WO2021199355A1 - Resin composition and adhesive tape - Google Patents

Resin composition and adhesive tape Download PDF

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Publication number
WO2021199355A1
WO2021199355A1 PCT/JP2020/014952 JP2020014952W WO2021199355A1 WO 2021199355 A1 WO2021199355 A1 WO 2021199355A1 JP 2020014952 W JP2020014952 W JP 2020014952W WO 2021199355 A1 WO2021199355 A1 WO 2021199355A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive
organic peroxide
resin composition
Prior art date
Application number
PCT/JP2020/014952
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French (fr)
Japanese (ja)
Inventor
靖史 土屋
彰大 加藤
Original Assignee
株式会社寺岡製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社寺岡製作所 filed Critical 株式会社寺岡製作所
Priority to CN202080099412.9A priority Critical patent/CN115362218B/en
Priority to KR1020227038169A priority patent/KR20230004554A/en
Priority to PCT/JP2020/014952 priority patent/WO2021199355A1/en
Priority to JP2022511418A priority patent/JPWO2021199355A1/ja
Priority to TW110109897A priority patent/TW202144504A/en
Publication of WO2021199355A1 publication Critical patent/WO2021199355A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to, for example, a resin composition and an adhesive tape having excellent dimensional stability and suppressed adhesive residue when used in a manufacturing process of electronic parts and semiconductor parts.
  • 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 pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled off, especially even when used in a high-temperature environment. Therefore, such adhesive tapes are widely used, for example, in the manufacturing process of electrical / electronic parts and semiconductor parts, for applications such as protection of members and parts, masking, temporary fixing, fixing during transportation, and splices.
  • a high load and a high temperature environment may occur due to the molding of the parts.
  • a fiber-reinforced prepreg impregnated with an uncured resin is laminated as an adhesive layer between circuit laminates on which a circuit pattern has been formed on the surface, and the temperature is high (for example, 180 ° C. or higher).
  • the temperature is high (for example, 180 ° C. or higher).
  • a pressure for example, 20 kg / cm 2 or more
  • a long time for example, 2 hours or more
  • the adhesive residue due to the dimensional change of the adhesive in the heat pressing process tends to be reduced by reducing the thickness of the adhesive layer of the tape.
  • the thickness of the pressure-sensitive adhesive layer is reduced, the cohesive force in the thickness direction is reduced, and adhesive residue may be generated when the tape is peeled off after the step.
  • the thickness of the pressure-sensitive adhesive layer is increased, the dimensional stability may be lowered and the amount of glue squeezed out during heat pressing may be increased.
  • the dimensional stability during the high temperature process (prevention of glue squeeze out) and the prevention of adhesive residue after the high temperature process have a contradictory relationship, and it is a characteristic that it is difficult to achieve both.
  • Patent Document 1 discloses a porous fluororesin sheet for use as a release protective sheet between a circuit fixing jig and a laminated circuit board in a laminated press process relating to a printed laminated circuit board.
  • this release protective sheet does not have an adhesive layer, it is not an adhesive tape. That is, since it does not have a fixing force to a specific part, it is not possible to selectively mask the part to be protected. Therefore, when this release protective sheet is used, it is necessary to use it on the entire surface to be protected, which is disadvantageous in terms of cost.
  • Patent Document 2 discloses an adhesive tape having at least a fluororesin-based film and an adhesive layer for forming a release surface.
  • this adhesive tape is an adhesive tape for mold release, and dimensional stability and adhesive residue during a high temperature process have not been studied.
  • the heat press test conditions for this adhesive tape are 150 ° C., pressure 5 kg / cm 2 , and 20 minutes press, and all the conditions are different from a general heat press step such as a heat press step for a laminated substrate. It is a loose condition.
  • Patent Document 3 discloses a silicone-based pressure-sensitive adhesive composition containing both a siloxane-based cross-linking agent having a SiH group and a peroxide-based cross-linking agent as the cross-linking agent.
  • this silicone-based pressure-sensitive adhesive composition remains in the silicone-based pressure-sensitive adhesive composition in an unreacted state of the peroxide-based cross-linking agent until it is used in the process. Therefore, it is expected that the peroxide-based cross-linking agent will gradually react during the process up to use such as manufacturing, storage, shipping, transportation, and customer storage. That is, its characteristics change before it is actually used in the process, which is disadvantageous in terms of stability over time.
  • an object of the present invention is a resin composition and adhesive having excellent dimensional stability when used in a high load / high temperature environment and suppressing adhesive residue when peeling after use in a high load / high temperature environment. To provide the tape.
  • the present invention contains a silicone raw rubber containing an alkenyl group, an MQ resin, a cross-linking agent, a platinum catalyst, and an organic peroxide.
  • the gel fraction after cross-linking is 45% or more and 60% or less.
  • the present invention is an adhesive tape having an adhesive layer composed of the resin composition after cross-linking.
  • the gel fraction of the pressure-sensitive adhesive layer is 45% or more and 60% or less.
  • the storage elastic modulus of the pressure-sensitive adhesive layer at 200 ° C. is 100,000 Pa or more and 1,000,000 Pa or less, and
  • the pressure-sensitive adhesive tape has a thickness of 2 ⁇ m or more and 10 ⁇ m or less.
  • a resin composition and an adhesive tape having excellent dimensional stability when used in a high load / high temperature environment and suppressing adhesive residue when peeling after being used in a high load / high temperature environment. Can be provided.
  • the resin composition of the present invention has the above effects, it is particularly useful as a material used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. Further, since the adhesive tape of the present invention has the above-mentioned effects, it is very useful for applications such as protection of adherends, masking, and temporary fixing in, for example, manufacturing processes of electric / electronic parts and semiconductors (particularly, heat pressing process). Is.
  • the resin composition of the present invention is a composition containing a silicone raw rubber containing an alkenyl group, an MQ resin, a cross-linking agent, a platinum catalyst, and an organic peroxide. It is particularly useful to use this resin composition as a pressure-sensitive adhesive composition (that is, an addition-curable silicone-based pressure-sensitive adhesive composition).
  • a pressure-sensitive adhesive composition that is, an addition-curable silicone-based pressure-sensitive adhesive composition.
  • the resin composition of the present invention is not limited to this, and may be used for various other uses.
  • the gel fraction after cross-linking of the resin composition of the present invention is 45% or more and 60% or less. If the gel fraction is less than 45%, the storage elastic modulus of the molten resin composition heated at a high temperature is lowered, and glue squeezing tends to occur. Further, the adhesion between the resin composition and the adherend is increased and the cohesive force of the resin composition is decreased, so that adhesive residue tends to occur. On the other hand, when the gel fraction exceeds 60%, the silicone raw rubber in the resin composition heated at a high temperature is oxidatively cleaved, the cohesive force of the resin composition is lowered, and adhesive residue tends to be generated.
  • the gel fraction may be 45% or more and 60% or less, but more preferably 50% or more and 60% or less. A specific method for measuring the gel fraction will be described in the column of Examples described later.
  • the storage elastic modulus of the resin composition of the present invention at 200 ° C. after crosslinking is 100,000 Pa or more and 1,000,000 Pa or less.
  • the storage elastic modulus may be 100,000 Pa or more and 1,000,000 Pa or less, but more preferably 100,000 or more and 400,000 or less. A specific method for measuring the storage elastic modulus will be described in the column of Examples described later.
  • Silicone raw rubber containing an alkenyl group used in the present invention is typically a polymer of a long-chain polydimethylsiloxane having a structure of D units [(CH 3) 2 SiO] , at least per molecule It is a polymer containing two alkenyl groups.
  • the present invention is not limited to this, and other types of raw silicone rubber may be used.
  • MQ resin used in the present invention is typically a polymer of a silicone resin having a three-dimensional structure of M units [(CH 3) 3 SiO 1/2 ] and Q units [SiO 2].
  • the present invention is not limited to this, and other types of MQ resins may be used.
  • the cross-linking agent used in the present invention is typically a polyorganosiloxane containing at least two SiH groups per molecule.
  • the present invention is not limited to this, and other types of cross-linking agents may be used.
  • the resin composition containing the above-mentioned silicone raw rubber containing an alkenyl group, an MQ resin, and a cross-linking agent is generally known as an addition-curable silicone-based pressure-sensitive adhesive.
  • 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, this addition-curable silicone-based pressure-sensitive adhesive is cured by heating under a platinum catalyst and causing a cross-linking reaction. It is known that the basic adhesive physical properties such as adhesive strength, holding power, and tack can be adjusted by changing the ratio of the silicone raw rubber and the MQ resin in the addition-curable silicone-based pressure-sensitive adhesive.
  • Various methods are known as methods for adjusting the gel fraction of the addition-curable silicone adhesive. For example, if the blending ratio of MQ resin to silicone raw rubber is lowered, the content ratio of alkenyl groups in silicone raw rubber (and / or MQ resin) is increased, or the amount of cross-linking agent added is increased, the gel after cross-linking is performed. The fraction tends to be high. On the other hand, when a non-crosslinked component (for example, silicone oil) is added, the gel fraction tends to decrease.
  • a non-crosslinked component for example, silicone oil
  • Various methods are known as methods for adjusting the storage elastic modulus of the addition-curable silicone adhesive. For example, when the molecular weight of the silicone raw rubber is increased, the crosslink density is increased, or the blending ratio of the MQ resin to the silicone raw rubber is decreased, the storage elastic modulus tends to increase.
  • each of the above adjustment methods can be used.
  • the resin composition of the present invention is not limited to that obtained by such an adjusting method.
  • the resin composition of the present invention further contains a platinum catalyst.
  • the platinum catalyst is a component that is activated by heating to promote the cross-linking reaction.
  • the type and amount of the platinum catalyst used are not particularly limited, and for example, various platinum catalysts known to be usable as an addition-curable silicone-based pressure-sensitive adhesive and the amount used thereof can be adopted. That is, in the present invention, for example, a commercially available platinum catalyst (curing catalyst for addition-curing silicone-based pressure-sensitive adhesive) may be used in an appropriate amount.
  • the resin composition of the present invention further contains an organic peroxide.
  • this organic peroxide is effective not only for general properties but also for exhibiting the effects of the present invention (suppression of adhesive residue, etc.).
  • the reason is not always clear, but one of the reasons is considered to be that free oxygen radicals generated by decomposition of organic peroxides are involved in the cross-linking reaction and preferably act on the cross-linking density and other properties.
  • the gel fraction and storage elastic modulus can also be adjusted by changing the content of the organic peroxide.
  • the type of organic peroxide is not particularly limited as long as it decomposes to generate free oxygen radicals.
  • 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.
  • One type of organic peroxide may be used alone, or two or more types may be used in combination.
  • Free oxygen radicals are generated by the decomposition of organic peroxides.
