KR20210104016A - Manufacturing method of adhesive tape and electronic component - Google Patents

Abstract

The present invention can also be used for a support that does not transmit light in the production of electronic components, and can suppress peeling and glue residue from an adherend and a support even when subjected to high-temperature treatment, and the adhesive tape using the adhesive tape An object of the present invention is to provide a method for manufacturing an electronic component. The present invention provides an adhesive tape having a non-UV-curable pressure-sensitive adhesive layer and an UV-curable pressure-sensitive adhesive layer laminated on the non-UV-curable pressure-sensitive adhesive layer, wherein the non-UV-curable pressure-sensitive adhesive layer has a tensile strength of 5.0 N/10 mm or more at 23 ° C. It is 20.0 N/10 mm or less, and it is an adhesive tape whose amount of outgassing when the said non-ultraviolet hardening-type adhesive layer is heated at 260 degreeC for 15 minutes is 10000 ppm or less.

Description

Manufacturing method of adhesive tape and electronic component

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

In a semiconductor chip manufacturing process, an adhesive tape is used to facilitate handling during processing of wafers or semiconductor chips 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 bonding the 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 damages an adherend such as a wafer or a semiconductor chip after the process is finished. It is calculated|required that it can peel without doing (henceforth "high adhesion and easy peeling").

As an adhesive composition realizing high adhesion and easy peeling, Patent Document 1 discloses an adhesive tape using a photocurable pressure-sensitive adhesive whose adhesive strength is lowered by curing by irradiation with light such as ultraviolet rays. By using a photocurable adhesive as an adhesive, while being able to fix a to-be-adhered body reliably during a processing process, it can peel easily by irradiating an ultraviolet-ray etc.

Japanese Patent Application Laid-Open No. 5-32946

In recent years, due to the thinning and miniaturization of semiconductor products, the substrate has also been thinned down to 100 µm or less (hereinafter, the thinned substrate is referred to as a thin substrate). Tape is being used. In manufacture of such a thin board|substrate, base materials, such as a polyimide film used as a base of a board|substrate, are fixed to a support body via a non-support type adhesive tape, and processing, such as wiring, is performed after that. However, the support used in the manufacture of the thin substrate is often an opaque material such as copper, aluminum, glass epoxy, etc. from the viewpoint of cost and handling, and in such an opaque support, an adhesive tape using a conventional photocurable pressure-sensitive adhesive can be cured. There was a problem that I couldn't. In response to this problem, an adhesive tape having a curable pressure-sensitive adhesive layer and a non-curable pressure-sensitive adhesive layer has been proposed. The adhesive tape can be cured even when the support is opaque by sticking the curable pressure-sensitive adhesive layer to an adherend such as a thin substrate and curing it, and then attaching the non-curable pressure-sensitive adhesive layer to the support.

On the other hand, in the manufacturing process of electronic components, such as a thin board|substrate, the high temperature process which applies heat of 150 degreeC or more may be performed. In the process accompanying such high-temperature treatment, when a conventional adhesive tape having a curable pressure-sensitive adhesive layer and a non-curable pressure-sensitive adhesive layer is used, the non-curable pressure-sensitive adhesive layer may be peeled off from the support without enduring the heat. Since the temperature of high-temperature processing is increasing with the advancement of technology, it can be used also for an opaque support body, and the adhesive tape which has additional heat resistance is calculated|required.

The present invention can also be used for a support that does not transmit light in the production of electronic components, and can suppress peeling and glue residue from an adherend and a support even when subjected to high-temperature treatment, and an adhesive tape using the adhesive tape An object of the present invention is to provide a method for manufacturing an electronic component.

A first aspect of the present invention is an adhesive tape having a non-UV-curable pressure-sensitive adhesive layer and a UV-curable pressure-sensitive adhesive layer laminated on the non-UV-curable pressure-sensitive adhesive layer, wherein the non-UV-curable pressure-sensitive adhesive layer has a tensile strength of 5.0 N at 23 ° C. They are /10 mm or more and 20.0 N/10 mm or less, and the amount of outgas when the said non-ultraviolet hardening-type adhesive layer is heated at 260 degreeC for 15 minutes is 10000 ppm or less, it is an adhesive tape.

A second aspect of the present invention is an adhesive tape having a non-UV-curable pressure-sensitive adhesive layer and an ultraviolet-curable pressure-sensitive adhesive layer laminated on the non-UV-curable pressure-sensitive adhesive layer, wherein the non-UV-curable pressure-sensitive adhesive layer is heated at 260° C. for 15 minutes The amount of outgassing is 10000 ppm or less, and the non-ultraviolet-curable pressure-sensitive adhesive layer contains (A') 92 to 97 wt% of an alkyl (meth)acrylic acid alkylester having 4 to 12 carbon atoms as a base polymer as a constituent component ( It is an adhesive tape containing a meth)acrylic-type copolymer, the epoxy-type compound containing a tertiary amine structure as a (B) hardening|curing agent, and (C) a filler.

Hereinafter, the present invention will be described in detail.

The adhesive tape of this invention has a non-UV curable adhesive layer and the ultraviolet curable adhesive layer laminated|stacked on the said non-UV curable adhesive layer.

When the adhesive tape has an ultraviolet curable adhesive layer, it can adhere to an adherend with sufficient adhesive force to protect the adherend, and by curing the ultraviolet curable adhesive layer after affixing, the adherend is reliably secured even when subjected to high temperature treatment can be protected Moreover, after protection becomes unnecessary, an adhesive tape can be peeled easily without damaging a to-be-adhered body. Further, since the adhesive tape has a non-UV-curable pressure-sensitive adhesive layer, the UV-curable pressure-sensitive adhesive layer is adhered to the adherend and the non-UV-curable pressure-sensitive adhesive layer can be adhered to the support after the UV-curable pressure-sensitive adhesive layer is cured. Even when it is opaque, an ultraviolet curable adhesive layer can be hardened. Moreover, from a viewpoint of being able to simplify a manufacturing process, you may irradiate an ultraviolet-ray immediately after affixing an adhesive tape to a to-be-adhered body, and you may harden an ultraviolet curable adhesive layer.

In a preferred embodiment of the present invention, the non-UV-curable pressure-sensitive adhesive layer is UV-transmissive. Here, the UV transmittance means that the light absorption wavelength band of the UV polymerization initiator contained in the UV curable pressure-sensitive adhesive layer overlaps with the wavelength band that transmits light of the non-UV curable pressure sensitive adhesive layer, and in particular, the light absorption wavelength band of the UV polymerization initiator and , It is preferable that the absorbance of the non-UV curable pressure-sensitive adhesive layer overlaps with a wavelength band of 0.2 or less. The non-UV-curable pressure-sensitive adhesive layer is UV-transmissive, so that the UV-curable pressure-sensitive adhesive layer may be irradiated with UV light through the non-UV-curable pressure-sensitive adhesive layer.

1st aspect of this invention WHEREIN: As for the said non-ultraviolet-ray-curable adhesive layer, the tensile strength in 23 degreeC is 5.0 N/10 mm or more and 20.0 N/10 mm or less.

The 2nd aspect of this invention WHEREIN: It is preferable that the tensile strength in 23 degreeC of the said non-ultraviolet-ray hardening-type adhesive layer is 5.0 N/10 mm or more and 20.0 N/10 mm or less.

When the tensile strength of the non-UV-curable pressure-sensitive adhesive layer is within the above range, the adhesive tape is less likely to tear at the time of peeling. From the viewpoint of further suppressing tearing of the adhesive tape during peeling, a preferable lower limit of the tensile strength of the non-UV-curable adhesive layer is 5.5 N/10 mm, a more preferable lower limit is 6.0 N/10 mm, and a preferable upper limit is 19.5 N/10 mm, and a more preferable upper limit is 19.0 N/10 mm.

