CN115362218B - Resin composition and adhesive tape - Google Patents

Resin composition and adhesive tape Download PDF

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Publication number
CN115362218B
CN115362218B CN202080099412.9A CN202080099412A CN115362218B CN 115362218 B CN115362218 B CN 115362218B CN 202080099412 A CN202080099412 A CN 202080099412A CN 115362218 B CN115362218 B CN 115362218B
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adhesive
silicone
organic peroxide
resin composition
adhesive layer
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CN115362218A (en
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土屋靖史
加藤彰大
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Teraoka Seisakusho Co Ltd
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Teraoka Seisakusho Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions 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
    • C08L83/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00Adhesives 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
    • C09J183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application discloses a resin composition, which comprises silicone raw rubber containing alkenyl, MQ resin, a cross-linking agent, a platinum catalyst and organic peroxide, wherein the percentage of gel after cross-linking is more than 45% and less than 60%, and the storage modulus at 200 ℃ after cross-linking is more than 100000Pa and less than 1000000 Pa; and an adhesive tape comprising an adhesive layer formed from the crosslinked resin composition, wherein the adhesive layer has a gel percentage of 45% to 60%, a storage modulus at 200 ℃ of the adhesive layer of 100000Pa to 1000000Pa, and a thickness of 2 [ mu ] m to 10 [ mu ] m.

Description

Resin composition and adhesive tape
Technical Field
The present application relates to a resin composition and an adhesive tape which are excellent in dimensional stability and suppressed in residual adhesive when used in, for example, a process for producing electronic parts and semiconductor parts.
Background
The silicone adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, and chemical resistance. In addition, the adhesive tape having the silicone adhesive layer is less likely to cause adhesive residue at the time of peeling even when used in an environment of particularly high temperature. Therefore, such an adhesive tape is widely used for, for example, protection, shielding, temporary fixing, fixing during transportation, splicing, and the like of members and components in manufacturing processes of electric, electronic, and semiconductor components.
In the manufacturing process of these electric, electronic and semiconductor components, a high-load and high-temperature environment may be used for molding the components. For example, in the process of manufacturing a printed circuit board, the surface of the printed circuit board is already provided withBetween circuit laminated boards forming a circuit pattern, a fiber-reinforced prepreg impregnated with an uncured resin is laminated as an adhesive layer, and the prepreg is laminated under high temperature (for example, 180 ℃ or higher) and high pressure (for example, 20 kg/cm) 2 The above), and a step of heating and pressing by a lamination press for a long period of time (for example, 2 hours or longer). In such a heating and pressing step, the surface of the laminated substrate needs to be protected by an adhesive tape or the like in order to prevent damage to the circuit formation on the surface of the laminated substrate and adhesion of uncured resin.
When a conventional pressure-sensitive adhesive tape having a silicone-based pressure-sensitive adhesive layer is used in a high-temperature, high-pressure, long-time hot-pressing process, the pressure-sensitive adhesive layer is pushed out by the pressing, and the pressure-sensitive adhesive layer changes in size. That is, the adhesive overflows from the end of the adhesive tape, and the overflowed portion becomes a residual adhesive after the adhesive tape is peeled off. In this step, the adhesive is heated at a high temperature and pressed against the adherend. Thus, the adhesive softened at high temperature is more firmly bonded to the adherend, and the adhesive thermally deteriorates due to high-temperature heating, reducing the cohesive force. As a result, when the adhesive tape is peeled off after the heating and pressing step, the bonding force between the adherend and the adhesive is stronger than the cohesive force of the adhesive layer, and the adhesive layer is cohesively broken to generate a residual adhesive.
The residual adhesive caused by the dimensional change of the adhesive in the heating and pressing process tends to be reduced by reducing the thickness of the adhesive layer of the adhesive tape. However, if the thickness of the adhesive layer is reduced, the cohesive force in the thickness direction is reduced, and there is a case where the adhesive tape is peeled off after the step, and a residual adhesive is generated. On the other hand, if the thickness of the adhesive layer is increased, dimensional stability may be lowered, and the adhesive bleeding during heating and pressing may be increased. As described above, the dimensional stability (anti-overflow) in the high temperature process and the anti-residual glue after the high temperature process are contradictory, and are characteristics that are difficult to be compatible.