  • the theoretical amount (that is, the theoretical amount of active oxygen of the organic peroxide) is calculated by the following formula (1).
  • a (%) (B x 16 / M) x 100 (1)
  • B indicates the number of peroxide bonds
  • M indicates the molecular weight of the organic peroxide.
  • the amount of the organic peroxide is not particularly limited, and may be appropriately determined according to various conditions such as the curing temperature, the decomposition temperature of the organic peroxide, the ratio of the silicone raw rubber and the MQ resin, and the molecular weight of the silicone component. good.
  • the product PA of the theoretical active oxygen amount A (%) is preferably 0.06 part by mass or more, more preferably 0.10 part by mass or more and 0.30 part by mass or less. By changing this product PA, the gel fraction and the storage elastic modulus can also be adjusted.
  • the resin composition of the present invention can also be obtained by adding a predetermined amount of a commercially available platinum catalyst and an organic peroxide to a commercially available addition-curable silicone-based pressure-sensitive adhesive.
  • a resin composition containing a cross-linked silicone structure is obtained, which exerts the effect of the present invention.
  • the cross-linking and curing reaction is usually carried out by heating.
  • cross-linking curing is possible even with ultraviolet irradiation.
  • the resin composition of the present invention can also be obtained, for example, by using a mixture of two or more commercially available silicone-based pressure-sensitive adhesives, a commercially available platinum catalyst, and an organic peroxide.
  • a silicone-based pressure-sensitive adhesive having a relatively high gel fraction and storage elastic modulus and a silicone-based pressure-sensitive adhesive having a relatively low gel fraction and storage elastic modulus are mixed at an appropriate ratio, and a platinum catalyst and a platinum catalyst and a storage elastic modulus are mixed.
  • the resin composition of the present invention can be obtained by blending an appropriate amount of organic peroxide.
  • the resin composition of the present invention is not limited to that obtained by such a method.
  • Additives may be added to the resin composition of the present invention for the purpose of improving various properties.
  • specific examples of the additive include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane, and polydimethylphenylsiloxane; antioxidants such as phenolic antioxidants and amines. Agent; silane coupling agent can be mentioned.
  • the adhesive tape of the present invention is an adhesive tape having an adhesive layer composed of the resin composition of the present invention after cross-linking.
  • This adhesive tape may be an adhesive tape having the adhesive layer on one side or both sides of the base film, or may be a baseless type adhesive tape without a base material.
  • the thickness of the adhesive layer of the adhesive tape is 2 ⁇ m or more and 10 ⁇ m or less, preferably 4 ⁇ m or more and 8 ⁇ m or less.
  • the pressure-sensitive adhesive layer can be formed by subjecting the resin composition of the present invention to a cross-linking and curing reaction.
  • the resin composition can be applied onto a base material and crosslinked and cured by heating or irradiation with ultraviolet rays to form an adhesive layer on the base material.
  • the resin composition may be applied onto a paper pattern or other film and crosslinked and cured by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer may be bonded to one or both sides of a base material. ..
  • the baseless type adhesive tape can be produced by forming an adhesive layer on a release paper or other film, and then laminating another release paper or other film on the adhesive layer.
  • a solvent may be added in order to reduce the viscosity of the resin composition at the time of application.
  • 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.
  • a resin film having high heat resistance that can be processed at a high temperature is preferable.
  • resins such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyethylene sulfide (PPS), and polytetrafluoroethylene (PTFE).
  • PI polyimide
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PEEK polyetheretherketone
  • PPS polyethylene sulfide
  • PTFE polytetrafluoroethylene
  • the thickness of the base material is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 5 to 125 ⁇ m.
  • the surface of the base material on which the pressure-sensitive adhesive layer is provided may be subjected to an easy-adhesion treatment, if necessary.
  • the easy-adhesion treatment include a primer treatment, a corona treatment, an etching treatment, a plasma treatment, and a sandblast treatment.
  • the adhesive tape of the present invention may be provided with a release liner.
  • the release liner is for protecting the adhesive layer of the adhesive tape, and is peeled off immediately before application to expose the adhesive and attach 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 woodfree paper, glassine paper, or synthetic resin film to a mold release agent treatment.
  • a release agent such as a fluorine-substituted alkyl-modified silicone resin may be used.
  • the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer one in which the surface of the polyethylene tale phthalate film is mold-released with a fluorine-substituted alkyl-modified silicone resin is preferable.
  • a resin film that has not been subjected to the mold release treatment may be used as the release liner.
  • Specific examples thereof include polyethylene terephthalate (PET) film, polyethylene (PE) film, and polypropylene (PP) film.
  • part means “part by mass”.
  • Example 1 First, a plurality of prototypes (A to F) of an addition-curable silicone-based adhesive (stock solution) were prepared. These plurality of prototypes are prototypes of adhesives adjusted so that the storage elastic modulus G'and the gel fraction after curing, which are measured by the methods described later, show various values. All of these prototypes are silicone-based adhesives composed of a silicone raw rubber containing an alkenyl group, an MQ resin, and a cross-linking agent.
  • Example 1 of these plurality of prototypes, when an appropriate amount of an organic peroxide is added, the storage elastic modulus G'after curing and the gel fraction become specific values described later, which is an addition-curable silicone.
  • the system adhesive (A) solid content concentration 60% was selected.
  • this addition-curing silicone-based pressure-sensitive adhesive stock solution (A) 100 parts of this addition-curing silicone-based pressure-sensitive adhesive stock solution (A), 197 parts of toluene as a diluting solvent, and an organic peroxide-type curing agent manufactured by Nichiyu Co., Ltd. as an organic peroxide (Nipper (registered trademark) BMT- K40, concentration of organic peroxide: 40%, theoretical amount of active oxygen in organic peroxide: 6.05%) 3.0 parts, platinum catalyst (NC-25, manufactured by Dow Toray Co., Ltd.) 0.3 The parts were uniformly mixed to obtain a pressure-sensitive adhesive solution (1).
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide with respect to 100 parts of the silicone pressure-sensitive adhesive is 0.12 parts.
  • the storage elastic modulus G'at 200 ° C. was 168628 Pa. Further, when the gel fraction measurement described later was performed on this pressure-sensitive adhesive liquid (1), the gel fraction was 46%.
  • the pressure-sensitive adhesive liquid (1) was applied to one side of a primer-treated polyimide (PI) film having a thickness of 25 ⁇ m so that the thickness of the pressure-sensitive adhesive layer after drying was 6 ⁇ m, and 60 in a drying furnace.
  • the solvent was removed by drying at ° C. for 1 minute, and the pressure was cured by heating at 200 ° C. for 1 minute to form an adhesive layer.
  • a polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m treated with a fluorine-substituted alkyl-modified silicone resin was attached to the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive tape.
  • the pressure-sensitive adhesive liquid (1) is applied onto the release liner so that the thickness after drying is 50 ⁇ m. 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 1 minute to form a pressure-sensitive adhesive layer composed 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.
  • a measurement sample is sandwiched between parallel disks ( ⁇ 8 mm), and a temperature rise rate of 10 ° C./min is applied using a dynamic viscoelasticity measuring device (manufactured by Rheometric Scientific, device name RDAIII) while applying shear strain at a frequency of 10 Hz. Then, the storage elastic modulus G'is measured in the range of -60 ° C to 300 ° C.
  • the pressure-sensitive adhesive liquid (1) is applied onto the release liner so that the thickness after drying is 50 ⁇ m. 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 1 minute to form a pressure-sensitive adhesive layer composed of the cured silicone-based pressure-sensitive adhesive composition, which is used as a measurement sample.
  • Example 2 Instead of 100 parts of the addition-curing silicone-based adhesive stock solution (A) (solid content concentration 60%), 50 parts of the addition-curing silicone-based pressure-sensitive adhesive stock solution (A) (solid content concentration 40%) and the addition-curing silicone type Adhesive in the same manner as in Example 1 except that a mixture of 50 parts of the adhesive stock solution (B) (solid content concentration 40% by mass) was used and the amount of organic peroxide was changed to 2.5 parts.
  • Liquid (2) was prepared to prepare an adhesive tape. 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (2), the storage elastic modulus G'at 200 ° C. was 124121Pa and the gel fraction was 55%.
  • the pressure-sensitive adhesive liquid (3) was prepared in the same manner as in Example 2 except that the amount of the organic peroxide was changed to 4.5 parts by mass, and a pressure-sensitive adhesive tape was prepared.
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.22 parts.
  • the storage elastic modulus G'at 200 ° C. was 2119861 Pa and the gel fraction was 60%.
  • ⁇ Comparative example 1> Except for changing the amount of add-curing silicone adhesive stock solution (A) to 25 parts, the amount of add-curing silicone adhesive stock solution (B) to 75 parts, and the amount of organic peroxide to 2.25 parts.
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0.12 parts.
  • the storage elastic modulus G'at 200 ° C. was 125270 Pa and the gel fraction was 62%.
  • An adhesive liquid (C3) was prepared in the same manner as in Example 2 except that no organic peroxide was added, to prepare an adhesive tape.
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0 part.
  • the storage elastic modulus G'at 200 ° C. was 240508 Pa and the gel fraction was 53%.
  • An adhesive liquid (C6) was prepared in the same manner as in Comparative Example 5 except that no organic peroxide was added, to prepare an adhesive tape.
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0 part.
  • the storage elastic modulus G'at 200 ° C. was 69702 Pa and the gel fraction was 34%.
  • a pressure-sensitive adhesive solution (C7) was prepared in the same manner as in Comparative Example 6 except for the above, and a pressure-sensitive adhesive tape was prepared.
  • the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide is 0 part.
  • the storage elastic modulus G'at 200 ° C. was 69045 Pa and the gel fraction was 44%.
  • Adhesive tape cut to 20 mm x 20 mm is attached to a Cu plate (Cl100p) whose surface has been polished with Picard liquid (manufactured by Nippon Shinryo Kogyo Co., Ltd.), and one reciprocation with a roller covered with a rubber layer weighing 2 kg. And crimped. Then, this was left to stand in an environment of 23 ° C. for 20 minutes to 1 hour to obtain a bonded sample for measurement. This sample was sandwiched between two SUS304 plates whose both sides were mirror-finished, and heat-pressed at a temperature of 200 ° C. and a pressure of 30 kg / cm 2 for 4 hours.
  • Comparative Examples 1 and 2 are examples in which the gel fraction after cross-linking of the pressure-sensitive adhesive composition is too high. As a result, adhesive residue was generated on the adhesive tapes of Comparative Examples 1 and 2.
  • Comparative Example 3 is an example in which an organic peroxide is not used in the pressure-sensitive adhesive composition. As a result, adhesive residue was generated on the adhesive tape of Comparative Example 3.
