TW202142650A - Thermally peelable adhesive tape - Google Patents

Abstract

In this thermally peelable adhesive tape having a thermally expandable adhesive layer containing thermally expandable particles and an adhesive component, the maximum expansion temperature of the thermally expandable particles is set to 170 DEG C or higher; and for a dynamic viscoelastic measurement (temperature range of -60 DEG C to 300 DEG C, temperature rising speed of 10 DEG C/minute, and frequency of 10 Hz) of the adhesive component, (1) the tan[delta] of the maximum expansion temperature of the thermally expandable particles is set to 0.120 or less, and (2) the storage modulus G' at 170 DEG C is set to at least 30,000 Pa, whereby a thermally peelable adhesive tape can be obtained which can be suitably used in a pressing step for a long time at normal temperature or at high temperature, has a prominent reduction in the adhesiveness of the adhesive layer when further heated after use in the pressing step, and can be easily peeled off without residual paste remaining on an adherend.

Description

Thermal peel adhesive tape

The present invention relates to a heat-peelable adhesive tape, which can be used well in various manufacturing steps including the manufacturing steps of electronic parts or semiconductor parts. After the adhesive tape is used in the pressing step and further heated, its adhesiveness is significantly reduced, and it can be easily peeled off without the paste remaining.

Generally, adhesive tapes with high heat resistance are widely used in the manufacturing steps of electronic parts and semiconductor parts. High heat-resistant adhesive tapes are widely used for temporary fixing of components or parts, fixing during transportation, reinforcement, protection, shielding, resin sealing, etc. in the heat treatment step when manufacturing electronic parts and semiconductor parts, for example. This application requires that the adhesive tape has a sufficiently high adhesion to the adherend during use, and can be easily peeled off after use without paste residue.

In recent years, various final products, including electronic equipment, have been required to be thinner and smaller. As a result, parts have also been thinner and smaller. When it is difficult to process thin parts with low rigidity, adhesive tape is sometimes used to improve workability. For example, in the manufacturing steps of thin substrates such as thin electronic circuit boards, the adhesive surface on one side of the double-sided adhesive tape is attached and fixed to a conveying board with higher rigidity, and the thin substrate is attached to the adhesive surface on the opposite side. It can improve the workability of parts installation or component processing on thin substrates. The processing of such a member includes, for example, a heat pressing step in which a semiconductor wafer is placed on a thin substrate and sealed with resin. Separate the thin substrate, the double-sided tape and the conveying plate obtained from the processing or installation of the components, and reuse the conveying plate for the processing of the thin substrate as necessary. In the above-mentioned temporary fixing of the thin substrate by the adhesive tape, sufficient adhesion is required in the processing step. On the other hand, if a large load is applied to the thin substrate when the adhesive tape is peeled off, the thin substrate will be damaged. Therefore, it is required that the adhesiveness of the adhesive tape be as low as possible when peeling off. In addition, regarding the material of the conveying plate, glass has also been used previously. However, the conveying plate made of glass is sometimes prone to deform in a high-temperature environment, or the linear expansion coefficient is significantly different from that of the product. Therefore, when it is used in a step with a harsher temperature than before, the use of stainless steel (SUS) or metals such as aluminum or copper, silicon, and copper foil laminates as the material of the conveying plate has increased.

In the manufacturing steps of this kind of thin substrate, instead of using a transfer plate, a single-sided adhesive tape using a substrate with higher rigidity (for example, a resin film of 50 μm to 125 μm) is attached to the thin substrate. Improve the workability when installing parts or processing components on thin substrates. After the processing or installation of the component is completed, the adhesive tape is peeled from the thin substrate. Even when using this method of use, sufficient adhesion is required in the processing steps. On the other hand, the lowest possible adhesion is required when peeling off the adhesive tape.

In addition, in recent years, electronic parts and semiconductor parts have been required to have higher heat resistance than the previous ones, mainly for automotive applications. Along with this, higher heat resistance is required for the materials constituting the parts (for example, the resin that seals the chip in the semiconductor package). Resins with higher heat resistance usually require higher heating temperature and longer heating time for hardening. Therefore, the adhesive tape used in the step of hardening the resin with higher heat resistance is also required to have higher heat resistance.

Previously, Patent Documents 1 to 6 disclosed an adhesive tape, which has sufficient adhesion from the initial stage of being attached to the adherend until it is used in the manufacturing process. However, by applying some external stimuli after use, Adhesion is significantly reduced.

Patent Document 1 discloses a light-sensitive adhesive tape and a manufacturing method thereof. Although the light-sensitive adhesive tape exhibits excellent initial adhesion characteristics to semiconductor substrates or film substrates, and has excellent adhesiveness during manufacturing steps such as dicing, By irradiating ultraviolet rays, the light-sensitive adhesive hardens and the adhesive force is significantly reduced. However, the photoreactive components contained in such adhesives whose adhesive strength is reduced due to ultraviolet radiation are generally low in heat resistance, so they are sometimes not suitable for use in high-temperature manufacturing steps. Furthermore, this light-sensitive adhesive cannot be used for the transport plate made of opaque materials such as metal or silicon as described above.

Patent Document 2 discloses a heat-resistant adhesive tape, which well prevents resin leakage in the sealing step, and when peeling off the heat-resistant adhesive tape, it can prevent peeling or breakage of the molded sealing resin, or paste residue , Which can improve the yield. The adhesive tape disclosed in Patent Document 2 has an ultraviolet curable adhesive layer. After irradiating the adhesive layer with ultraviolet rays and heating at 200°C for 1 hour, the adhesive force measured in accordance with JISZ0237 is 1 N/19 m or less. . However, the adhesive tape disclosed in Patent Document 2 is used based on the premise that ultraviolet rays are irradiated before the sealing step (ie heating step) performed by the sealing resin, so that the adhesive layer induces ultraviolet rays. The hardening reaction reduces the adhesion, and then injects resin and heats and hardens. That is, Patent Document 2 does not mention anything about applying an external stimulus after the heating step to make the adhesive tape easy to peel off. This adhesive tape, like the adhesive tape of Patent Document 1, cannot be used for a transport plate made of a material that does not transmit light such as metal or silicon.

Patent Documents 3 to 6 disclose a heat-peelable pressure-sensitive adhesive sheet in which, when heated to a predetermined temperature, the heat-expandable microspheres contained in the heat-expandable adhesive layer are foamed, and the adhesive force is significantly reduced. The heat-peelable adhesive sheets disclosed in these patent documents heat the adhesive layer (heat-expandable adhesive layer) containing heat-expandable microspheres as a foaming agent after achieving the purpose of adhesion of articles including the adherend. As a result, the adhesive force is reduced, and the adherend can be easily separated from the heat-peelable adhesive sheet. The main reason for the decrease of the adhesive force of the adhesive layer is that the adhesive layer foams or swells due to heating, and the surface of the adhesive layer becomes concave and convex, and the adhesive area with the adherend is reduced. The heat-peelable adhesive sheets disclosed in these patent documents are not premised on being used in a long-term high-temperature heating step, and these patent documents do not mention anything about using them in a high-temperature or normal-temperature long-term pressurization step. It is a technology to further heat it to make it easy to peel off. If these thermally foamed peel-off adhesive tapes are used in high-temperature and long-term pressurization steps, the following problems may occur: • The heat-expandable particles foam when pressurized, and the adhesion between the adherend and the adherend in the step is reduced; • When the heat-expandable particles foam when pressurized, the size of the heat-expandable peel-off adhesive tape itself or the size specified by the heat-expandable peel-off adhesive tape changes, resulting in poor processing; • The adhesive components are thermally degraded, the cohesive force is reduced, and the paste residue is generated on the adherend after foaming and peeling.

Patent Document 6 discloses a thermally peelable adhesive tape, which can prevent the thermally expandable adhesive layer from being deformed due to the deformation of the adhesive in the step of laminating and pressing the green sheet during the manufacturing step of the ceramic capacitor. It is considered that this heat-peelable adhesive tape can be used well to prevent positional deviation in the pressing step at room temperature for a short time. However, Patent Document 6 does not mention anything about the foaming and releasability of the adhesive layer after use in a long time press step at high temperature or normal temperature, or the residual property of the paste on the adherend after peeling, and high temperature heating. Contents such as suppression of foaming of thermally expandable particles in the pressing step. In addition, the heat-expandable particles used in Examples 1 to 3 of Patent Document 6 are those that start to expand at 120°C. For example, when they are used in a step of hot pressing at 170°C for 1 hour, it is assumed that there will be hot pressing. When foaming occurs. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-139905 [Patent Document 2] Japanese Patent Laid-Open No. 2012-46763 [Patent Document 3] Japanese Patent Laid-Open No. 11-166164 [Patent Document 4] Japanese Patent Laid-Open No. 2007-246823 [Patent Document 5] Japanese Patent Laid-Open No. 2016-155919 [Patent Document 6] International Publication No. 2005/087887

(The problem to be solved by the invention)

The purpose of the present invention is to provide a thermally peelable adhesive tape, which is used in the pressure step of the adherend in various manufacturing steps including the manufacturing steps of electronic parts or semiconductor parts, which can be used at high temperatures well. Or it is used in a long time pressing step at room temperature, and if it is further heated after the pressing step is used, the adhesion of the adhesive layer will be significantly reduced, and it can be easily peeled off without leaving paste on the adherend. (Technical means to solve the problem)

In order to achieve the above-mentioned object, the inventors conducted intensive research and found that by making a heat-peelable adhesive tape with a heat-expandable adhesive layer containing adhesive components and heat-expandable particles meet the following requirements, It is very effective in terms of adaptability when used in a long-term pressurization step, easy peeling or paste residue during heating, and suppression of foaming of heat-expandable particles during high-temperature pressurization. •The amount of heat-expandable particles added to the adhesive component is in a predetermined range. • The maximum expansion temperature of thermally expandable particles is within the predetermined range. • The parameters in the determination of dynamic viscoelasticity of adhesive components are in the established range. The inventors of the present invention completed the present invention based on the above-mentioned new knowledge.

