CN108368413B - Adhesive composition and adhesive tape - Google Patents
Adhesive composition and adhesive tape Download PDFInfo
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- CN108368413B CN108368413B CN201680071843.8A CN201680071843A CN108368413B CN 108368413 B CN108368413 B CN 108368413B CN 201680071843 A CN201680071843 A CN 201680071843A CN 108368413 B CN108368413 B CN 108368413B
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- adhesive
- silicone
- adhesive composition
- toluene
- swelling
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- 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
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- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Disclosed is an adhesive composition containing a crosslinked silicone component, having a gel fraction (the ratio of insoluble components when immersed in toluene for 1 day at normal temperature) of 45% or more and less than 70%, and having a swelling degree (the ratio of swelling due to toluene absorption when immersed for 1 day) with respect to toluene of 290% or less. The adhesive composition and the adhesive tape have excellent fixing force of members, can be peeled off without paste residue even if used in a high-temperature environment, and have little change in adhesive force even if the adhesive-peeling process is repeated.
Description
Technical Field
The present invention relates to an adhesive composition and an adhesive tape which are excellent in the fixing force of a member in an adhesive tape used in the production process of, for example, electric and electronic parts, can be peeled off without leaving a paste even when used in a high-temperature environment, and are less likely to change in adhesive force even when the adhesive tape is repeatedly subjected to adhesion-peeling.
Background
The silicone adhesive composition is excellent in heat resistance, cold resistance, weather resistance, electrical insulation, chemical resistance, and adhesiveness to various adherends. The adhesive tape further having the silicone adhesive layer is less likely to leave a paste after peeling, particularly when used in a high-temperature environment. Therefore, such an adhesive tape is widely used for protection, masking, temporary fixing, transportation fixing, and the like of parts in the production process of various parts such as electric and electronic parts.
The conventional adhesive tape is unstable in adhesiveness when used repeatedly, and needs to be exchanged every about 1 time. Specifically, the adhesive surface is cracked due to repeated peeling, and the tape is more likely to fuse to an adherend, and the adhesive strength is increased, and the tape may not be peeled. Further, when the adhesive strength is lowered due to repeated peeling, for example, a low molecular component in the adhesive or a component contributing to the adhesion performance moves to the adherend, the fixing force to the member is insufficient, and the member may peel off in the process. In addition, the adhesive may deteriorate when repeatedly used in a high-temperature environment, and the paste may remain on the component.
Conventionally, a large number of silicone adhesive compositions and adhesive tapes have been studied which are less likely to cause paste residue after peeling (for example, patent documents 1 to 4). However, the problem of stability of the adhesive strength after peeling has not been studied at all.
Patent document 5 discloses a double-sided adhesive tape for attaching a transparent protective cover to an information display screen such as a display panel, in which an adsorption layer containing a silicone resin as a main component is laminated on one surface of a base film, and an adhesive layer formed of an acrylic adhesive is laminated on the other surface. Although this re-application of the silicone-adsorbed layer is assumed, this document does not mention stability of the adhesive force in repeated peeling, nor does it mention basic adhesive properties such as adhesive force. Further, since the adhesive layer is always a silicone resin and only a slight amount of suction force is required to obtain a weight enough not to peel off the adhesive tape having a weight enough to cover the protective cover from the display panel, the adhesive layer is fundamentally different from an adhesive tape used in a manufacturing process of an electric or electronic component or the like and used for an application of a force (i.e., a fixing force) for applying a certain external force and fixing another component.