  • Comparative Example 4 is an example in which the storage elastic modulus of the pressure-sensitive adhesive composition after cross-linking is too low. As a result, the adhesive tape of Comparative Example 4 had adhesive squeeze out and adhesive residue.
  • Comparative Example 5 is an example in which the gel fraction and storage elastic modulus after cross-linking of the pressure-sensitive adhesive composition are too low. As a result, the adhesive tape of Comparative Example 4 had adhesive squeeze out and adhesive residue.
  • Comparative Examples 6 and 7 are examples in which no organic peroxide is used in the pressure-sensitive adhesive composition and the gel fraction and storage elastic modulus after cross-linking of the pressure-sensitive adhesive composition are too low. As a result, the adhesive tapes of Comparative Examples 6 and 7 had adhesive squeeze out and adhesive residue.
  • Reference example 1 is an example in which the thickness of the adhesive layer is too thick.
  • the adhesive tape of Reference Example 1 had adhesive squeeze out and adhesive residue. From this result, it can be understood that when the resin composition (adhesive composition) of the present invention is used for the use of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, the thickness of the pressure-sensitive adhesive layer is preferably relatively thin.
  • the resin composition of the present invention is particularly useful as a material for forming an adhesive layer of an adhesive tape, for example.
  • the adhesive tape of the present invention is long at high temperature (for example, 180 ° C. or higher) and high pressure (for example, 20 kg / cm 2 or higher) during a process that requires treatment in a high load / high temperature environment, for example, in the manufacturing process of a printed laminated substrate. It is very useful for protection of adherends (for example, the surface of a laminated substrate), masking, temporary fixing, and fixing during transportation in a step of heating and pressing for a time (for example, 2 hours or more).

Abstract

Disclosed are: a resin composition that comprises an alkenyl group-containing silicone raw rubber, an MQ resin, a crosslinking agent, a platinum catalyst and an organic peroxide, that has a gel fraction of 45-60% after crosslinking, and that has a storage modulus of 100,000-1,000,000Pa at a temperature of 200°C after crosslinking; and an adhesive tape having an adhesive agent layer formed from said resin composition after crosslinking, wherein the adhesive agent layer has a gel fraction of 45-60%, the adhesive agent layer has a storage modulus of 100,000-1,000,000Pa at a temperature of 200°C, and the adhesive agent layer has a thickness of 2-10μm.

Description

樹脂組成物及び粘着テープResin composition and adhesive tape
　本発明は、例えば、電子部品や半導体部品の製造工程で使用される場合の寸法安定性に優れ、糊残りが抑制された樹脂組成物及び粘着テープに関する。 The present invention relates to, for example, a resin composition and an adhesive tape having excellent dimensional stability and suppressed adhesive residue when used in a manufacturing process of electronic parts and semiconductor parts.
　シリコーン系粘着剤組成物は、耐熱性、耐寒性、耐候性、電気絶縁性及び耐薬品性に優れている。さらにシリコーン系粘着剤層を有する粘着テープは、特に高温環境下で使用しても剥離時に糊残りしにくい。したがって、そのような粘着テープは、例えば電気・電子部品や半導体部品の製造工程において、部材や部品の保護、マスキング、仮固定、搬送時固定、スプライス等の用途に広く利用されている。 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 pressure-sensitive adhesive layer is less likely to leave adhesive residue when peeled off, especially even when used in a high-temperature environment. Therefore, such adhesive tapes are widely used, for example, in the manufacturing process of electrical / electronic parts and semiconductor parts, for applications such as protection of members and parts, masking, temporary fixing, fixing during transportation, and splices.
　これらの電気・電子部品や半導体部品の製造工程において、部品の成型のために高荷重及び高温環境となる場合がある。例えばプリント積層基板の製造工程において、回路パターンを表面に形成済みの回路積層板の間に、接着層として未硬化の樹脂を含侵させた繊維強化プリプレグを積層し、高温（例えば１８０℃以上）、高圧力（例えば２０ｋｇ／ｃｍ２以上）で、長時間（例えば２時間以上）、積層プレス機で加熱プレスする工程がある。このような加熱プレス工程では積層基板表面の回路への傷の形成や未硬化の樹脂の接着を防止する為に、積層基板表面をテープ等で保護する必要がある。 In the manufacturing process of these electric / electronic parts and semiconductor parts, a high load and a high temperature environment may occur due to the molding of the parts. For example, in the manufacturing process of a printed laminated circuit board, a fiber-reinforced prepreg impregnated with an uncured resin is laminated as an adhesive layer between circuit laminates on which a circuit pattern has been formed on the surface, and the temperature is high (for example, 180 ° C. or higher). There is a step of heat-pressing with a laminated press machine at a pressure (for example, 20 kg / cm 2 or more) for a long time (for example, 2 hours or more). In such a heat pressing process, it is necessary to protect the surface of the laminated substrate with tape or the like in order to prevent the formation of scratches on the circuit on the surface of the laminated substrate and the adhesion of the uncured resin.
　従来のシリコーン系粘着剤層を有する粘着テープを高温、高圧力、長時間の加熱プレス工程に使用すると、押圧により粘着剤層が押し出され、粘着剤層の寸法変化が起こる。すなわちテープ端部より糊はみだしが発生し、はみ出した部分がテープ剥離後糊残りとなる。またこのような工程中は、粘着剤が被着体に高温で加熱しながら押し付けられる。したがって、高温で軟化した粘着剤が被着体とより強固に結合し、かつ高温加熱によって粘着剤が熱劣化し凝集力が低下する。その結果、加熱プレス工程後にテープを剥離する際に、被着体と粘着剤の結合力が粘着剤層の凝集力に勝り、粘着剤層が凝集破壊を起こして糊残りが発生する。 When a conventional adhesive tape having a silicone-based pressure-sensitive adhesive layer is used in a high-temperature, high-pressure, long-time heating press process, the pressure-sensitive adhesive layer is extruded by pressing, and the size of the pressure-sensitive adhesive layer changes. That is, the glue squeezes out from the end of the tape, and the squeezed out portion becomes the adhesive residue after the tape is peeled off. Further, during such a process, the adhesive is pressed against the adherend while being heated at a high temperature. Therefore, the pressure-sensitive adhesive softened at a high temperature binds more firmly to the adherend, and the pressure-sensitive adhesive is thermally deteriorated by high-temperature heating to reduce the cohesive force. As a result, when the tape is peeled off after the heat pressing step, the bonding force between the adherend and the pressure-sensitive adhesive exceeds the cohesive force of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer undergoes cohesive failure to generate adhesive residue.
　加熱プレス工程における粘着剤の寸法変化による糊残りは、テープの粘着剤層の厚さを薄くすることにより低減できる傾向にある。しかし、粘着剤層の厚さを薄くすると、厚さ方向における凝集力が低下し、工程後にテープを剥離する際に糊残りが発生する場合がある。一方、粘着剤層の厚さを厚くすると、寸法安定性が低下し、加熱プレス時の糊はみだしが増加する場合がある。このように高温工程中の寸法安定性（糊はみだし防止）と高温工程後の糊残り防止は背反関係にあり、その両立が困難な特性である。 The adhesive residue due to the dimensional change of the adhesive in the heat pressing process tends to be reduced by reducing the thickness of the adhesive layer of the tape. However, if the thickness of the pressure-sensitive adhesive layer is reduced, the cohesive force in the thickness direction is reduced, and adhesive residue may be generated when the tape is peeled off after the step. On the other hand, if the thickness of the pressure-sensitive adhesive layer is increased, the dimensional stability may be lowered and the amount of glue squeezed out during heat pressing may be increased. As described above, the dimensional stability during the high temperature process (prevention of glue squeeze out) and the prevention of adhesive residue after the high temperature process have a contradictory relationship, and it is a characteristic that it is difficult to achieve both.
　特許文献１には、プリント積層基板に関する積層プレス工程において、回路固定治具と積層回路板との間に離型保護シートとして使用する為の多孔質フッ素樹脂シートが開示されている。ただし、この離型保護シートは粘着剤層を有していないので、粘着テープではない。すなわち特定箇所への固定力を有していないので、保護したい部分を選択的にマスキングすることは出来ない。したがって、この離型保護シートを用いる場合は、保護したい面の全面に使用する必要があり、コストの面で不利である。 Patent Document 1 discloses a porous fluororesin sheet for use as a release protective sheet between a circuit fixing jig and a laminated circuit board in a laminated press process relating to a printed laminated circuit board. However, since this release protective sheet does not have an adhesive layer, it is not an adhesive tape. That is, since it does not have a fixing force to a specific part, it is not possible to selectively mask the part to be protected. Therefore, when this release protective sheet is used, it is necessary to use it on the entire surface to be protected, which is disadvantageous in terms of cost.
　特許文献２には、離型面を構成する為のフッ素樹脂系フィルムと粘着剤層を少なくとも有する粘着テープが開示されている。ただし、この粘着テープは離型用粘着テープであり、高温工程時の寸法安定性や糊残りについての検討はされていない。また、この粘着テープにおける加熱プレス試験条件は、１５０℃、圧力５ｋｇ／ｃｍ２、２０分間プレスであり、いずれの条件も、例えば、積層基板の加熱プレス工程のような一般的な加熱プレス工程より緩い条件である。 Patent Document 2 discloses an adhesive tape having at least a fluororesin-based film and an adhesive layer for forming a release surface. However, this adhesive tape is an adhesive tape for mold release, and dimensional stability and adhesive residue during a high temperature process have not been studied. Further, the heat press test conditions for this adhesive tape are 150 ° C., pressure 5 kg / cm 2 , and 20 minutes press, and all the conditions are different from a general heat press step such as a heat press step for a laminated substrate. It is a loose condition.
　特許文献３には、架橋剤としてＳｉＨ基を有するシロキサン系架橋剤と過酸化物系架橋剤の両方を含有するシリコーン系感圧接着剤組成物が開示されている。ただし、このシリコーン系感圧接着剤組成物は、工程に使用するまでは、過酸化物系架橋剤が未反応の状態でシリコーン系感圧接着剤組成物中に残存する。したがって、製造、保管、出荷、運送、顧客での保管などの使用までのプロセス中に、過酸化物系架橋剤が徐々に反応することが想定される。すなわち、実際に工程に使用されるまでにその特性が変化することとなり、経時安定性の点で不利である。 Patent Document 3 discloses a silicone-based pressure-sensitive adhesive composition containing both a siloxane-based cross-linking agent having a SiH group and a peroxide-based cross-linking agent as the cross-linking agent. However, this silicone-based pressure-sensitive adhesive composition remains in the silicone-based pressure-sensitive adhesive composition in an unreacted state of the peroxide-based cross-linking agent until it is used in the process. Therefore, it is expected that the peroxide-based cross-linking agent will gradually react during the process up to use such as manufacturing, storage, shipping, transportation, and customer storage. That is, its characteristics change before it is actually used in the process, which is disadvantageous in terms of stability over time.