That is, the heat-peelable adhesive tape of the present invention has a heat-expandable adhesive layer containing an adhesive component and heat-expandable particles, and is characterized in that the heat-expandable adhesive layer contains 4 parts by mass relative to 100 parts by mass of the adhesive component For the above thermally expandable particles, the maximum expansion temperature of the thermally expandable particles is 170°C or higher, and is measured in the dynamic viscoelasticity of the adhesive components (temperature range -60°C to 300°C, heating rate 10°C/min, frequency 10 Hz), (1) The tanδ at the maximum expansion temperature of the above thermally expandable particles is 0.120 or less, and (2) The storage modulus G'at 170°C is above 30,000 Pa. The hot-pressing treatment method of the adherend of the present invention is a hot-pressing treatment method of the adherend with the temporarily fixed heat-peelable adhesive tape, which is characterized in that it includes: The step of temporarily fixing the above-mentioned adhesive tape to the adherend; The step of hot-pressing the above-mentioned adherend with the adhesive tape temporarily fixed; The step of heating the adhesive tape temporarily fixed to the adherend subjected to the hot pressing process to a temperature for peeling; and The step of peeling the adhesive tape heated to the temperature for peeling from the adherend. (Compared with the effect of previous technology)

The heat-peelable adhesive tape of the present invention has a heat-expandable adhesive layer containing adhesive components and heat-expandable particles. The heat-expandable particles have a maximum expansion temperature in a predetermined range and have a dynamic viscoelasticity measurement under a predetermined condition of the adhesive composition. Established physical properties. With the structure and physical properties of the heat-expandable adhesive layers, it is possible to provide a heat-peelable adhesive tape, which suppresses the foaming of the heat-expandable particles contained in the adhesive layer during a long time pressing step at high or normal temperature. By further heating after the pressurization step, the adhesiveness of the heat-expandable adhesive layer is significantly reduced, and the paste is not easy to remain on the adherend.

The heat-peelable adhesive tape of the present invention has at least a heat-expandable adhesive layer. [Thermally expandable adhesive layer] The heat-expandable adhesive layer contains at least an adhesive component for imparting adhesiveness and heat-expandable particles (foaming agent) for imparting heat expansion. The heat-expandable adhesive layer contains 4 parts by mass or more of heat-expandable particles with respect to 100 parts by mass of the adhesive component. The maximum expansion temperature of heat-expandable particles is 170°C or higher, and the adhesive components are tested in dynamic viscoelasticity (temperature range -60°C～300°C, heating rate 10°C/min, frequency 10 Hz), and meet: (1) The tanδ at the maximum expansion temperature of the above thermally expandable particles is 0.120 or less, and (2) The storage modulus G'at 170°C is above 30,000 Pa.

The maximum expansion temperature of thermally expandable particles is a value obtained according to the following measurement method. If the maximum expansion temperature of the thermally expandable particles is less than 170°C, the following problems may occur. • The heat-expandable particles expand (foam) during the hot pressing step at high temperature (for example, 170°C) for a long time, and the adhesion with the adherend decreases during the step. If the adhesion between the adherend and the adherend is reduced, for example, in the cleaning step of the part, the cleaning liquid penetrates into the interface between the adherend and the adhesive. In addition, the size of the heat-expandable adhesive layer itself or the size specified by the heat-expandable adhesive layer may change, which may cause defects in the processing of parts. When the amount of heat-expandable particles added to 100 parts by mass of the adhesive component is less than 4 parts by mass, the expansion of the heat-expandable particles is insufficient, and the surface of the adhesive layer is difficult to become uneven. Therefore, it is necessary to use it after pressurization. When it is thermally peeled off, the effect of reducing the adhesiveness may not be sufficiently obtained in some cases. If the tanδ of the adhesive component at the maximum expansion temperature of the heat-expandable particle is higher than 0.120, that is, when the viscosity term in the adhesive composition is significantly higher than the elastic term, the force generated by the maximum expansion of the heat-expandable particle is likely to become heat And escape. That is, it is difficult for the surface of the adhesive layer to become uneven by the force generated by the expansion of the thermally expandable particles. As a result, it is difficult to reduce the adhesive force with the adherend. If the storage modulus G'at 170°C of the adhesive component is less than 30,000 Pa, the heat-expandable particles may foam at high temperature and long-term pressurization. In addition, if the storage modulus G'of the adhesive component is less than 30,000 Pa, the cohesive force of the heat-expandable adhesive layer is also weak, so it is easy to leave the paste on the adherend when peeling after use in a high temperature environment.

[Adhesive Ingredients] The adhesive components meet the requirements related to the established parameters in the dynamic viscoelasticity measurement (temperature range -60℃～300℃, heating rate 10℃/min, frequency 10 Hz). That is, the tan δ at the maximum expansion temperature of the thermally expandable particles is 0.120 or less, preferably 0.001 or more and 0.120 or less, more preferably 0.001 or more and 0.110 or less, and particularly preferably 0.001 or more and 0.100 or less. Furthermore, the storage modulus G'at 170° C. is 30,000 Pa or more, preferably 30,000 Pa or more and 1,000,000 Pa or less, more preferably 40,000 Pa or more and 1,000,000 Pa or less, particularly preferably 50,000 Pa or more and 1,000,000 Pa or less.

As the adhesive component, for example, it can be selected from acrylic adhesive, rubber adhesive, silicone adhesive, polyester adhesive, polyamide adhesive, urethane adhesive, fluorine adhesive Among the agents, an adhesive with the above-mentioned characteristics is appropriately selected and used. The adhesive can be used alone or in combination of two or more kinds.

In the present invention, as the adhesive, acrylic adhesives, rubber-based adhesives, and silicone-based adhesives can be particularly favorably used.

啉。The type of acrylic adhesive is not particularly limited, and various well-known acrylic adhesives mainly composed of acrylic copolymers can be used. As the acrylic copolymer, for example, an acrylic copolymer obtained by copolymerizing (meth)acrylate, a carboxyl group-containing monomer, and other monomers contained as necessary can be used. Specific examples of (meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-butyl meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth) ) Nonyl acrylate, isononyl (meth)acrylate, and lauryl (meth)acrylate. Specific examples of carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid (anhydride), fumaric acid, 2-carboxy-1-butene, 2- Carboxy-1-pentene, 2-carboxy-1-hexene, 2-carboxy-1-heptene. Specific examples of other monomers include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and other hydroxyl-containing monomers ; Acrylonitrile; Styrene; 2-Hydroxymethylethyl acrylamide; Vinyl acetate; Acrylic acid

Morpholine.

The acrylic copolymer is particularly preferably an acrylic polymer (A) having a hydroxyl group and a carboxyl group, which contains an alkyl (meth)acrylate (A1) having an alkyl group having 4 to 12 carbon atoms, and Alkyl (meth)acrylate (A2), carboxyl group-containing monomer (A3), hydroxyl group-containing monomer (A4) and other monomers (A5) containing alkyl groups of 1 to 3 atoms (A5) As a constituent. The components (A1), (A2), (A3), (A4), and (A5) can be used individually by one component, or two or more components can be used in combination.

Specific examples of the alkyl (meth)acrylate (A1) having an alkyl group having 4 to 12 carbon atoms include n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate. Furthermore, as the (meth)acrylic acid alkyl ester monomer (A2) having an alkyl group having 1 to 3 carbon atoms, methyl (meth)acrylate, ethyl (meth)acrylate, (methyl) ) Alkyl (meth)acrylates having an alkyl group having 1 to 3 carbon atoms, such as propyl acrylate. In 100% by mass of the total constituents (monomer units) of the acrylic copolymer (A), the sum of the component amounts of the alkyl (meth)acrylate (A1) and (A2) is preferably selected from 50% by mass The above range is more preferably selected from the range of 60% by mass or more, and particularly preferably is selected from the range of 70% by mass or more.

Specific examples of the carboxyl group-containing monomer (A3) include (meth)acrylic acid, itaconic acid, crotonic acid, maleic acid (anhydride), fumaric acid, 2-carboxy-1-butene , 2-carboxy-1-pentene, 2-carboxy-1-hexene, 2-carboxy-1-heptene. In 100% by mass of the total constituents (monomer units) of the acrylic copolymer (A), the compounding amount of the carboxyl group-containing monomer (A3) is preferably selected from the range of 0.5-15% by mass, more preferably It is selected from the range of 1 to 12% by mass, and particularly preferably selected from the range of 1 to 10% by mass.

Specific examples of the hydroxyl group-containing monomer (A4) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In 100% by mass of the total constituents (monomer units) of the acrylic copolymer (A), the compounding amount of the hydroxyl-containing monomer (A4) is preferably selected from the range of 0.05-15% by mass, more preferably It is selected from the range of 0.07-12% by mass, particularly preferably selected from the range of 0.1-10% by mass.

啉。於丙烯酸系共聚合體(A)之構成成分(單體單位)100質量%中，添加乙酸乙烯酯時其調配量較佳為選自0.1～10質量%之範圍。於丙烯酸系共聚合體(A)之總構成成分(單體單位)100質量%中，添加丙烯醯

啉時其調配量較佳為選自0.1～10質量%之範圍。As other monomers (A5), vinyl acetate and acrylic acid are preferred

Morpholine. In 100% by mass of the constituent components (monomer unit) of the acrylic copolymer (A), when vinyl acetate is added, the blending amount is preferably selected from the range of 0.1-10% by mass. In 100% by mass of the total constituents (monomer unit) of the acrylic copolymer (A), acrylamide is added

In the case of morpholine, the blending amount is preferably selected from the range of 0.1 to 10% by mass.