Patent documents 6 to 8 disclose a jig for holding and transporting a printed wiring board, in which a weak adhesive resin is applied to a jig base made of a plate body. These patent documents do not relate to the stability of the adhesive force not only when peeling is repeated, but also do not mention basic adhesive properties such as adhesive force, and cannot be said to be sufficiently verified. In the patent document, a weakly adhesive agent is used, but if the adhesive agent has weak adhesiveness, the adhesive force is not always stable when the adhesive agent is repeatedly peeled off. Further, the fixing force and paste retention to the component were not verified.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-275450
Patent document 2: japanese patent laid-open publication No. 2003-96429
Patent document 3: japanese patent laid-open publication No. 2003-193226
Patent document 4: japanese laid-open patent publication No. 2004-168808
Patent document 5: japanese patent laid-open publication No. 2015-199878
Patent document 6: japanese patent laid-open No. 2001-144430
Patent document 7: japanese patent laid-open publication No. 2003-332795
Patent document 8: japanese patent laid-open publication No. 2004-359270
Disclosure of Invention
Problems to be solved by the invention
The present inventors have focused on the problem of stability of adhesion after peeling, and have developed an adhesive tape that can be repeatedly used for the purpose of reducing the cost in the production process of various components such as electric and electronic components. That is, an object of the present invention is to provide an adhesive composition and an adhesive tape which have excellent fixing force of members, can be peeled off without leaving paste even when used in a high-temperature environment, and have little change in adhesive force even when adhesion-peeling is repeated.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the balance between the gel fraction and the degree of swelling of a silicone adhesive layer is related to the change in adhesive strength and other various properties when the silicone adhesive layer is repeatedly used, thereby completing the present invention.
That is, the present invention relates to a silicone adhesive composition containing a crosslinked silicone structure, having a gel fraction of 45% or more and less than 70% as measured by the following method, and having a swelling degree with respect to toluene of 290% or less as measured by the following method.
The "gel fraction" is the ratio of insoluble components when the silicone adhesive composition is immersed in toluene for 1 day at room temperature, and is obtained by the following formula.
Gel fraction (%) - (C/A). times.100
A: initial quality of Silicone adhesive composition
C: quality of drying of Silicone adhesive composition after immersion in toluene (drying conditions: 130 ℃ C., 2 hours)
The "swelling degree" is a swelling ratio due to toluene absorption when the silicone adhesive composition is immersed in toluene at room temperature for 1 day, and is obtained by the following formula.
The degree of swelling (%) ((B-A)/A). times.100%
A: initial quality of Silicone adhesive composition
B: swelling quality of silicone adhesive composition after toluene impregnation
Further, the present invention relates to an adhesive tape having an adhesive layer formed of the adhesive composition on at least one surface of a substrate.
Effects of the invention
The present invention provides an adhesive composition and an adhesive tape which have excellent fixing force of members, can be peeled off without leaving paste even when used in a high-temperature environment, and have little change in adhesive force even when adhesion-peeling is repeated. In particular, since the adhesive tape of the present invention has the above-mentioned specific adhesive layer, in the production process of various parts such as electric and electronic parts at high temperature, for example, the parts are not peeled off during the process, the paste is less likely to remain after peeling, and even if the adhesion-peeling is repeated, the adhesive tape is less likely to change in adhesion, and therefore, the adhesive tape can be used repeatedly, and is very useful in terms of cost reduction.
Drawings
FIG. 1 is a graph in which the comprehensive evaluation of examples and comparative examples is summarized in the correlation between gel fraction and swelling degree.
Fig. 2 is a schematic view for explaining a fixing force test in examples and comparative examples.
Detailed Description
< adhesive composition >
The adhesive composition of the present invention is an adhesive composition containing a silicone adhesive as a main component. The adhesive composition of the present invention has a gel fraction of 45% or more and less than 70%, preferably 48 to 65%, and more preferably 50 to 60%. The adhesive composition of the present invention has a swelling degree of 290% or less, preferably 260% or less, and more preferably 230% or less, with respect to toluene. Specific methods for measuring the gel fraction and the degree of swelling are described in the columns of examples described below. In general, the degree of swelling depends on the crosslink density of the adhesive composition. When the crosslinking density is high, the three-dimensionally crosslinked polymer chains constituting the adhesive are less likely to expand and the degree of swelling is low even when the adhesive is immersed in toluene. On the other hand, when the crosslinking density is low, the polymer chain tends to be extended, and the degree of swelling tends to be high.