特開平０４－１７９５２０号公報Japanese Unexamined Patent Publication No. 04-179520 国際公開第２０１６／１７４７１３号International Publication No. 2016/174713 特開２００２－２７５４５０号公報Japanese Unexamined Patent Publication No. 2002-275450
　本発明者らは、粘着テープに要求される特性のうち、特に高荷重・高温環境下で使用される用途における粘着テープの寸法安定性及び糊残りに関する課題を解決する為に鋭意検討を行った。すなわち本発明の目的は、高荷重・高温環境下で使用する際の寸法安定性に優れ、かつ高荷重・高温環境下で使用した後に剥離する際の糊残りが抑制された樹脂組成物及び粘着テープを提供することにある。 Among the properties required for adhesive tapes, the present inventors have diligently studied in order to solve the problems related to the dimensional stability and adhesive residue of the adhesive tape, especially in applications used under high load and high temperature environments. .. That is, an object of the present invention is a resin composition and adhesive having excellent dimensional stability when used in a high load / high temperature environment and suppressing adhesive residue when peeling after use in a high load / high temperature environment. To provide the tape.
　本発明者らは上記目的を達成すべく鋭意検討した結果、特定の成分と特定の物性を有する樹脂組成物が非常に有効であることを見出し、本発明を完成するに至った。 As a result of diligent studies to achieve the above object, the present inventors have found that a resin composition having a specific component and a specific physical property is very effective, and have completed the present invention.
　すなわち本発明は、アルケニル基を含有するシリコーン生ゴムと、ＭＱレジンと、架橋剤と、白金触媒と、有機過酸化物とを含み、
　架橋後のゲル分率が４５％以上６０％以下であり、
　架橋後の２００℃における貯蔵弾性率が１０００００Ｐａ以上１００００００Ｐａ以下である樹脂組成物である。 That is, the present invention contains a silicone raw rubber containing an alkenyl group, an MQ resin, a cross-linking agent, a platinum catalyst, and an organic peroxide.
The gel fraction after cross-linking is 45% or more and 60% or less.
A resin composition having a storage elastic modulus at 200 ° C. after cross-linking of 100,000 Pa or more and 1,000,000 Pa or less.
　さらに本発明は、架橋後の前記樹脂組成物により構成される粘着剤層を有する粘着テープであって、
　前記粘着剤層のゲル分率が４５％以上６０％以下であり、
　前記粘着剤層の２００℃における貯蔵弾性率が１０００００Ｐａ以上１００００００Ｐａ以下であり、且つ、
　前記粘着剤層の厚さが２μｍ以上１０μｍ以下である粘着テープである。 Further, the present invention is an adhesive tape having an adhesive layer composed of the resin composition after cross-linking.
The gel fraction of the pressure-sensitive adhesive layer is 45% or more and 60% or less.
The storage elastic modulus of the pressure-sensitive adhesive layer at 200 ° C. is 100,000 Pa or more and 1,000,000 Pa or less, and
The pressure-sensitive adhesive tape has a thickness of 2 μm or more and 10 μm or less.
　本発明によれば、高荷重・高温環境下で使用する際の寸法安定性に優れ、かつ高荷重・高温環境下で使用した後に剥離する際の糊残りが抑制された樹脂組成物及び粘着テープを提供できる。 According to the present invention, a resin composition and an adhesive tape having excellent dimensional stability when used in a high load / high temperature environment and suppressing adhesive residue when peeling after being used in a high load / high temperature environment. Can be provided.
　本発明の樹脂組成物は上記効果を有するので、特に粘着テープの粘着剤層に使用する材料として非常に有用である。また、本発明の粘着テープは上記効果を有するので、例えば電気・電子部品や半導体の製造工程（特に、熱プレス工程）において、被着体の保護、マスキング、仮固定等の用途に非常に有用である。 Since the resin composition of the present invention has the above effects, it is particularly useful as a material used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. Further, since the adhesive tape of the present invention has the above-mentioned effects, it is very useful for applications such as protection of adherends, masking, and temporary fixing in, for example, manufacturing processes of electric / electronic parts and semiconductors (particularly, heat pressing process). Is.
　＜樹脂組成物＞
　本発明の樹脂組成物は、アルケニル基を含有するシリコーン生ゴムと、ＭＱレジンと、架橋剤と、白金触媒と、有機過酸化物とを含む組成物である。この樹脂組成物は、特に粘着剤組成物（すなわち付加硬化型シリコーン系粘着剤組成物）として使用することが有用である。ただし、本発明の樹脂組成物はこれに限定されず、その他の様々な用途に使用しても構わない。 <Resin composition>
The resin composition of the present invention is a composition containing a silicone raw rubber containing an alkenyl group, an MQ resin, a cross-linking agent, a platinum catalyst, and an organic peroxide. It is particularly useful to use this resin composition as a pressure-sensitive adhesive composition (that is, an addition-curable silicone-based pressure-sensitive adhesive composition). However, the resin composition of the present invention is not limited to this, and may be used for various other uses.
　本発明の樹脂組成物の架橋後のゲル分率は４５％以上６０％以下ある。このゲル分率が４５％未満であると、高温加熱された溶融状態の樹脂組成物の貯蔵弾性率が低下し、糊はみだしが発生する傾向にある。また、樹脂組成物と被着体との密着性が高まり且つ樹脂組成物の凝集力が低下して、糊残りが発生する傾向にある。一方、このゲル分率が６０％を超えると、高温加熱された樹脂組成物中のシリコーン生ゴムが酸化開裂し、樹脂組成物の凝集力が低下して、糊残りが発生する傾向にある。このゲル分率は４５％以上６０％以下であれば良いが、特に５０％以上６０％以下であることがより好ましい。ゲル分率の具体的な測定方法は、後述する実施例の欄に記載する。 The gel fraction after cross-linking of the resin composition of the present invention is 45% or more and 60% or less. If the gel fraction is less than 45%, the storage elastic modulus of the molten resin composition heated at a high temperature is lowered, and glue squeezing tends to occur. Further, the adhesion between the resin composition and the adherend is increased and the cohesive force of the resin composition is decreased, so that adhesive residue tends to occur. On the other hand, when the gel fraction exceeds 60%, the silicone raw rubber in the resin composition heated at a high temperature is oxidatively cleaved, the cohesive force of the resin composition is lowered, and adhesive residue tends to be generated. The gel fraction may be 45% or more and 60% or less, but more preferably 50% or more and 60% or less. A specific method for measuring the gel fraction will be described in the column of Examples described later.
　本発明の樹脂組成物の架橋後の２００℃における貯蔵弾性率は１０００００Ｐａ以上１００００００Ｐａ以下である。この貯蔵弾性率が１０００００Ｐａ未満であると、高温加熱された溶融状態の樹脂組成物の弾性が低下し、例えば熱プレス工程等の高荷重・高温工程において一旦変形した樹脂組成物の形状があまり元に戻らず、糊はみだしが発生する傾向にある。この貯蔵弾性率は１０００００Ｐａ以上１００００００Ｐａ以下であれば良いが、特に１０００００以上４０００００以下であることがより好ましい。貯蔵弾性率の具体的な測定方法は、後述する実施例の欄に記載する。 The storage elastic modulus of the resin composition of the present invention at 200 ° C. after crosslinking is 100,000 Pa or more and 1,000,000 Pa or less. When this storage elastic modulus is less than 100,000 Pa, the elasticity of the molten resin composition heated at a high temperature decreases, and the shape of the resin composition once deformed in a high load / high temperature process such as a hot pressing process is too much original. There is a tendency for glue to squeeze out without returning to. The storage elastic modulus may be 100,000 Pa or more and 1,000,000 Pa or less, but more preferably 100,000 or more and 400,000 or less. A specific method for measuring the storage elastic modulus will be described in the column of Examples described later.
　本発明に用いるアルケニル基を含有するシリコーン生ゴムは、代表的には、Ｄ単位［(CH3)2SiO］からなる構造を有するポリジメチルシロキサンの長鎖の重合体であって、１分子当たり少なくとも２個のアルケニル基を含有する重合体である。ただし本発明はこれに限定されず、これ以外の種類のシリコーン生ゴムを使用しても良い。 Silicone raw rubber containing an alkenyl group used in the present invention is typically a polymer of a long-chain polydimethylsiloxane having a structure of D units [(CH 3) 2 SiO] , at least per molecule It is a polymer containing two alkenyl groups. However, the present invention is not limited to this, and other types of raw silicone rubber may be used.
　本発明に用いるＭＱレジンは、代表的には、Ｍ単位［(CH3)3SiO1/2］とＱ単位［SiO2］からなる３次元構造を有するシリコーンレジンの重合体である。ただし本発明はこれに限定されず、これ以外の種類のＭＱレジンを使用しても良い。 MQ resin used in the present invention is typically a polymer of a silicone resin having a three-dimensional structure of M units [(CH 3) 3 SiO 1/2 ] and Q units [SiO 2]. However, the present invention is not limited to this, and other types of MQ resins may be used.
　本発明に用いる架橋剤は、代表的には、１分子当たり少なくとも２個のＳｉＨ基を含有するポリオルガノシロキサンである。ただし本発明はこれに限定されず、これ以外の種類の架橋剤を使用しても良い。 The cross-linking agent used in the present invention is typically a polyorganosiloxane containing at least two SiH groups per molecule. However, the present invention is not limited to this, and other types of cross-linking agents may be used.
　以上のようなアルケニル基を含有するシリコーン生ゴムと、ＭＱレジンと、架橋剤とを含む樹脂組成物は、一般に、付加硬化型シリコーン系粘着剤として知られている。付加硬化型シリコーン系粘着剤は、例えば、アルケニル基を含有するシリコーン生ゴムからなる主剤と、ＭＱレジンと、ＳｉＨ基を含有するポリオルガノシロキサンからなる架橋剤とを含む。そして、この付加硬化型シリコーン系粘着剤は、白金触媒下で加熱して架橋反応させることにより硬化する。そして、この付加硬化型シリコーン系粘着剤中のシリコーン生ゴムとＭＱレジンの比率を変えることで、粘着力、保持力、タック等の基本的な粘着物性を調整できることが知られている。 The resin composition containing the above-mentioned silicone raw rubber containing an alkenyl group, an MQ resin, and a cross-linking agent is generally known as an addition-curable silicone-based pressure-sensitive adhesive. 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, this addition-curable silicone-based pressure-sensitive adhesive is cured by heating under a platinum catalyst and causing a cross-linking reaction. It is known that the basic adhesive physical properties such as adhesive strength, holding power, and tack can be adjusted by changing the ratio of the silicone raw rubber and the MQ resin in the addition-curable silicone-based pressure-sensitive adhesive.