The acrylic copolymer (A) may further contain monomers other than the above-exemplified monomers as constituent components.

In the acrylic adhesive, a crosslinking agent that is reactive with the functional group of the acrylic copolymer is usually used. As the crosslinking agent, for example, isocyanate compounds, acid anhydrides, amine compounds, epoxy compounds, metal chelate compounds, aziridine compounds, and melamine compounds can be used. One kind of these crosslinking agents may be used as needed, or two or more kinds may be used in combination. Relative to 100 parts by mass of the acrylic copolymer, the blending amount of the crosslinking agent is usually selected from the range of 0.1-15 parts by mass, more preferably selected from the range of 0.3-12 parts by mass, and particularly preferably selected from the range of 0.5-10 parts by mass The scope.

You can also add at least one of the following ingredients to the acrylic adhesive as needed: rosin, terpene, petroleum, lavender-indene, pure single system, phenol, xylene, etc. adhesion imparting agent resin ; Paraffin-based processing oil and other mineral oils; polyester-based plasticizers; softeners including vegetable oils; aromatic secondary amines, monophenols, bisphenols, polyphenols, benzimidazoles, sub Phosphoric acid and other anti-aging agents. In addition, saturated hydrocarbon resins can also be formulated in acrylic adhesives.

The acrylic adhesive may further contain at least one of additives such as a silane coupling agent and an antioxidant, if necessary.

As the silane coupling agent, a silane coupling agent containing a glycidyl group is particularly preferred. Specific examples include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane, ginseng isocyanurate (trimethoxysilyl propyl) ester, etc. One of these may be used, or two or more of them may be used in combination. With respect to 100 parts by mass of the acrylic copolymer (A), the compounding amount of the silane coupling agent is preferably selected from the range of 0.01 to 0.5 parts by mass, more preferably selected from the range of 0.02 to 0.5 parts by mass, and particularly preferably selected from The range of 0.03 to 0.3 parts by mass.

As the antioxidant, a hindered phenol-based antioxidant is particularly preferred. With respect to 100 parts by mass of the acrylic copolymer (A), the blending amount of the antioxidant is preferably selected from the range of 0.01 to 1 part by mass, more preferably selected from the range of 0.02 to 0.7 part by mass.

In order to satisfy the above parameters with the acrylic adhesive, for example, increasing the theoretical Tg of the acrylic copolymer can be mentioned. Since acrylic copolymers with a higher theoretical Tg generally have higher cohesion between the polymers, the storage modulus G'tends to increase in a high-temperature environment. In addition, since G'is higher in a high-temperature environment, the tanδ under a relatively high-temperature environment also becomes lower. The theoretical Tg can usually be calculated by the FOX formula, and by increasing the ratio of the (A2) component, (A3) component, (A4) component, and (A5) component in the entire acrylic copolymer, the theoretical Tg also increases. In addition, an increase in the weight average molecular weight (Mw) of the acrylic copolymer can also be exemplified as a method. If the weight average molecular weight (Mw) is higher, the cohesive force of the polymers will generally increase, and the fluidity will also decrease. Therefore, the storage modulus G'under high temperature environment will increase, and the tanδ under high temperature environment will also decrease. . Furthermore, the addition amount of the crosslinking agent for bonding the acrylic copolymers to each other is also preferably larger. If the amount of the crosslinking agent added is large, the three-dimensional network structure formed by the crosslinking of acrylic copolymers will be formed more firmly. As a result, G'will increase and tanδ will decrease even in a high temperature environment.

The type of rubber-based adhesive is not particularly limited, and various well-known rubber-based adhesives mainly composed of rubber components can be used. Specific examples of rubber components include: butyl rubber, polyisobutylene rubber, isoprene rubber, styrene-isobutylene-styrene block copolymer, styrene-isoprene block copolymer, benzene Ethylene-butadiene rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, styrene-ethylene-butene-styrene block copolymer , Styrene-ethylene-propylene-styrene block copolymer, styrene-ethylene-propylene block copolymer and other synthetic rubbers; natural rubber. One rubber component can be used, or two or more rubber components can be used in combination. The so-called butyl rubber refers to a rubber usually mainly composed of a copolymer of isobutylene and 1 to 3% by mass of isoprene.

When a rubber-based adhesive is used for the adhesive layer, the adhesive composition constituting the adhesive layer preferably contains a rubber-based adhesive and a saturated hydrocarbon resin. Saturated hydrocarbon resin is a hydrocarbon resin without unsaturated bonds, and is a component used to improve the adhesion of the adhesive layer.

The type of saturated hydrocarbon resin is not particularly limited. For example, various alicyclic or aliphatic saturated hydrocarbon resins known as adhesion imparting agents can be used. One type of saturated hydrocarbon resin may be used, or two or more types of saturated hydrocarbon resin may be used in combination. Particularly preferred is an alicyclic saturated hydrocarbon resin, and more preferred is a hydrocarbon resin from which unsaturated bonds have been removed by hydrogenation treatment. As a commercial product of saturated hydrocarbon resin, there is hydrogenated petroleum resin. The so-called hydrogenated petroleum resin refers to a resin obtained by hydrogenating a petroleum resin (for example, an aromatic petroleum resin, an aliphatic petroleum resin, a copolymerized petroleum resin of an alicyclic component and an aromatic component, etc.). Among them, hydrogenated petroleum resins (alicyclic saturated hydrocarbon resins) obtained by hydrogenating aromatic petroleum resins are preferred. The hydrogenated petroleum resin can be obtained from a commercially available product (for example, Arkon (trade name, registered trademark) P-100 manufactured by Arakawa Chemical Industry Co., Ltd.). The blending amount of the saturated hydrocarbon resin is preferably selected from the range of 0.01-100 parts by mass relative to 100 parts by mass of the adhesive component, more preferably selected from the range of 0.1-80 parts by mass. The higher the content of saturated hydrocarbon resin, the higher the adhesion.

In order to satisfy the above-mentioned parameters with a rubber-based adhesive, for example, increasing the molecular weight of the rubber component and increasing the cohesive force of the adhesive component can be exemplified. In addition, even if the rubber component is vulcanized by sulfur or resin to form a three-dimensional network structure formed by the cross-linking of the rubber components more firmly, G'under a high temperature environment can be increased and tanδ can be reduced.

As specific examples of the silicone adhesive used in the present invention, the following adhesives can be cited, which mainly contain: silicone rubber (polysiloxane having a structure containing D unit [(CH ₃ ) ₂ SiO]) Long-chain polymer of methylsiloxane); and MQ resin (polysiloxane with a three-dimensional structure _{including M units [(CH 3} ) ₃ SiO _1/2 ] and Q units [SiO _4/2] Polymer of resin). Adhesives containing this silicone rubber and MQ resin have better adhesion than silicone rubber monomers. In addition, by changing the ratio of silicone rubber to MQ resin in the adhesive, the basic adhesive properties such as adhesion, retention, and tack can be controlled. Furthermore, it is also possible to control the adhesive properties by changing the ratio of the M unit to the Q unit of the MQ resin, or changing the molecular weight. Polysiloxane adhesives are roughly classified into addition hardening type and peroxide hardening type according to their hardening mechanism.

The addition-curing polysiloxane adhesive includes, for example, a main agent containing polysiloxane rubber containing alkenyl groups, MQ resin, and a crosslinking agent containing polyorganosiloxane containing SiH groups. In addition, it is cured by being heated under a platinum catalyst to undergo a cross-linking reaction. Regarding the polysiloxane rubber containing alkenyl groups, a polyorganosiloxane having at least two alkenyl groups (such as vinyl groups) bonded to silicon atoms in one molecule is representative. Regarding the polyorganosiloxane containing SiH groups, a representative one is a polyorganosiloxane having at least two hydrogen atoms bonded to silicon atoms in a molecule.

The peroxide-curing silicone adhesive includes, for example, a main agent containing a silicone rubber that does not contain alkenyl groups, and MQ resin. In addition, a peroxide such as benzoyl peroxide is added as a hardening agent, and the solvent is removed, and then heated at a high temperature to harden.

The silicone adhesive can also be blended with more than two types of silicone adhesives to improve various properties. However, the type or amount of the silicone-based adhesive blended needs to be appropriately selected in a manner that does not impair the effect of the invention.

In order to meet the above-mentioned adhesive parameters with silicone adhesives, for example, it can be achieved by appropriately adjusting the ratio of silicone rubber to silicone resin. Specifically, the ratio (mass basis) of silicone rubber to silicone resin is preferably in the range of 30/70 to 90/10. If the ratio of silicone rubber is smaller than this range, the cohesive force under high temperature environment tends to become weaker, so the storage modulus G'also becomes lower and tanδ becomes higher. Conversely, if the ratio of polysilicone rubber is large, it is difficult to exhibit sufficient initial adhesion, and it is difficult to adhere to the adherend. Furthermore, if it is an addition-hardening silicone adhesive, by adjusting the content of the alkenyl group in the silicone rubber or the amount of the crosslinking agent to control the bonding of the silicone components to each other, the storage can be controlled finally Modulus G'or tanδ. If the alkenyl content of the silicone rubber or the amount of crosslinking agent is increased, the sufficient storage modulus G'at high temperature will become higher and the tanδ will become lower. If it is a peroxide-cured silicone adhesive, the storage modulus G'or tanδ can be controlled by the amount of peroxide added. If the amount of peroxide added is increased, the sufficient storage modulus G'at high temperature will increase and tanδ will decrease.

Each adhesive described above may further contain at least one other component as needed. Specific examples include: solvents such as toluene; additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, flame retardants, electrical conductivity improvers, and thermal conductivity improvers; carbon black, calcium oxide, oxidation Fillers or pigments such as magnesium, silicon oxide, zinc oxide, and titanium oxide.