Patent document 1 discloses a porous fluororesin sheet used as a release protective sheet between a circuit fixing jig and a laminated circuit board in a lamination pressing step for a printed laminated substrate. However, the release protective sheet does not have an adhesive layer, and is therefore not an adhesive tape. That is, since the fixing force to a specific portion is not provided, a portion to be protected cannot be selectively shielded. Therefore, in the case of using the release protective sheet, it is necessary to use the release protective sheet over 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 film and an adhesive layer for forming a release surface. However, this pressure-sensitive adhesive tape is a pressure-sensitive adhesive tape for release, and no study has been made on dimensional stability and residual adhesive at the time of high-temperature processing. In addition, the pressure and heat test conditions of the adhesive tape were 150℃and a pressure of 5kg/cm 2 The conditions of 20 minutes pressing are all more relaxed than those of a general heating pressing process such as a heating pressing process of a laminated substrate.
Patent document 3 discloses a silicone pressure-sensitive adhesive composition containing both a silicone crosslinking agent having SiH groups and a peroxide crosslinking agent as crosslinking agents. However, before the silicone pressure-sensitive adhesive composition is used in the process, the peroxide-based crosslinking agent remains in the silicone pressure-sensitive adhesive composition in an unreacted state. Therefore, it is expected that the peroxide-based crosslinking agent reacts gradually during the process of use before production, storage, shipment, transportation, storage at the customer site, and the like. That is, the characteristics change before the process is actually used in the process, which is disadvantageous from the aspect of stability over time.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 04-179520
Patent document 2: international publication No. 2016/174713
Patent document 3: japanese patent laid-open No. 2002-275450
Disclosure of Invention
Problems to be solved by the application
The present inventors have made intensive studies to solve the problems of dimensional stability and adhesive residue of an adhesive tape, among the characteristics required for the adhesive tape, particularly in applications where the adhesive tape is used under high-load and high-temperature environments. That is, an object of the present application is to provide a resin composition and an adhesive tape which are excellent in dimensional stability when used under a high-load and high-temperature environment and in which residual adhesive is suppressed when peeled off after use under a high-load and high-temperature environment.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object and as a result, have found that a resin composition having a specific component and specific physical properties is very effective, and have completed the present application.
Namely, the present application is a resin composition comprising an alkenyl group-containing silicone raw rubber, an MQ resin, a crosslinking agent, a platinum catalyst and an organic peroxide,
the percentage of gel after crosslinking is 45% or more and 60% or less,
the storage modulus at 200 ℃ after crosslinking is 100000Pa to 1000000 Pa.
The present application also provides an adhesive tape having an adhesive layer formed of the above-mentioned resin composition after crosslinking,
the adhesive layer has a gel percentage of 45% or more and 60% or less,
the adhesive layer has a storage modulus at 200 ℃ of 100000Pa to 1000000Pa,
and the thickness of the adhesive layer is 2 μm or more and 10 μm or less.
Effects of the application
According to the present application, a resin composition and an adhesive tape which are excellent in dimensional stability when used under a high-load and high-temperature environment and in which residual adhesive is suppressed when peeled off after use under a high-load and high-temperature environment can be provided.
The resin composition of the present application has the above-described effects, and is therefore particularly useful as a material used for an adhesive layer of an adhesive tape. The pressure-sensitive adhesive tape of the present application has the above-described effects, and is therefore useful for applications such as protection, shielding, temporary fixation, and the like of an adherend in, for example, a process for producing an electric or electronic component or a semiconductor (particularly, a hot-pressing process).
Detailed Description
< resin composition >
The resin composition of the present application is a composition comprising an alkenyl group-containing silicone raw rubber, an MQ resin, a crosslinking agent, a platinum catalyst, and an organic peroxide. The resin composition is particularly useful as an adhesive composition (i.e., an addition-curable silicone adhesive composition). However, the resin composition of the present application is not limited thereto, and can be used for various other applications.