　付加硬化型シリコーン系粘着剤のゲル分率を調整する方法としては、様々な方法が知られている。例えば、シリコーン生ゴムに対するＭＱレジンの配合比率を低くしたり、シリコーン生ゴム（及び／又はＭＱレジン）中のアルケニル基の含有比率を高くしたり、あるいは架橋剤の添加量を増やすと、架橋後のゲル分率が高くなる傾向にある。一方、非架橋成分（例えばシリコーンオイル等）を添加すると、そのゲル分率が低下する傾向にある。 Various methods are known as methods for adjusting the gel fraction of the addition-curable silicone adhesive. For example, if the blending ratio of MQ resin to silicone raw rubber is lowered, the content ratio of alkenyl groups in silicone raw rubber (and / or MQ resin) is increased, or the amount of cross-linking agent added is increased, the gel after cross-linking is performed. The fraction tends to be high. On the other hand, when a non-crosslinked component (for example, silicone oil) is added, the gel fraction tends to decrease.
　付加硬化型シリコーン系粘着剤の貯蔵弾性率を調整する方法としても、様々な方法が知られている。例えば、シリコーン生ゴムの分子量を高くしたり、架橋密度を高くしたり、シリコーン生ゴムに対するＭＱレジンの配合比率を低くすると、貯蔵弾性率が高くなる傾向にある。 Various methods are known as methods for adjusting the storage elastic modulus of the addition-curable silicone adhesive. For example, when the molecular weight of the silicone raw rubber is increased, the crosslink density is increased, or the blending ratio of the MQ resin to the silicone raw rubber is decreased, the storage elastic modulus tends to increase.
　特定のゲル分率及び貯蔵弾性率を示す本発明の樹脂組成物を得る為には、以上の各調整方法を利用できる。ただし、本発明の樹脂組成物はそのような調整方法で得たものに限定されない。 In order to obtain the resin composition of the present invention showing a specific gel fraction and storage elastic modulus, each of the above adjustment methods can be used. However, the resin composition of the present invention is not limited to that obtained by such an adjusting method.
　本発明の樹脂組成物は、さらに白金触媒を含む。白金触媒は加熱により活性化して架橋反応を促進させる成分である。白金触媒の種類や使用量は特に限定されず、例えば、付加硬化型シリコーン系粘着剤として使用可能なことが知られている各種の白金触媒及びその使用量を採用できる。すなわち本発明においては、例えば市販の白金触媒（付加硬化型シリコーン系粘着剤用の硬化触媒）を適正量で使用すれば良い。 The resin composition of the present invention further contains a platinum catalyst. The platinum catalyst is a component that is activated by heating to promote the cross-linking reaction. The type and amount of the platinum catalyst used are not particularly limited, and for example, various platinum catalysts known to be usable as an addition-curable silicone-based pressure-sensitive adhesive and the amount used thereof can be adopted. That is, in the present invention, for example, a commercially available platinum catalyst (curing catalyst for addition-curing silicone-based pressure-sensitive adhesive) may be used in an appropriate amount.
　本発明の樹脂組成物は、さらに有機過酸化物を含む。本発明者らの知見によれば、この有機過酸化物は一般的な特性の為だけでなく、本発明の効果（糊残りの抑制など）を発現する為にも有効である。その理由は必ずしも明らかではないが、有機過酸化物の分解により発生する遊離酸素ラジカルが架橋反応に関与し、架橋密度及びその他の特性に好適に作用することが理由の一つと考えられる。なお、有機過酸化物の含有量を変更することによって、ゲル分率や貯蔵弾性率を調整することもできる。 The resin composition of the present invention further contains an organic peroxide. According to the findings of the present inventors, this organic peroxide is effective not only for general properties but also for exhibiting the effects of the present invention (suppression of adhesive residue, etc.). The reason is not always clear, but one of the reasons is considered to be that free oxygen radicals generated by decomposition of organic peroxides are involved in the cross-linking reaction and preferably act on the cross-linking density and other properties. The gel fraction and storage elastic modulus can also be adjusted by changing the content of the organic peroxide.
　有機過酸化物の種類は特に限定されず、分解して遊離酸素ラジカルを発生するものであれば良い。特に、ジベンゾイルパーオキサイド及びその誘導体が好ましい。具体例としては、ジベンゾイルパーオキサイド、４,４'－ジメチルジベンゾイルパーオキサイド、３,３'－ジメチルジベンゾイルパーオキサイド、２,２'－ジメチルジベンゾイルパーオキサイド、２,２',４,４'－テトラクロロジベンゾイルパーオキサイド及びクミルパーオキサイドが挙げられる。有機過酸化物は１種単独で使用しても良いし、２種以上を併用しても良い。 The type of organic peroxide 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. One type of organic peroxide may be used alone, or two or more types may be used in combination.
　遊離酸素ラジカルは、有機過酸化物の分解によって発生する。その理論量（すなわち有機過酸化物の理論活性酸素量）は、下記式（１）により算出される。
　Ａ（％）＝（Ｂ×１６／Ｍ）×１００　　　（１）
［式（１）中、Ａは有機過酸化物の理論活性酸素量を示し、Ｂは過酸化結合の数を示し、Ｍは有機過酸化物の分子量を示す。］ Free oxygen radicals are generated by the decomposition of organic peroxides. The theoretical amount (that is, the theoretical amount of active oxygen of the organic peroxide) is calculated by the following formula (1).
A (%) = (B x 16 / M) x 100 (1)
[In the formula (1), A indicates the theoretical active oxygen amount of the organic peroxide, B indicates the number of peroxide bonds, and M indicates the molecular weight of the organic peroxide. ]
　本発明において、有機過酸化物の量は特に制限されず、硬化温度、有機過酸化物の分解温度、シリコーン生ゴムとＭＱレジンの比率、シリコーン成分の分子量等の諸条件に応じて適宜決定すれば良い。ただし、先に説明したアルケニル基を含有するシリコーン生ゴム、ＭＱレジン及び架橋剤の合計１００質量部に対する有機過酸化物の量Ｐ（質量部）と前記式（１）で表される有機過酸化物の理論活性酸素量Ａ（％）の積ＰＡは、好ましくは０.０６質量部以上、より好ましくは０.１０質量部以上０.３０質量部以下である。なお、この積ＰＡを変更することによって、ゲル分率や貯蔵弾性率を調整することもできる。 In the present invention, the amount of the organic peroxide is not particularly limited, and may be appropriately determined according to various conditions such as the curing temperature, the decomposition temperature of the organic peroxide, the ratio of the silicone raw rubber and the MQ resin, and the molecular weight of the silicone component. good. However, the amount P (parts by mass) of the organic peroxide with respect to a total of 100 parts by mass of the silicone raw rubber containing the alkenyl group, the MQ resin and the cross-linking agent described above and the organic peroxide represented by the above formula (1). The product PA of the theoretical active oxygen amount A (%) is preferably 0.06 part by mass or more, more preferably 0.10 part by mass or more and 0.30 part by mass or less. By changing this product PA, the gel fraction and the storage elastic modulus can also be adjusted.
　以上説明した各成分は、例えば市販品として得ることができる。例えば、市販の付加硬化型シリコーン系粘着剤に、市販の白金触媒及び有機過酸化物を所定量添加することによっても、本発明の樹脂組成物を得ることができる。ただし、ゲル分率や貯蔵弾性率が本発明の範囲内になるように組成及びその他の条件を適宜調整する必要がある。そして、これを架橋硬化させることにより、架橋されたシリコーン構造を含む樹脂組成物が得られ、これが本発明の効果を奏する。架橋硬化反応は通常は加熱によって行う。ただし、各成分の種類によっては紫外線照射でも架橋硬化は可能である Each component described above can be obtained as a commercially available product, for example. For example, the resin composition of the present invention can also be obtained by adding a predetermined amount of a commercially available platinum catalyst and an organic peroxide to a commercially available addition-curable silicone-based pressure-sensitive adhesive. However, it is necessary to appropriately adjust the composition and other conditions so that the gel fraction and the storage elastic modulus are within the range of the present invention. Then, by cross-linking and curing this, a resin composition containing a cross-linked silicone structure is obtained, which exerts the effect of the present invention. The cross-linking and curing reaction is usually carried out by heating. However, depending on the type of each component, cross-linking curing is possible even with ultraviolet irradiation.
　本発明の樹脂組成物は、例えば、２種以上の市販のシリコーン系粘着剤の混合物及び市販の白金触媒及び有機過酸化物を用いて得ることもできる。具体的には、例えばゲル分率及び貯蔵弾性率が比較的高いシリコーン系粘着剤と、ゲル分率及び貯蔵弾性率が比較的低いシリコーン系粘着剤とを適当な比率で混合し、白金触媒及び適量の有機過酸化物を配合することによって、本発明の樹脂組成物を得ることができる。ただし本発明の樹脂組成物は、このような方法で得たものに限定されない。 The resin composition of the present invention can also be obtained, for example, by using a mixture of two or more commercially available silicone-based pressure-sensitive adhesives, a commercially available platinum catalyst, and an organic peroxide. Specifically, for example, a silicone-based pressure-sensitive adhesive having a relatively high gel fraction and storage elastic modulus and a silicone-based pressure-sensitive adhesive having a relatively low gel fraction and storage elastic modulus are mixed at an appropriate ratio, and a platinum catalyst and a platinum catalyst and a storage elastic modulus are mixed. The resin composition of the present invention can be obtained by blending an appropriate amount of organic peroxide. However, the resin composition of the present invention is not limited to that obtained by such a method.
　本発明の樹脂組成物には、各種特性の向上を目的として添加剤を添加しても良い。添加剤の具体例としては、カーボンブラック、シリカ等の無機充填剤；シリコーンレジン、ポリジメチルシロキサン、ポリジメチルフェニルシロキサン等のポリオルガノシロキサン；フェノール系酸化防止剤、アミン系酸化防止剤等の酸化防止剤；シランカップリング剤が挙げられる。 Additives may be added to the resin composition of the present invention for the purpose of improving various properties. Specific examples of the additive include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane, and polydimethylphenylsiloxane; antioxidants such as phenolic antioxidants and amines. Agent; silane coupling agent can be mentioned.
　＜粘着テープ＞
　本発明の粘着テープは、架橋後の本発明の樹脂組成物により構成される粘着剤層を有する粘着テープである。この粘着テープは、基材フィルムの片面又は両面にその粘着剤層を有する粘着テープであっても良いし、基材が無いベースレスタイプの粘着テープであっても良い。また、基材の片面に架橋後の本発明の樹脂組成物により構成される粘着剤層を有し、もう一方の面には他の粘着剤層（従来の粘着剤層）を有する両面粘着テープであっても良い。 <Adhesive tape>
The adhesive tape of the present invention is an adhesive tape having an adhesive layer composed of the resin composition of the present invention after cross-linking. This adhesive tape may be an adhesive tape having the adhesive layer on one side or both sides of the base film, or may be a baseless type adhesive tape without a base material. A double-sided adhesive tape having a pressure-sensitive adhesive layer composed of the resin composition of the present invention after cross-linking on one side of the base material and another pressure-sensitive adhesive layer (conventional pressure-sensitive adhesive layer) on the other side. It may be.
