JP6974479B2 - Silicone adhesive composition and adhesive tape - Google Patents

Description

INDUSTRIAL APPLICABILITY For example, in an adhesive tape used in the manufacturing process of electronic parts and semiconductor parts, the present invention has high adhesiveness to members when used in a high temperature environment, and no adhesive residue remains after use in a high temperature environment. The present invention relates to a peelable silicone-based pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape.

The silicone-based pressure-sensitive adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. Further, the adhesive tape having a silicone-based adhesive layer does not easily leave adhesive residue even when used in a high temperature environment. Therefore, such adhesive tapes are widely used, for example, in the manufacturing process of electronic parts and semiconductor parts, for applications such as protection of members and parts, masking, temporary fixing, fixing during transportation, and splices.

In recent years, tapes may be used at a higher temperature than before in the manufacturing process of these electronic parts and semiconductor parts. For example, when lead-free solder is used in the reflow process in mounting electronic components, the reflow temperature may be higher than before (for example, 280 to 300 ° C.). It is necessary to further improve the heat resistance of the silicone-based adhesive so that it can be peeled off without adhesive residue even after being used in such a high temperature environment.

Further, in the manufacturing process of electronic parts and semiconductor parts, the silicone-based adhesive is also required to have adhesiveness capable of strongly fixing the member during use in a high temperature environment. For example, in the manufacturing process of an electronic component, when fixing an FPC in a bent state, strong adhesiveness capable of suppressing the repulsion of FPCs (Flexible Printed Circuits) and continuing to fix the member is required.

Conventionally, many silicone-based adhesives and adhesive tapes that do not easily leave adhesive residue have been proposed. For example, Patent Document 1 discloses a silicone-based pressure-sensitive adhesive composition having no adhesive residue in a adhesive residue test at 250 to 290 ° C. Patent Document 2 discloses a silicone-based pressure-sensitive adhesive composition having no adhesive residue in a adhesive residue test at 250 ° C. Patent Document 3 discloses an adhesive tape for surface protection, which has a small increase in adhesive force when reflowed at 260 ° C. in the manufacturing process of a semiconductor component and has a small amount of foreign matter (adhesive residue) transferred to the component.

Patent Documents 1 to 3 relate to adhesive tapes used in the manufacturing process of electronic parts and semiconductor parts, and the temperature of the environment in which they are used is assumed to be 250 to 290 ° C, 250 ° C, and 260 ° C. However, in recent years, in the manufacturing process of electronic parts and semiconductor parts and other processes, the adhesive tape may be used at a temperature exceeding 290 ° C (for example, 300 ° C). When a conventional general adhesive tape is used in such a high temperature environment, adhesive residue is likely to occur at the time of peeling. Further, even with a conventional adhesive tape (Patent Documents 1 to 3) of a type that does not easily leave adhesive residue, if it is used in a temperature environment higher than expected, adhesive residue may occur at the time of peeling.

Further, in a high temperature environment, the cohesive force of the adhesive generally decreases remarkably. Therefore, when the member is fixed with the adhesive tape while suppressing the repulsion of the member in a high temperature environment, the adhesiveness of the adhesive tape is lowered, the repulsion of the member cannot be suppressed, and the member is peeled off at the interface between the adhesive and the adherend. Sometimes. For example, as shown in FIG. 2 (A), the electronic component material 12 is fixed to the carrier 13 with the adhesive tape 11, and the FPC 15 is fixed to the carrier 13 with the adhesive tape 14 as shown in FIG. 2 (B). .. In this case, as shown in FIG. 2C, the adhesive tape 14 cannot suppress the repulsion of the FPC 15 and may be peeled off from the carrier 13 in a high temperature process such as laminating parts or reflowing. In addition, the cohesive force inside the adhesive is weaker than the adhesive force at the interface between the adhesive and the adherend, and there is a possibility that peeling may occur while causing cohesive failure inside the adhesive. On the other hand, Patent Documents 1 and 2 do not mention adhesiveness in a high temperature environment. Since Patent Document 3 aims to suppress an increase in adhesive strength after use in a high temperature environment and allow light peeling, it is considered that it is not suitable for applications such as suppressing strong repulsion in a high temperature environment and adhering members. ..

Japanese Unexamined Patent Publication No. 2015-193803 Japanese Unexamined Patent Publication No. 2008-156497 Japanese Unexamined Patent Publication No. 2013-147540

The present inventors have developed to solve the above-mentioned problems of the conventional adhesive tape when used in a high temperature environment. That is, an object of the present invention is to provide a silicone-based pressure-sensitive adhesive composition and an adhesive tape which have high adhesiveness to a member when used in a high-temperature environment and can be peeled off without adhesive residue after use in a high-temperature environment. It is in.