The percentage of gel after crosslinking of the resin composition of the present application is 45% or more and 60% or less. If the gel percentage is less than 45%, the storage modulus of the resin composition in a molten state after high-temperature heating is lowered, and a tendency of gum overflow is generated. In addition, the adhesion between the resin composition and the adherend is improved, and the cohesive force of the resin composition is reduced, so that the adhesive residue tends to occur. On the other hand, if the gel percentage is more than 60%, the silicone rubber in the resin composition after high-temperature heating is oxidized and cracked, and the cohesive force of the resin composition is lowered, and the resin composition tends to generate residual rubber. The gel percentage is not less than 45% and not more than 60%, and particularly not less than 50% and not more than 60%. Specific methods for determining the gel percentage are described in the examples column below.
The storage modulus at 200 ℃ after crosslinking of the resin composition of the present application is 100000Pa to 1000000 Pa. If the storage modulus is less than 100000Pa, the elasticity of the resin composition in a molten state after high-temperature heating is reduced, and for example, the shape of the resin composition temporarily deformed in a high-load high-temperature process such as a hot pressing process is less likely to be recovered, and a flash tends to occur. The storage modulus is not less than 100000Pa and not more than 1000000Pa, but particularly not less than 100000Pa and not more than 400000 Pa. Specific measurement methods of the storage modulus are described in the column of examples described later.
The alkenyl-containing silicone raw rubber used in the present application typically has a structural unit containing D [ (CH) 3 ) 2 SiO]Long chain polymers of polydimethylsiloxanes of the structure (C),and is a polymer containing at least 2 alkenyl groups per 1 molecule. However, the present application is not limited to this, and other types of silicone raw rubber may be used.
The MQ resin used in the present application typically has a resin composition comprising M units [ (CH) 3 ) 3 SiO 1/2 ]And Q units [ SiO ] 2 ]A three-dimensional structure of a silicone resin. However, the present application is not limited to this, and other types of MQ resins may be used.
The crosslinking agent used in the present application is typically a polyorganosiloxane containing at least 2 SiH groups per 1 molecule. However, the present application is not limited to this, and other types of crosslinking agents may be used.
As an addition-curable silicone-based adhesive, a resin composition containing an alkenyl group-containing silicone raw rubber, an MQ resin, and a crosslinking agent as described above is generally known. The addition-curable silicone-based adhesive includes, for example: a main agent comprising an alkenyl-containing silicone green, an MQ resin, and a crosslinking agent comprising a SiH-containing polyorganosiloxane. The addition-curable silicone adhesive is cured by heating under a platinum catalyst to perform a crosslinking reaction. It is also known that basic adhesive properties such as adhesive force, holding force, and tackiness can be adjusted by changing the ratio of silicone raw rubber to MQ resin in the addition-curable silicone-based adhesive.
Various methods are known for adjusting the gel percentage of an addition-curable silicone-based adhesive. For example, if the blending ratio of MQ resin to silicone raw rubber is reduced, the content of alkenyl groups in silicone raw rubber (and/or MQ resin) is increased, or the amount of the crosslinking agent added is increased, the gel percentage after crosslinking tends to be high. On the other hand, if a non-crosslinking component (for example, silicone oil or the like) is added, the gel percentage tends to be low.
Various methods are known for adjusting the storage modulus of addition-curable silicone adhesives. For example, when the molecular weight of the silicone raw rubber is increased, the crosslinking density is increased, and the blending ratio of MQ resin to the silicone raw rubber is decreased, the energy storage modulus tends to be high.
In order to obtain the resin composition of the present application exhibiting a specific gel percentage and storage modulus, the above respective adjustment methods may be employed. However, the resin composition of the present application is not limited to the resin composition obtained by such a method of adjustment.
The resin composition of the present application further comprises a platinum catalyst. The platinum catalyst is a component that promotes a crosslinking reaction after activation by heating. The type and amount of the platinum catalyst are not particularly limited, and for example, various platinum catalysts which are known to be usable as addition-curable silicone adhesives and the amount thereof can be used. That is, in the present application, for example, a commercially available platinum catalyst (curing catalyst for addition-curable silicone-based adhesives) may be used in an appropriate amount.
