CN109476962B - Pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- CN109476962B CN109476962B CN201680087979.8A CN201680087979A CN109476962B CN 109476962 B CN109476962 B CN 109476962B CN 201680087979 A CN201680087979 A CN 201680087979A CN 109476962 B CN109476962 B CN 109476962B
- Authority
- CN
- China
- Prior art keywords
- pressure
- silicone
- adhesive
- sensitive adhesive
- adhesive composition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Classifications
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The pressure-sensitive adhesive sheet has an adhesive layer containing a silicone adhesive composition containing a crosslinked silicone structure, and has a gel fraction of 40% or less, which is the ratio of insoluble components when the silicone adhesive composition is immersed in toluene for 1 day, and a probe tack of 0.9N or less. The pressure-sensitive adhesive sheet has a non-tacky adhesive layer surface, exhibits a stable and appropriate adhesive force when pressed with fingers and a palm, is easy to position, re-adhere, and re-peel, and is easy to manufacture and store.
Description
Technical Field
The present invention relates to a pressure-sensitive adhesive sheet, wherein the surface of an adhesive layer is not sticky, and the pressure-sensitive adhesive sheet exhibits stable and appropriate adhesive force when pressed by fingers and palms, and is easy to position, re-stick and re-peel.
Background
Conventionally, pressure-sensitive adhesive sheets that are attached with fingers, palms, and the like have been widely used for fixing, protecting, masking, and the like articles. However, in a conventional general pressure-sensitive adhesive sheet, the surface of the adhesive layer is sticky, and when it contacts an object to be adhered, an adhesive force is generated immediately, and it is difficult to perform positioning and re-adhesion. In addition, wrinkles and air bubbles are easily generated.
On the other hand, for example, patent document 1 discloses a pressure-sensitive adhesive sheet which has no tackiness at normal temperature by providing a core-shell type adhesive layer, and exhibits adhesive force by breaking the shell layer when a pressure of a certain level or more is applied. However, such a pressure-sensitive adhesive sheet has a complicated step in forming the core-shell type adhesive layer, and adjustment of the pressure capable of breaking the shell layer is not easy.
Patent document 2 discloses an adhesive tape which is substantially free of tackiness and which is produced by using an adhesive containing a polyester having a polycarbonate structure and a polymer having a specific SP value in an adhesive layer, the adhesive having a weight average molecular weight of 2 ten thousand or more. However, such an adhesive may exhibit an unintended adhesive force in summer or in a high-temperature atmosphere, and conversely, may not be sufficiently adhered even when pressed in winter or in a low-temperature atmosphere.
Patent document 3 discloses an acrylic curable adhesive composition which has low initial tackiness, has adhesive force of such a degree that it can be re-attached to an object to be attached at the time of bonding, and is strongly bonded by a heat curing reaction after the attachment. However, the adhesive strength by the curing reaction is generally quite high, and the adhesive tape is difficult to be peeled again, and therefore, the adhesive tape cannot be used for masking tapes and protective sheets. Furthermore, the adhesive tape needs to be stored at a low temperature before use.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2012-102207
Patent document 2: japanese laid-open patent publication No. 11-61080
Patent document 3: japanese laid-open patent publication No. 7-216338
Disclosure of Invention
The purpose of the present invention is to provide a pressure-sensitive adhesive sheet in which the surface of the adhesive layer is not sticky, which exhibits stable and appropriate adhesive force when pressed with fingers or the palm, which is easy to position, re-adhere, and re-peel, and which is easy to manufacture and store.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that a silicone adhesive layer having a specific gel fraction and probe tackiness is very effective, and have completed the present invention.
That is, the present invention is a pressure-sensitive adhesive sheet having an adhesive layer containing a silicone-based adhesive composition containing a crosslinked silicone structure, and having a gel fraction of 40% or less as measured by the following method and a probe adhesiveness of 0.9N or less as measured by the following method.
(gel fraction)
The gel fraction, which is the ratio of insoluble components when the silicone adhesive composition is immersed in toluene for 1 day, is obtained by the following general formula.
Gel fraction (%) - (C/A). times.100%
A: initial quality of Silicone adhesive composition
C: drying quality of Silicone adhesive composition after immersion in toluene (drying conditions: 130 ℃ C., 2 hours)
(Probe tack)
The force (probe tack) required for peeling a cylindrical probe 5mm in diameter from the adhesive surface in the vertical direction was measured according to the probe tack test method based on JIS Z0237, and the load was 100gf/cm2The contact time was 1 second, and the peeling speed was 1 cm/sec.