When the gel fraction and the swelling degree are within the specific ranges of the present invention, sufficient fixing force, paste residue prevention property, and stability of adhesive force during repeated use can be obtained. If the gel fraction is less than 45%, the fixing force is further strengthened, while paste residue due to insufficient cohesive force is likely to occur, and the adhesive force is unstable when repeatedly used. On the other hand, if the gel fraction exceeds 70%, a sufficient fixing force cannot be obtained. Even if the gel fraction is in the range of 45% or more and less than 70%, if the swelling degree exceeds 290%, paste residue due to insufficient cohesive force caused by low crosslinking density is likely to occur, and the adhesive force is unstable when repeatedly used.
Specific examples of the silicone adhesive used in the present invention include those mainly comprising a silicone raw rubber (comprising a D unit [ (CH)3)2SiO]Long-chain polymer of polydimethylsiloxane) and MQ resin (containing M units [ (CH)3)3SiO1/2]And Q unit [ SiO2]Polymers of silicone resins of three-dimensional structure). Such adhesives comprising silicone green gum and MQ resin are superior in adhesion to silicone green gum monomers. In addition, basic adhesive properties such as adhesive force, holding power, and tack (tack) can be controlled by changing the ratio of silicone raw rubber to MQ resin in the adhesive. Silicone adhesives are roughly classified into addition curing type and peroxide curing type depending on their curing structure. The addition-curable silicone adhesive is cured by heating a main agent comprising a raw silicone rubber having an alkenyl group and a crosslinking agent comprising a polyorganosiloxane having an SiH group in the presence of, for example, a platinum catalyst to cause a crosslinking reaction. At this time, the crosslinking density can be changed by appropriately adjusting the amount of the crosslinking agent. The peroxide-curable silicone adhesive is cured by adding a peroxide such as benzoyl peroxide as a curing agent, removing the solvent, and then heating at high temperature, for example. At this time, the crosslinking density of the adhesive can be changed by appropriately adjusting the amount of the peroxide to be added. The silicone adhesive may be used in combination of 2 or more. In particular, the adhesive composition of the present invention preferably contains an addition-curable silicone adhesive which is cured by crosslinking.
The adhesive composition of the present invention can be obtained using commercially available products. For example, a commercially available silicone adhesive is crosslinked and cured to obtain an adhesive composition having desired physical properties. Specifically, the adhesive composition of the present invention containing a crosslinked silicone structure can be obtained by crosslinking and curing the silicone-based adhesive exemplified above. The crosslinking and curing reaction is usually carried out by heating, but depending on the type of the adhesive or curing agent, crosslinking and curing can be carried out even by condensation reaction or ultraviolet irradiation.
The adhesive composition having a specific gel fraction and swelling degree of the present invention can be obtained, for example, by using a mixture of 2 or more commercially available silicone adhesives. Specifically, for example, a silicone adhesive having a relatively high gel fraction and swelling degree and a silicone adhesive having a relatively low gel fraction and swelling degree are mixed at an appropriate ratio and crosslinked and cured, whereby an adhesive composition having a gel fraction and swelling degree within the range of the present invention can be obtained. However, the adhesive composition of the present invention is not limited to the product obtained by such a method.
In the adhesive composition of the present invention, additives may be added 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 resins, polydimethylsiloxanes, and polydimethylphenylsiloxanes; antioxidants such as phenol antioxidants and amine antioxidants; a silane coupling agent. However, the kind and amount of the additive need to be appropriately selected in such a manner that the effect of the invention is not impaired.
< adhesive tape >
The adhesive tape of the present invention is an adhesive tape having an adhesive layer formed from the adhesive composition of the present invention described above on at least one surface of a substrate, and typically an adhesive tape having the adhesive layer on one surface or both surfaces of a substrate film. The thickness of the adhesive layer is not particularly limited, but is preferably 2 to 150. mu.m, more preferably 5 to 100. mu.m, and particularly preferably 10 to 75 μm.