　粘着テープの粘着剤層の厚さは、２μｍ以上１０μｍ以下であり、好ましくは４μｍ以上８μｍ以下である。粘着剤層の厚さを２μｍ以上１０μｍ以下とすることにより、高荷重・高温環境下で使用された場合に寸法安定性が向上し、糊残りが抑制される傾向にある。 The thickness of the adhesive layer of the adhesive tape is 2 μm or more and 10 μm or less, preferably 4 μm or more and 8 μm or less. By setting the thickness of the pressure-sensitive adhesive layer to 2 μm or more and 10 μm or less, dimensional stability is improved when used in a high load / high temperature environment, and adhesive residue tends to be suppressed.
　粘着剤層は、本発明の樹脂組成物を架橋硬化反応させることにより形成できる。例えば、樹脂組成物を基材上に塗布し、加熱又は紫外線照射により架橋硬化させて基材上に粘着剤層を形成できる。また、樹脂組成物を離型紙又はその他のフィルム上に塗布し、加熱又は紫外線照射により架橋硬化させて粘着剤層を形成し、この粘着剤層を基材の片面又は両面に貼り合せることもできる。ベースレスタイプの粘着テープは、離型紙又はその他のフィルム上に粘着剤層を形成し、次いで粘着剤層の上に別の離型紙又はその他のフィルムを貼り合わせすることにより製造できる。 The pressure-sensitive adhesive layer can be formed by subjecting the resin composition of the present invention to a cross-linking and curing reaction. For example, the resin composition can be applied onto a base material and crosslinked and cured by heating or irradiation with ultraviolet rays to form an adhesive layer on the base material. Alternatively, the resin composition may be applied onto a paper pattern or other film and crosslinked and cured by heating or ultraviolet irradiation to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer may be bonded to one or both sides of a base material. .. The baseless type adhesive tape can be produced by forming an adhesive layer on a release paper or other film, and then laminating another release paper or other film on the adhesive layer.
　塗布の際の樹脂組成物の粘度を下げる為に、溶剤を添加しても良い。溶剤の具体例としては、トルエン、キシレン等の芳香族系溶剤；ヘキサン、オクタン、イソパラフィン等の脂肪族系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；酢酸エチル、酢酸イソブチル等のエステル系溶剤；ジイソプロピルエーテル、１,４－ジオキサン等のエーテル系溶剤が挙げられる。 A solvent may be added in order to reduce the viscosity of the resin 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.
　塗工方法は特に限定されず、公知方法を用いれば良い。その具体例としては、コンマコーター、リップコーター、ロールコーター、ダイコーター、ナイフコーター、ブレードコーター、ロッドコーター、キスコーター又はグラビアコーターを用いた塗工；スクリーン塗工；浸漬塗工；キャスト塗工が挙げられる。 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.
　基材は特に限定されないが、フィルム状の基材が好ましい。特に、高温下で処理可能な耐熱性の高い樹脂フィルムが好ましい。その具体例としては例えば、ポリイミド（ＰＩ）、ポリエチレンテレフタラート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエチレンサルファイド（ＰＰＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等の樹脂フィルムが挙げられる。これらのフィルムを単層、または２層以上の積層フィルムとして使用することができる。中でもポリイミドフィルムが好ましい。基材の厚さは特に限定されないが、好ましくは５～２００μｍ、より好ましくは５～１２５μｍである。 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 resins such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyethylene sulfide (PPS), and polytetrafluoroethylene (PTFE). Film is mentioned. These films can be used as a single layer or as 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 125 μm.
　さらに、基材の粘着剤層を設ける面には、必要に応じて易接着処理を施しても良い。易接着処理としては、例えば、プライマー処理、コロナ処理、エッチング処理、プラズマ処理、サンドブラスト処理などが挙げられる。 Further, the surface of the base material on which the pressure-sensitive adhesive layer is provided may be subjected to an easy-adhesion treatment, if necessary. Examples of the easy-adhesion treatment include a primer treatment, a corona treatment, an etching treatment, a plasma treatment, and a sandblast treatment.
　本発明の粘着テープには剥離ライナーを設けても良い。剥離ライナーとは、粘着テープの粘着剤層を保護する為のものであり、貼り付け直前に剥離し、粘着剤を露出させて被着体に粘着テープを貼り付ける。剥離ライナーの種類は特に限定されず、公知の剥離ライナーを使用できる。その具体例としては、上質紙、グラシン紙、合成樹脂フィルム等の基材の表面に離型剤処理を施したものが挙げられる。離型剤処理には、例えばフッ素置換アルキル変性シリコーン樹脂等の離型剤を用いれば良い。特に、シリコーン系粘着剤層に積層する剥離ライナーとしては、ポリエチレンタレフタレートフィルムの表面をフッ素置換アルキル変性シリコーン樹脂で離型処理したものが好ましい。また、粘着剤層の粘着性が低い場合は、離型処理の施されていない樹脂フィルムを剥離ライナーとして使用しても良い。その具体例としては、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレン（ＰＥ）フィルム、ポリプロピレン（ＰＰ）フィルムが挙げられる。 The adhesive tape of the present invention may be provided with a release liner. The release liner is for protecting the adhesive layer of the adhesive tape, and is peeled off immediately before application to expose the adhesive and attach 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 woodfree paper, glassine paper, or synthetic resin film to a mold release agent treatment. For the release agent treatment, for example, a 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, one in which the surface of the polyethylene tale phthalate film is mold-released with a fluorine-substituted alkyl-modified silicone resin is preferable. When the adhesiveness of the pressure-sensitive adhesive layer is low, a resin film that has not been subjected to the mold release treatment may be used as the release liner. Specific examples thereof include polyethylene terephthalate (PET) film, polyethylene (PE) film, and polypropylene (PP) film.
　以下、実施例により本発明をさらに詳細に説明する。ただし、本発明はこれら実施例に限定されるものではない。以下の記載において「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. In the following description, "part" means "part by mass".
　＜実施例１＞
　まず、付加硬化型シリコーン系粘着剤（原液）の複数の試作品（Ａ～Ｆ）を用意した。これら複数の試作品は、後述する方法で測定される硬化後の貯蔵弾性率Ｇ'及びゲル分率が様々な値を示すように調整した粘着剤の試作品である。なお、これらの試作品はいずれも、アルケニル基を含有するシリコーン生ゴムと、ＭＱレジンと、架橋剤とからなるシリコーン系粘着剤である。 <Example 1>
First, a plurality of prototypes (A to F) of an addition-curable silicone-based adhesive (stock solution) were prepared. These plurality of prototypes are prototypes of adhesives adjusted so that the storage elastic modulus G'and the gel fraction after curing, which are measured by the methods described later, show various values. All of these prototypes are silicone-based adhesives composed of a silicone raw rubber containing an alkenyl group, an MQ resin, and a cross-linking agent.
　実施例１においては、これら複数の試作品のうち、有機過酸化物を適量添加した場合に硬化後の貯蔵弾性率Ｇ'が及びゲル分率が、後述する特定の値になる付加硬化型シリコーン系粘着剤（Ａ）（固形分濃度６０％）を選択した。 In Example 1, of these plurality of prototypes, when an appropriate amount of an organic peroxide is added, the storage elastic modulus G'after curing and the gel fraction become specific values described later, which is an addition-curable silicone. The system adhesive (A) (solid content concentration 60%) was selected.
　そして、この付加硬化型シリコーン系粘着剤原液（Ａ）１００部、希釈溶剤としてトルエン１９７部、有機過酸化物として日油株式会社製の有機過酸化物型硬化剤（ナイパー(登録商標)ＢＭＴ－Ｋ４０、有機過酸化物の濃度：４０％、有機過酸化物中の理論活性酸素量：６.０５％）３.０部、白金触媒（ＮＣ－２５、ダウ・東レ株式会社製）０.３部を均一に混合し、粘着剤液（１）を得た。この粘着剤液（１）において、シリコーン粘着剤１００部に対しての有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。 Then, 100 parts of this addition-curing silicone-based pressure-sensitive adhesive stock solution (A), 197 parts of toluene as a diluting solvent, and an organic peroxide-type curing agent manufactured by Nichiyu Co., Ltd. as an organic peroxide (Nipper (registered trademark) BMT- K40, concentration of organic peroxide: 40%, theoretical amount of active oxygen in organic peroxide: 6.05%) 3.0 parts, platinum catalyst (NC-25, manufactured by Dow Toray Co., Ltd.) 0.3 The parts were uniformly mixed to obtain a pressure-sensitive adhesive solution (1). 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 with respect to 100 parts of the silicone pressure-sensitive adhesive is 0.12 parts.
　この粘着剤液（１）に対して、後述する動的粘弾性測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は１６８６２８Ｐａであった。またこの粘着剤液（１）に対して、後述するゲル分率測定を行ったところ、ゲル分率は４６％であった。 When the dynamic viscoelasticity measurement described later was performed on this pressure-sensitive adhesive liquid (1), the storage elastic modulus G'at 200 ° C. was 168628 Pa. Further, when the gel fraction measurement described later was performed on this pressure-sensitive adhesive liquid (1), the gel fraction was 46%.
　次に、プライマー処理した厚さ２５μｍのポリイミド（ＰＩ）フィルムの片面に、粘着剤液（１）を乾燥後の粘着剤層の厚さが６μｍになるように塗布し、乾燥炉内にて６０℃で１分間乾燥して溶剤を除去し、２００℃で１分間加熱硬化して粘着剤層を形成した。そして剥離ライナーとしてフッ素置換アルキル変性シリコーン樹脂で離型処理した厚さ５０μｍのポリエチレンテレフタラート（ＰＥＴ）フィルムを粘着剤層に貼り合わせ、粘着テープを得た。 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 6 μm, and 60 in a drying furnace. The solvent was removed by drying at ° C. for 1 minute, and the pressure was cured by heating at 200 ° C. for 1 minute to form an adhesive layer. 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.
　［動的粘弾性測定］
　粘着剤液（１）を剥離ライナー上に、乾燥後の厚さが５０μｍになるように塗布する。続いて乾燥炉内にて６０℃で１分間乾燥して溶剤を除去する。そして、２００℃で１分間加熱することによりシリコーン成分を硬化して、硬化後のシリコーン系粘着剤組成物からなる粘着剤層を形成する。この操作を複数繰り返すことにより積層して厚さ２ｍｍの粘着剤層の積層体を形成し、これを測定用サンプルとする。 [Dynamic viscoelasticity measurement]
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 1 minute to form a pressure-sensitive adhesive layer composed 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.