As a result of diligent studies to achieve the above object, the present inventors have found that specific physical properties in the dynamic viscoelasticity measurement of the silicone-based pressure-sensitive adhesive composition after curing with an organic peroxide are in a high temperature environment (for example, 280 to 300 ° C.). ) We have found that it is related to various performances such as adhesiveness when used underneath and anti-glue residue after use, and have completed the present invention.

That is, the present invention includes a silicone structure in which the silicone component is cured by an organic peroxide, and dynamic viscoelasticity measurement after curing (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz). In
(1) Storage elastic modulus G'at 300 ° C is 12000 Pa or more,
(2) Tan δ at 300 ° C is 0.04 or more and 0.21 or less,
(3) Temperature The peak temperature of tan δ existing in the range of -60 ° C to 150 ° C is 6 ° C or higher and 60 ° C or lower .
The silicone component is a silicone- based pressure-sensitive adhesive composition containing silicone raw rubber and MQ resin.

Further, the present invention is an adhesive tape having an adhesive layer made of the above-mentioned silicone-based adhesive composition.

According to the present invention, there is provided a silicone-based pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape which have high adhesiveness to a member when used in a high-temperature environment and can be peeled off without adhesive residue after use in a high-temperature environment. In particular, since the adhesive tape of the present invention has the above-mentioned specific adhesive layer, protection, masking, and provisional of an adherend are used in a process that requires treatment in a high temperature environment, for example, a manufacturing process of an electronic component or a semiconductor component. It is very useful for applications such as fixing, fixing during transportation, and splices.

It is a schematic cross-sectional view for demonstrating the evaluation method of the resilience test in an Example. It is a schematic cross-sectional view for demonstrating the peeling in the high temperature process of the conventional adhesive tape.

<Adhesive composition>
The pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive containing a silicone structure in which the silicone component is cured by an organic peroxide as a main component . In the dynamic viscoelasticity measurement (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz) of the silicone-based pressure-sensitive adhesive composition after curing, (1) the storage elastic modulus G'at 300 ° C was determined. It is 12000 Pa or more, preferably 15,000 Pa or more, more preferably 18,000 Pa or more, and (2) the tan δ at 300 ° C. is 0.04 or more and 0.21 or less, preferably 0.06 or more and 0.21 or less, more preferably 0.21 or less. It is 08 or more and 0.21 or less, and (3) the peak temperature of tan δ appearing in the temperature range of -60 ° C to 150 ° C is 6 ° C or more and 60 ° C or less, preferably 9 ° C or more and 57 ° C or less, more preferably 12. ° C or higher and 54 ° C or lower. Specific methods for measuring the peak temperatures of the storage elastic moduli G', tan δ and tan δ will be described in the column of Examples described later.

If the storage elastic modulus G', tan δ at 300 ° C. and the peak temperature of tan δ appearing in the temperature range of -60 ° C to 150 ° C. are within the specific range of the present invention, use in a high temperature environment (for example, 300 ° C.). However, it has strong adhesion to parts during use and can be peeled off without adhesive residue after use. If the storage elastic modulus G'at 300 ° C. is less than 12000 Pa, the adhesive deteriorates severely during use in a high temperature environment, and therefore, when peeled off after high temperature heating, adhesive residue is likely to remain. Further, when the storage elastic modulus G'is extremely low, the cohesive force of the pressure-sensitive adhesive is remarkably weakened during high-temperature heating, and the pressure-sensitive adhesive may be peeled off from the member due to the cohesive failure of the pressure-sensitive adhesive during the process.

Even if the storage elastic modulus G'at 300 ° C is 12000 Pa or more, if the tan δ at 300 ° C is less than 0.04, that is, if the viscosity term is significantly lower than the elastic term, the adhesive is applied to the adherend. It is thought that it is difficult to get wet and spread. Therefore, peeling at the interface between the adhesive and the adherend due to insufficient adhesiveness is likely to occur. On the other hand, when the tan δ at 300 ° C. exceeds 0.21, that is, when the viscosity term is significantly higher than the elastic term, the heat deterioration is severe and the glue tends to remain when peeled off after high temperature heating.

Even if the storage elastic modulus G'and tan δ at 300 ° C are in an appropriate range, if the peak temperature of tan δ existing in the temperature range of -60 ° C to 150 ° C exceeds 60 ° C or is less than 6 ° C, the temperature is high. When peeled off after drying, there is a tendency for adhesive to remain on the edges, albeit slightly.