The resin composition of the present application further comprises an organic peroxide. According to the findings of the present inventors, the organic peroxide is effective not only for exhibiting general characteristics but also for exhibiting the effects of the present application (inhibition of residual gum, etc.). The reason for this is not necessarily clear, but one of the reasons is considered to be that free oxygen radicals generated by decomposition of the organic peroxide participate in the crosslinking reaction, and properly act on the crosslinking density and other characteristics. The gel percentage and storage modulus can also be adjusted by changing the content of the organic peroxide.
The type of the organic peroxide is not particularly limited as long as it is a substance that generates free oxygen radicals after decomposition. Dibenzoyl peroxide and its derivatives are particularly preferred. Specific examples thereof include dibenzoyl peroxide, 4 '-dimethylbenzoyl peroxide, 3' -dimethylbenzoyl peroxide, 2', 4' -tetrachlorodibenzoyl peroxide, and cumyl peroxide. The organic peroxide may be used alone or in combination of 2 or more.
Free oxygen is generated by the decomposition of free oxygen gene organic peroxides. The stoichiometry (i.e., the theoretical active oxygen content of the organic peroxide) was calculated using the following formula (1).
A(%)=(B×16/M)×100 (1)
In the formula (1), A represents the theoretical active oxygen amount of the organic peroxide, B represents the number of peroxide bonds, and M represents the molecular weight of the organic peroxide. ]
In the present application, the amount of the organic peroxide is not particularly limited as long as it is appropriately determined according to the respective conditions such as the curing temperature, the decomposition temperature of the organic peroxide, the ratio of the silicone raw rubber to the MQ resin, the molecular weight of the silicone component, and the like. However, the product PA of the amount P (parts by mass) of the organic peroxide and the theoretical active oxygen amount a (%) of the organic peroxide represented by the above formula (1) is preferably 0.06 parts by mass or more, more preferably 0.10 parts by mass or more and 0.30 parts by mass or less, relative to 100 parts by mass of the total of the alkenyl group-containing silicone raw rubber, MQ resin, and crosslinking agent described above. The gel percentage and storage modulus can be adjusted by changing the product PA.
The above-described components are available as commercial products, for example. For example, the resin composition of the present application can 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 adhesive. However, the composition and other conditions need to be appropriately adjusted so that the gel percentage and storage modulus fall within the scope of the present application. Further, by crosslinking and curing it, a resin composition containing a silicone structure after crosslinking, which exhibits the effects of the present application, can be obtained. The crosslinking curing reaction is usually carried out by heating. However, the crosslinking curing can be performed by ultraviolet irradiation depending on the types of the components.
The resin composition of the present application can be obtained by using a mixture of 2 or more commercially available silicone adhesives, a commercially available platinum catalyst, and an organic peroxide. Specifically, for example, a silicone-based adhesive having a high gel percentage and a low storage modulus and a silicone-based adhesive having a low gel percentage and a low storage modulus are mixed in an appropriate ratio, and a platinum catalyst and an appropriate amount of an organic peroxide are blended, whereby the resin composition of the present application can be obtained. However, the resin composition of the present application is not limited to the resin composition obtained by such a method.
In the resin composition of the present application, additives may be added for the purpose of improving various characteristics. Specific examples of the additive include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resins, polydimethylsiloxane, and polydiphenyl siloxane; antioxidants such as phenol antioxidants and amine antioxidants; a silane coupling agent.
< adhesive tape >
The adhesive tape of the present application is an adhesive tape having an adhesive layer formed from the crosslinked resin composition of the present application. The pressure-sensitive adhesive tape may be a pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer on one or both sides of a substrate film, or may be a substrate-free pressure-sensitive adhesive tape having no substrate. The pressure-sensitive adhesive tape may be a double-sided pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer formed of the resin composition of the present application after crosslinking on one side of a substrate and having another pressure-sensitive adhesive layer (conventional pressure-sensitive adhesive layer) on the other side.
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape has a thickness of 2 μm or more and 10 μm or less, preferably 4 μm or more and 8 μm or less. When the thickness of the pressure-sensitive adhesive layer is set to 2 μm or more and 10 μm or less, dimensional stability is improved when used under a high-load and high-temperature environment, and the residual adhesive tends to be suppressed.