The adhesive layer can be formed by subjecting the adhesive composition to a crosslinking curing reaction. For example, the adhesive composition may be applied to a substrate, and crosslinked and cured by heating, condensation reaction, or ultraviolet irradiation to form an adhesive layer on the substrate. Alternatively, the adhesive composition may be applied to a release paper or other film, crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form an adhesive layer, and the adhesive layer may be bonded to one surface or both surfaces of a substrate.
In order to reduce the viscosity of the adhesive composition at the time of coating, a solvent may be added. Specific examples of the solvent include tolueneAromatic solvents such as benzene 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, diisopropyl ether and 1, 4-bis (isopropyl) ether
Ether solvents such as alkanes.
The coating method is not particularly limited as long as a known method is used. Specific examples thereof include coating using a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a bar coater, a kiss roll coater, or a gravure coater; coating a screen; dip coating; and (5) casting and coating.
The substrate is not particularly limited, and is preferably a film-like substrate. Particularly, a resin film having high heat resistance which can be processed at high temperature is preferable. Specific examples thereof include resin films such as Polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamide imide (PAI), polyether sulfone (PES), and Polytetrafluoroethylene (PTFE). These films may be used as a single layer or as a laminated film having 2 or more layers. Among them, a polyimide film is preferable. The thickness of the base material is not particularly limited, but is preferably 2 to 180 μm, more preferably 5 to 100 μm, and particularly preferably 12 to 75 μm.
Further, the surface of the substrate on which the adhesive agent layer is provided may be subjected to an easy adhesion treatment as necessary. Examples of the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, blast treatment, and the like.
The adhesive tape of the present invention may be provided with a release liner. The release liner is a substance for protecting the adhesive layer of the adhesive tape, and is peeled off immediately before the application to expose the adhesive and attach the adhesive tape to an adherend. 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 subjecting the surface of a base material such as a paper for a railroad forest, a cellophane, or a synthetic resin film to a release agent treatment. For the treatment of the release agent, for example, a release agent such as a fluorine-substituted alkyl-modified silicone resin may be used. In particular, as the release liner laminated on the silicone adhesive layer, a release liner obtained by subjecting the surface of a polyethylene terephthalate film to a release treatment with a fluorine-substituted alkyl-modified silicone resin is preferable.
Examples
The present invention will be described in further detail below with reference to examples. However, the present invention is not limited to these examples. In the following description, "part" is "part by mass".
< example 1 >
An addition-curable silicone adhesive base solution (trade name SD-4560, manufactured by tokyo ken corporation) having a solid content concentration of 60 mass% was uniformly mixed with 70 parts of an addition-curable silicone adhesive base solution (trade name SD-4587L, manufactured by tokyo ken corporation) having a solid content concentration of 40 mass%, 54 parts of toluene as a diluent solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by tokyo ken corporation) as a curing catalyst to obtain an adhesive liquid (1).
Next, an adhesive liquid (1) was applied to one surface of a Polyimide (PI) film having a thickness of 25 μm and subjected to primer treatment so that the thickness of the adhesive layer after drying became 30 μm, and the resultant was cured and dried at 130 ℃ for 2 minutes in a drying furnace to form an adhesive layer. Then, a release liner (a 50 μm thick PET film subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the adhesive layer to obtain an adhesive tape.
< example 2 >
An addition-curable silicone adhesive base solution (trade name SD-4560, manufactured by tokyo ken corporation) having a solid content concentration of 60 mass% was uniformly mixed with 50 parts of an addition-curable silicone adhesive base solution (trade name SD-4587L, manufactured by tokyo ken corporation) having a solid content concentration of 40 mass%, 43 parts of toluene as a diluent solvent, and 0.3 part of a platinum catalyst (trade name NC-25, manufactured by tokyo ken corporation) as a curing catalyst to obtain an adhesive liquid (2). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (2) was used.