The silicone component of the silicone-based pressure-sensitive adhesive used in the present invention preferably contains a raw silicone rubber and an MQ resin. Specific examples mainly silicone raw rubber (D units polymeric long-chain polydimethylsiloxane having a structure of _{[(CH 3) 2 SiO]} ) and MQ resin (M units [(CH _{3) 3} SiO _{1 / 2} ] and a polymer of a silicone resin having a three-dimensional structure having a structure consisting of a Q unit [SiO _4/2]). Such a pressure-sensitive adhesive containing silicone raw rubber and MQ resin is superior in adhesiveness as compared with silicone raw rubber alone. Further, by changing the ratio of the raw silicone rubber and the MQ resin in the adhesive, it is possible to control the basic adhesive properties such as adhesive force, holding force, and tack. Silicone-based pressure-sensitive adhesives are roughly classified into addition-curing type and peroxide-curing type depending on the curing mechanism, and the peroxide-curing type silicone-based pressure-sensitive adhesive is used in the present invention.

The peroxide-curable silicone-based pressure-sensitive adhesive contains, for example, a main agent made of silicone raw rubber containing no alkenyl group and an MQ resin. Then, an organic peroxide such as benzoyl peroxide is added as a curing agent, the solvent is removed, and then the mixture is heated at a high temperature to cure.

The silicone raw rubber contained in the peroxide curing type silicone adhesive, D units [(CH _{3) 2} SiO] to that introduced a phenyl group instead of the methyl group _{(i.e., [(CH 3) (C} 6 _{H 5) SiO] [(C} 6 H 5) 2 SiO] may be used.

The organic peroxide used as a curing agent is not particularly limited as long as it decomposes to generate free oxygen radicals. In particular, dibenzoyl peroxide and its derivatives are preferable. Specific examples include dibenzoyl peroxide, 4,4'-dimethyldibenzoyl peroxide, 3,3'-dimethyldibenzoyl peroxide, 2,2'-dimethyldibenzoyl peroxide, 2,2', 4, Examples thereof include 4'-tetrachlorodibenzoyl peroxide and cumyl peroxide.

The form of the curing agent composed of organic peroxide is not particularly limited. The organic peroxide may be used as it is, or may be used in a form diluted in an organic solvent, dispersed in water, or dispersed in silicone oil to form a paste. Further, the organic peroxide may be used alone or in combination of two or more.

Free oxygen radicals that contribute to the curing reaction are generated by the decomposition of organic peroxides. The theoretical amount (that is, the theoretical active oxygen amount of the organic peroxide) is calculated by the following formula (1).
Theoretical amount of organic peroxide (%) = (number of peroxide bonds x 16 / molecular weight of organic peroxide) x 100 (%) (1)

As the amount of the organic peroxide added increases, the crosslink density increases, so that the storage elastic modulus G'is likely to increase and the tan δ tends to decrease. The organic peroxide may be added in an amount P such that the storage elastic modulus G'and tan δ at 300 ° C. of the cured pressure-sensitive adhesive composition are within the range of the present invention. The suitable amount P (parts by mass) of the organic peroxide varies depending on the conditions such as the curing temperature, the decomposition temperature of the organic peroxide, the ratio of the raw silicone rubber to the MQ resin, and the molecular weight of the silicone component. It may be decided as appropriate. However, the amount of organic peroxide P (parts by mass) is the amount of organic peroxide P (parts by mass) and the theory of organic peroxide represented by the above formula (1) with respect to 100 parts by mass of the silicone component. The product PA (parts by mass) of the amount of active oxygen A (%) is preferably 0.090 to 0.300 parts by mass, more preferably 0.120 to 0.280 parts by mass, and particularly preferably 0.150 to 0.260. It is recommended to add it so that it becomes a mass part. If the amount of PA is too high, coloring or adhesive residue, which is considered to be caused by the residue of unreacted organic peroxide, may occur.

The pressure-sensitive adhesive composition of the present invention may be blended with an addition-curable silicone-based pressure-sensitive adhesive for the purpose of improving various properties. However, it is necessary to appropriately select the type and amount of the addition-curable silicone-based pressure-sensitive adhesive so that the effects of the invention are not impaired.

The addition-curable silicone-based pressure-sensitive adhesive contains, for example, a main agent made of a silicone raw rubber containing an alkenyl group, an MQ resin, and a cross-linking agent made of a polyorganosiloxane containing a SiH group. Then, it is cured by heating under a platinum catalyst and causing a cross-linking reaction. The silicone raw rubber containing an alkenyl group is typically a polyorganosiloxane having at least two alkenyl groups (for example, vinyl groups) bonded to a silicon atom in one molecule. The polyorganosiloxane containing a SiH group is typically a polyorganosiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule.