The adhesive layer may be formed by subjecting the resin composition of the present application to a crosslinking curing reaction. For example, the resin composition may be applied to a substrate, and crosslinked and cured by heating or ultraviolet irradiation to form an adhesive layer on the substrate. Alternatively, the resin composition may be coated on a release paper or other film, and then crosslinked and cured by heating or ultraviolet irradiation to form an adhesive layer, and the adhesive layer may be bonded to one or both surfaces of a substrate. The adhesive tape without a base material can be manufactured by forming an adhesive layer on a release paper or other film, and then attaching another release paper or other film on the adhesive layer.
In order to reduce the viscosity of the resin composition at the time of coating, a solvent may be added. Specific examples of the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane, isoparaffin, and the like; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate; ether solvents such as diisopropyl ether and 1, 4-dioxane.
The coating method is not particularly limited as long as a known method is used. Specific examples thereof include coating using a comma type blade coater, a die lip coater, a roll coater, a die coater, a blade coater, a bar coater, a kiss coater, or a gravure coater; silk screen coating; dip coating; and (5) casting and coating.
The substrate is not particularly limited, but a film-shaped substrate is preferable. Particularly, a resin film having high heat resistance, which can be processed at a high temperature, is preferable. Specific examples thereof include resin films such as Polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), and Polytetrafluoroethylene (PTFE). These films may be used in the form of a single layer or a laminate film of 2 or more layers. Among them, polyimide films are preferable. The thickness of the base material is not particularly limited, but is preferably 5 to 200. Mu.m, more preferably 5 to 125. Mu.m.
The surface of the substrate on which the adhesive layer is provided may be subjected to an easy-to-adhere treatment as needed. Examples of the easy-to-adhere treatment include a primer treatment, a corona treatment, an etching treatment, a plasma treatment, and a sandblasting treatment.
The release liner may be provided on the adhesive tape of the present application. The release liner is a member for protecting the adhesive layer of the adhesive tape, and is used to attach the adhesive tape to an adherend after the adhesive is released immediately before the attachment. The type of the release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include release liners obtained by treating the surface of a base material such as a high-grade paper, cellophane, or a synthetic resin film with a release agent. For the mold release agent treatment, for example, a mold release agent such as a fluorine-substituted alkyl-modified silicone resin may be used. In particular, as the release liner laminated on the silicone-based pressure-sensitive adhesive layer, a release liner in which the surface of a polyethylene terephthalate film is subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin is preferable. In addition, in the case where the adhesiveness of the adhesive layer is low, a resin film which is not subjected to release treatment may be used as the release liner. Specific examples thereof include polyethylene terephthalate (PET) film, polyethylene (PE) film, and polypropylene (PP) film.
Examples
The present application will be described in further detail with reference to examples. However, the present application is not limited to these examples. In the following description, "parts" means "parts by mass".
Example 1]
First, a plurality of test pieces (a to F) of an addition-curable silicone-based adhesive (stock solution) were prepared. These test pieces are prepared by adjusting the storage modulus G' and the gel percentage after curing by a method described later so as to show various values. These test articles were silicone-based adhesives containing alkenyl-containing silicone raw rubber, MQ resin, and a crosslinking agent.
In example 1, among these multiple test products, an addition-curable silicone-based adhesive (a) (solid content concentration 60%) was selected, in which the storage modulus G' and gel percentage after curing when an appropriate amount of an organic peroxide was added were specified as described below.
Thereafter, 100 parts of the addition-curable silicone adhesive stock solution (A), 197 parts of toluene as a diluent solvent, 3.0 parts of an organic peroxide curing agent (Nyper (Japanese: kogyo-I) (registered trademark)) BMT-K40, 40% of the concentration of the organic peroxide, 6.05% of the theoretical active oxygen content in the organic peroxide, and 0.3 parts of a platinum catalyst (NC-25, dow Toray Co., ltd.) were uniformly mixed to obtain an adhesive solution (1). In the 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 relative to 100 parts of the silicone adhesive is 0.12 parts.
As a result of the dynamic viscoelasticity measurement described later on the adhesive liquid (1), the storage modulus G' at 200℃was 168628Pa. The gel percentage of the adhesive liquid (1) was measured as described later, and the gel percentage was 46%.