[Thermally expandable particles] As the heat-expandable particles, heat-expandable particles having a maximum expansion temperature of 170°C or higher can be preferably used. Thermally expandable particles can be used singly or in combination of two or more kinds. The heat-expandable particles can be appropriately selected from known heat-expandable microspheres, and microencapsulated heat-expandable particles are preferred. Examples of such thermally expandable particles include those obtained by encapsulating a gasifying agent such as a liquid low-boiling hydrocarbon such as isobutane, propane, and pentane in a thermoplastic polymer shell. When such heat-expandable particles are heated, the polymer shell is softened, and the liquid low-boiling hydrocarbon contained in the inside is vaporized and expanded due to the pressure. As the material forming the thermoplastic polymer shell, for example, vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene dichloride Ethylene, poly turpentine, etc.

As thermally expandable particles with a maximum expansion temperature of 170°C or higher, for example, it can be used well: Matsumoto Oil & Fat Pharmaceutical Co., Ltd. is manufactured under the trade name "Matsumoto Microsphere" series (for example, the trade name is "Matsumoto Microsphere FN-180SSD", "Matsumoto Microsphere FN-180SD", "Matsumoto Microsphere FN-180D", "Matsumoto Microsphere FN-190SSD", "Matsumoto Microsphere F-190D", "Matsumoto Microsphere F-260D") and other commercially available products.

In order to obtain the objective effect of the present invention, thermally expandable particles having a maximum expansion temperature of 170°C or higher, particularly preferably 180°C or higher and 320°C or lower, can be used well.

In the present invention, the maximum expansion temperature of the thermally expandable particles can be determined by using a thermal analysis device TMA (TMA7100, manufactured by Hitachi High-Tech Science Inc.). The maximum expansion temperature of heat-expandable particles is when the heat-expandable particles are put into a 5 mmϕ aluminum pot and the inner lid is covered, and the analysis is performed in the compression mode (load: 0.05 N, heating rate: 10°C/min). The temperature at which the expansion of the particle becomes the maximum. For the convenience of description, set this temperature as TFmax. If heated to a temperature higher than the maximum expansion temperature, the gas inside the heat-expandable particles will penetrate the polymer shell, so it usually shrinks without breaking.

Furthermore, in order to efficiently and stably reduce the adhesive force of the heat-expandable adhesive layer by heat treatment, heat-expandable particles having a volume expansion rate of 5 times or more can be used well.

With respect to 100 parts by mass of the resin component contained in the heat-expandable adhesive layer, the blending amount of the heat-expandable particles can be appropriately set to 4 parts by mass or more according to the required initial adhesion or the reduction of the peeling force after foaming, etc. The range is preferably set to a range of 5 parts by mass or more, more preferably set to a range of 5 parts by mass or more and less than 100 parts by mass, and particularly preferably set to be 7 parts by mass or more and less than 80 parts by mass The range of parts is more preferably appropriately set to a range of 10 parts by mass or more and 50 parts by mass.

The heat-expandable particles may be exposed to a high temperature and high humidity environment such as a temperature of 65° C. and a relative humidity of 80%, for example, the foamability may be reduced. Therefore, the thermally peelable adhesive tape using thermally expandable particles is best stored in a high-temperature and high-humidity environment. Furthermore, in order to maintain thermal releasability even in a state where the foamability has been reduced, the blending amount of the thermally expandable particles is preferably 7 parts by mass or more with respect to 100 parts by mass of the resin component contained in the thermally expandable adhesive layer.

The average particle size of the heat-expandable particles can be appropriately selected according to the thickness of the heat-expandable adhesive layer, etc. The average particle diameter of heat-expandable particles having shapes such as microspheres may be preferably selected from the range of 100 μm or less, more preferably selected from the range of 80 μm or less, and particularly preferably selected from the range of 1 μm or more and 50 μm or less. Scope. Thermally expandable particles of the target average particle size can be selected from commercially available products and used. Alternatively, the adjustment of the particle size of the heat-expandable particles may be performed during the production process of the heat-expandable particles, or the commercially available heat-expandable particles may be adjusted by a known method (for example, classification). In order to obtain the smoothness of the heat-expandable adhesive layer, the particle size of the heat-expandable particles is preferably kept uniform.

The thickness of the thermally expandable adhesive layer is not particularly limited. For example, it is preferably selected from the range of 5 μm to 200 μm, more preferably selected from the range of 10 μm to 150 μm, and particularly preferably selected from the range of 15 μm to 100 μm. Scope.

Furthermore, as a method of foaming the heat-expandable particles in the heat-expandable adhesive layer, it can be appropriately selected from known heat expansion methods and adopted. Specifically, as the heating treatment for expanding the heat-expandable particles, for example, heating means such as a hot plate, a hot-air dryer, an infrared heater, etc. can be used as appropriate. The heating temperature during the heat treatment only needs to be higher than the foaming start temperature of the heat-expandable particles in the heat-expandable adhesive layer. The conditions of the heat treatment can be appropriately set by the heating means, the material of the adherend, or the heat capacity.

[Layer composition of heat-peelable adhesive tape] As the layer structure of the heat-peelable adhesive tape of the present invention, a layer composed of only a heat-expandable adhesive layer without other layers, or a layer composed of a heat-expandable adhesive layer and other layers can be exemplified. The heat-peelable adhesive tape composed of only a heat-expandable adhesive layer can be a heat-peelable adhesive tape composed of a single-layer heat-expandable adhesive layer, or it may be a heat-peelable adhesive tape with several different heat-expandable adhesive layers . As another layer used as needed, a base material, a release liner, etc. are mentioned. As the form of the heat-peelable adhesive tape having at least one of a base material and a release liner, the following forms can be exemplified. (1) Thermally peelable adhesive tape with thermally expandable adhesive layers on both sides of the substrate. (2) A heat-peelable adhesive tape with a heat-expandable adhesive layer on only one side of the substrate. (3) A heat-peelable adhesive tape with a heat-expandable adhesive layer on one side of the substrate and a non-heat-expandable adhesive layer (adhesive layer without heat-expandability) on the other side. (4) A heat-peelable adhesive tape with a heat-expandable adhesive layer on the release liner. (5) A thermally peelable adhesive tape with a thermally expandable adhesive layer and a non-thermally expandable adhesive layer on the release liner. Furthermore, when the heat-expandable adhesive layer is formed on both sides of the substrate, at least one of the heat-expandable adhesive layers may have the characteristics of the present invention described above. The heat-expandable adhesive layer and the non-heat-expandable adhesive layer that are different from the heat-expandable adhesive layer of the present invention can be selected in such a way that the target function or effect of the heat-peelable adhesive tape can be obtained. In addition, in the case of the above-mentioned (1) to (3), a release liner may be provided on the heat-expandable adhesive layer or the non-heat-expandable adhesive layer.

[Other layers] [Substrate] The base material can be used as a member of a heat-peelable adhesive tape, for example, it can be used as a support for a heat-expandable adhesive layer or the like. The substrate is not particularly limited, and known films, non-woven fabrics, foams, cloth, paper, and combinations thereof can be used. Preferably, it is a film-like base material that is easy to obtain uniform thickness in the manufacturing steps of a thin substrate. Particularly preferred is a resin film having heat resistance required under the use environment. As specific examples thereof, for example, polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) and the like can be mentioned. Esters; polyphenylene sulfide (PPS), polyamide imine (PAI), polyether sulfide (PES), polytetrafluoroethylene (PTFE) and other resin films. These films can be used as a single layer, or used as a laminated film of two or more layers. The laminated film may include more than one combination of multiple layers composed of different materials. As a heat-resistant resin film, a polyimide film with excellent dimensional stability at high temperatures is particularly preferred. The thickness of the substrate is not particularly limited, but is preferably selected from the range of 1 μm or more and 200 μm or less, more preferably selected from the range of 2 μm or more and 150 μm or less, and particularly preferably selected from the range of 2 μm or more and 125 μm The following range.

It is also possible to implement easy-adhesion treatment on the surface of the substrate where the adhesive layer is provided as needed. As easy adhesion treatment, for example, primer treatment, corona treatment, etching treatment, plasma treatment, sandblasting treatment, etc. may be mentioned. You can choose one of them, or a combination of two or more.

If necessary, surface treatment such as antistatic may be applied to the substrate. As the antistatic treatment, treatment with an antistatic agent such as a cationic surfactant, an anionic surfactant, or a nonionic surfactant may be mentioned. In addition, the base material may be colored by printing or kneading as needed.

[Non-thermally expandable adhesive layer] The adhesive used to form the non-heat-expandable adhesive layer is not particularly limited, and the adhesive exemplified in the description of the heat-expandable adhesive layer can be used in the same manner. As the adhesive, for example, known adhesives such as acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, polyamide adhesives, and urethane adhesives can be used. Agent. These adhesives can be used alone or in combination of two or more kinds. In the non-thermally expandable adhesive layer, at least one of additives such as an adhesive imparting agent, a coloring pigment, an anti-aging agent, an antioxidant, an antistatic agent, a crosslinking agent, and a silane coupling agent can also be blended.

The thickness of the non-thermally expandable adhesive layer is, for example, preferably selected from the range of 200 μm or less, more preferably selected from the range of 1 μm or more and 150 μm or less, and particularly preferably selected from the range of 1 μm or more and 100 μm or less. Furthermore, as a method for forming the non-thermally expandable adhesive layer, the same method as the above-mentioned thermally expandable adhesive layer (for example, the method of coating on a substrate, coating on a release liner to form the adhesive layer and then transferring it Method of printing on the substrate, etc.).