Additives may be added to the pressure-sensitive adhesive composition of the present invention for the purpose of improving various properties. Specific examples of the additive include inorganic additives such as carbon black, silica, and platinum-based compounds; polyorganosiloxanes such as silicone resin, polydimethylsiloxane, and polydimethylphenylsiloxane; phenol-based antioxidants and amine-based antioxidants. Antioxidants such as; silane coupling agents; antistatic agents such as cationic surfactants, anionic surfactants, nonionic surfactants and the like. However, it is necessary to appropriately select the type and amount of the additive so that the effect of the invention is not impaired.

<Adhesive tape>
The adhesive tape of the present invention is an adhesive tape having an adhesive layer composed of the pressure-sensitive adhesive composition of the present invention described above on at least one side of a base material, and typically, the pressure-sensitive adhesive layer is provided on one side or both sides of a base material film. It is an adhesive tape having the above, or a baseless type adhesive tape without a base material. Of these, an adhesive tape having an adhesive layer on at least one side of the base material is preferable. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 5 to 125 μm, more preferably 10 to 100 μm, and particularly preferably 15 to 75 μm.

A solvent may be added in order to reduce the viscosity of the pressure-sensitive adhesive composition at the time of application. Specific examples of the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane and isoparaffin; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate. ; Examples include ether solvents such as diisopropyl ether and 1,4-dioxane.

The coating method is not particularly limited, and a known method may be used. Specific examples thereof include coating using a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater or gravure coater; screen coating; immersion coating; cast coating. Be done.

The base material is not particularly limited, but a film-like base material is preferable. In particular, a resin film having high heat resistance that can be processed at a high temperature is preferable. Specific examples thereof include polyimide (PI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamideimide (PAI), and polyethersulphon (PAI). Examples thereof include resin films such as PES) and polytetrafluoroethylene (PTFE). These films can be used as a single layer or a laminated film having two or more layers. Of these, a polyimide film is preferable. The thickness of the base material is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm, and particularly preferably 5 to 125 μm.

If necessary, an easy-adhesion treatment may be applied to the surface of the base material on which the pressure-sensitive adhesive layer is provided. Examples of the easy-adhesion treatment include a primer treatment, a corona treatment, an etching treatment, a plasma treatment, and a sandblast treatment.

The surface of the base material opposite to the pressure-sensitive adhesive layer may be surface-treated such as antistatic. Examples of the antistatic treatment include treatment with an antistatic agent such as a cationic surfactant, anionic surfactant, and nonionic surfactant.

The adhesive tape of the present invention may be provided with a release liner. The peeling liner is for protecting the adhesive layer of the adhesive tape, and is peeled off immediately before sticking to expose the adhesive and stick the adhesive tape to the adherend. The type of the release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include those obtained by subjecting the surface of a base material such as high-quality paper, glassine paper, or synthetic resin film to a mold release agent treatment. For the mold release agent treatment, a mold release agent such as a fluorine-substituted alkyl-modified silicone resin may be used. In particular, as the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer, a polyethylene tale phthalate film whose surface is mold-released with a fluorine-substituted alkyl-modified silicone resin is preferable. Further, although the peeling may be heavy, a resin film that has not been subjected to the mold release treatment may be used as the peeling liner. Specific examples thereof include a polyimide (PI) film, a polyethylene terephthalate (PET) film, a polyethylene (PE) film, and a polypropylene (PP) film.

Since the adhesive tape of the present invention has excellent heat resistance as described above, it is particularly useful for applications used in a high temperature environment (preferably exceeding 280 ° C., more preferably 290 ° C. or higher, particularly preferably 300 ° C. or higher). .. Specific examples thereof include applications such as protection of members and parts, masking, temporary fixing, fixing during transportation, and splices in the manufacturing process of electronic parts and semiconductor parts.

However, the use of the adhesive tape of the present invention is not limited to the use in the high temperature environment as described above. For example, in recent years, plasma treatment may be performed in the manufacturing process of various electronic components. The temperature itself during plasma treatment is about room temperature to 120 ° C, but in that case, the side surface of the end of the adhesive tape may be directly exposed to plasma, and as a result, adhesive residue is likely to occur at the end. .. On the other hand, since the adhesive tape of the present invention has a characteristic that adhesive does not easily remain, the problem can be reduced even when it is used in a process including plasma treatment. That is, the adhesive tape of the present invention is also very useful in applications where the problem of adhesive residue occurs due to factors other than temperature.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples. In the following description, "part" means "part by mass".