< example 3 >
An addition-curable silicone adhesive base solution (trade name SD-4560, manufactured by tokyo ken corporation) having a solid content concentration of 60 mass% was mixed uniformly in 20 parts, an addition-curable silicone adhesive base solution (trade name SD-4587L, manufactured by tokyo ken corporation) having a solid content concentration of 40 mass%, 26 parts of toluene as a diluent solvent, and 0.3 part of a platinum catalyst (trade name NC-25, manufactured by tokyo ken corporation) as a curing catalyst to obtain an adhesive liquid (3). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (3) was used.
< comparative example 1 >
100 parts of an addition curing type silicone adhesive stock solution (trade name SD-4587L, manufactured by Toronto Corning Co., Ltd.) having a solid content concentration of 40 mass%, 33 parts of toluene as a diluent solvent, and 0.3 part of a platinum catalyst (trade name NC-25, manufactured by Toronto Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (4). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (4) was used.
< comparative example 2 >
100 parts of an addition curing type silicone adhesive stock solution (trade name SD-4580, manufactured by Toronto Corning Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toronto Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (5). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (5) was used.
< comparative example 3 >
100 parts of an addition curing silicone adhesive stock solution (trade name SD-4584, manufactured by Toronto Corning Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toronto Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (6). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (6) was used.
< comparative example 4 >
100 parts of an addition curing type silicone adhesive stock solution (trade name SD-4560, manufactured by Toronto Corning Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toronto Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (7). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (7) was used.
< comparative example 5 >
100 parts of an addition curing type silicone adhesive stock solution (trade name SD-4570, manufactured by Toronto Corning Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.3 parts of a platinum catalyst (trade name NC-25, manufactured by Toronto Corning Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (8). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (8) was used.
< comparative example 6 >
100 parts of an addition-curable silicone adhesive stock solution (trade name: KR-3700, manufactured by shin-Etsu chemical Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.5 parts of a platinum catalyst (trade name: CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (9). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (9) was used.
< comparative example 7 >
100 parts of an addition-curable silicone adhesive stock solution (trade name: KR-3701, manufactured by shin-Etsu chemical Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.5 parts of a platinum catalyst (trade name: CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (10). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (10) was used.
< comparative example 8 >
100 parts of an addition-curable silicone adhesive stock solution (trade name: KR-3704, manufactured by shin-Etsu chemical Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 0.5 parts of a platinum catalyst (trade name: CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.) as a curing catalyst were uniformly mixed to obtain an adhesive solution (11). An adhesive tape was obtained in the same manner as in example 1, except that the adhesive liquid (11) was used and an untreated PET film having a thickness of 38 μm was used as a release liner.
< comparative example 9 >
100 parts of a peroxide-curable silicone adhesive stock solution (trade name: SH-4280, manufactured by Toray Corning Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 3.0 parts of a curing agent (trade name: Nyper (registered trade name): BMT-40, manufactured by Nichigan Co., Ltd.) were uniformly mixed to obtain an adhesive solution (12).
Then, an adhesive liquid (12) was applied to one surface of the Polyimide (PI) film having a thickness of 25 μm and subjected to primer treatment so that the thickness of the adhesive layer after drying became 30 μm. The solvent was removed at 60 ℃ for 1 minute in a drying furnace, and the mixture was further cured and dried at 180 ℃ for 2 minutes to form an adhesive layer. Then, a release liner (a 50 μm thick PET film subjected to a release treatment with a fluorine-substituted alkyl-modified silicone resin) was bonded to the adhesive layer to obtain an adhesive tape.
< comparative example 10 >
100 parts of a peroxide-curable silicone adhesive stock solution (trade name KR-100, manufactured by shin-Etsu chemical Co., Ltd.) having a solid content concentration of 60 mass%, 71 parts of toluene as a diluent solvent, and 3.0 parts of a curing agent (trade name Nyper (registered trade name) BMT-40, manufactured by Nichio oil Co., Ltd.) were uniformly mixed to obtain an adhesive solution (13). An adhesive tape was obtained in the same manner as in comparative example 9, except that the adhesive liquid (13) was used.