Effects of the invention
When the pressure-sensitive adhesive sheet of the present invention has a large area, for example, the pressure-sensitive adhesive sheet is temporarily fixed by lightly pressing four corners with fingers or a palm. When the sticking position is deviated, the tape is peeled off and temporarily fixed again. When the sticking position is correct, the whole is pressed to be firmly fixed. In particular, the pressure-sensitive adhesive sheet of the present invention can easily perform the above-mentioned temporary fixing because the pressure-sensitive adhesive sheet of the present invention does not have a tacky adhesive layer and can exhibit a stable and appropriate adhesive force when pressed with a finger or a palm, and can be easily attached to an accurate position even with a pressure-sensitive adhesive sheet having a large area. In addition, if the whole body is uniformly pressed after the four corners are temporarily fixed, wrinkling and air bubbles are not easy to generate.
Further, since the pressure-sensitive adhesive sheet of the present invention uses a silicone adhesive as the adhesive layer, it can be produced more easily than the core-shell adhesive described in patent document 1, for example. Further, the adhesive force is more stable than that of the specific adhesive described in patent document 2. Further, compared to the thermosetting adhesive described in patent document 3, it is easier to re-attach and re-peel, and can be stored at room temperature.
Detailed Description
< adhesive composition >
The adhesive composition used in the present invention is an adhesive composition containing a silicone adhesive as a main component. The gel fraction of the adhesive composition is 40% or less, preferably 20% or more and 40% or less, and more preferably 25% or more and 35% or less. The adhesive composition has a probe tack of 0.9N or less, preferably 0.5N or less, and more preferably 0.2N or less. If the gel fraction and the probe tackiness fall within the specified ranges of the present invention, the adhesive layer is not tacky and exhibits stable and appropriate adhesive force when pressed with fingers or palm. The specific measurement method of gel fraction and probe tack is described in the examples section below.
The swelling degree of the adhesive composition with respect to toluene is not particularly limited, but is preferably 200% to 650%, more preferably 300% to 550%. 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 do not easily diffuse even when immersed in toluene, and the degree of swelling is low. On the other hand, when the crosslinking density is low, the polymer chain is easily diffused and the degree of swelling is high. The swelling degree was measured by the following method.
(degree of swelling)
The swelling degree, which is the swelling ratio based on the absorption of toluene when the silicone adhesive composition is immersed in toluene at room temperature for 1 day, 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
Specific examples of the silicone-based adhesive used in the present invention include those mainly containing silicone raw rubber (having a silicone-containing group)D unit ((CH)3)2Long-chain polymer of polydimethylsiloxane of the structure of SiO) and MQ resin (having a structure containing M units ((CH)3)3SiO1/2) And Q unit (SiO)4/2) A polymer of the three-dimensional structure silicone resin of (a). The adhesive containing the silicone raw rubber and the MQ resin is superior in adhesiveness to the silicone raw rubber alone. Further, by changing the ratio of the silicone raw rubber and the MQ resin in the adhesive, basic adhesive physical properties such as adhesive force, holding power, adhesiveness, and the like can be controlled. Silicone adhesives are largely classified into addition curing type and peroxide curing type according to their curing mechanism.
The addition curing type silicone adhesive contains, for example: a main agent composed of a silicone raw rubber having an alkenyl group, an MQ resin, and a crosslinking agent composed of a polysiloxane having an SiH group. Further, it is cured by heating under a platinum catalyst to cause a crosslinking reaction. For the silicone raw rubber having an alkenyl group, a polysiloxane having at least 2 alkenyl groups (e.g., vinyl groups) bonded to silicon atoms in 1 molecule is representative. For polysiloxane having SiH group, polysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in 1 molecule is representative. Generally, an addition-curable silicone adhesive has the following tendency: if the compounding ratio of the MQ resin to the silicone raw rubber is increased or the content ratio of the alkenyl group in the silicone raw rubber (and/or MQ resin) is decreased, the gel fraction becomes low. In general, the following tendency is exhibited: if the compounding ratio of the MQ resin to the silicone raw rubber is increased, or the crosslinking density of the adhesive is increased, the probe tackiness becomes low. Therefore, as a method for obtaining an adhesive composition having a specific gel fraction and probe adhesiveness using an addition-curable silicone-based adhesive, for example, a method of appropriately adjusting the blending ratio of the MQ resin to the silicone raw rubber and the alkenyl content ratio in the silicone raw rubber (and/or MQ resin) is known. However, the adhesive composition used in the present invention is not limited to one obtained by such a conditioning method.