<Example 1>
First, a plurality of prototypes (I to VIII) of a peroxide-curable silicone-based pressure-sensitive adhesive stock solution were prepared. In these plurality of prototypes, the peak temperatures of the stored elastic moduli G', tan δ and tan δ after curing, which are measured by the method described later, show various values by appropriately changing the mixing ratio of MQ resin to the raw silicone rubber. It is a prototype of the adhesive adjusted in this way. All of these prototypes use the same type of raw silicone rubber and MQ resin.

In Example 1, of these plurality of prototypes, the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I) in which the tanδ peak temperature, the storage elastic modulus at 300 ° C., and the tanδ at 300 ° C. become specific values described later. ) Was selected.

Then, 100 parts of the peroxide curing type silicone pressure-sensitive adhesive stock solution (I) having a solid content concentration of 50% by mass, 67 parts of toluene as a diluting solvent, and organic peroxide type curing manufactured by Nichiyu Co., Ltd. as an organic peroxide. 5.0 parts of the agent (Nipper (registered trademark) BMT-K40, concentration of organic peroxide: 40%, theoretical active oxygen amount in organic peroxide: 6.05%) is uniformly mixed, and the pressure-sensitive adhesive liquid is mixed. (1) was obtained. In this pressure-sensitive adhesive liquid (1), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.242 parts.

When the dynamic viscoelasticity measurement described later was performed on this pressure-sensitive adhesive liquid (1), the peak temperature of tan δ was 28 ° C., the storage elastic modulus G'at 300 ° C. was 51358 Pa, and the tan δ at 300 ° C. was 0.07. Met.

Next, the pressure-sensitive adhesive liquid (1) was applied to one side of a primer-treated polyimide (PI) film having a thickness of 25 μm so that the thickness of the pressure-sensitive adhesive layer after drying was 38 μm, and 60 in a drying furnace. The solvent was removed by drying at ° C. for 1 minute, and the adhesive layer was formed by heating and curing at 200 ° C. for 2 minutes. Then, as a release liner, a polyethylene terephthalate (PET) film having a thickness of 50 μm treated with a fluorine-substituted alkyl-modified silicone resin was attached to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.

[Dynamic Viscoelasticity Measurement of Adhesive Composition]
The pressure-sensitive adhesive liquid (1) is applied onto the release liner so that the thickness after drying is 50 μm. Subsequently, the solvent is removed by drying in a drying oven at 60 ° C. for 1 minute. Then, the silicone component is cured by heating at 200 ° C. for 2 minutes to form a pressure-sensitive adhesive layer made of the cured silicone-based pressure-sensitive adhesive composition. By repeating this operation a plurality of times, a laminated body of a pressure-sensitive adhesive layer having a thickness of 2 mm is formed, and this is used as a measurement sample.

The measurement sample is sandwiched between parallel disks (φ8 mm), and the temperature rise rate is 10 ° C./min while applying shear strain at a frequency of 10 Hz using a dynamic viscoelasticity measuring device (manufactured by Rheometric Scientific, device name RDAIII). The storage elastic modulus (G') and the loss elastic modulus (G ″) are measured in the range of −60 ° C. to 300 ° C., and the storage elastic modulus (G ′) and the loss elastic modulus (G ″) are as follows. The loss tangent tan δ is calculated by the formula of.
tan δ = modulus of loss (G'') / modulus of storage (G')

Further, the calculated loss tangent (tan δ) is plotted against the temperature to create a loss tangent curve, and the temperature at which the loss tangent (tan δ) peaks in the range of −60 ° C. to 150 ° C. is recorded.

<Example 2>
The pressure-sensitive adhesive liquid (2) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 3.75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (2), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (2), the peak temperature of tan δ was 29 ° C., the storage elastic modulus G'at 300 ° C. was 41968Pa, and the tan δ at 300 ° C. was 0.11.

<Example 3>
The pressure-sensitive adhesive liquid (3) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 3 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (3), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.157 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (3), the temperature of tan δ was 24 ° C., the storage elastic modulus G'at 300 ° C. was 32229 Pa, and the tan δ at 300 ° C. was 0.16. ..

<Example 4>
3. Use the peroxide-curable silicone-based adhesive stock solution (II) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I) to reduce the amount of organic peroxide. The pressure-sensitive adhesive liquid (4) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (4), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (4), the tan δ peak temperature was 9 ° C., the storage elastic modulus G'at 300 ° C. was 31491 Pa, and the tan δ at 300 ° C. was 0.06.