In addition, the tensile strength of the non-UV-curable pressure-sensitive adhesive layer is a sample obtained by cutting the non-UV-curable pressure-sensitive adhesive layer to a thickness of 200 μm and a width of 10 mm, and under the conditions of 23° C. and 50% RH, Tensilon UCE500 (Orientec Co., Ltd.) ) can be used to measure the tensile strength at a speed of 300 mm/min and a distance between marks of 40 mm.

The amount of outgassing when the said non-ultraviolet hardening-type adhesive layer heats the said non-UV hardening-type adhesive layer at 260 degreeC for 15 minute(s) is 10000 ppm or less.

In the manufacture of electronic components accompanying high-temperature treatment, in order to protect electronic components, when an adhesive tape having a general non-UV-curable pressure-sensitive adhesive layer and a UV-curable pressure-sensitive adhesive layer is used, the non-UV-curable pressure-sensitive adhesive layer is decomposed by the heat of high-temperature treatment and a large amount of outgas is generated. Since the generated outgas foams the non-UV-curable pressure-sensitive adhesive layer and lowers its strength and adhesive strength, peeling occurs between the support and the non-UV-curable pressure-sensitive adhesive layer at the time of peeling, leaving an adhesive tape on the side of the adherend (glue residue) causes a problem. In the adhesive tape of the present invention, the amount of outgas generated by the non-UV-curable pressure-sensitive adhesive layer is small, that is, the non-UV-curable pressure-sensitive adhesive layer is not easily decomposed by heat. An adhesive tape can be made hard to remain. From the viewpoint of further suppressing residual adhesive tape on the adherend, the amount of outgas is preferably 7500 ppm or less, more preferably 5500 ppm or less, still more preferably 4000 ppm or less, and particularly preferably 3500 ppm or less. . The lower limit of the amount of outgas is not particularly limited, and it is preferable that the lower limit is lower. For example, the lower limit is preferably 1000 ppm.

The amount of outgas is, for example, cut out the non-UV curable pressure-sensitive adhesive layer to 5 mm × 5 mm, thermal desorption GC-MS (thermal desorption device: TurboMatrix 350, manufactured by Perkin Elmer, GC-MS device: JMS Q1000, Nippon Electronics Co., Ltd. It can be obtained as the amount of gas (ppm in terms of toluene: μg/g) when measured using the

In addition, detailed measurement conditions are as follows.

Sample heating conditions: 260 °C, 15 min (20 mL/min)

Secondary Desorption: 350℃, 40 min

Split: inlet 25 ml/min, outlet 25 ml/min

Injection amount: 2.5%

Column: EQUITY-1 (non-polar, manufactured by SIGMA-ALDRICH) 0.32 mm × 60 m × 0.25 μm

GC temperature increase: 40 ℃ (4 min) → 10 ℃/min rate of temperature increase → 300 ℃ (10 min)

He flow rate: 1.5 ml/min

Ionization voltage: 70 eV

MS measurement range: 29 ∼ 600 amu (scan 500 ms)

MS temperature: ion source; 230 ℃, interface ; 250 ℃

It is preferable that the said non-ultraviolet-ray-curable adhesive layer has a tack strength of 10-300 gf/3 mmφ.

By the tack strength of the non-UV-curable pressure-sensitive adhesive layer is within the above range, the non-UV-curable pressure-sensitive adhesive layer and the support are more reliably adhered, and the adhesive tape is easily peeled from the interface between the UV-curable pressure-sensitive adhesive layer and the adherend by peeling. can From the viewpoint of making it easier to peel the adhesive tape from the interface between the UV-curable pressure-sensitive adhesive layer and the adherend, a more preferable lower limit of the tack strength is 15 gf/3 mmφ, a more preferable lower limit is 20 gf/3 mmφ, and a more preferable upper limit Silver is 270 gf/3 mmφ, and a more preferable upper limit is 250 gf/3 mmφ.

In addition, the tack strength can be measured by cutting the non-UV curable pressure-sensitive adhesive layer to 10 mm × 10 mm to prepare a measurement sample, and measuring the obtained measurement sample by performing a probe tack measurement. In addition, the instrument to be used and measurement conditions can be carried out as follows.

Tacking tester: TAC1000, manufactured by RHESCA (or its equivalent)

Probe diameter: 3 mmφ

Crimping load: 100 g

Crimping time: 1 second

Contact speed: 30 mm min

Peeling speed: 600 mm/min

It is preferable that the said non-ultraviolet-ray-curable adhesive layer has a gel fraction of 80 % or more.

When the gel fraction of the non-UV-curable pressure-sensitive adhesive layer is 80% or more, the chemical resistance of the non-UV-curable pressure-sensitive adhesive layer is improved.

From the viewpoint of further improving chemical resistance, the gel fraction is more preferably 95% or more, and still more preferably 97% or more. Although the upper limit of the said gel fraction is not specifically limited, Usually, it is 100 % or less. In addition, the gel fraction can be measured by the following method.

Only 0.1 g of the non-UV-curable adhesive layer of the obtained adhesive tape is scraped off, immersed in 50 ml of ethyl acetate, and shaken in a shaker at a temperature of 23 degrees at a temperature of 120 rpm for 24 hours (hereinafter, the non-UV-curable adhesive layer that has been scraped off is a pressure-sensitive adhesive) called composition). After shaking, using a metal mesh (scale interval #200 mesh), ethyl acetate and ethyl acetate are absorbed, and the swollen pressure-sensitive adhesive composition is separated. The adhesive composition after isolation|separation is dried on 110 degreeC conditions for 1 hour. The weight of the pressure-sensitive adhesive composition containing the metal mesh after drying is measured, and the gel fraction of the non-UV curable pressure-sensitive adhesive layer is calculated using the following formula.

Gel fraction (wt%) = 100 x (W ₁ -W ₂ )/W ₀

(W ₀ : initial pressure-sensitive adhesive composition weight, W ₁ : pressure-sensitive adhesive composition weight including the metal mesh after drying, W ₂ : initial weight of the metal mesh)

The non-UV curable pressure-sensitive adhesive constituting the non-UV-curable pressure-sensitive adhesive layer is not particularly limited as long as it is non-UV-curable and satisfies the tensile strength and outgassing amount, but it is preferable that the base polymer has a functional group capable of reacting with an epoxy group. .

Examples of the functional group capable of reacting with the epoxy 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. Especially, it is preferable that it is at least 1 sort(s) chosen from the group which consists of a carboxyl group, a hydroxyl group, a phenol group, an ester group, and an amino group from a point with high reactivity.

As said base polymer, an acryl-type polymer, a silicone-type polymer, a urethane-type polymer, etc. are mentioned, for example.

In the first aspect of the present invention, the non-UV-curable pressure-sensitive adhesive layer comprises (A) as a base polymer (a) 92 to 97 wt% of (meth)acrylic acid alkylester having 4 to 12 carbon atoms in the alkyl group, and (b) It is preferable to contain 3.0 to 8.0 weight% of a carboxyl group-containing monomer as a structural component, (c) weight average molecular weight 700,000 or more (d) It is preferable to contain the (meth)acrylic-type copolymer whose molecular weight distribution is 2-6.

In the second aspect of the present invention, the non-UV-curable pressure-sensitive adhesive layer comprises (A') 92 to 97% by weight of an alkyl (meth)acrylic acid alkylester having 4 to 12 carbon atoms as a base polymer as a constituent component ( It contains a meth)acrylic copolymer. Also in the second aspect of the present invention, the (meth)acrylic copolymer contains 92 to 97% by weight of (meth)acrylic acid alkylester having 4 to 12 carbon atoms in the alkyl group, and 3.0 to 8.0% by weight of a carboxyl group-containing monomer. , it is preferable that the weight average molecular weight is 700,000 or more, and molecular weight distribution is 2-6.