　測定用サンプルを平行円盤（φ８ｍｍ）の間に挟み、動的粘弾性測定装置（Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社製、装置名ＲＤＡIII）を用いて、周波数１０Ｈｚのせん断ひずみを加えながら、昇温速度１０℃／分で、－６０℃～３００℃の範囲において貯蔵弾性率Ｇ'を測定する。 A measurement sample is sandwiched between parallel disks (φ8 mm), and a temperature rise rate of 10 ° C./min is applied using a dynamic viscoelasticity measuring device (manufactured by Rheometric Scientific, device name RDAIII) while applying shear strain at a frequency of 10 Hz. Then, the storage elastic modulus G'is measured in the range of -60 ° C to 300 ° C.
　［ゲル分率測定］
　粘着剤液（１）を剥離ライナー上に、乾燥後の厚さが５０μｍになるように塗布する。続いて乾燥炉内にて６０℃で１分間乾燥して溶剤を除去する。そして、２００℃で１分間加熱することによりシリコーン成分を硬化して、硬化後のシリコーン系粘着剤組成物からなる粘着剤層を形成し、これを測定用サンプルとする。 [Measurement of gel fraction]
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 1 minute to form a pressure-sensitive adhesive layer composed of the cured silicone-based pressure-sensitive adhesive composition, which is used as a measurement sample.
　得られたサンプルを５０ｍｍ×５０ｍｍに断裁し、剥離ライナーを剥離し、シート状のシリコーン系粘着剤組成物からなる測定用サンプルを得た。そしてこの測定用サンプルを、初期質量（Ｘ）の２５０倍量以上のトルエンに常温（２３℃）で1日間浸漬し膨潤させた。浸漬後に測定用サンプルを取り出し、１３０℃の乾燥機で２時間乾燥させて吸収した溶媒を除去し、乾燥質量（Ｙ）（＝乾燥したシリコーン系粘着剤組成物の質量）を測定した。シリコーン系粘着剤組成物のゲル分率は下記式によって得た。
ゲル分率（％）＝（Ｙ／Ｘ）×１００％ The obtained sample was cut into 50 mm × 50 mm, the release liner was peeled off, and a measurement sample composed of a sheet-shaped silicone-based pressure-sensitive adhesive composition was obtained. Then, this measurement sample was immersed in toluene in an amount of 250 times or more the initial mass (X) at room temperature (23 ° C.) for 1 day to swell. After the immersion, the measurement sample was taken out and dried in a dryer at 130 ° C. for 2 hours to remove the absorbed solvent, and the dry mass (Y) (= mass of the dried silicone-based pressure-sensitive adhesive composition) was measured. The gel fraction of the silicone-based pressure-sensitive adhesive composition was obtained by the following formula.
Gel fraction (%) = (Y / X) x 100%
　＜実施例２＞
　付加硬化型シリコーン系粘着剤原液（Ａ）（固形分濃度６０％）１００部の代わりに、付加硬化型シリコーン系粘着剤原液（Ａ）（固形分濃度４０％）５０部と付加硬化型シリコーン系粘着剤原液（Ｂ）（固形分濃度４０質量％）５０部の混合物を使用し、有機過酸化物の量を２.５部に変更したこと以外は、実施例１と同様の方法で粘着剤液（２）を調製し、粘着テープを作製した。粘着剤液（２）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。また、粘着剤液（２）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は１２４１２１Ｐａ、ゲル分率は５５％であった。 <Example 2>
Instead of 100 parts of the addition-curing silicone-based adhesive stock solution (A) (solid content concentration 60%), 50 parts of the addition-curing silicone-based pressure-sensitive adhesive stock solution (A) (solid content concentration 40%) and the addition-curing silicone type Adhesive in the same manner as in Example 1 except that a mixture of 50 parts of the adhesive stock solution (B) (solid content concentration 40% by mass) was used and the amount of organic peroxide was changed to 2.5 parts. Liquid (2) was prepared to prepare an adhesive tape. 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (2), the storage elastic modulus G'at 200 ° C. was 124121Pa and the gel fraction was 55%.
　＜実施例３＞
　有機過酸化物の量を４.５質量部に変更したこと以外は、実施例２と同様の方法で粘着剤液（３）を調製し、粘着テープを作製した。粘着剤液（３）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.２２部である。また、粘着剤液（３）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は２１９８６１Ｐａ、ゲル分率は６０％であった。 <Example 3>
The pressure-sensitive adhesive liquid (3) was prepared in the same manner as in Example 2 except that the amount of the organic peroxide was changed to 4.5 parts by mass, 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 0.22 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (3), the storage elastic modulus G'at 200 ° C. was 2119861 Pa and the gel fraction was 60%.
　＜比較例１＞
　付加硬化型シリコーン系粘着剤原液（Ａ）の量を２５部、付加硬化型シリコーン系粘着剤原液（Ｂ）の量を７５部、有機過酸化物の量を２.２５部に変更したこと以外は、実施例２と同様の方法で粘着剤液（Ｃ１）を調製し、粘着テープを作製した。粘着剤液（Ｃ１）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。また、粘着剤液（Ｃ１）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は１２５２７０Ｐａ、ゲル分率は６２％であった。 <Comparative example 1>
Except for changing the amount of add-curing silicone adhesive stock solution (A) to 25 parts, the amount of add-curing silicone adhesive stock solution (B) to 75 parts, and the amount of organic peroxide to 2.25 parts. Prepared an adhesive liquid (C1) in the same manner as in Example 2 to prepare an adhesive tape. 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C1), the storage elastic modulus G'at 200 ° C. was 125270 Pa and the gel fraction was 62%.
　＜比較例２＞
　付加硬化型シリコーン系粘着剤原液（Ａ）（固形分濃度６０％）１００部の代わりに、付加硬化型シリコーン系粘着剤原液（Ｂ）（固形分濃度４０％）１００部を使用し、有機過酸化物の量を２部に変更したこと以外は、実施例１と同様の方法で粘着剤液（Ｃ２）を調製し、粘着テープを作製した。粘着剤液（Ｃ２）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。また、粘着剤液（Ｃ２）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は１３６７５７Ｐａ、ゲル分率は６９％であった。 <Comparative example 2>
Instead of 100 parts of the addition-curing silicone adhesive stock solution (A) (solid content concentration 60%), 100 parts of the addition curing silicone adhesive stock solution (B) (solid content concentration 40%) is used, and organic excess is used. An adhesive liquid (C2) was prepared in the same manner as in Example 1 except that the amount of oxide was changed to 2 parts, and an 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C2), the storage elastic modulus G'at 200 ° C. was 136757 Pa and the gel fraction was 69%.
　＜比較例３＞
　有機過酸化物を添加しなかったこと以外は、実施例２と同様の方法で粘着剤液（Ｃ３）を調製し、粘着テープを作製した。粘着剤液（Ｃ３）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０部である。また、粘着剤液（Ｃ３）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は２４０５０８Ｐａ、ゲル分率は５３％であった。 <Comparative example 3>
An adhesive liquid (C3) was prepared in the same manner as in Example 2 except that no organic peroxide was added, to prepare an adhesive tape. 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 part. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C3), the storage elastic modulus G'at 200 ° C. was 240508 Pa and the gel fraction was 53%.
　＜比較例４＞
　付加硬化型シリコーン系粘着剤原液（Ａ）（固形分濃度６０％）１００部の代わりに、付加硬化型シリコーン系粘着剤原液（Ｃ）（固形分濃度９０質量％）２５部と付加硬化型シリコーン系粘着剤原液（Ｄ）（固形分濃度９０質量％）７５部の混合物を使用し、有機過酸化物の量を４.５部に変更したこと以外は、実施例１と同様の方法で粘着剤液（Ｃ４）を調製し、粘着テープを作製した。粘着剤液（Ｃ４）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。また、粘着剤液（Ｃ４）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は１７６２０Ｐａ、ゲル分率は４８％であった。 <Comparative example 4>
Instead of 100 parts of the addition-curing silicone-based pressure-sensitive adhesive stock solution (A) (solid content concentration 60%), 25 parts of the addition-curing silicone-based pressure-sensitive adhesive stock solution (C) (solid content concentration 90% by mass) and the addition-curing silicone Adhesive in the same manner as in Example 1 except that a mixture of 75 parts of the system adhesive stock solution (D) (solid content concentration 90% by mass) was used and the amount of organic peroxide was changed to 4.5 parts. An agent solution (C4) was prepared to prepare an adhesive tape. 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C4), the storage elastic modulus G'at 200 ° C. was 17620 Pa and the gel fraction was 48%.
　＜比較例５＞
　付加硬化型シリコーン系粘着剤原液（Ａ）（固形分濃度６０％）１００部の代わりに、付加硬化型シリコーン系粘着剤原液（Ｅ）（固形分濃度６０質量％）１００部を使用したこと以外は、実施例１と同様の方法で粘着剤液（Ｃ５）を調製し、粘着テープを作製した。粘着剤液（Ｃ５）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０.１２部である。また、粘着剤液（Ｃ５）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は９８８８０Ｐａ、ゲル分率は４４％であった。 <Comparative example 5>
Except for the fact that 100 parts of the addition-curing silicone adhesive stock solution (E) (solid content concentration 60% by mass) was used instead of 100 parts of the addition-curing silicone adhesive stock solution (A) (solid content concentration 60%). Prepared an adhesive liquid (C5) in the same manner as in Example 1 to prepare an adhesive tape. 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 0.12 parts. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C5), the storage elastic modulus G'at 200 ° C. was 98880 Pa and the gel fraction was 44%.
　＜比較例６＞
　有機過酸化物を添加しなかったこと以外は、比較例５と同様の方法で粘着剤液（Ｃ６）を調製し、粘着テープを作製した。粘着剤液（Ｃ６）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０部である。また、粘着剤液（Ｃ６）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は６９７０２Ｐａ、ゲル分率は３４％であった。 <Comparative Example 6>
An adhesive liquid (C6) was prepared in the same manner as in Comparative Example 5 except that no organic peroxide was added, to prepare an adhesive tape. 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 part. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C6), the storage elastic modulus G'at 200 ° C. was 69702 Pa and the gel fraction was 34%.