<Example 5>
3. Use the peroxide-curable silicone-based adhesive stock solution (III) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I), and adjust the amount of organic peroxide. The pressure-sensitive adhesive liquid (5) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (5), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (5), the peak temperature of tan δ was 57 ° C., the storage elastic modulus G'at 300 ° C. was 33843 Pa, and the tan δ at 300 ° C. was 0.14.

<Example 6>
100 parts of stock solution (I) of peroxide-curing silicone-based pressure-sensitive adhesive having a solid content concentration of 50% by mass, 67 parts of toluene as a diluting solvent, and an organic peroxide-type curing agent (Niper) manufactured by Nichiyu Co., Ltd. as an organic peroxide. (Registered trademark) BMT-K40, concentration of organic peroxide: 40%, theoretical amount of active oxygen in organic peroxide: 6.05%) 5.0 parts, CAT-PL-50T (Shinetsu Kagaku) as a platinum compound (Manufactured by Kogyo Co., Ltd.) 0.5 parts were uniformly mixed to obtain a pressure-sensitive adhesive liquid (6). An adhesive tape was produced in the same manner as in Example 1 except that the adhesive liquid (6) was used. In the pressure-sensitive adhesive liquid (6), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.242 parts. When dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (6), the peak temperature of tan δ was 71797 Pa at a peak temperature of 30 ° C. and 300 ° C., and tan δ at 300 ° C. was 0.07.

<Comparative Example 1>
The pressure-sensitive adhesive liquid (C1) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 7.5 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C1), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.363 part. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C1), the peak temperature of tan δ was 28 ° C., the storage elastic modulus G'at 300 ° C. was 65375 Pa, and the tan δ at 300 ° C. was 0.03.

<Comparative Example 2>
The pressure-sensitive adhesive liquid (C2) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 2.5 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C2), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.121 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C2), the peak temperature of tan δ was 32 ° C., the storage elastic modulus G'at 300 ° C. was 23081 Pa, and the tan δ at 300 ° C. was 0.22.

<Comparative Example 3>
The pressure-sensitive adhesive liquid (C3) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 1.25 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C3), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.061 part. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C3), the peak temperature of tan δ was 32 ° C., the storage elastic modulus G'at 300 ° C. was 6910 Pa, and the tan δ at 300 ° C. was 0.54.

<Comparative Example 4>
The pressure-sensitive adhesive liquid (C4) was prepared in the same manner as in Example 1 except that the amount of the organic peroxide was changed to 0.625 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C4), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.030 part. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C4), the peak temperature of tan δ was 32 ° C., the storage elastic modulus G'at 300 ° C. was 616 Pa, and the tan δ at 300 ° C. was 1.39.

<Comparative Example 5>
3. Use the peroxide-curable silicone-based adhesive stock solution (IV) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I), and adjust the amount of organic peroxide. The pressure-sensitive adhesive liquid (C5) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C5), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C5), the peak temperature of tan δ was -17 ° C, the storage elastic modulus G'at 300 ° C was 82461 Pa, and tan δ at 300 ° C was 0.05. ..

<Comparative Example 6>
3. Use the peroxide-curable silicone-based adhesive stock solution (V) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I), and adjust the amount of organic peroxide. The pressure-sensitive adhesive liquid (C6) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C6), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C6), the peak temperature of tan δ was 87 ° C., the storage elastic modulus G'at 300 ° C. was 15214 Pa, and the tan δ at 300 ° C. was 0.18.

<Comparative Example 7>
3. Use a peroxide-curable silicone-based adhesive stock solution (VI) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I) to reduce the amount of organic peroxide. The pressure-sensitive adhesive liquid (C7) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C7), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C7), the peak temperature of tan δ was 32 ° C., the storage elastic modulus G'at 300 ° C. was 10545 Pa, and the tan δ at 300 ° C. was 0.24.

<Comparative Example 8>
3. Use a peroxide-curable silicone-based adhesive stock solution (VII) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based adhesive stock solution (I) to reduce the amount of organic peroxide. The pressure-sensitive adhesive liquid (C8) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C8), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C8), the peak temperature of tan δ was 51 ° C., the storage elastic modulus G'at 300 ° C. was 6294 Pa, and the tan δ at 300 ° C. was 0.28.

<Comparative Example 9>
3. Use the peroxide-curable silicone-based adhesive stock solution (VIII) (solid content concentration 50% by mass) instead of the peroxide-curable silicone-based pressure-sensitive adhesive stock solution (I), and adjust the amount of organic peroxide. The pressure-sensitive adhesive liquid (C8) was prepared in the same manner as in Example 1 except that it was changed to 75 parts, and a pressure-sensitive adhesive tape was prepared. In the pressure-sensitive adhesive liquid (C8), the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.182 parts. When the dynamic viscoelasticity was measured for the pressure-sensitive adhesive liquid (C8), the peak temperature of tan δ was 51 ° C., the storage elastic modulus G'at 300 ° C. was 9806 Pa, and the tan δ at 300 ° C. was 0.20.