[Release Liner] As the release liner, a known release paper or the like can be used. The release liner is used as a protective material for the heat-expandable adhesive layer, and is peeled off when the heat-peelable adhesive sheet is attached to the adherend. As a release liner, for example, it is also possible to use: a base material with a release layer such as a plastic film (for example, PET film) or paper that has been surface-treated with a release agent such as a silicone-based, long-chain alkyl-based, fluorine-based, etc.; A low-adhesion base material containing non-polar polymers such as fluorine-based resins (for example, polytetrafluoroethylene) or olefin-based resins (for example, polyethylene, polypropylene, etc.).

An embodiment of a thermally peelable adhesive tape having a base material and a release liner as other layers will be described with reference to FIG. 1. Fig. 1 is a schematic cross-sectional view in the thickness direction showing an embodiment of the heat-peelable adhesive tape of the present invention. The heat-peelable adhesive sheet 1 shown in Fig. 1 has a substrate 2, a heat-expandable adhesive layer 3, and a release liner 4. The two heat-expandable adhesive layers 3 may be the same or different. The two-layer release liner 4 can be the same release liner or different release liners.

The heat-peelable adhesive sheet 1 shown in FIG. 1 has the form of a double-sided adhesive tape including two heat-expandable adhesive layers 3 formed on both sides of a substrate 2 respectively. In the form of the double-sided adhesive tape, at least one of the two adhesive layers may be the heat-expandable adhesive layer of the present invention. For example, regarding the form of the double-sided adhesive tape, at least one of the two adhesive layers 3 may be the heat-expandable adhesive layer of the present invention, and the other layer may be a heat-expandable adhesive layer other than the heat-expandable adhesive layer of the present invention or have no thermal expansion The adhesive layer (non-thermally expandable adhesive layer).

[Manufacturing method of heat-peelable adhesive tape] The heat-peelable adhesive tape containing the heat-expandable adhesive layer can be manufactured by the following method: coating a layer-forming composition material containing resin components and heat-expandable particles on a substrate for forming the heat-expandable adhesive layer, and heat The heat-expandable adhesive layer formed by crosslinking the coating layer is peeled from the base material for forming the heat-expandable adhesive layer. A heat-peelable adhesive tape having a heat-expandable adhesive layer on the base material or release liner that is a component of the heat-peelable adhesive tape can be manufactured by, for example, forming a layer containing a resin component and heat-expandable particles. The composition material is coated on a substrate or a release liner, and the coating layer is heated to cause a crosslinking reaction to form a thermally expandable adhesive layer. In addition, a layer forming composition material containing resin components and heat-expandable particles may be coated on a release liner (for example, a PET film treated with silicone), and the coating layer may undergo a cross-linking reaction by heating , And then transferred to one or both sides of the substrate, thereby forming a heat-peelable adhesive tape. It is very important that the heating temperature for crosslinking is sufficiently lower than the foaming start temperature of the heat-expandable particles. For the formation of the coating layer, a known coating device such as a roll coater, a die nozzle coater, and a die lip coater can be used. In the case of heating after coating, it is also possible to remove the solvent in the layer-forming material while heating the cross-linking reaction. In the case of forming the heat-expandable adhesive layer by transfer, in order to improve the adhesion between the base material and the heat-expandable adhesive layer, and to obtain surface smoothness, it is preferable to laminate by a heated roller or the like.

The heat-peelable adhesive tape of the present invention can be used well for the heat-pressing treatment of the adherend to which the heat-peelable adhesive tape is temporarily fixed. One form of the use method of the heat-peelable adhesive tape of the present invention in the hot pressing process of the adherend includes: temporarily fixing the adhesive tape of the above-mentioned structure to the adherend; and adhering to the temporarily fixed adhesive tape. The step of heat-pressing the body; the step of heating the adhesive tape temporarily fixed to the adherend after the heat-pressing process to the temperature for peeling; and the step of heating the adhesive tape heated to the temperature for peeling from the adherend Steps of peeling. One form of the hot-pressing processing method of the adherend using this method of use is the hot-pressing processing method of the adherend with the temporarily fixed heat-peelable adhesive tape, including: temporarily fixing the heat-peelable adhesive tape of the above-mentioned structure The step of the adherend; the step of heat-pressing the adherend with the adhesive tape temporarily fixed; the step of heating the adhesive tape temporarily fixed to the adherend after the hot-pressing process to a temperature for peeling And the step of peeling the adhesive tape heated to the temperature for peeling from the adherend. The form of temporarily fixing the heat-peelable adhesive tape to the adherend includes: temporary fixation of adherends to each other, temporary fixation during transportation of adherends, reinforcement of adherends, protection or shielding, and application of adherences Resin sealing, etc. In addition, as the hot pressing step, the hot pressing step in the manufacturing steps of electronic parts and semiconductor parts can be exemplified. As the conditions for the hot pressing step of the heat-peelable adhesive tape of the present invention, a temperature of 120 to 240°C, a time of 5 minutes to 10 hours, and a pressure of 5 to 40 kgf/cm ² can be mentioned. [Example]

Hereinafter, examples and comparative examples are taken as examples to further describe the present invention in detail, but the present invention is not limited in any way by these examples. In the following description, "parts" means parts by mass.

<Preparation example of acrylic copolymer> The acrylic copolymer with the composition shown in Table 1 was polymerized. The blending ratio of each component in Table 1 shows the ratio when the total of components A1 to A5 is 100 parts. The theoretical Tg and weight average molecular weight (Mw) of each acrylic copolymer are listed in Table 1 as a reference. The theoretical Tg is a value calculated by the FOX formula and can be adjusted by appropriately selecting the composition of the acrylic monomer. In addition, the weight average molecular weight (Mw) is a value obtained by measuring the molecular weight of the acrylic copolymer in terms of standard polystyrene by the GPC method using the following measuring device and conditions. • Device: LC-2000 series (manufactured by JASCO Corporation) •Tube column: ShodexKF-806M×2 pieces, ShodexKF-802×1 pieces • Eluent: Tetrahydrofuran (THF) • Flow rate: 10 mL/min • Column temperature: 40℃ • Injection volume: 100 μL • Detector: Refractometer (RI) •Measurement sample: The acrylic polymer is dissolved in THF to prepare a solution with a concentration of 0.5% by mass of the acrylic polymer, and the dirt is removed by filtration with a filter. The weight average molecular weight (Mw) is based on the polymerization of acrylic copolymers. The type and amount of polymerization initiator can be selected appropriately (for example, 0.1 parts by mass of lauryl peroxide is selected relative to 100 parts by mass of acrylic monomers ), the type and amount of the chain transfer agent (for example, 0.1 parts by mass of n-dodecyl mercaptan is selected relative to 100 parts by mass of acrylic monomer), the polymerization start concentration (for example, 50% by mass), etc. are adjusted.

[Table 1] Table 1 Preparation example of component A acrylic copolymer No. A1 A2 A3 A4 A5 Theoretical Tg Mw 1 2-EHA: 70 BA: 14.9 MA: 5 AA: 10 4-HBA: 0.1 - -66.9 1.29 million 2 2-EHA: 70 BA: 5 MA: 10 AA: 10 2-HEA: 5 - -63.2 1.01 million 3 2-EHA: 10 MA: 20 EA: 50 AA: 10 4-HBA: 6 2-HEA: 4 - -17.9 670,000 4 2-EHA: 87.9 MA: 3 AA: 7 2-HEA: 0.1 VAc: 2 -74.5 1.11 million 5 2-EHA: 86 MA: 3 AA: 7 2-HEA: 2 VAc: 2 -73.4 440,000 6 2-EHA: 90 - AA: 3 4-HBA: 0.1 VAc: 5 ACMO: 1.9 -76.2 750,000

啉The abbreviations in Table 1 indicate the following compounds. "2-EHA": 2-ethylhexyl acrylate "BA": n-butyl acrylate "MA": Methyl acrylate "EA": Ethyl acrylate "AA": Acrylic acid "4-HBA": Acrylic acid-4 -Hydroxybutyl ester "2-HEA": 2-hydroxyethyl acrylate "VAc": Vinyl acetate "ACMO": Acrylic acid

Morpholine

<Examples 1-12 and Comparative Examples 1-8: Production of heat-peelable acrylic adhesive tape> As shown in Table 2, with respect to 100 parts of the solid content of the acrylic copolymer (component A) obtained in Table 1, the crosslinking agent (component B) and antioxidant (component C) are mixed at a predetermined mixing ratio (mass basis) ), silane coupling agent (component D), toluene (diluent solvent), to obtain an adhesive composition. Furthermore, with respect to 100 parts of adhesive components, a foaming agent (component F) was mixed at the compounding ratio (mass basis) shown in Table 2 to prepare a thermally expandable adhesive composition.

[Table 2] Table 2 Preparation example of thermally expandable adhesive composition (acrylic) Adhesive components (acrylic, solid content ratio) Foaming agent Ingredient A Ingredient B Ingredient C Ingredient D Ingredient F Example 1 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Example 2 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 5 Example 3 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 10 Example 4 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 50 Example 5 No. 1: 100 B1: 1.67 C1: 0.67 D1: 0.03 F1: 30 Example 6 No. 2: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Example 7 No. 3: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Example 8 No. 4: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Example 9 No. 4: 100 B1: 1.67 C1: 0.67 D1: 0.03 F1: 30 Example 10 No.5: 100 B1: 1.67 C1: 0.67 D1: 0.03 F1: 30 Example 11 No.6: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Example 12 No.6: 100 B1: 1.67 C1: 0.67 D1: 0.03 F1: 30 Comparative example 1 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 none Comparative example 2 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 3 Comparative example 3 No. 1: 100 B1: 0.50 C1: 0.67 D1: 0.03 F2: 30 Comparative example 4 No. 1: 100 B1: 0.08 C1: 0.67 D1: 0.03 F1: 30 Comparative example 5 No. 1: 100 B1: 0.17 C1: 0.67 D1: 0.03 F1: 30 Comparative example 6 No. 1: 100 B2: 4.50 C1: 0.67 D1: 0.03 F1: 30 Comparative example 7 No.5: 100 B1: 0.50 C1: 0.67 D1: 0.03 F1: 30 Comparative example 8 No.5: 100 B1: 0.20 C1: 0.67 D1: 0.03 F1: 30

The heat-expandable adhesive composition was coated on a PET film with a thickness of 50 μm that was treated with silicone release. Then, the diluting solvent is removed at 90 to 100°C, and dried, and crosslinked to form a thermally expandable adhesive layer. The heat-expandable adhesive layer was laminated and transferred on both sides of a polyimide film with a thickness of 12 μm. Furthermore, using a desktop laminator, lamination was performed at a temperature of 100°C. It was then aged at 40°C for 3 days to obtain a double-sided heat-peelable adhesive tape. The heat-expandable adhesive composition is applied so that the thickness of the adhesive layer on one side after lamination becomes 50 μm. The thickness of the obtained double-sided adhesive tape became 112 μm.