By using the (meth)acrylic acid alkylester having 4 to 12 carbon atoms in the alkyl group as a constituent component, it is possible to obtain a non-UV-curable pressure-sensitive adhesive layer that is more excellent in adhesive strength (preferably has UV transmittance). Moreover, by using a carboxyl group-containing monomer as a structural component, the cohesive force of a non-ultraviolet-ray-curable adhesive can be improved, and larger adhesive force can be provided. In addition, when the UV-curable pressure-sensitive adhesive layer contains a silicone compound, since the carboxyl group, which is a polar group, inhibits the approach of the low-polar silicone compound, it is possible to suppress the silicone compound from bleed out to the non-UV-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 (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl ( meth)acrylate and the like. Among these, butyl acrylate is preferable from the viewpoint of excellent adhesive strength.

As said carboxyl group-containing monomer, acrylic acid, methacrylic acid, etc. are mentioned, for example. Among them, acrylic acid is preferable from the viewpoint of imparting high adhesive force.

When content of the C4-C12 (meth)acrylic-acid alkylester of the said alkyl group is 92 to 97 weight%, it can be set as the adhesive tape which is more excellent in adhesive force. When the carboxyl group-containing monomer is 3.0 wt% or more, when the UV-curable pressure-sensitive adhesive layer contains a silicone compound, the bleed-out of the silicone compound to the non-UV-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 in an appropriate range, and when the UV-curable pressure-sensitive adhesive layer contains a silicone compound, the non-UV-curable pressure-sensitive adhesive layer of the silicone compound Bleedout can be further suppressed.

As for content of the said (meth)acrylic acid alkylester in the said (meth)acrylic-type copolymer, from a viewpoint of further suppression of bleedout, a more preferable lower limit is 93 weight%, a more preferable lower limit is 94 weight%, A more preferable upper limit is 96% by weight. The content of the carboxyl group-containing monomer in the (meth)acrylic copolymer is, from the viewpoint of further suppression of bleedout, a more preferable lower limit of 4.0% by weight, a more preferable upper limit of 7.0% by weight, and a still more preferable upper limit of 6.0% by weight. .

Since the (meth)acrylic copolymer has a large weight average molecular weight of 700,000 or more and a narrow molecular weight distribution of 2 to 6, the tensile strength of the non-UV-curable pressure-sensitive adhesive layer and the amount of outgas can be easily adjusted within the above range. have. In addition, molecular weight distribution refers to ratio (Mw/Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) here. A more preferable minimum of the said weight average molecular weight is 750,000, and a more preferable minimum is 800,000. Although the upper limit of the said weight average molecular weight is not specifically limited, From a viewpoint of handleability, for example, a preferable upper limit is 1.2 million. Moreover, a more preferable lower limit of the said molecular weight distribution is 2.5, a more preferable lower limit is 3, a more preferable upper limit is 5.5, and a still more preferable upper limit is 5. The weight average molecular weight and molecular weight distribution may be determined using GPC measurement, and specifically, the method shown in Examples may be used.

As a method of obtaining the said (meth)acrylic-type copolymer which has the said weight average molecular weight and molecular weight distribution, solution polymerization, emulsion polymerization, living radical polymerization, etc. are mentioned, for example.

In the first aspect of the present invention, the non-UV-curable pressure-sensitive adhesive layer preferably contains an epoxy-based compound as the (B) curing agent, and more preferably contains an epoxy-based compound containing a tertiary amine structure.

2nd aspect of this invention WHEREIN: The said non-ultraviolet-ray-curable adhesive layer contains the epoxy-type compound containing a tertiary amine structure as (B) hardening|curing agent.

When the non-UV-curable pressure-sensitive adhesive layer contains an epoxy-based compound, the base polymer is cross-linked to improve the chemical resistance and heat resistance of the non-UV-curable pressure-sensitive adhesive layer. Moreover, the gel fraction of the base polymer after crosslinking is improved, and it becomes a molecular structure which does not move easily. Therefore, when the said ultraviolet curable adhesive layer contains a silicone compound, the bleed-out with respect to the non-ultraviolet-curable adhesive layer of a silicone compound is inhibited, and sufficient adhesive force can be exhibited even when it is stored for a long period of time. Examples of the epoxy compound include N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine), methylglycidylether, 3,4-epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl) adipate, bisphenol A diglycidyl ether, diglycidyl ether condensate of bisphenol A, novolac resin and epichlorohydrin-modified products of cresol resin. Especially, it is preferable that it is an epoxy-type compound containing a tertiary amine structure.

Since the base polymer before crosslinking reaction with the epoxy compound has a low gel fraction and has a structure in which molecules are easy to move, when the UV-curable pressure-sensitive adhesive layer contains a silicone compound, the silicone compound tends to bleed out. Therefore, when the speed|rate of a crosslinking reaction is slow, it will become a cause that a silicone compound bleeds out in a large amount to a non-ultraviolet-ray-curable adhesive layer. When a tertiary amino group is present in the non-UV-curable pressure-sensitive adhesive layer, the tertiary amino group acts as a catalyst for the crosslinking reaction, and the speed of the crosslinking reaction of the base polymer is increased, so that the reaction is completed early. When the crosslinking reaction is completed early, the silicone compound is less likely to bleed out to the non-UV-curable pressure-sensitive adhesive layer, so that an adhesive tape having sufficient adhesive strength can be obtained even when stored for a long period of time. N,N,N',N'-tetraglycidyl-1,3-benzenedi (methanamine) etc. are mentioned as an epoxy compound which has the said tertiary amine.

The content of the curing agent (the epoxy compound) in the non-UV-curable pressure-sensitive adhesive layer has a preferable lower limit of 0.1 parts by weight, a more preferable lower limit of 0.2 parts by weight, and a more preferable lower limit of 0.3 parts by weight with respect to 100 parts by weight of the base polymer. , A preferable upper limit is 0.5 parts by weight, a more preferable upper limit is 0.45 parts by weight, and a more preferable upper limit is 0.4 parts by weight. When the content of the epoxy compound is within the above range, the base polymer can be crosslinked sufficiently and quickly, and the bleed-out of the silicone compound to the non-UV-curable pressure-sensitive adhesive layer can be further suppressed.

1st aspect of this invention WHEREIN: It is preferable that the said non-ultraviolet-ray hardening-type adhesive layer contains (C) filler.

The 2nd aspect of this invention WHEREIN: The said non-ultraviolet hardening-type adhesive layer contains (C) filler.

Heat resistance can be improved by the said non-UV hardening-type adhesive layer containing a filler. As said filler, a silica filler, an aluminum filler, a calcium filler, a boron filler, a magnesium filler, a zirconia filler, etc. are mentioned, for example. Especially, it is preferable that it is a silica filler.

It is preferable that the said silica filler is a silica filler oxide at the point which can suppress more the bleed-out of a silicone compound when the said ultraviolet curable adhesive layer contains a silicone compound. Since the silica filler oxide has a hydrophilic group and has a high polarity, it is possible to prevent a low polar substance from approaching by containing the silica filler oxide in the non-ultraviolet-curable pressure-sensitive adhesive layer. Therefore, when the said ultraviolet curable adhesive layer contains the silicone compound which is low polarity, it can suppress that a silicone compound bleeds out to a non-ultraviolet hardenable adhesive layer.