The following evaluations were performed on the adhesive tapes of the above Examples and Comparative Examples. The results are shown in Table 1.

[Adhesive strength against SUS at room temperature (23 ° C) and adhesive residue]
Adhesive tape cut to a width of 20 mm was attached to a polished SUS plate, reciprocated once with a roller covered with a rubber layer weighing 2 kg, crimped, and left in a 23 ° C. environment for 20 to 40 minutes. Then, a tensile tester was used to measure the force required to peel the tape at a speed of 300 mm / min at an angle of 180 °. In addition, the presence or absence of adhesive residue on the SUS plate after peeling was visually confirmed and evaluated according to the following criteria.
◯: No glue residue.
Δ: There is a slight adhesive residue only at the pasted end.
×: There is adhesive residue.

[Adhesive strength against SUS and adhesive residue after drying and heating at 280 ° C]
Adhesive tape cut to a width of 20 mm is attached to a heat-resistant polished SUS plate, reciprocated once with a roller covered with a rubber layer weighing 2 kg, crimped, left at room temperature (23 ° C) for 20 minutes, and at 280 ° C. It was heated in a dryer for 1 hour. This was taken out and allowed to cool at room temperature (23 ° C.). Then, using a tensile tester, the force (adhesive force) required to peel the tape at an angle of 180 ° at a speed of 300 mm / min was measured. In addition, the presence or absence of adhesive residue on the SUS plate after peeling was visually confirmed and evaluated according to the above criteria.

[Adhesive strength against SUS and adhesive residue after reflow at 300 ° C]
An adhesive tape cut to a width of 20 mm was attached to a heat-resistant polished SUS plate, crimped by reciprocating once with a roller covered with a rubber layer weighing 2 kg, and heated in a reflow furnace at 300 ° C. for 10 minutes. Then, using a tensile tester, the force (adhesive force) required to peel the tape at an angle of 180 ° at a speed of 300 mm / min was measured. In addition, the presence or absence of adhesive residue on the SUS plate after peeling was visually confirmed and evaluated according to the above criteria.

[Repulsion resistance test]
As shown in FIG. 1 (A), a double-sided tape 2 (manufactured by Teraoka Seisakusho Co., Ltd., No. 760H # 25) was attached to the lower surface of the polished SUS plate 1. Further, a polyimide film 3 (Kapton 500H) having a width of 25 mm, a length of 90 mm, and a thickness of 0.125 mm was attached to the lower surface of the double-sided tape 2 so that the end portion having a length of 40 mm protruded. Next, as shown in FIG. 1 (B), the protruding portion of the polyimide film 3 was bent at a position 10 mm from the end of the SUS plate 1, and this was fixed with an adhesive tape 4 having a width of 20 mm, and this was used as a sample. Then, each sample was left at room temperature (23 ° C.) for 1 hour in a dryer at 280 ° C. or for 10 minutes in a reflow oven at 300 ° C. Each sample was taken out, the peeling distance a of the adhesive tape 4 shown in FIG. 1C was measured, and evaluated according to the following criteria. ○: The peeling distance a was within 5 mm Δ: The peeling distance a was more than 5 mm and within 10 mm. X: The peeled distance a exceeds 10 mm

[comprehensive evaluation]
The results of each of the above measurements were comprehensively evaluated according to the following criteria.
○: Those that were ○ in all measurements △: Those that did not have × but had △ ×: Those that had even one ×

<Evaluation result>
As shown in Table 1, the adhesive tapes of Examples 1 to 6 do not leave adhesive residue even when peeled off after heating at 280 to 300 ° C., and also have adhesiveness capable of withstanding the repulsion of members during heating and suppressing peeling. showed that.

In Comparative Example 1, the storage elastic modulus G'at 300 ° C. is sufficiently high, and the peak temperature of tan δ is also within an appropriate range. However, since the tan δ at 300 ° C. is too low, the adhesiveness to the member is low, and significant peeling occurs in the repulsion resistance test in a high temperature environment. In addition, since the PA portion was more than the appropriate range, a slight adhesive residue was generated at the pasted end portion when the PA portion was peeled off after high temperature heating.