The abbreviations in Table 2 indicate the following ingredients. "B1": Epoxy crosslinking agent (manufactured by Soken Chemical Co., Ltd., trade name E-5XM, solid content 5%) "B2": Isocyanate-based crosslinking agent (manufactured by Tosoh Co., Ltd., brand name Coronaate L-45E, solid content 45%) "C1": Antioxidant (manufactured by BASF, trade name Irganox 1010) "D1": Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403, solid content 10%) "F1": Thermally expandable microcapsules (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., trade name Matsumoto Microsphere FN-180SSD, maximum expansion temperature 192°C) "F2": Thermally expandable microcapsules (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd., trade name Matsumoto Microsphere FN-100SSD, maximum expansion temperature 162°C)

<Example 13: Production of heat-peelable silicone adhesive tape> First, prepare two kinds of trial products (I, II) of addition-curing silicone adhesive stock solution. These trial products were cured by appropriately changing the mixing ratio of MQ resin to polysiloxane rubber, the type of MQ resin, the amount of polysiloxane rubber, and the amount of cross-linking. The storage modulus G', tanδ presents various values to adjust the prototype of the adhesive. In Example 13, among the trial products, the storage modulus G'at 170°C was 125,770 Pa, and the tanδ at the maximum expansion temperature of the thermally expandable particles F1 was 0.053. Agent stock solution (I). Prepare 100 parts of addition-curing polysiloxane adhesive stock solution (I) with a solid content concentration of 50% by mass, 25 parts of toluene as a dilution solvent, and platinum catalyst as a hardening catalyst (manufactured by Shin-Etsu Chemical Co., Ltd.) , CAT-PL-50T) 1.25 parts of silicone adhesive composition. Furthermore, 15 parts of heat-expandable microcapsule F1 (manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., trade name Matsumoto Microsphere FN-180SSD, maximum expansion temperature 192°C) as a foaming agent was mixed to prepare a heat-expandable adhesive composition.

Apply the thermally expandable adhesive composition to one side of the primer-treated polyimide (PI) film with a thickness of 50 μm so that the thickness of the adhesive layer after drying becomes 50 μm, in a drying oven Dry it at 120°C for 2 minutes, remove the solvent and heat it to harden to form a heat-expandable adhesive layer. Then, as a release liner, a polyethylene terephthalate (PET) film with a thickness of 50 μm, which has been subjected to release treatment with a fluorine-substituted alkyl-modified silicone resin, is attached to the adhesive layer to obtain heat Peel-off single-sided adhesive tape.

<Comparative Example 9: Production of thermally peelable silicone adhesive tape> In Comparative Example 9, an addition-curing silicone adhesive stock solution (II) with a storage modulus G'at 170°C of 39,749 Pa and a tanδ at the maximum expansion temperature of the thermally expandable particles F1 of 0.532 was selected. The following silicone adhesive composition was prepared, which contained 100 parts of addition-curing polysilicone adhesive stock solution (II) with a solid content concentration of 50% by mass, 25 parts of toluene as a diluting solvent, and one of the hardening catalysts Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) 1.25 parts. Furthermore, 15 parts of heat-expandable microcapsule F1 (manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd., trade name Matsumoto Microsphere FN-180SSD, maximum expansion temperature 192°C) as a foaming agent was mixed to prepare a heat-expandable adhesive composition. Except for this, a heat-peelable single-sided adhesive tape was obtained by the same method as in Example 13.

The heat-peelable adhesive tapes obtained in Examples 1-13 and Comparative Examples 1-9 were evaluated by the following methods. The results are shown in Table 3-1 to Table 3-4.

(a) [Dynamic viscoelasticity measurement of adhesive composition] Regarding the acrylic adhesive composition, according to the compounding composition shown in Table 2, which does not contain thermally expandable microcapsules (F), crosslinking is added to 100 parts of the solid content of the acrylic copolymer (A) obtained in Table 1 Agent (B), antioxidant (C), and silane coupling agent (D) are mixed to prepare an adhesive composition for sample preparation for measurement. Regarding the silicone adhesive composition, the adhesive composition for sample preparation for measurement was prepared by the same method as in Example 13 and Comparative Example 9 except that it did not contain thermally expandable microcapsules (F).

Separately use each adhesive composition as a test sample. In the case of an acrylic adhesive composition, apply it to the thickness of the silicone release treatment so that the thickness after drying becomes 50 μm On 50 μm PET film. Then, the solvent is removed at 90 to 100°C, dried, and crosslinked to form an adhesive layer. The adhesive layer was laminated to form a laminate with a thickness of 2 mm, which was then aged at 40°C for 3 days, and this was used as a sample for measurement. In the case of the silicone adhesive composition, the thickness after drying becomes 50 μm, and it is applied to the polysiloxane with a thickness of 50 μm after the fluorine-substituted alkyl-modified silicone resin is released. On PET film. Then, it was dried in a drying oven at 120°C for 2 minutes, the solvent was removed, and it was heated and hardened to form an adhesive layer. The adhesive layer was laminated to form a laminate with a thickness of 2 mm, which was used as a sample for measurement.

The measurement sample is sandwiched between parallel discs (ϕ8 mm), and a dynamic viscoelasticity measuring device (manufactured by Rheometric Scientific, device name RDAIII) is used. While applying a shear strain of 10 Hz on one side, Heating rate, measuring storage modulus (G') and loss elastic modulus (G'') in the range of -50℃～300℃. According to the storage modulus (G') and loss elastic modulus (G''), use the following formula to calculate the loss tangent tanδ. tanδ=loss modulus of elasticity (G'')/storage modulus (G') Table 3-1 shows the storage modulus (G') at 23°C, 170°C, and the measured value of tanδ at the maximum expansion temperature TFmax°C.

(b) Determination of TFmax The maximum expansion temperature (TFmax) of the thermally expandable particles is measured by the above method.

[Evaluation of Acrylic Double-sided Thermal Peeling Adhesive Tape] (c) [Initial peeling force of copper foil, initial peeling force of heat-peelable adhesive tape relative to copper plate] The samples (double-sided adhesive tape) described in Examples 1 to 12 and Comparative Examples 1 to 8 cut into widths of 10 mm and length of 90 mm were placed on a copper plate with a thickness of 0.7 mm, a width of 25 mm and a length of 125 mm ( It is assumed to be a transfer board) and the glossy surface of a copper foil with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm (assumed to be a substrate product, electrolytic copper foil manufactured by Futian Metal Co., Ltd.), and the like are bonded together. Press a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min to press and bond once, and place it at 23°C for 20-40 minutes. After that, using a tensile testing machine, measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90° under an environment of 23°C. Then, a tensile testing machine was used to measure the force required to peel the tape from the copper plate at a speed of 300 mm/min and an angle of 90°.

(d) [Peeling force of copper foil during heat-peeling treatment, peeling force of heat-peelable adhesive tape with respect to copper plate] The samples (double-sided adhesive tape) described in Examples 1 to 12 and Comparative Examples 1 to 8 cut into widths of 10 mm and length of 90 mm were placed on a copper plate with a thickness of 0.7 mm, a width of 25 mm and a length of 125 mm ( It is assumed to be a transfer board) and a copper foil (assumed to be a substrate product) with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm (assumed to be a substrate product). A roller covered by a rubber layer with a weight of 2 kg was pressed back and forth once at a speed of 300 mm/min, and then heated with a dryer at 200°C for 3 minutes. Leave to cool at 23°C for more than 1 hour, then use a tensile testing machine to measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is any paste on the adherend Agent residue. Then, using a tensile testing machine, measure the force required to peel the tape from the copper plate at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is any paste residue on the adherend.

The peeling force and paste residue during the heat peeling treatment were determined based on the following criteria. (Peeling force of copper foil during heat peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Paste residue of copper foil during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad). (Peeling force of heat-peelable adhesive tape with respect to copper plate during heat-peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Residual of paste on copper plate during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad).

(e) [Suppression of foaming under high temperature and long time pressurization] The evaluation of (d) above is good (all evaluations are A) Examples 1-12 and Comparative Examples 2, 3, 7, and 8 are evaluated in the following manner Suppresses foaming during high temperature and long time pressurization. The samples (double-sided adhesive tape) described in Examples 1 to 12 and Comparative Examples 2, 3, 7, and 8 cut to a width of 10 mm and a length of 90 mm were arranged in a thickness of 0.7 mm, a width of 25 mm, and a length of 125 The copper plate (assumed to be a conveying plate) with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm (assumed to be a substrate product) are bonded together. After pressing a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min, a heating press is used to apply a pressure of 26 kg/ to the entire test piece at a temperature of 170°C. cm ² is pressurized for 1 hour. At this time, in order to apply pressure evenly, a silicone rubber sheet (IS-825, hardness 50°, manufactured by IRUMAGAWA RUBBER CO., LTD.) with a thickness of 1 mm, a width of 25 mm, and a length of 125 mm was laid under the copper plate , Place the silicone rubber sheet cut to a width of 10 mm and a length of 90 mm on the test piece, and press it with it. After leaving to cool at 23°C for 1 hour or more, the tape was peeled off from the copper foil and the copper plate, and the presence or absence of foaming was confirmed visually, and the obtained results were evaluated according to the following criteria. A: The heat-expandable adhesive layer is not foamed during hot pressing (good). B: The thermally expandable adhesive layer is foamed during hot pressing (bad).