The silica filler oxide is not particularly limited, and for example, silicon-aluminum-boron complex oxide, silicon-titanium complex oxide, silica-titania complex oxide, magnesium-aluminum-silicon complex oxide, hexamethylcyclotrisiloxane, tetrameth Toxysilane, chlorosilane, monosilane, etc. are mentioned. Among them, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, and silica-titania composite oxide are preferable from the viewpoint of having similar physical properties to silica generally used as an inorganic filler.

When the silica filler is a silica filler oxide, it is preferable that at least a part of the surface of the silica filler oxide is hydrophobized.

When at least a part of the hydrophilic groups present in the silica filler oxide is substituted with a hydrophobic group, dispersibility in the base polymer can be improved. The said hydrophobic group is not specifically limited, For example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned. Among them, from the viewpoint of dispersibility in the base polymer, the silica filler oxide after hydrophobization preferably has a monomethylsilyl group, a dimethylsilyl group or a trimethylsilyl group. In particular, it is more preferable that at least a portion of the silica filler oxide has a monomethylsilyl group in view of the excellent balance between the effect of suppressing the bleedout of the silicone compound to the non-UV-curable pressure-sensitive adhesive layer and the dispersibility of the base polymer. In addition, as mentioned above, since a silica filler oxide blocks the access of a silicone compound by its hydrophilicity, it is hard to exhibit the effect as a silica filler oxide by substituting all the hydrophobic groups on the surface of a silica filler oxide.

When the silica filler oxide has a monomethylsilyl group, a dimethylsilyl group, or a trimethylsilyl group at least in part, the silica filler oxide preferably has the functional group 100 m 2 /g or more with an original specific surface area, 140 m 2 / It is more preferable to have more than g. When a silica filler oxide has the said functional group on the surface in the said range, the dispersibility with respect to the base polymer of a silica filler oxide can be improved more.

Although the average particle diameter of the said filler is not specifically limited, A preferable lower limit is 0.06 micrometers, a more preferable lower limit is 0.07 micrometers, a preferable upper limit is 2 micrometers, and a more preferable upper limit is 1 micrometer. When the average particle diameter of a filler is the said range, the dispersibility with respect to a non-ultraviolet hardening-type adhesive can be improved more.

Although content of the said filler is not specifically limited, A preferable lower limit is 3 weight part with respect to 100 weight part of said base polymers, A preferable upper limit is 20 weight part.

When content of a filler is 3 weight part or more, the heat resistance of the adhesive tape obtained more can be improved. When content of a silica filler is 20 weight part or less, it can be set as the adhesive tape which has sufficient adhesive force. From the viewpoint of further improvement of the heat resistance of the adhesive tape, the content of the silica filler with respect to 100 parts by weight of the base polymer has a more preferable lower limit of 6 parts by weight, a more preferable lower limit of 8 parts by weight, and a more preferable upper limit of 18 parts by weight, A more preferable upper limit is 15 parts by weight, and a particularly preferable upper limit is 13 parts by weight.

The said non-ultraviolet-ray hardening-type adhesive layer may contain the tackifier.

When the said ultraviolet curable adhesive layer contains a tackifier, adhesive force can be raised more. However, since a tackifier also becomes a generation|occurrence|production cause of an outgas at the time of a high temperature process, it is preferable not to use it as much as possible, or to reduce the quantity to be used. Then, when using a tackifier, it is preferable that the said non-UV curable adhesive layer contains 30 weight part or less of a tackifier with respect to 100 weight part of said (meth)acrylic-type copolymers. By making content of a tackifier into the said range, generation|occurrence|production of the outgas by a heat|fever can be suppressed and it can be made easy to adjust to the said amount of outgas. A more preferable upper limit of the said tackifier is 20 weight part, and a more preferable upper limit is 10 weight part. Although the lower limit of the said tackifier is not specifically limited, From a viewpoint of making the amount of generation of outgas as small as possible, it is preferable that it is 0 weight part, From a viewpoint of improving adhesive force more, it is preferable that it is 3 weight part.

The said non-ultraviolet-ray-curable adhesive layer may contain well-known additives, such as a plasticizer, resin, surfactant, a wax, and a microparticles|fine-particles filler. As for the said additive, 1 or 2 or more types may be used.

Although the thickness of the said non-UV-curable adhesive layer is not specifically limited, It is preferable that a preferable lower limit is 5 micrometers, a more preferable lower limit is 10 micrometers, a preferable upper limit is 100 micrometers, and it is preferable that a more preferable upper limit is 60 micrometers. If the thickness of the non-UV-curable pressure-sensitive adhesive layer is within the above range, it is adhered to the support with sufficient adhesive force, and the adherend can be reliably fixed.

As said ultraviolet curable adhesive component which comprises the said ultraviolet curable adhesive layer, it has a polymerizable polymer as a main component, and contains the ultraviolet polymerization initiator as a polymerization initiator is mentioned, for example. The polymerizable polymer is, for example, a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth)acrylic polymer) in advance, and radical polymerization with a functional group reacting with the functional group in the molecule It can be obtained by reacting a compound (hereinafter, referred to as a functional group-containing unsaturated compound) having an unsaturated bond.

The functional group-containing (meth)acrylic polymer uses, as a main monomer, an acrylic acid alkyl ester and/or an methacrylic acid alkyl ester having an alkyl group having carbon atoms in the range of 2 to 18, and this and a functional group-containing monomer, and, if necessary, Accordingly, it is obtained by copolymerizing other monomers for modification copolymerizable with them by a conventional method. The weight average molecular weight of the said functional group containing (meth)acrylic-type polymer is about 200,000-2 million normally. In addition, in this specification, a weight average molecular weight can be normally determined by GPC method, and the method specifically shown by an Example can be used.

As said functional group containing monomer, a carboxyl group containing monomer, a hydroxyl group containing monomer, an epoxy group containing monomer, an isocyanate group containing monomer, an amino group containing monomer, etc. are mentioned, for example. Acrylic acid, methacrylic acid, etc. are mentioned as said carboxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include hydroxyethyl acrylate and hydroxyethyl methacrylate. As said epoxy group containing monomer, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned. As said isocyanate group containing monomer, acrylic acid isocyanate ethyl, methacrylic acid isocyanate ethyl, etc. are mentioned. Examples of the amino group-containing monomer include aminoethyl acrylate and aminoethyl methacrylate.

Various monomers used for general (meth)acrylic polymers, such as vinyl acetate, acrylonitrile, and styrene, are mentioned as another copolymerizable monomer for modification|modification, for example.

As the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth)acrylic polymer, the same functional group-containing monomer as described above can be used depending on the functional group of the functional group-containing (meth)acrylic polymer. 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, an amide group-containing monomer such as a carboxyl group-containing monomer or acrylamide is used. When the functional group is an amino group, an epoxy group-containing monomer is used.

What is activated by irradiating the said ultraviolet-ray polymerization initiator with the ultraviolet-ray of a wavelength of 200-410 nm is mentioned, for example. Examples of such ultraviolet polymerization initiators include acetophenone derivative compounds, benzoin ether compounds, ketal derivative compounds, phosphine oxide derivative compounds, bis (η5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethyl thioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane, and the like. Methoxyacetophenone etc. are mentioned as said acetophenone derivative compound. As said benzoin ether type compound, benzoin propyl ether, benzoin isobutyl ether, etc. are mentioned. As said ketal derivative compound, benzyl dimethyl ketal, acetophenone diethyl ketal, etc. are mentioned. These ultraviolet polymerization initiators may be used independently and 2 or more types may be used together.

It is preferable that the said ultraviolet curable adhesive layer contains a radically polymerizable polyfunctional oligomer or a monomer. When the said ultraviolet curable adhesive layer contains a radically polymerizable polyfunctional oligomer or monomer, ultraviolet curability improves.