Then, an adhesive liquid (1) was applied to one side of the Polyimide (PI) film having a thickness of 25 μm after the primer treatment so that the thickness of the dried adhesive layer became 6 μm, and the adhesive layer was formed by drying the polyimide film in a drying oven at 60 ℃ for 1 minute to remove the solvent and curing the polyimide film at 200 ℃ for 1 minute. Thereafter, a 50 μm thick polyethylene terephthalate (PET) film, which was subjected to release treatment with a fluorine-substituted alkyl-modified silicone resin, was bonded to the adhesive layer as a release liner to obtain an adhesive tape.
[ dynamic viscoelasticity measurement ]
The adhesive liquid (1) was coated on the release liner so that the thickness after drying was 50. Mu.m. The solvent was then removed by drying in a drying oven at 60℃for 1 minute. Thereafter, the silicone component was cured by heating at 200 ℃ for 1 minute, and an adhesive layer containing the cured silicone adhesive composition was formed. This operation was repeated a plurality of times, whereby a laminate of adhesive layers having a thickness of 2mm was laminated, and this was used as a sample for measurement.
The storage modulus G' was measured by sandwiching the measurement sample between parallel disks (. Phi.8 mm) and applying a shear strain having a frequency of 10Hz using a dynamic viscoelasticity measuring apparatus (manufactured by Rheometric Scientific Co., ltd., apparatus name RDAIII) at a heating rate of 10 ℃/min in a range of-60 ℃ to 300 ℃.
[ determination of gel percentage ]
The adhesive liquid (1) was coated on the release liner so that the thickness after drying was 50. Mu.m. The solvent was then removed by drying in a drying oven at 60℃for 1 minute. Thereafter, the silicone component was cured by heating at 200 ℃ for 1 minute, and an adhesive layer containing the cured silicone adhesive composition was formed, which was used as a measurement sample.
The obtained sample was cut into 50mm×50mm, and the release liner was peeled off to obtain a sheet-like sample for measurement containing the silicone-based adhesive composition. Thereafter, the measurement sample was immersed in toluene in an amount of 250 times or more the initial mass (X) at room temperature (23 ℃) for 1 day to swell. After dipping, the measurement sample was taken out, dried in a dryer at 130 ℃ for 2 hours, and the absorbed solvent was removed, and the dry mass (Y) (=mass of the dried silicone-based adhesive composition) was measured. The gel percentage of the silicone adhesive composition was obtained by the following formula.
Gel percent (%) = (Y/X) ×100%
Example 2 ]
An adhesive tape was produced by the same method as in example 1, except that the adhesive liquid (2) was prepared by changing the amount of the organic peroxide to 2.5 parts by using a mixture of 50 parts of the addition-curable silicone adhesive stock solution (a) (solid content: 60%) and 50 parts of the addition-curable silicone adhesive stock solution (B) (solid content: 40% by mass) instead of 100 parts of the addition-curable silicone adhesive stock solution (a) (solid content: 40% by mass). In the 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 was 0.12 part. Further, the adhesive liquid (2) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 124121Pa, and the gel percentage was 55%.
Example 3 ]
An adhesive tape was produced by preparing an adhesive liquid (3) in the same manner as in example 2, except that the amount of the organic peroxide was changed to 4.5 parts by mass. In the 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 was 0.22 part. Further, the adhesive liquid (3) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 219861Pa, and the gel percentage was 60%.
Comparative example 1]
An adhesive tape was produced by the same method as in example 2, except that the amount of the addition-curable silicone-based adhesive stock solution (a) was changed to 25 parts, the amount of the addition-curable silicone-based adhesive stock solution (B) was changed to 75 parts, and the amount of the organic peroxide was changed to 2.25 parts, to prepare an adhesive solution (C1). In the 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 was 0.12 part. Further, the adhesive liquid (C1) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 125270Pa, and the gel percentage was 62%.