(f) [Peeling force of copper foil and peeling force of heat-peelable adhesive tape with respect to copper plate when heated and peeled after high temperature and long time pressurization] Examples of (A-evaluation) evaluated as good for the above (e) and In the comparative example, the peeling force of the copper foil and the peeling force of the heat-peelable adhesive tape relative to the copper plate when subjected to heat peeling treatment after high temperature and long time pressure were evaluated according to the following methods. The samples (double-sided adhesive tape) described in Examples 1-12 and Comparative Example 2 cut into width 10 mm and length 90 mm were placed on a copper plate with a thickness of 0.7 mm, a width of 25 mm, and a length of 125 mm (assumed to be The transfer board) and the copper foil (assumed to be a substrate product) with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm are bonded together. After pressing a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min, a heating press is used to apply a pressure of 26 kg/ to the entire test piece at a temperature of 170°C. cm ² is pressurized for 1 hour. At this time, in order to apply pressure evenly, a silicone rubber sheet (IS-825, hardness 50°, manufactured by IRUMAGAWA RUBBER CO., LTD.) with a thickness of 1 mm, a width of 50 mm, and a length of 125 mm was laid under the copper plate. , Place the silicone rubber sheet cut to a width of 10 mm and a length of 90 mm on the test piece, and press it with it. Leave it to cool for more than 1 hour at 23°C, and then heat it with a dryer at 200°C for 3 minutes. Leave to cool at 23°C for more than 1 hour, then use a tensile testing machine to measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is any paste on the adherend Agent residue. Then, use a tensile testing machine to measure the force required to peel the tape from the copper plate at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is any paste residue on the adherend.

Evaluate the peeling of the copper foil and the peeling of the tape from the copper plate according to the following criteria. (Peeling force of copper foil during heat peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Paste residue of copper foil during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad). (Peeling force of heat-peelable adhesive tape with respect to copper plate during heat-peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Residual of paste on copper plate during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad).

[Evaluation of polysiloxane-based heat-peelable single-sided adhesive tape] (g)[Initial peeling force of copper foil] The samples described in Example 13 and Comparative Example 9 cut to a width of 10 mm and a length of 90 mm (assumed to be a single-sided adhesive tape for reinforcement during transportation) were attached to a thickness of 35 μm, a width of 10 mm, and a length of 90 mm. The glossy surface of mm copper foil (assumed to be a substrate product, electrolytic copper foil manufactured by Futian Metal Co., Ltd.). Press a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min to press and bond once, and place it at 23°C for 20-40 minutes. After that, use a tensile testing machine to measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90° in an environment of 23°C. At this time, the substrate side of the single-sided adhesive tape was fixed to the SUS plate with a paper double-sided adhesive tape (No. 778 manufactured by Teraoka Manufacturing Co., Ltd.) for measurement.

(h) [Peeling force of copper foil during heat peeling treatment] The samples described in Example 13 and Comparative Example 9 cut to a width of 10 mm and a length of 90 mm (assumed to be a single-sided adhesive tape for reinforcement during transportation) were attached to a thickness of 35 mm, a width of 10 mm, and a length of 90 mm. The glossy surface of mm copper foil (assumed to be a substrate product, electrolytic copper foil manufactured by Futian Metal Co., Ltd.). A roller covered by a rubber layer with a weight of 2 kg was pressed back and forth once at a speed of 300 mm/min, and then heated with a dryer at 200°C for 3 minutes. Leave to cool for more than 1 hour at 23°C, then use a tensile testing machine to measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is paste on the adherend Residue. At this time, the substrate side of the single-sided adhesive tape was fixed to the SUS plate with a paper double-sided adhesive tape (No. 778 manufactured by Teraoka Manufacturing Co., Ltd.) for measurement.

The peeling force and paste residue during the heat peeling treatment were judged according to the following criteria. (Peeling force of copper foil during heat peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Paste residue of copper foil during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad).

(i) [Suppression of foaming under high temperature and long time pressing] For the examples of (h) evaluated as good (all evaluated as A), the foaming inhibition under high temperature and long time pressing was evaluated according to the following method. The sample described in Example 13 (assumed to be a single-sided adhesive tape for reinforcement during transportation) cut to a width of 10 mm and a length of 90 mm was attached to a copper foil with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm The glossy surface (assumed to be a substrate product, electrolytic copper foil manufactured by Futian Metal Co., Ltd.). After pressing a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min, a heating press is used to apply a pressure of 26 kg/ to the entire test piece at a temperature of 170°C. cm ² is pressurized for 1 hour. At this time, in order to apply the pressure evenly, a silicone rubber sheet with a thickness of 1 mm, a width of 25 mm, and a length of 125 mm (IS-825, hardness 50 °, manufactured by IRUMAGAWA RUBBER CO., LTD.), the silicone rubber sheet cut to a width of 10 mm and a length of 90 mm is placed on the test piece, and pressed by sandwiching it. After leaving to cool at 23°C for 1 hour or more, the tape was peeled from the copper foil, the presence or absence of foaming was confirmed visually, and the obtained results were evaluated according to the following criteria. A: The heat-expandable adhesive layer is not foamed during hot pressing (good). B: The thermally expandable adhesive layer is foamed during hot pressing (bad).

(j) [Peeling force of copper foil after heating and peeling treatment after high temperature and long time press] For the example (h) evaluated as good (A evaluation), the following method is used to evaluate the high temperature and long time pressure after heating The peeling force of the copper foil during the peeling process. The sample described in Example 13 (assumed to be a single-sided adhesive tape for reinforcement during transportation) cut to a width of 10 mm and a length of 90 mm was attached to a copper foil with a thickness of 35 μm, a width of 10 mm, and a length of 90 mm The glossy surface (assumed to be a substrate product, electrolytic copper foil manufactured by Futian Metal Co., Ltd.). After pressing a roller covered by a rubber layer with a weight of 2 kg at a speed of 300 mm/min, a heating press is used to apply a pressure of 26 kg/ to the entire test piece at a temperature of 170°C. cm ² is pressurized for 1 hour. At this time, in order to apply pressure evenly, a silicone rubber sheet (IS-825, hardness 50 °, manufactured by IRUMAGAWA RUBBER CO., LTD.), the silicone rubber sheet cut to a width of 10 mm and a length of 90 mm is placed on the test piece, and pressed by sandwiching it. Leave to cool at 23°C for more than 1 hour, and then heat it with a dryer at 200°C for 3 minutes. Leave to cool at 23°C for more than 1 hour, then use a tensile testing machine to measure the force required to peel the copper foil from the tape at a speed of 300 mm/min and an angle of 90°, and visually confirm whether there is any paste on the adherend Agent residue. At this time, the substrate side of the single-sided adhesive tape was fixed to the SUS plate with a paper double-sided adhesive tape (No. 778 manufactured by Teraoka Manufacturing Co., Ltd.) for measurement.

The peeling of copper foil was evaluated according to the following criteria. (Peeling force of copper foil during heat peeling treatment) A: Natural peeling during heating, or the peeling force is less than 20% of the initial peeling force (good). B: The peeling force is 20% or more of the initial peeling force (bad). (Paste residue of copper foil during heat peeling treatment) A: No paste remains (good). B: Paste remains (bad).

[Table 3-1] Table 3-1 Adhesive Viscoelasticity of adhesive components Number of additions of F Maximum expansion temperature of F TFmax(℃) G'(*10^5 Pa) Tanδ 23℃ 170°C TFmax(℃) Example 1 Ac 2.98 0.90 0.019 30 192 2 Ac 2.98 0.90 0.019 5 192 3 Ac 2.98 0.90 0.019 10 192 4 Ac 2.98 0.90 0.019 50 192 5 Ac 5.21 2.89 0.002 30 192 6 Ac 4.58 0.98 0.017 30 192 7 Ac 6.01 2.96 0.013 30 192 8 Ac 1.27 0.49 0.023 30 192 9 Ac 4.84 4.10 0.003 30 192 10 Ac 3.66 2.66 0.006 30 192 11 Ac 0.93 0.57 0.024 30 192 12 Ac 2.03 2.42 0.003 30 192 13 Si 1.47 1.26 0.053 30 192 Comparative example 1 Ac 2.98 0.90 0.019 0 192 2 Ac 2.98 0.90 0.019 3 192 3 Ac 2.98 0.90 0.029 30 162 4 Ac 2.32 0.30 0.210 30 192 5 Ac 2.39 0.40 0.126 30 192 6 Ac 4.93 0.43 0.219 30 192 7 Ac 1.64 0.29 0.039 30 192 8 Ac 2.04 0.24 0.115 30 192 9 Si 8.82 0.40 0.532 30 192