The polyfunctional oligomer or monomer preferably has a weight average molecular weight of 10,000 or less, and more preferably, has a weight average molecular weight of 5000 or less so that the three-dimensional network of the ultraviolet curable pressure-sensitive adhesive layer by irradiation with ultraviolet rays is efficiently achieved. The number of radically polymerizable unsaturated bonds in a molecule|numerator is 2-20. The weight average molecular weight may be determined using, for example, GPC measurement, and specifically, the method shown in Examples may be used.

The polyfunctional oligomer or monomer is, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylic rate, dipentaerythritol hexaacrylate, or the same methacrylates mentioned above. Other examples include 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, and methacrylates similar to those described above. These polyfunctional oligomers or monomers may be used independently and 2 or more types may be used together.

It is preferable that the said ultraviolet curing adhesive layer contains a silicone compound.

When the said ultraviolet curable adhesive layer contains a silicone compound, since a silicone compound bleeds out at the interface of an ultraviolet curable adhesive layer and to-be-adhered body, an adhesive tape can be peeled easily after completion|finish of a process. Moreover, since a silicone compound is excellent in heat resistance, even if it is a case where it is a case where it is a case where it is a case where it is a process with heating 150 degreeC or more, the seizure etc. of an ultraviolet curable adhesive layer can be suppressed, and a paste|pool residue can be suppressed.

It is preferable that the said silicone compound has the functional group which can crosslink with the said ultraviolet curable 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, so that the silicone compound adheres to the adherend. contamination is suppressed. The functional value of the silicone compound is, for example, 2 to 6 valence, preferably 2 to 4 valence, more preferably 2 valence. The functional group is appropriately determined by the functional group contained in the UV-curable pressure-sensitive adhesive component, for example, when the UV-curable pressure-sensitive adhesive component is a photocurable pressure-sensitive adhesive containing a (meth)acrylic acid alkylester-based polymerizable polymer as a main component, (meth) ) Select an acrylic group and a crosslinkable functional group.

The functional group crosslinkable with the (meth)acryl group is a functional group having an unsaturated double bond, and specifically, a silicone compound containing, for example, a vinyl group, a (meth)acryl group, an allyl group, a maleimide group, etc. is selected. .

It is preferable that the said silicone compound has a weight average molecular weight of 300-50000.

When the weight average molecular weight of a silicone compound is 300 or more, the bleedout with respect to a non-ultraviolet-ray-curable adhesive layer can be suppressed more with the magnitude|size of the molecular size. When a weight average molecular weight is 50000 or less, it bleeds out at the interface of an ultraviolet curable adhesive layer and to-be-adhered body, and adhesion promotion can be suppressed more. A more preferable lower limit of the weight average molecular weight of the silicone compound is 400, a more preferable lower limit is 500, a more preferable upper limit is 10000, and a still more preferable upper limit is 5000. In addition, in this invention, the weight average molecular weight of a silicone compound can be determined by GPC analysis, and the method specifically shown in an Example can be used.

As a silicone compound which has the said functional group and a weight average molecular weight, silicone diacrylate is mentioned, for example. When silicone diacrylate is used, heat resistance and releasability are further improved.

The preferable content of the silicone compound has a lower limit of 1 part by weight, an upper limit of 50 parts by weight, a more preferable lower limit of 10 parts by weight, and a more preferable upper limit of 40 parts by weight with respect to 100 parts by weight of the polymerizable polymer. When content of the said silicone compound is the said range, while being able to protect a to-be-adhered body with sufficient adhesive force, an adhesive tape can be peeled more easily after completion|finish of protection.

The said ultraviolet curable adhesive layer may contain well-known additives, such as inorganic fillers, such as fumed silica, a plasticizer, resin, surfactant, wax, and a particulate filler.

Although the thickness of the said ultraviolet curable adhesive layer is not specifically limited, It is preferable that a lower limit is 5 micrometers and an upper limit is 100 micrometers. If the thickness of the said ultraviolet curable adhesive layer is the said range, a to-be-adhered body can be protected with sufficient adhesive force, and also the glue residue at the time of peeling can also be suppressed. From a viewpoint of further improving adhesive force and further suppressing the glue residue at the time of peeling, a more preferable minimum of the thickness of the said ultraviolet curable adhesive layer is 10 micrometers, and a more preferable upper limit is 60 micrometers.

It is preferable that the adhesive tape of this invention is a non-support type double-sided adhesive tape which does not have a base material. In the case of the support type having a substrate, the silicone compound does not bleed out at the interface on the side of the support, but since a heat-resistant substrate must be used, the cost is lower than that of the non-support type.

In the adhesive tape of the present invention, it is preferable that a release film (preferably UV-transmissive) is laminated on the surface opposite to the surface of the non-UV-curable pressure-sensitive adhesive layer on which the UV-curable pressure-sensitive adhesive layer is laminated.

By having a release film on a non-UV hardening-type adhesive layer, while being able to protect a non-UV hardening-type adhesive layer until the time of sticking to a to-be-adhered body, the handleability of an adhesive tape can be improved. Moreover, when a release film is ultraviolet-transmitting, the hardening process mentioned later can be implemented, protecting a non-ultraviolet-ray hardening-type adhesive layer.

The release film is not particularly limited, for example, polyethylene naphthalate (PEN), polyimide (PI), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), and UV-transmissive films such as polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polybutylene naphthalate, butanediol terephthalate polytetramethylene glycol copolymer, and butanediol terephthalate polycaprolactone copolymerization. Among them, polyethylene terephthalate (PET) is preferable.

In the adhesive tape of the present invention, as long as the UV-curable adhesive layer and the non-UV-curable adhesive layer are located in the outermost layer (the layer in contact with the adherend), another layer may be provided between the UV-curable adhesive layer and the non-UV-curable adhesive layer. .

It is preferable that the tensile strength in 23 degreeC before hardening of the adhesive tape of this invention is 2.5-10 N/10mm.

When the tensile strength of the adhesive tape before hardening is the said range, an adhesive tape can be made hard to tear at the time of peeling. From a viewpoint of further suppressing the tear of the adhesive tape at the time of peeling, a more preferable lower limit of the tensile strength before hardening of the said adhesive tape is 3.0 N/10 mm, a more preferable lower limit is 3.5 N/10 mm, A more preferable upper limit is 9.5 N/ 10 mm, a more preferable upper limit is 9.0 N/10 mm. In addition, the tensile strength before hardening of the said adhesive tape can be measured by the method similar to the tensile strength of the said non-ultraviolet-ray-curable adhesive layer.

In the adhesive tape of this invention, it is preferable that the gel fraction of the said ultraviolet curable adhesive layer is 80 % or more after ultraviolet curing.

When the gel fraction of the ultraviolet curing pressure-sensitive adhesive layer is equal to or more than the lower limit, the chemical resistance of the adhesive tape can be further improved, and the bleed-out of the silicone compound to the non-UV-curable pressure-sensitive adhesive layer over time can be further suppressed. . A more preferable minimum of the gel fraction of the said ultraviolet curable adhesive layer is 85 %, and a more preferable minimum is 90 %. Although the upper limit of the gel fraction of the said ultraviolet curable adhesive layer is not specifically limited, It is preferable that it is 99 %. Moreover, when an adhesive tape has layers other than an ultraviolet curable adhesive layer and a non-ultraviolet-ray-curable adhesive layer, it is preferable that the layer also satisfy|fills the said gel fraction.

The method for manufacturing the adhesive tape of this invention is not specifically limited, A conventionally well-known method can be used. For example, on the film subjected to the release treatment, the solution of the UV-curable pressure-sensitive adhesive component is coated and dried to form an UV-curable pressure-sensitive adhesive layer, and a non-UV-curable pressure-sensitive adhesive layer is formed on the film subjected to another release treatment in the same manner. Then, it can manufacture by bonding an ultraviolet curable adhesive layer and a non-ultraviolet hardening-type adhesive layer.