Comparative example 2 ]
An adhesive tape was produced in the same manner as in example 1, except that 100 parts of the addition-curable silicone adhesive stock solution (B) (solid content: 40%) was used instead of 100 parts of the addition-curable silicone adhesive stock solution (a) (solid content: 60%) and the amount of the organic peroxide was changed to 2 parts, and an adhesive solution (C2) was prepared. In the 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 was 0.12 part. Further, the adhesive liquid (C2) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 136757Pa, and the gel percentage was 69%.
Comparative example 3 ]
An adhesive tape was produced by preparing an adhesive liquid (C3) in the same manner as in example 2, except that an organic peroxide was not added. In the 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 was 0 part. Further, the adhesive liquid (C3) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 240508Pa, and the gel percentage was 53%.
Comparative example 4 ]
An adhesive tape was produced in the same manner as in example 1, except that the adhesive liquid (C4) was prepared by changing the amount of the organic peroxide to 4.5 parts by using a mixture of 25 parts of the addition-curable silicone adhesive stock liquid (C) (solid content concentration 90 mass%) and 75 parts of the addition-curable silicone adhesive stock liquid (D) (solid content 90 mass%) in place of 100 parts of the addition-curable silicone adhesive stock liquid (a) (solid content 60%). In the 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 was 0.12 part. Further, the adhesive liquid (C4) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 17620Pa, and the gel percentage was 48%.
Comparative example 5 ]
An adhesive tape was produced in the same manner as in example 1, except that 100 parts of the addition-curable silicone adhesive stock solution (E) (solid content 60 mass%) was used instead of 100 parts of the addition-curable silicone adhesive stock solution (a) (solid content 60 mass%), and an adhesive solution (C5) was prepared. In the 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 was 0.12 part. Further, the adhesive liquid (C5) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 98880Pa, and the gel percentage was 44%.
Comparative example 6 ]
An adhesive tape was produced by preparing an adhesive liquid (C6) in the same manner as in comparative example 5, except that an organic peroxide was not added. In the 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 was 0 part. Further, the adhesive liquid (C6) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 69702Pa, and the gel percentage was 34%.
Comparative example 7 ]
An adhesive tape was produced in the same manner as in comparative example 6, except that 100 parts of the addition-curable silicone-based adhesive stock solution (F) (solid content 60 mass%) was used instead of 100 parts of the addition-curable silicone-based adhesive stock solution (E) (solid content 60 mass%), and an adhesive solution (C7) was prepared. In the 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 was 0 part. Further, the adhesive liquid (C7) was subjected to dynamic viscoelasticity measurement and gel percentage measurement, and as a result, the storage modulus G' at 200℃was 69045Pa, and the gel percentage was 44%.
< 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. Mu.m.
The adhesive tapes of the above examples and comparative examples were evaluated as follows. The results are shown in Table 1.
[ determination of adhesive overflow after Hot pressing and residual adhesive after stripping ]
An adhesive tape cut to 20mm×20mm was attached to a Cu plate (Cl 100 p) subjected to polishing treatment with a PIKAL polishing liquid (manufactured by japan abrasive industry co.) on the surface, and the resultant was pressed by a roller covered with a rubber layer weighing 2kg and reciprocated 1 time. Thereafter, the sample was left to stand at 23℃for 20 minutes to 1 hour to obtain a bonded sample for measurement. The sample was sandwiched between mirror-finished 2 pieces of SUS304 plates at 200℃under a pressure of 30kg/cm 2 The heating and pressing were performed for 4 hours. The adhesive overflow after the heat pressing and the adhesive residue after the tape peeling were observed at a magnification of 100 times by using a microscope (VHX-6000, manufactured by KEYENCE), and evaluated based on the following criteria.
(spilled glue after hot pressing)
"good" is shown in the following description: no glue overflow from the 4 sides or corners was observed.
"×": glue overflow from the 4 sides or corners was observed.
(residual glue after Hot pressing)
O: no adhesive residue was observed on the adhesive side.
X: the adhesive residue was observed on the adhesive face.
TABLE 1
< evaluation results >
As shown in Table 1, the adhesive tapes of examples 1 to 3 did not produce residual and flash after hot pressing at 200 ℃.
Comparative examples 1 and 2 are examples in which the gel percentage of the adhesive composition after crosslinking is too high. As a result, the adhesive tapes of comparative examples 1 and 2 were left with adhesive residues.