In Comparative Example 2, the storage elastic modulus G'at 300 ° C. is sufficiently high, and the peak temperature of tan δ is also within an appropriate range. However, since tan δ at 300 ° C. was too high, adhesive residue was generated when the tan δ was peeled off after heating at 300 ° C.

In Comparative Examples 3 and 4, the peak temperature of tan δ is within an appropriate range. However, since the storage elastic modulus G'at 300 ° C. was too low and the tan δ at 300 ° C. was too high, peeling due to cohesive fracture occurred in the repulsion resistance test in a high temperature environment. In addition, adhesive residue was generated even after peeling after high temperature heating.

In Comparative Examples 5 and 6, the storage elastic modulus G'is sufficiently high, and the tan δ at 300 ° C. is also within an appropriate range. However, in Comparative Example 5, the peak temperature of tan δ was too low, and in Comparative Example 6, the peak temperature of tan δ was too high, so that a small amount of adhesive residue was generated at the pasted end.

In Comparative Examples 7 and 8, the peak temperature of tan δ is within an appropriate range. However, since the storage elastic modulus G'at 300 ° C. was too low and the tan δ was too high, adhesive residue was generated after high temperature heating.

In Comparative Example 9, the peak temperature of tan δ is also within an appropriate range, and tan δ at 300 ° C. is also within an appropriate range. However, since the storage elastic modulus G'at 300 ° C. was too low, adhesive residue was generated after high temperature heating.

The pressure-sensitive adhesive composition of the present invention is particularly useful as a material for forming a pressure-sensitive adhesive layer of, for example, a pressure-sensitive adhesive tape. The adhesive tape of the present invention is extremely suitable for applications such as protection of adherends, masking, temporary fixing, fixing during transportation, and splices in processes that require processing in a high temperature environment, for example, in the manufacturing process of electronic parts and semiconductor parts. It is useful for. Further, it is very useful in applications where the problem of adhesive residue occurs due to factors other than temperature, such as a process including plasma treatment.

1 SUS plate 2 Double-sided tape 3 Polyimide film 4 Adhesive tape 11 Adhesive tape 12 Electronic component material 13 Transporter 14 Adhesive tape 15 FPC

Claims (10)

In the dynamic viscoelastic measurement after curing (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz), the silicone component contains a silicone structure cured by an organic peroxide.
(1) Storage elastic modulus G'at 300 ° C is 12000 Pa or more,
(2) Tan δ at 300 ° C is 0.04 or more and 0.21 or less,
(3) Temperature The peak temperature of tan δ existing in the range of -60 ° C to 150 ° C is 6 ° C or higher and 60 ° C or lower .
A silicone-based pressure-sensitive adhesive composition containing a silicone raw rubber and an MQ resin as a silicone component. In dynamic viscoelasticity measurement (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz)
(1') The silicone-based pressure-sensitive adhesive composition according to claim 1, wherein the storage elastic modulus G'at 300 ° C. is 15,000 Pa or more. In dynamic viscoelasticity measurement (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz)
(2') The silicone-based pressure-sensitive adhesive composition according to claim 1, wherein the tan δ at 300 ° C. is 0.06 or more and 0.21 or less. In dynamic viscoelasticity measurement (temperature range -60 ° C to 300 ° C, heating rate 10 ° C / min, frequency 10 Hz)
(3') The silicone-based pressure-sensitive adhesive composition according to claim 1, wherein the peak temperature of tan δ existing in the temperature range of −60 ° C. to 150 ° C. is 9 ° C. or higher and 57 ° C. or lower. The product PA (mass part) of the amount P (mass part) of the organic peroxide and the theoretical active oxygen amount A (%) of the organic peroxide represented by the following formula (1) is 100 parts by mass of the silicone component. The silicone-based pressure-sensitive adhesive composition according to claim 1, which is 0.090 part by mass or more and 0.30 part by mass or less.
Theoretical amount of organic peroxide (%) = (number of peroxide bonds x 16 / molecular weight of organic peroxide) x 100 (%) (1) An adhesive tape having an adhesive layer made of the silicone-based adhesive composition according to claim 1. The adhesive tape according to claim 6, which has an adhesive layer on at least one side of the base material. The adhesive tape according to claim 7 , wherein the base material is a resin film. Resin films include polyimide (PI) film, polyether ether ketone (PEEK) film, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polyphenylene sulfide (PPS) film, polyamideimide (PAI) film, and poly. The adhesive tape according to claim 8, which is a film selected from the group consisting of an ether sulfone (PES) film and a polytetrafluoroethylene (PTFE) film. The adhesive tape according to claim 6, which is a heat-resistant adhesive tape used in a high temperature environment exceeding 290 ° C.

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