< gel fraction and swelling degree of adhesive composition >
The adhesive solutions (1) to (13) obtained in examples and comparative examples were applied to a release liner so that the thickness after drying was 50 to 200 μm. Subsequently, the resultant was heated in a drying oven, cured and dried to prepare an adhesive composition, which was used as a sample. The heating temperature at this time was the same as in each of the examples and comparative examples. That is, the temperatures were 130 ℃ for 2 minutes in the case of the adhesive liquids (1) to (11), and 60 ℃ for 1 minute and 180 ℃ for 2 minutes in the case of the adhesive liquids (12) and (13).
The obtained sample was cut into 50mm × 50mm, and the release liner was peeled off to obtain a measurement sample made of the sheet-like adhesive composition. The initial mass (a) (-the mass of the adhesive composition before swelling) of the sample for measurement was measured. Then, the measurement sample was immersed in toluene in an amount of 250 times or more the initial mass (A) for 1 day at room temperature (23 ℃ C.) to swell the sample. After the immersion, the measurement sample was taken out, and the swelling mass (B) (-mass of the adhesive composition swollen with toluene) was measured. The measurement sample was further dried in a dryer at 130 ℃ for 2 hours, and the absorbed solvent was removed to measure the dry mass (C) (-the mass of the dried adhesive composition). The gel fraction and swelling degree of the adhesive composition were obtained by the following formulas.
Gel fraction (%) - (C/A). times.100
The degree of swelling (%) ((B-A)/A). times.100%
< adhesion to SUS at Normal temperature (23 ℃ C.) >
The adhesive tape cut to a width of 20mm was stuck to a ground SUS plate, pressure-bonded 1 time in a reciprocating manner with a roller having a weight of 2kg coated with a rubber layer, and left at 23 ℃ for 20 to 40 minutes. Then, the force required to peel the tape at an angle of 180 ° at a speed of 300 mm/min was measured using a tensile tester.
< adhesion to SUS and paste residue after repeated heating (200 ℃ C. and 230 ℃ C.) >)
The adhesive tape cut into a width of 20mm was stuck to a ground SUS plate, pressure-bonded 1 time in a reciprocating manner with a roller having a weight of 2kg covered with a rubber layer, and left in a drier at 200 ℃ and 230 ℃ for 30 minutes. It was taken out and allowed to cool at room temperature. Then, the force required to peel the tape at an angle of 180 ° at a speed of 300 mm/min (1 st after-heating adhesion) was measured using a tensile tester. The peeled adhesive tape was attached to a polished SUS plate again, and the adhesive force after heating was measured for the 2 nd time in the same manner as for the 1 st time. Thereafter, the adhesion after heating was repeatedly measured up to the 10 th time. The residual paste at the time of peeling was visually checked at each time, and evaluated according to the following criteria.
O: no paste residue
X: has paste residue
< rate of change of adhesive force >
When the adhesive force after heating was repeatedly measured 10 times, the change rate of the adhesive force was calculated according to the following formula (tables 1 and 2), and the maximum and minimum change rates were described (table 3).
Change ratio (%) of adhesion after heating/adhesion after heating of 1 st × 100%
< holding force test >
As shown in fig. 2, 75g of weight 2 (attachment area 20mm × 25mm) was attached to the adhesive layer 1b side (lower side) of the adhesive tape 1 to which both ends were fixed, and left in a 200 ℃ drying machine for 1 hour to confirm the presence or absence of dropping of the weight 2, and the fixing force was evaluated according to the following criteria.
O: the weight of the balance does not fall down
X: weight of the sliding weight falls down
The results of the above measurements are shown in tables 1 to 3. Further, the comprehensive evaluation of examples and comparative examples is summarized in the graph of the correlation between the gel fraction and the swelling degree shown in fig. 1.