Although the use of the adhesive tape of this invention is not specifically limited, It is especially preferable as a protective tape in manufacture of electronic components, such as an electronic board and a semiconductor chip, which has a manufacturing process accompanying high temperature treatment using an opaque support body. Can be used.

As a manufacturing method of such an electronic component, the manufacturing method of the following electronic component is mentioned, for example. That is, an adherend sticking step of affixing from the ultraviolet curable pressure-sensitive adhesive layer to an adherend; a curing step of curing the ultraviolet curable pressure-sensitive adhesive layer by irradiating ultraviolet light; and a heat treatment step of treating the adherend at a high temperature of 150° C. or higher, and a peeling step of peeling the adherend from the adhesive tape. In the manufacturing method of such an electronic component, the effect of this invention can be expressed especially advantageously.

An adherend sticking step of affixing the adhesive tape of the present invention from an ultraviolet curable pressure-sensitive adhesive layer to an adherend; a curing step of curing the ultraviolet curable pressure-sensitive adhesive layer by irradiating ultraviolet light; A method for manufacturing an electronic component is also one of the present invention, comprising a support attaching step, a heat treatment step of treating the adherend at a high temperature of 150° C. or higher, and a peeling step of peeling the adherend from the adhesive tape.

In the manufacturing method of the electronic component of this invention, first, the sticking process of affixing the adhesive tape of this invention which has an ultraviolet curable adhesive layer and a non-UV curable adhesive layer to a to-be-adhered body from the said ultraviolet curable adhesive layer is performed.

Examples of the adherend include a silicon wafer, a semiconductor chip, a base material for manufacturing an electronic substrate, a material for an electronic component, and the like. A polyimide film, a glass epoxy board|substrate, etc. are mentioned as said base material.

In the manufacturing method of the electronic component of this invention, then, the hardening process which irradiates an ultraviolet-ray and hardens the said ultraviolet curable adhesive layer is implemented.

By hardening an ultraviolet curable adhesive layer, an adhesive tape can be peeled easily from to-be-adhered body after completion|finish of a process, suppressing glue residue. In the manufacturing method of the electronic component of this invention, since an ultraviolet curable adhesive layer is hardened before affixing an adhesive tape to a support body, even if a support body is a material which does not transmit light, an ultraviolet curable adhesive layer can be hardened. Moreover, when the non-UV-curable adhesive layer of an adhesive tape is ultraviolet-transmitting, even if it irradiates an ultraviolet-ray to an ultraviolet-curable adhesive layer from the non-UV-curable adhesive layer side, an ultraviolet curable adhesive layer can fully be hardened. Further, since the UV-curable pressure-sensitive adhesive layer is cured after being adhered to the adherend, even if the UV-curable pressure-sensitive adhesive layer is cured before treating the adherend, the adhesive tape is not immediately peeled off from the adherend.

The irradiation conditions of the light for curing the ultraviolet curable pressure-sensitive adhesive layer can be appropriately adjusted by a combination of the polymerizable polymer and the ultraviolet polymerization initiator to be used. For example, when using the polymerizable polymer which has unsaturated double bonds, such as a vinyl group, in a side chain, and the ultraviolet-ray polymerization initiator activated by the wavelength of 200-410 nm, by irradiating the light of a wavelength of 365 nm or more, the said ultraviolet-ray The 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 with a wavelength of 365 nm with an illuminance of 5 mW or more, more preferably irradiate with an illuminance of 10 mW or more, and irradiate with an illuminance of 20 mW or more. It is more preferable, and it is especially preferable to irradiate with the illumination intensity of 50 mW or more. Moreover, it is preferable to irradiate the light of wavelength 365nm with the integrated illuminance of 300 mJ or more, It is more preferable to irradiate with the integrated illuminance of 500 mJ or more and 10000 mJ or less, It is irradiated with the integrated illuminance of 500 mJ or more and 7500 mJ or less. It is more preferable to do so, and it is especially preferable to irradiate with an integrated illuminance of 1000 mJ or more and 5000 mJ or less.

In the manufacturing method of the electronic component of this invention, the support body sticking process of sticking a support body on the non-ultraviolet hardening-type adhesive layer next is implemented.

In the method for manufacturing an electronic component of the present invention, since the pressure-sensitive adhesive layer of the adhesive tape is divided into an ultraviolet curable pressure sensitive adhesive layer and a non-UV curable pressure sensitive adhesive layer, even when the curing step is performed before the support is adhered, the non-UV curable pressure sensitive adhesive layer is cured there is no Therefore, an adhesive tape can be stuck to a support body with sufficient adhesive force. Moreover, when an adhesive tape has the said ultraviolet-transmissive release film, the said release film is peeled from after completion|finish of the said hardening process to before the said support body sticking process.

In the manufacturing method of the electronic component of this invention, then, the heat processing process of processing a to-be-adhered body at high temperature 150 degreeC or more is implemented.

As said heat treatment process, a board|substrate manufacturing process, a chip mounting process, etc. are mentioned. In the substrate manufacturing process, heat treatment is typically performed at 150° C. or higher, and in the chip mounting process, heat treatment is typically performed at 200° C. or higher. In the method for manufacturing an electronic component of the present invention, since the ultraviolet curable pressure-sensitive adhesive layer is cured before the heat treatment step, even when a treatment involving a high temperature of 150° C. or higher is performed in the heat treatment step, adhesion promotion is suppressed, and the adherend after the treatment is finished can be easily peeled off. Moreover, since a silicone compound is contained in an ultraviolet curable adhesive layer, adhesion promotion can be suppressed more.

Next, the manufacturing method of the electronic component of this invention has the peeling process of peeling the said to-be-adhered body from the said adhesive tape. In the said hardening process, since the ultraviolet curable adhesive layer is bridge|crosslinked and hardened|cured, it can peel easily and suppressing a glue residue from a to-be-adhered body from an adhesive tape. Moreover, since the amount of outgassing of the non-ultraviolet hardening-type adhesive layer of an adhesive tape is 10000 ppm or less, in the said heat processing process, the non-ultraviolet-ray hardening-type adhesive layer is not easily foamed by outgas. As a result, since the adhesive tape does not peel easily between a support body and a non-ultraviolet-ray-curable adhesive layer, the case where an adhesive tape remains on the side surface of a to-be-adhered body at the time of peeling is also suppressed. In addition, since the non-UV-curable pressure-sensitive adhesive layer has a tensile strength within a certain range, the adhesive tape does not easily tear at the time of peeling.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive tape which can be used also for the support body which does not transmit light in the manufacture of an electronic component, and can suppress peeling from a to-be-adhered body and a support body, even when high-temperature treatment is performed, and adhesive tape thereof, The manufacturing method of the used electronic component can be provided.

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

(Example 1)

(Manufacture of non-ultraviolet curing adhesive)

97 parts by weight of butyl acrylate as a (meth)acrylic acid alkylester, 3 parts by weight of acrylic acid and 120 parts by weight of ethyl acetate as a carboxyl group-containing monomer are added to a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after nitrogen substitution, the reactor is heated to initiate reflux. Then, 0.1 part by weight of azobisisobutyronitrile was added as a polymerization initiator into the reactor. It was made to reflux at 70 degreeC for 5 hours, and the solution of the (meth)acrylic-type copolymer (base polymer) was obtained. About the obtained (meth)acrylic-type copolymer, as a result of measuring the weight average molecular weight and molecular weight distribution of polystyrene conversion by GPC method, it was 1 million and 3, respectively. In addition, the measuring apparatus and measurement conditions were carried out as follows.

Measuring device: 2690 Separations Model, manufactured by Waters

Column: GPC KF-806L, manufactured by Showa Denko.