Comparative example 3 is an example in which no organic peroxide was used in the adhesive composition. As a result, the adhesive tape of comparative example 3 produced a residual adhesive.
Comparative example 4 is an example in which the storage modulus of the adhesive composition after crosslinking is too low. As a result, the adhesive tape of comparative example 4 was subject to adhesive overflow and adhesive residue.
Comparative example 5 is an example in which the gel percentage after crosslinking of the adhesive composition is too low in storage modulus. As a result, the adhesive tape of comparative example 4 was subject to adhesive overflow and adhesive residue.
Comparative examples 6 and 7 are examples in which no organic peroxide was used in the adhesive composition and the gel percentage after crosslinking of the adhesive composition was too low. As a result, the adhesive tapes of comparative examples 6 and 7 were subject to adhesive overflow and adhesive residue.
Reference example 1 is an example in which the thickness of the adhesive layer is excessively large. As a result, the adhesive tape of reference example 1 was subject to adhesive overflow and adhesive residue. From the results, it can be understood that in the case where the resin composition (adhesive composition) of the present application is used for the purpose of the adhesive layer of an adhesive tape, the thickness of the adhesive layer thereof is preferably relatively thin.
Industrial applicability
The resin composition of the present application is particularly useful, for example, as a material for forming an adhesive layer of an adhesive tape. The pressure-sensitive adhesive tape of the present application is used in a process requiring treatment under a high-load and high-temperature environment, for example, in a process for producing a printed laminate substrate, at a high temperature (for example, 180 ℃ or higher), under a high pressure (for example, 20 kg/cm) 2 The above) is useful for the purpose of protecting, masking, temporarily fixing, and fixing an adherend (for example, a surface of a laminated substrate) in a process of heating and pressing for a long period of time (for example, 2 hours or more).

Claims (3)

1. A resin composition comprising an alkenyl group-containing silicone raw rubber, an MQ resin, a crosslinking agent, a platinum catalyst and an organic peroxide,
the percentage of gel after crosslinking is 50% or more and 60% or less,
the storage modulus at 200 ℃ after crosslinking is 100000Pa or more and 1000000Pa or less,
the gel percentage was determined as follows:
coating an adhesive liquid containing the resin composition on a release liner so that the thickness after drying is 50 μm, drying in a drying oven at 60 ℃ for 1 minute to remove the solvent,
thereafter, the silicone component was cured by heating at 200℃for 1 minute to form an adhesive layer containing the cured silicone adhesive composition, which was used as a sample for measurement,
the obtained sample was cut into 50mm×50mm, the release liner was peeled off to obtain a sheet-like sample for measurement containing the silicone-based adhesive composition, and the sample for measurement was then immersed in toluene in an amount of 250 times or more of the initial mass X at room temperature of 23℃for 1 day to swell the sample,
after dipping, the measurement sample was taken out, dried in a dryer at 130℃for 2 hours, and the absorbed solvent was removed to measure a dry mass Y, wherein dry mass Y=the mass of the dried silicone-based adhesive composition,
the gel percentage of the silicone-based adhesive composition was obtained using the following formula:
gel percentage= (Y/X) X100%,
wherein the gel percentage is in%.
2. The resin composition according to claim 1, wherein,
the product PA of the amount P of the organic peroxide and the theoretical active oxygen amount A of the organic peroxide represented by the following formula (1) relative to 100 parts by mass of the total of the alkenyl group-containing silicone rubber, the MQ resin and the crosslinking agent is 0.06 parts by mass or more, wherein the unit of P is parts by mass and A is a% value;
A=(B×16/M)×100 (1)
in the formula (1), A represents the theoretical active oxygen amount of the organic peroxide, B represents the number of peroxide bonds, and M represents the molecular weight of the organic peroxide.
3. An adhesive tape for temporary fixation of electronic parts, which has an adhesive layer formed of the resin composition of claim 1 after crosslinking,
the adhesive layer has a gel percentage of 50% or more and 60% or less,
the adhesive layer has a storage modulus at 200 ℃ of 100000Pa or more and 1000000Pa or less, and
the thickness of the adhesive layer is 2 [ mu ] m or more and 10 [ mu ] m or less.
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