the step of heating the electronic component.