Detector: Differential Refractometer

Sample flow rate: 1 ml/min

Column temperature: 40℃

Eluent: ethyl acetate

Then, with respect to 100 parts by weight of the solid content of the (meth)acrylic copolymer contained in the solution of the obtained (meth)acrylic copolymer, 0.35 parts by weight of the epoxy curing agent and 10 parts by weight of the silica filler are added, stirred and non-UV An ethyl acetate solution of the curable pressure-sensitive adhesive was obtained. In addition, the following things were used for an epoxy curing agent and a silica filler.

Epoxy curing agent: Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, tertiary amino group-containing epoxy curing agent

Silica filler: Tokuyama Co., Ltd., Leorosil MT-10

(Manufacture of UV-curable adhesive)

Prepare a reactor equipped with a thermometer, a stirrer, and a cooling tube, and in this reactor, 94 parts by weight of 2-ethylhexyl acrylate as (meth)acrylic acid alkylester, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, D After adding 0.01 parts by weight of uryl mercaptan and 80 parts by weight of ethyl acetate, the reactor was heated to initiate reflux. Subsequently, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator into the reactor, and polymerization was started under reflux. Next, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane is added after 1 hour and 2 hours from the start of polymerization, and further 4 hours from the start of polymerization Thereafter, 0.05 parts by weight of t-hexyl peroxypivalate was added to continue the polymerization reaction. And 8 hours after the polymerization start, 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 the functional group-containing (meth)acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound was added and reacted to obtain a polymerizable polymer . Then, based on 100 parts by weight of the resin solid content of the obtained polymerizable polymer ethyl acetate solution, 20 parts by weight of silicone diacrylate as a silicone compound, 3 parts by weight of silica filler, 30 parts by weight of urethane acrylate, 0.7 parts by weight of an isocyanate-based crosslinking agent , 1 part by weight of a photopolymerization initiator were mixed to obtain an ethyl acetate solution of an ultraviolet curable pressure-sensitive adhesive. In addition, silicone diacrylate, a silica filler, a urethane acrylate, an isocyanate type crosslinking agent, and a photoinitiator used the following things.

Silicone diacrylate: EBECRYL 350, manufactured by Daicel Allnex, weight average molecular weight 1000

Silica filler: Leorosil MT-10, manufactured by Tokuyama Corporation

Urethane acrylate: UN-5500, manufactured by Negami Industries

Isocyanate-based crosslinking agent: Colonate L, manufactured by Nippon Urethane Industry Co., Ltd.

Photopolymerization initiator: Esacure One, manufactured by Nihon Shiba Hegner

(Production of adhesive tape)

The obtained ultraviolet curable pressure-sensitive adhesive solution was coated with a doctor knife on a 50 µm polyethylene terephthalate (PET) film having a release treatment on one side so that the dry film had a thickness of 40 µm, and heated at 110° C. for 5 minutes to obtain a coating solution. It dried and obtained the ultraviolet curing adhesive layer.

The obtained non-UV curable pressure-sensitive adhesive solution was coated with a doctor knife on a transparent PET film having a thickness of 50 μm that had been subjected to release treatment on one side so that the dry film had a thickness of 40 μm, and heated at 110° C. for 5 minutes to dry the coating solution. , a non-UV-curable pressure-sensitive adhesive layer was obtained.

The surfaces on which the PET film of the obtained ultraviolet curable adhesive layer and the non-ultraviolet hardening-type adhesive layer are not laminated|stacked were bonded together, and the adhesive tape was obtained.

(Measurement of tensile strength)

An adhesive tape comprising only a non-UV-curable pressure-sensitive adhesive layer was prepared by the above method. Using the obtained non-ultraviolet-curable pressure-sensitive adhesive layer to a thickness of 200 µm and a width of 10 mm as a sample, using a Tensilon UCE500 (manufactured by Orientec Corporation) at 23°C and 50%RH at a speed of 300 mm/min, between the marks Tensile strength was measured at a distance of 40 mm. By the same method, the tensile strength before hardening was measured about the obtained adhesive tape.

(Measurement of out gas volume)

The adhesive tape which consists only of a non-UV hardening-type adhesive layer was manufactured by the said method, and the adhesive tape which consists only of the obtained non-UV hardening-type adhesive layer was cut out to 5 mm x 5 mm, and the measurement sample was manufactured. About the obtained measurement sample, it measured using thermal desorption GC-MS, and made the obtained gas amount (toluene conversion ppm: microgram/g) into outgas amount. In addition, the instrument used and measurement conditions are as follows.

Thermal desorption device: TurboMatrix 350, manufactured by PerkinElmer

GC-MS device: JMS Q1000, manufactured by Nippon Electronics Co., Ltd.

Sample heating conditions: 260 °C, 15 min (20 mL/min)

Secondary Desorption: 350℃, 40 min

Split: inlet 25 ml/min, outlet 25 ml/min

Injection amount: 2.5%

Column: EQUITY-1 (non-polar, manufactured by SIGMA-ALDRICH) 0.32 mm × 60 m × 0.25 μm

GC temperature increase: 40 ℃ (4 min) → 10 ℃/min rate of temperature increase → 300 ℃ (10 min)

He flow rate: 1.5 ml/min

Ionization voltage: 70 eV

MS measurement range: 29 ∼ 600 amu (scan 500 ms)

MS temperature: ion source; 230 ℃, interface ; 250 ℃

(Measurement of tack strength)

In the above method, as a measurement sample, an adhesive tape comprising only a non-UV-curable pressure-sensitive adhesive layer was prepared. The adhesive tape which consists only of the obtained non-ultraviolet-ray hardening-type adhesive layer was cut out to 10 mm x 10 mm, and the measurement sample was prepared. About the obtained measurement sample, the probe tack measurement was performed. In addition, the instrument used and measurement conditions are as follows.

Tacking tester: TAC1000, manufactured by RHESCA

Probe diameter: 3 mmφ

Crimping load: 100 g

Crimping time: 1 second

Contact speed: 30 mm min

Peeling speed: 600 mm/min

(Measurement of gel fraction)

Only 0.1 g of the non-UV-curable pressure-sensitive adhesive layer of the obtained adhesive tape was scraped off, immersed in 50 ml of ethyl acetate, and shaken on a shaker at a temperature of 23 degrees and 120 rpm for 24 hours (hereinafter, the non-UV-curable pressure-sensitive adhesive layer that was scraped off was applied to the pressure-sensitive adhesive tape). called composition). After shaking, ethyl acetate and ethyl acetate were absorbed using a metal mesh (scale interval #200 mesh), and the swollen pressure-sensitive adhesive composition was separated. The adhesive composition after isolation|separation was dried on 110 degreeC conditions for 1 hour. The weight of the pressure-sensitive adhesive composition including the metal mesh after drying was measured, and the gel fraction of the non-UV-curable pressure-sensitive adhesive layer was calculated using the following formula. The results are shown in Tables 1 and 2.

Gel fraction (wt%) = 100 x (W ₁ -W ₂ )/W ₀

(W ₀ : initial pressure-sensitive adhesive composition weight, W ₁ : pressure-sensitive adhesive composition weight including the metal mesh after drying, W ₂ : initial weight of the metal mesh)

(Examples 2 to 11, Comparative Examples 1 to 11)

The amount of butyl acrylate, acrylic acid, and silica filler in the non-UV-curable pressure-sensitive adhesive layer is as shown in Tables 1 and 2, and the weight average molecular weight and molecular weight distribution of the base polymer by changing the polymerization conditions are as shown in Tables 1 and 2, and tackifying Except having added the amount shown in Tables 1 and 2, the adhesive tape was manufactured like Example 1, and each physical property was measured. In addition, as a tackifier, UN5500 by Negami Kogyo Co., Ltd. was used. As the isocyanate-based curing agent, Colonate L manufactured by Tosoh Corporation was used.