[ Table 1]
[ Table 2]
[ Table 3]
< evaluation result >
As shown in Table 3, in examples 1 to 3, even when the adhesive force was repeatedly used at 200 ℃ and 230 ℃ for 10 times, the change in the adhesive force after heating was within. + -. 15% of the initial value, and the adhesive force was extremely stable when the adhesive force was repeatedly used. Further, no paste remains, and the fixing force of the member is sufficient.
In comparative example 1, the gel fraction was not decreased, but the swelling degree was high (i.e., the crosslinking density was low), so that no paste remained, but if the paste was repeatedly used at 230 ℃, the adhesive force was significantly increased, and the adhesive force was unstable when the paste was repeatedly used.
In comparative examples 2 to 3 and comparative examples 6 to 7, the gel fraction was reduced and the swelling degree was high, so that paste residue was generated if the paste was repeatedly used at 230 ℃. In addition, the adhesive strength varies greatly when used repeatedly.
In comparative examples 4 to 5, no paste remained because of low swelling degree, but the adhesive strength stability was poor when repeatedly used because of low gel fraction.
In comparative example 8 (a weakly adhesive), since the gel fraction is high and the swelling degree is high, paste residue is likely to occur, and the stability of the adhesive force is poor when repeatedly used. Further, since the gel fraction is high, the fixing force of the member is also poor.
In comparative examples 9 to 10 (peroxide-curable adhesives), the gel fraction was reduced, and the swelling degree was high, so that paste retention was likely to occur, and the stability of the adhesive strength was poor when the adhesive was repeatedly used.
Industrial applicability
The adhesive 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 useful for, for example, protection, masking, temporary fixing, transportation fixing, and the like of various parts in the production process of electric and electronic parts.
Description of the symbols
1 adhesive tape
1a base material
1b adhesive layer
2 sliding weight of steelyard
Claims (7)
1. A silicone adhesive composition comprising a crosslinked silicone structure, having a gel fraction of 45% or more and less than 70% as measured by the following method, and having a swelling degree with respect to toluene of 290% or less as measured by the following method,
the "gel fraction" is the ratio of insoluble components when the silicone adhesive composition is immersed in toluene for 1 day at room temperature, and is obtained by the following formula,
gel fraction (%) - (C/A). times.100
A: the initial mass of the silicone-based adhesive composition,
c: the drying quality of the silicone adhesive composition after the impregnation with toluene was 130 ℃ for 2 hours,
"swelling degree" is a swelling ratio due to toluene absorption when the silicone adhesive composition is immersed in toluene for 1 day at room temperature, and the swelling degree is obtained by the following formula,
the degree of swelling (%) ((B-A)/A). times.100%
A: the initial mass of the silicone-based adhesive composition,
b: swelling quality of silicone adhesive composition after toluene impregnation.
2. The silicone adhesive composition according to claim 1, wherein the gel fraction is 48 to 65%.
3. The silicone adhesive composition according to claim 1, having a swelling degree of 260% or less.
4. The silicone-based adhesive composition according to claim 1, comprising an addition-curable silicone adhesive that is crosslink-cured.
5. An adhesive tape comprising a substrate and, disposed on at least one surface thereof, an adhesive layer comprising the adhesive composition according to claim 1.