The peroxide-curable silicone adhesive contains, for example, a main agent composed of a silicone raw rubber having no alkenyl group and an MQ resin. Further, a peroxide such as benzoyl peroxide is added as a curing agent, and the solvent is removed, followed by heating at a high temperature to cure the resin. Generally, the peroxide-curable silicone adhesive has the following tendency: if the mixing ratio of the MQ resin to the silicone raw rubber is increased or the amount of the peroxide to be added is decreased, the gel fraction is lowered. In general, the following tendency is exhibited: if the compounding ratio of the MQ resin to the silicone raw rubber is increased and the crosslinking density of the adhesive is reduced, the probe tackiness becomes low. Therefore, as a method for obtaining an adhesive composition having a specific gel fraction and probe adhesiveness by using a peroxide-curable silicone adhesive, for example, a method of appropriately adjusting the compounding ratio of MQ resin to silicone raw rubber and the addition amount of peroxide is known. However, the adhesive composition used in the present invention is not limited to one obtained by such a conditioning method.
The silicone adhesive may be used in combination with 2 or more kinds. In particular, the adhesive composition used in the present invention preferably contains an addition-curable silicone adhesive cured by crosslinking. The crosslinking and curing reaction of the silicone adhesive is usually carried out by heating, but depending on the type of the adhesive or curing agent, crosslinking and curing may be carried out by condensation reaction or ultraviolet irradiation. In the case of using an addition curing type silicone adhesive, the amount of the crosslinking agent composed of SiH group-containing polysiloxane may be appropriately adjusted.
The adhesive composition of the present invention having a specific gel fraction and probe adhesiveness can also be obtained by using a mixture of 2 or more silicone adhesives. Specifically, for example, an adhesive composition having a gel fraction and a probe tack falling within the scope of the present invention can be obtained by mixing a silicone adhesive having a high gel fraction and a high probe tack and a silicone adhesive having a low gel fraction and a low probe tack at an appropriate ratio, and then crosslinking and curing the mixture. However, the adhesive composition used in the present invention is not limited to being obtained by such a method.
Additives may also be added to the adhesive composition for the purpose of improving various characteristics. Specific examples of the additive include inorganic fillers such as carbon black and silica; polysiloxanes such as silicone resins, polydimethylsiloxane, and polydimethylsiloxane; 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 so as not to impair the effect of the invention.
< pressure-sensitive adhesive sheet >
The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the above-described adhesive composition, and typically, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the adhesive composition on at least one surface of a substrate. Further, the pressure-sensitive adhesive sheet may be a matrix-free type pressure-sensitive adhesive sheet having no base material. The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 100. mu.m, more preferably 5 to 75 μm, and particularly preferably 10 to 50 μm.
The pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition of the present invention on one surface of a substrate and a pressure-sensitive adhesive layer containing another pressure-sensitive adhesive composition on the other surface.
The adhesive layer can be formed by subjecting the adhesive composition to a crosslinking curing reaction. For example, an adhesive composition is applied to a substrate, and crosslinked and cured by heating, condensation reaction, or ultraviolet irradiation, thereby forming 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, condensation reaction, or ultraviolet irradiation to form an adhesive layer, and the adhesive layer may be bonded to one 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 aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane and isoparaffin; ketone solvents such as methylethylketone and methylisobutylketone; second stepEster solvents such as ethyl acetate and isobutyl acetate; diisopropyl ether, 1, 4-bis
Ether solvents such as alkanes.
The coating method is not particularly limited, and any known method may be used. Specific examples thereof include coating using a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, a bar coater, a kiss coater, or a gravure coater; screen coating; dip coating; and (5) casting and coating.
The substrate is not particularly limited, and a film-like substrate is preferable. Specific examples thereof include resin films of Polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamide imide (PAI), polyether sulfone (PES), Polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), and Polyethylene (PE). These films may be used in the form of a single layer, or in the form of a laminated film having 2 or more layers. The thickness of the base material is not particularly limited, but is preferably 3 to 200. mu.m, more preferably 5 to 160 μm, and particularly preferably 12 to 130 μm.
The surface of the substrate on which the adhesive layer is provided may be subjected to an easy adhesion treatment as needed. Examples of the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, and blast treatment.