<Evaluation>

About the adhesive tape obtained by the Example and the comparative example, the following method evaluated. The results are shown in Tables 1 and 2.

(1) Evaluation of substrate after heat treatment

The surface by the side of the ultraviolet curing adhesive layer of an adhesive tape was affixed to the board|substrate (TPWB-S02-READCUT, the Taisho Electronics company make), and the laminated body was obtained. Then, by using a high-pressure mercury ultraviolet irradiator, the irradiance of 365 nm ultraviolet rays on the surface of the adhesive tape is adjusted to 100 mW/cm 2 and irradiated for 30 seconds from the non-UV-curable pressure-sensitive adhesive layer side, the UV-curable pressure-sensitive adhesive layer is crosslinked and cured. Then, the non-ultraviolet hardening-type adhesive layer of a laminated body was affixed on the CCL support body (copper clad laminated board), and the heat treatment for 6 minutes at 260 degreeC was implemented 3 times in total. After completion of the heat treatment, the adhesive tape was peeled from the substrate. Peeling of an adhesive tape, foaming of a non-ultraviolet-ray hardening-type adhesive layer, and adhesive residual of a board|substrate were evaluated as follows.

(Evaluation of peeling of adhesive tape)

Observe the adhesive tape after the heat treatment with the naked eye, and “○” indicates that there is no peeling or voids at the interface between the UV-curable adhesive layer and the substrate, “Δ” indicates that there is some peeling or voids, and peeling or voids on the entire surface. The case where there exists was made into "x", and evaluation of peeling of an adhesive tape was performed.

(Evaluation of foaming of non-ultraviolet-ray-curable pressure-sensitive adhesive layer)

After the heat treatment, the non-UV-curable adhesive layer of the adhesive tape was visually observed to indicate that there is no foaming in “◎”, in the case of almost no foaming in “○”, in the case of some foaming in “Δ”, and foaming over the entire surface. Foaming of the non-UV-curable pressure-sensitive adhesive layer was evaluated by taking the case of “x” as “x”.

(Evaluation of glue residue on the substrate)

Observe the substrate after peeling with an optical microscope. When there is no glue residue, "◎", when there is almost no glue residue, "○", when there is some glue residue, "△", and the glue residue is on the entire surface. The case was regarded as "x", and the residual glue on the substrate was evaluated.

(2) Evaluation of chemical resistance

The polyimide film was affixed to the ultraviolet curing adhesive layer of the obtained adhesive tape, the CCL board (copper-clad laminated board) was affixed to the non-ultraviolet hardening-type adhesive layer, and the measurement sample was prepared. The obtained measurement sample was immersed in Fine Alpha (made by Arakawa Chemical Industry Co., Ltd.) at 70 degreeC for 2 hours, and it was made to dry in 110 degreeC oven for 1 hour. The weight loss rate before and after immersion was measured.

When the weight loss rate before and after immersion is 3.0% or less, "◎", when it is greater than 3.0% and less than 5.0%, is "○", when it is greater than 5.0% and less than 8.0%, "Δ" is greater than 8.0%, or from the adherend. Chemical resistance was evaluated by making the case where the tape peeled as "x".

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, the adhesive tape which can be used also for the support body which does not transmit light in the manufacture of an electronic component, and can suppress peeling from a to-be-adhered body and a support body, even when high-temperature treatment is performed, and adhesive tape thereof, The manufacturing method of the used electronic component can be provided.

Claims (10)

An adhesive tape having a non-UV-curable pressure-sensitive adhesive layer and an UV-curable pressure-sensitive adhesive layer laminated on the non-UV-curable pressure-sensitive adhesive layer,
The non-UV-curable pressure-sensitive adhesive layer has a tensile strength at 23°C of 5.0 N/10 mm or more and 20.0 N/10 mm or less, and
The amount of outgas when the said non-ultraviolet hardening-type adhesive layer is heated at 260 degreeC for 15 minute(s) is 10000 ppm or less, The adhesive tape. The method of claim 1,
The tack strength of the non-UV-curable adhesive layer is 10-300 gf/3 mmφ, the adhesive tape. 3. The method according to claim 1 or 2,
The non-UV curable pressure-sensitive adhesive layer,
(A) as a base polymer (a) 92 to 97 wt% of (meth)acrylic acid alkylester having 4 to 12 carbon atoms in the alkyl group, and (b) 3.0 to 8.0 wt% of a carboxyl group-containing monomer as constituent components, (c) ) a weight average molecular weight of 700,000 or more (d) a (meth)acrylic copolymer having a molecular weight distribution of 2 to 6;
(B) an epoxy compound containing a tertiary amine structure as a curing agent;
(C) contains a filler;
An adhesive tape containing 0.1 to 0.5 parts by weight of the curing agent and 3 to 20 parts by weight of the filler based on 100 parts by weight of the base polymer. 4. The method of claim 1, 2 or 3,
The non-UV curable pressure-sensitive adhesive layer, the (meth) acrylic copolymer 100 parts by weight of the adhesive tape containing 30 parts by weight or less of the tackifier. 5. The method of claim 1, 2, 3 or 4,
The said ultraviolet curable adhesive layer contains an ultraviolet curable adhesive component, and the silicone compound whose weight average molecular weights which have the said ultraviolet curable adhesive component and the functional group crosslinkable are 300-50000, The adhesive tape. 6. The method of claim 1, 2, 3, 4 or 5, wherein
The adhesive tape, wherein the gel fraction of the non-UV-curable pressure-sensitive adhesive layer is 80% or more. 7. The method of claim 1, 2, 3, 4, 5 or 6,
The adhesive tape whose tensile strength in 23 degreeC before hardening is 2.5-10 N/10mm. An adhesive tape having a non-UV-curable pressure-sensitive adhesive layer and an UV-curable pressure-sensitive adhesive layer laminated on the non-UV-curable pressure-sensitive adhesive layer,
The amount of outgas when the said non-ultraviolet hardening-type adhesive layer is heated at 260 degreeC for 15 minutes is 10000 ppm or less, and
The non-UV curable pressure-sensitive adhesive layer,
(A') a (meth)acrylic copolymer containing 92 to 97% by weight of an alkyl (meth)acrylic acid alkylester having 4 to 12 carbon atoms as a base polymer as a constituent component;
(B) an epoxy compound containing a tertiary amine structure as a curing agent;
(C) An adhesive tape containing a filler. 9. The method of claim 1, 2, 3, 4, 5, 6, 7 or 8,
an adherend affixing step of affixing to the adherend from the ultraviolet curable pressure-sensitive adhesive layer;
A curing step of curing the UV-curable pressure-sensitive adhesive layer by irradiating UV light;
A support affixing step of affixing a support on the non-UV-curable pressure-sensitive adhesive layer;
A heat treatment process of treating the adherend at a high temperature of 150° C. or higher;
The adhesive tape used in the manufacturing method of an electronic component including the peeling process of peeling the said to-be-adhered body from the said adhesive tape. The adhesive tape of Claims 1, 2, 3, 4, 5, 6, 7, 8 or 9 is applied from the said ultraviolet curable adhesive layer to a to-be-adhered body. an adherend sticking step to be affixed;
A curing step of curing the UV-curable pressure-sensitive adhesive layer by irradiating UV light;
A support affixing step of affixing a support on the non-UV-curable pressure-sensitive adhesive layer;
A heat treatment step of treating the adherend at a high temperature of 150° C. or higher;
The manufacturing method of an electronic component including the peeling process of peeling the said to-be-adhered body from the said adhesive tape.