　＜比較例７＞
　付加硬化型シリコーン系粘着剤原液（Ｅ）（固形分濃度６０質量％）１００部の代わりに、付加硬化型シリコーン系粘着剤原液（Ｆ）（固形分濃度６０質量％）１００部を使用したこと以外は、比較例６と同様の方法で粘着剤液（Ｃ７）を調製し、粘着テープを作製した。粘着剤液（Ｃ７）において、有機過酸化物の量Ｐと有機過酸化物の理論活性酸素量Ａの積ＰＡは０部である。また、粘着剤液（Ｃ７）に対して動的粘弾性測定及びゲル分率測定を行ったところ、２００℃における貯蔵弾性率Ｇ'は６９０４５Ｐａ、ゲル分率は４４％であった。 <Comparative Example 7>
100 parts of the addition-curing silicone adhesive stock solution (F) (solid content concentration 60% by mass) was used instead of 100 parts of the addition-curing silicone adhesive stock solution (E) (solid content concentration 60% by mass). A pressure-sensitive adhesive solution (C7) was prepared in the same manner as in Comparative Example 6 except for the above, 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 part. Further, when the dynamic viscoelasticity measurement and the gel fraction measurement were performed on the pressure-sensitive adhesive liquid (C7), the storage elastic modulus G'at 200 ° C. was 69045 Pa and the gel fraction was 44%.
　＜参考例１＞
　粘着剤層の厚さを１３μｍに変更したこと以外は、実施例２と同様の方法で粘着テープを作製した。 <Reference example 1>
An adhesive tape was produced in the same manner as in Example 2 except that the thickness of the adhesive layer was changed to 13 μm.
　以上の実施例及び比較例の粘着テープに対し、以下の評価を行った。結果を表１に示す。 The following evaluations were performed on the adhesive tapes of the above Examples and Comparative Examples. The results are shown in Table 1.
　［熱プレス後の糊はみだし及び剥離後糊残り測定］
　２０ｍｍ×２０ｍｍに断裁した粘着テープを、表面をピカール液（日本磨料工業株式会社製）にて研磨処理したＣｕ板（Ｃｌ１００ｐ）に貼り付け、重さ２ｋｇのゴム層で被覆されたローラーで１往復させて圧着した。そして、これを２３℃環境下で２０分～１時間放置し、測定用貼り合わせサンプルを得た。このサンプルを、両面が鏡面加工された２枚のＳＵＳ３０４板で挟み、温度２００℃、圧力３０ｋｇ／ｃｍ２で４時間加熱プレスした。加熱プレス後の糊はみだし及びテープを剥離した後の糊残りを、マイクロスコープ（ＶＨＸ－６０００、株式会社キーエンス製）を用いて倍率１００倍にて観察し、以下の基準で評価した。
　（熱プレス後の糊はみだし）
　「〇」：４辺又は角からの糊はみだしは観察されなかった。
　「×」：４辺又は角からの糊はみだしが観察された。
　（熱プレス後の糊残り）
　　〇：貼り付け面において糊残りは観察されなかった。
　　×：貼り付け面において糊残りが観察された。 [Measurement of glue squeeze out after hot pressing and glue residue after peeling]
Adhesive tape cut to 20 mm x 20 mm is attached to a Cu plate (Cl100p) whose surface has been polished with Picard liquid (manufactured by Nippon Shinryo Kogyo Co., Ltd.), and one reciprocation with a roller covered with a rubber layer weighing 2 kg. And crimped. Then, this was left to stand in an environment of 23 ° C. for 20 minutes to 1 hour to obtain a bonded sample for measurement. This sample was sandwiched between two SUS304 plates whose both sides were mirror-finished, and heat-pressed at a temperature of 200 ° C. and a pressure of 30 kg / cm 2 for 4 hours. The glue squeezed out after the heat press and the glue residue after the tape was peeled off were observed with a microscope (VHX-6000, manufactured by KEYENCE CORPORATION) at a magnification of 100 times, and evaluated according to the following criteria.
(Glue sticks out after hot pressing)
"○": No glue squeezed out from the four sides or corners was observed.
"X": Glue squeezing out from four sides or corners was observed.
(Remaining glue after hot pressing)
〇: No adhesive residue was observed on the sticking surface.
X: Adhesive residue was observed on the sticking surface.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　＜評価結果＞
　表１に示すように、実施例１～３の粘着テープは、２００℃で熱プレス後の糊残り及び糊はみだしが発生しなかった。 <Evaluation result>
As shown in Table 1, the adhesive tapes of Examples 1 to 3 did not generate adhesive residue and adhesive squeeze after hot pressing at 200 ° C.
　比較例１及び２は、粘着剤組成物の架橋後のゲル分率が高過ぎる例である。その結果、比較例１及び２の粘着テープには糊残りが発生した。 Comparative Examples 1 and 2 are examples in which the gel fraction after cross-linking of the pressure-sensitive adhesive composition is too high. As a result, adhesive residue was generated on the adhesive tapes of Comparative Examples 1 and 2.
　比較例３は、粘着剤組成物に有機過酸化物を使用しない例である。その結果、比較例３の粘着テープには糊残りが発生した。 Comparative Example 3 is an example in which an organic peroxide is not used in the pressure-sensitive adhesive composition. As a result, adhesive residue was generated on the adhesive tape of Comparative Example 3.
　比較例４は、粘着剤組成物の架橋後の貯蔵弾性率が低過ぎる例である。その結果、比較例４の粘着テープには糊はみだし及び糊残りが発生した。 Comparative Example 4 is an example in which the storage elastic modulus of the pressure-sensitive adhesive composition after cross-linking is too low. As a result, the adhesive tape of Comparative Example 4 had adhesive squeeze out and adhesive residue.
　比較例５は、粘着剤組成物の架橋後のゲル分率及び貯蔵弾性率が低過ぎる例である。その結果、比較例４の粘着テープには糊はみだし及び糊残りが発生した。 Comparative Example 5 is an example in which the gel fraction and storage elastic modulus after cross-linking of the pressure-sensitive adhesive composition are too low. As a result, the adhesive tape of Comparative Example 4 had adhesive squeeze out and adhesive residue.
　比較例６及び７は、粘着剤組成物に有機過酸化物を使用せず、かつ粘着剤組成物の架橋後のゲル分率及び貯蔵弾性率が低過ぎる例である。その結果、比較例６及び７の粘着テープには糊はみだし及び糊残りが発生した。 Comparative Examples 6 and 7 are examples in which no organic peroxide is used in the pressure-sensitive adhesive composition and the gel fraction and storage elastic modulus after cross-linking of the pressure-sensitive adhesive composition are too low. As a result, the adhesive tapes of Comparative Examples 6 and 7 had adhesive squeeze out and adhesive residue.
　参考例１は、粘着剤層の厚さが厚すぎる例である。その結果、参考例１の粘着テープには糊はみだし及び糊残りが発生した。この結果から、本発明の樹脂組成物（粘着剤組成物）を粘着テープの粘着剤層の用途に使用する場合は、その粘着剤層の厚さは比較的薄い方が好ましいことを理解できる。 Reference example 1 is an example in which the thickness of the adhesive layer is too thick. As a result, the adhesive tape of Reference Example 1 had adhesive squeeze out and adhesive residue. From this result, it can be understood that when the resin composition (adhesive composition) of the present invention is used for the use of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, the thickness of the pressure-sensitive adhesive layer is preferably relatively thin.
　本発明の樹脂組成物は、例えば粘着テープの粘着剤層形成する為の材料として特に有用である。本発明の粘着テープは高荷重・高温環境下で処理が必要となる工程、例えばプリント積層基板の製造工程中、高温（例えば１８０℃以上）、高圧力（例えば２０ｋｇ／ｃｍ２以上）で、長時間（例えば２時間以上）加熱プレスする工程において、被着体（例えば、積層基盤表面）の保護、マスキング、仮固定、搬送時固定の用途に非常に有用である。 The resin composition of the present invention is particularly useful as a material for forming an adhesive layer of an adhesive tape, for example. The adhesive tape of the present invention is long at high temperature (for example, 180 ° C. or higher) and high pressure (for example, 20 kg / cm 2 or higher) during a process that requires treatment in a high load / high temperature environment, for example, in the manufacturing process of a printed laminated substrate. It is very useful for protection of adherends (for example, the surface of a laminated substrate), masking, temporary fixing, and fixing during transportation in a step of heating and pressing for a time (for example, 2 hours or more).

Claims (3)

  1. 　アルケニル基を含有するシリコーン生ゴムと、ＭＱレジンと、架橋剤と、白金触媒と、有機過酸化物とを含み、
    　架橋後のゲル分率が４５％以上６０％以下であり、
    　架橋後の２００℃における貯蔵弾性率が１０００００Ｐａ以上１００００００Ｐａ以下である樹脂組成物。     It contains a silicone raw rubber containing an alkenyl group, an MQ resin, a cross-linking agent, a platinum catalyst, and an organic peroxide.
    The gel fraction after cross-linking is 45% or more and 60% or less.
    A resin composition having a storage elastic modulus at 200 ° C. after cross-linking of 100,000 Pa or more and 1,000,000 Pa or less.
  2. 　アルケニル基を含有するシリコーン生ゴム、ＭＱレジン及び架橋剤の合計１００質量部に対する有機過酸化物の量Ｐ（質量部）と下記式（１）で表される有機過酸化物の理論活性酸素量Ａ（％）の積ＰＡが０.０６質量部以上である請求項１記載の樹脂組成物。
    　Ａ（％）＝（Ｂ×１６／Ｍ）×１００　　　（１）
    ［式（１）中、Ａは有機過酸化物の理論活性酸素量を示し、Ｂは過酸化結合の数を示し、Ｍは有機過酸化物の分子量を示す。］     Amount P (parts by mass) of organic peroxide and theoretical active oxygen amount A of organic peroxide represented by the following formula (1) with respect to a total of 100 parts by mass of silicone raw rubber containing an alkenyl group, MQ resin and cross-linking agent. The resin composition according to claim 1, wherein the product PA of (%) is 0.06 parts by mass or more.
    A (%) = (B x 16 / M) x 100 (1)
    [In the formula (1), A indicates the theoretical active oxygen amount of the organic peroxide, B indicates the number of peroxide bonds, and M indicates the molecular weight of the organic peroxide. ]
  3. 　架橋後の請求項１記載の樹脂組成物により構成される粘着剤層を有する粘着テープであって、
    　前記粘着剤層のゲル分率が４５％以上６０％以下であり、
    　前記粘着剤層の２００℃における貯蔵弾性率が１０００００Ｐａ以上１００００００Ｐａ以下であり、且つ、
    　前記粘着剤層の厚さが２μｍ以上１０μｍ以下である粘着テープ。     An adhesive tape having an adhesive layer composed of the resin composition according to claim 1 after crosslinking.
    The gel fraction of the pressure-sensitive adhesive layer is 45% or more and 60% or less.
    The storage elastic modulus of the pressure-sensitive adhesive layer at 200 ° C. is 100,000 Pa or more and 1,000,000 Pa or less, and
    An adhesive tape having an adhesive layer having a thickness of 2 μm or more and 10 μm or less.
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