[Table 3-2] Table 3-2 [Evaluation Results of Acrylic Double-Sided Thermal Peeling Adhesive Tape] No heat treatment (c) Initial (d) Heated peeling treatment Copper foil Copper plate Copper foil Copper plate Peeling force N/10 mm Peeling force N/10 mm Peeling force N/10 mm Paste residue Peeling force N/10 mm Paste residue Example 1 2.01 1.45 Natural peeling: A A Natural peeling: A A 2 3.50 2.31 Natural peeling: A A Natural peeling: A A 3 2.69 2.11 Natural peeling: A A Natural peeling: A A 4 0.83 1.19 Natural peeling: A A Natural peeling: A A 5 0.33 1.03 Natural peeling: A A Natural peeling: A A 6 1.70 1.46 Natural peeling: A A Natural peeling: A A 7 2.89 4.44 Natural peeling: A A Natural peeling: A A 8 1.99 1.06 Natural peeling: A A Natural peeling: A A 9 0.51 0.45 Natural peeling: A A Natural peeling: A A 10 0.86 0.82 Natural peeling: A A Natural peeling: A A 11 1.03 0.78 Natural peeling: A A Natural peeling: A A 12 0.25 0.26 Natural peeling: A A Natural peeling: A A Comparative example 1 5.53 3.27 5.36 (97%): B A 5.14 (157%): B A 2 3.47 2.68 Natural peeling: A A Natural peeling: A A 3 1.78 1.63 Natural peeling: A A 0.08 (5%): A A 4 3.10 1.92 4.98 (161%): B B 4.98 (259%): B B 5 3.13 2.13 1.83 (58%): B B 0.80 (38%): B B 6 2.37 1.57 3.38 (143%): B B 2.30 (146%): B B 7 2.13 1.18 Natural peeling: A A Natural peeling: A A 8 2.17 3.44 Natural peeling: A A Natural peeling: A A

[Table 3-3] [Evaluation Results of Acrylic Double-sided Thermal Peeling Adhesive Tape] Has heat treatment Comprehensive Evaluation (e) No heat peeling treatment (f) Heated peeling treatment Foam suppression Copper foil Copper plate Peeling force N/10 mm Paste residue Peeling force N/10 mm Paste residue Example 1 A Natural peeling: A A Natural peeling: A A A 2 A Natural peeling: A A Natural peeling: A A A 3 A Natural peeling: A A Natural peeling: A A A 4 A Natural peeling: A A Natural peeling: A A A 5 A Natural peeling: A A Natural peeling: A A A 6 A Natural peeling: A A Natural peeling: A A A 7 A Natural peeling: A A Natural peeling: A A A 8 A Natural peeling: A A Natural peeling: A A A 9 A Natural peeling: A A Natural peeling: A A A 10 A Natural peeling: A A Natural peeling: A A A 11 A Natural peeling: A A Natural peeling: A A A 12 A Natural peeling: A A Natural peeling: A A A Comparative example 1 B 2 A 1.59 (46%): B A 0.38 (14%): A A B 3 B B 4 B 5 B 6 B 7 B B 8 B B

[Table 3-4] Table 3-4 [Evaluation results of polysilicone heat-peelable single-sided adhesive tape] No heat treatment Has heat treatment Comprehensive Evaluation (g) Initial (h) Heated peeling treatment (i) No heat peeling treatment (j) With heat peeling treatment Copper foil Copper foil Foam suppression Copper foil Peeling force N/10 mm Peeling force N/10 mm Paste residue Peeling force N/10 mm Paste residue Example 13 0.52 Natural peeling: A A A Natural peeling: A A A Comparative example 9 0.80 0.78 (38%): B B B

[evaluation result] According to the evaluation results of Table 3-2 to Table 3-4, it can be seen that Examples 1 to 13 satisfying the requirements of the present invention have obtained good results: even after the hot pressing step at high temperature and long time, the heat peeling treatment is still carried out. It is easy to peel off, and the paste is not easy to remain on the adherend. Furthermore, even during hot pressing, the expansion of the thermally expandable particles can be suppressed.

In Comparative Example 1, since it did not contain heat-expandable particles, it was not easily peeled even if it was subjected to a heat peeling treatment. Regarding Comparative Example 2, when the heat-pressing process was not performed, the heat-peeling process was performed to facilitate peeling. However, since the amount of foaming agent added to the adhesive component is less than 4 parts, if the heat peeling treatment is performed after hot pressing at a high temperature for a long time, the peeling force against the copper foil assumed to be the substrate product component cannot be obtained. Fully reduce the effect.

Regarding Comparative Example 3, when the heat-pressing process was not performed, the heat-peeling process was performed to facilitate peeling. On the other hand, since the maximum expansion temperature of the heat-expandable particles is less than 170°C, it is impossible to suppress the expansion of the heat-expandable particles in high-temperature and long-term hot pressing.

In Comparative Examples 4 to 6 and Comparative Example 9, since the tanδ of the adhesive component at the maximum expansion temperature of the heat-expandable particles was higher than 0.120, they were not easily peeled after the heat peeling treatment even if the pressure was not applied for a long time at a high temperature.

In Comparative Examples 7 to 8, since the tanδ of the adhesive component at the maximum expansion temperature of the heat-expandable particles was less than 0.120, when the heat-pressing treatment was not performed, the heat-peeling treatment was easily performed. However, since the storage modulus G'at 170°C is less than 30,000 Pa, the expansion of thermally expandable particles cannot be suppressed during high-temperature and long-term hot pressing.

For example, in Patent Document 6, the range of the storage modulus G'of the heat-expandable adhesive layer at a relatively low temperature such as 23°C or 95°C is specified, and it may be used well within this range, but according to Table 3- The above evaluation results shown in 2~Table 3-4 show that although the storage modulus G'at room temperature is relatively high, the storage modulus G'at high temperature (for example, 170°C) is not necessarily high. Therefore, it can be considered that the technique disclosed in Patent Document 6 is suitable for the pressurization step at room temperature for a short period of time (for example, room temperature, 3M Pa, 3 seconds, 100 times in the examples). For the purpose of peeling, it needs to meet the parameters specified in the present invention when it is used in the high temperature and long time pressurization step. In addition, Examples 1 to 3 described in Patent Document 6 used low-temperature-expandable thermally expandable particles (according to the examples in the specification of Patent Document 6, foaming started at 120°C, and foaming and peeling occurred at 130°C) ), it can be assumed that the heat-pressing treatment at high temperature (for example, 170°C) cannot suppress the foaming of the heat-expandable particles. (Industrial availability)

The heat-peelable adhesive tape of the present invention can be effectively used in the manufacturing steps of electronic parts or semiconductor parts, such as temporary fixing of parts, fixing during transportation, reinforcement, protection, shielding, resin sealing and other steps that require high-temperature heating. Especially, it is very useful in the step of hardening the sealing resin, etc., which needs to be easily peeled off after the pressurizing step at high temperature and long time without leaving the paste.

1: Heat-peelable adhesive sheet 2: Substrate 3: Thermally expandable adhesive layer 4: Release the liner

Fig. 1 is a cross-sectional view schematically showing an example of the structure of the heat-peelable adhesive tape of the present invention in the thickness direction.

1: Heat-peelable adhesive sheet

2: Substrate

3: Thermally expandable adhesive layer

4: Release the liner

Claims (14)

A heat-peelable adhesive tape, which has a heat-expandable adhesive layer containing adhesive components and heat-expandable particles, and is characterized in that: The heat-expandable adhesive layer contains 4 parts by mass or more of the heat-expandable particles with respect to 100 parts by mass of the adhesive component, The maximum expansion temperature of the thermally expandable particles is 170°C or higher, and, In the dynamic viscoelasticity measurement of the above-mentioned adhesive components (temperature range -60℃～300℃, heating rate 10℃/min, frequency 10 Hz), (1) The tanδ at the maximum expansion temperature of the above thermally expandable particles is 0.120 or less, and (2) The storage modulus G'at 170°C is above 30,000 Pa. The heat-peelable adhesive tape according to claim 1, wherein the heat-expandable particles are contained in an amount of 5 parts by mass or more with respect to 100 parts by mass of the resin component contained in the heat-expandable adhesive layer. The heat-peelable adhesive tape of claim 1, wherein the heat-expandable particles are contained in a ratio of 7 parts by mass or more and less than 80 parts by mass relative to 100 parts by mass of the resin component contained in the heat-expandable adhesive layer. The heat-peelable adhesive tape of claim 1, wherein the adhesive component is any one of an acrylic adhesive, a rubber adhesive, and a silicone adhesive. The heat-peelable adhesive tape of claim 1, wherein the maximum thermal expansion temperature of the heat-expandable particles is 180°C or more and 320°C or less. The heat-peelable adhesive tape of claim 1, wherein the tanδ is 0.001 or more and 0.110 or less, and the storage modulus G'is 40,000 Pa or more and 1,000,000 Pa or less. Such as the heat-peelable adhesive tape of claim 1, which has a heat-expandable adhesive layer on at least one surface of the substrate. The heat-peelable adhesive tape of claim 1, which has the above-mentioned heat-expandable adhesive layer on both sides of the substrate. The heat-peelable adhesive tape of claim 7 or 8, wherein the base material is a resin film. The heat-peelable adhesive tape of claim 9, wherein the base material is a polyimide film. The heat-peelable adhesive tape of claim 1, which is used to temporarily fix the adherend in the hot pressing step of the adherend. The heat-peelable adhesive tape of claim 11, wherein the hot-pressing step includes a hot-pressing step with a temperature of 120-240°C, a time of 5 minutes to 10 hours, and a pressure of 5-40 kgf/cm ² by the hot pressing step After heating for peeling, the peeling force of the adherend is significantly reduced. A method for using a heat-peelable adhesive tape, which is a method of using a heat-peelable adhesive tape in the hot pressing process of an adherend, and is characterized in that it includes: The step of temporarily fixing the heat-peelable adhesive tape of claim 1 to the adherend; The step of hot-pressing the above-mentioned adherend with the adhesive tape temporarily fixed; The step of heating the heat-peelable adhesive tape temporarily fixed to the adherend subjected to the hot-pressing process to the temperature for peeling; and The step of peeling the heat-peelable adhesive tape heated to the temperature for peeling from the adherend. Such as the use method of the heat-peelable adhesive tape of claim 13, wherein the hot pressing step includes a hot pressing step at a temperature of 120 to 240°C, a time of 5 minutes to 10 hours, and a pressure of 5 to 40 kgf/cm ² .

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