6. The adhesive tape according to claim 5, wherein the substrate is a resin film.
7. The adhesive tape according to claim 6, wherein the resin film is a polyimide film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015241566 | 2015-12-10 | ||
| JP2015-241566 | 2015-12-10 | ||
| PCT/JP2016/084638 WO2017098919A1 (en) | 2015-12-10 | 2016-11-22 | Adhesive composition and adhesive tape |
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| Publication Number | Publication Date |
|---|---|
| CN108368413A CN108368413A (en) | 2018-08-03 |
| CN108368413B true CN108368413B (en) | 2021-02-02 |
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| CN201680071843.8A Active CN108368413B (en) | 2015-12-10 | 2016-11-22 | Adhesive composition and adhesive tape |
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| JP (1) | JP6626125B2 (en) |
| KR (1) | KR102232802B1 (en) |
| CN (1) | CN108368413B (en) |
| WO (1) | WO2017098919A1 (en) |
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| JP7427552B2 (en) * | 2020-07-10 | 2024-02-05 | 日東電工株式会社 | Silicone adhesive and adhesive tape |
| TW202319233A (en) * | 2021-07-20 | 2023-05-16 | 日商東洋紡股份有限公司 | Laminate roll |
| TW202304706A (en) * | 2021-07-20 | 2023-02-01 | 日商東洋紡股份有限公司 | laminate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354939A (en) * | 2000-06-14 | 2001-12-25 | Shin Etsu Chem Co Ltd | Silicone pressure-sensitive adhesive composition |
| JP2002275450A (en) * | 2001-03-21 | 2002-09-25 | Nitto Denko Corp | Silicone-based pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using the same |
| CN1493635A (en) * | 2002-09-30 | 2004-05-05 | 日东电工株式会社 | Sticking processing method for heat-resisting sheet and sticking band |
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| CA2266945C (en) | 1994-12-09 | 2002-04-02 | Brent Townshend | High speed encoder and encoding method |
| JP3328248B2 (en) | 1999-11-15 | 2002-09-24 | 株式会社 大昌電子 | Jig for mounting printed wiring board and method for mounting printed wiring board |
| JP4060585B2 (en) | 2001-12-25 | 2008-03-12 | 日東電工株式会社 | Masking adhesive tape and method of using the same |
| JP3435157B1 (en) | 2002-05-13 | 2003-08-11 | 株式会社 大昌電子 | Holding and conveying jig and holding and conveying method |
| JP2004091703A (en) * | 2002-09-02 | 2004-03-25 | Shin Etsu Chem Co Ltd | Conductive silicone self-adhesive composition and self-adhesive tape |
| JP4180353B2 (en) | 2002-11-18 | 2008-11-12 | 信越化学工業株式会社 | Silicone adhesive composition and adhesive tape |
| JP3857254B2 (en) | 2003-06-03 | 2006-12-13 | 株式会社 大昌電子 | Holding and conveying jig |
| KR100740926B1 (en) | 2005-12-30 | 2007-07-19 | 주식회사 케이씨씨 | Silicone pressure sensitive adhesive composition having anti-adhesive property |
| US8933187B2 (en) * | 2011-12-08 | 2015-01-13 | Momentive Performance Material Inc. | Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof |
| JP6251111B2 (en) | 2014-04-10 | 2017-12-20 | フジコピアン株式会社 | Double-sided adhesive film and protective member for information display screen using the same |
| KR20160083583A (en) * | 2014-12-31 | 2016-07-12 | 삼성전자주식회사 | Adhesive film and optical member comprising the same |
-
2016
- 2016-11-22 WO PCT/JP2016/084638 patent/WO2017098919A1/en active Application Filing
- 2016-11-22 CN CN201680071843.8A patent/CN108368413B/en active Active
- 2016-11-22 KR KR1020187017330A patent/KR102232802B1/en active IP Right Grant
- 2016-11-22 JP JP2017555011A patent/JP6626125B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354939A (en) * | 2000-06-14 | 2001-12-25 | Shin Etsu Chem Co Ltd | Silicone pressure-sensitive adhesive composition |
| JP2002275450A (en) * | 2001-03-21 | 2002-09-25 | Nitto Denko Corp | Silicone-based pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using the same |
| CN1493635A (en) * | 2002-09-30 | 2004-05-05 | 日东电工株式会社 | Sticking processing method for heat-resisting sheet and sticking band |
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| Publication number | Publication date |
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| WO2017098919A1 (en) | 2017-06-15 |
| KR20180084120A (en) | 2018-07-24 |
| JPWO2017098919A1 (en) | 2018-09-13 |
| KR102232802B1 (en) | 2021-03-25 |
| JP6626125B2 (en) | 2019-12-25 |
| CN108368413A (en) | 2018-08-03 |
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