The pressure-sensitive adhesive sheet of the present invention may be further provided with a release liner. The release liner is used for protecting the adhesive layer of the pressure-sensitive adhesive sheet, and is peeled off before the attachment to expose the adhesive and attach the pressure-sensitive adhesive sheet to an object to be attached. The type of release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include materials obtained by subjecting the surface of a substrate such as a backing paper, cellophane paper, or synthetic resin film to a release agent treatment. For the release agent treatment, for example, a release agent such as a fluorine-substituted alkyl-modified silicone resin can 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. In addition, when the adhesive layer has low adhesiveness, a resin film which is not subjected to release treatment may be used as the release liner. Specific examples thereof include polyethylene terephthalate (PET) films, Polyethylene (PE) films, and polypropylene (PP) films.
The pressure-sensitive adhesive sheet of the present invention is applied under a pressure of 0.03kg/cm2The adhesion to SUS after pressing for 1 minute is 1.9N/20mm or less, preferably 0.15N/20mm or less, more preferably 0.25N/20mm or less. The 0.03kg/cm2The pressure condition of (2) may be an index of the adhesive force generated only when the pressure-sensitive adhesive sheet is brought into contact with the adherend. That is, if the adhesion force of this test is low, the pressure-sensitive adhesive sheet does not exhibit an unnecessary adhesion force. The specific measurement method is described in the examples section below.
The pressure-sensitive adhesive sheet of the present invention is useful for applications requiring that the pressure-sensitive adhesive sheet does not stick to an adherend when merely contacting the adherend, and that the pressure-sensitive adhesive sheet can exhibit stable and appropriate adhesive force when pressed with a finger or a palm. For example, the adhesive is useful for protection, decoration, masking, fixation, and the like, and specific examples thereof include applications in which it is necessary to adhere the adhesive to an object having a large area such as a wall, window glass, an automobile, and a train without generating wrinkles or air bubbles, and applications in which it is necessary to fix a precision member or the like that needs to be accurately positioned.
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" means "part by mass".
< example 1>
First, a plurality of test pieces (I to IV) of an addition curing silicone adhesive stock solution were prepared. These are test pieces of an adhesive in which gel fraction, swelling degree, and probe tack after crosslinking and curing, which are measured by the method described later, are adjusted to various values by appropriately changing the alkenyl content ratio in silicone raw rubber (and/or MQ resin) of the mixing ratio of MQ resin to silicone raw rubber. Note that the same MQ resin was used for all of these test pieces. In the present example, an addition-curable silicone-based adhesive stock solution (I) having a gel fraction of 37% after crosslinking and curing, a degree of swelling of 399% and a probe tack of 0.48N was selected and used for the plurality of test pieces. Specifically, 100 parts of an addition-curable silicone adhesive stock solution (I) having a solid content concentration of 60 mass%, 100 parts of toluene as a diluent solvent, and 0.9 parts of a platinum catalyst as a curing catalyst were uniformly mixed to obtain an adhesive solution (1).
Next, an adhesive liquid (1) was applied to one surface of a Polytetrafluoroethylene (PTFE) film having a thickness of 25 μm and subjected to primer treatment so that the thickness of the dried adhesive layer became 10 μm, and curing and drying were performed in a drying oven at 80 ℃ for 2 minutes and at 130 ℃ for 2 minutes to form an adhesive layer. Then, an untreated PET film having a thickness of 25 μm as a release liner was bonded to the adhesive layer to obtain an adhesive sheet.
< example 2>
An adhesive liquid (2) was prepared in the same manner as in example 1 except that an addition curing type silicone adhesive stock solution (II) (solid content concentration of 60 mass%) having a gel fraction of 35%, a degree of swelling of 358%, and a probe tack of 0.06N after crosslinking curing was selected and used instead of the adhesive stock solution (I) from the above-described test pieces to prepare an adhesive tape.
< example 3>
An adhesive liquid (3) was prepared in the same manner as in example 1 except that an addition-curable silicone-based adhesive stock solution (III) (solid content concentration of 60 mass%) having a gel fraction of 32%, a degree of swelling of 384%, and a probe tack of 0.02N after crosslinking and curing was selected and used instead of the adhesive stock solution (I) from the above-described test pieces to prepare an adhesive tape.
< example 4>
An adhesive liquid (4) was prepared in the same manner as in example 1 except that an addition curing type silicone adhesive stock solution (IV) (solid content concentration of 60 mass%) having a gel fraction after crosslinking and curing of 30%, a swelling degree of 350%, and a probe tack of 0.01N was selected and used instead of the adhesive stock solution (I) from the above-described test pieces to prepare an adhesive tape.
< comparative example 1>
An adhesive liquid (5) was prepared in the same manner as in example 1 except that an addition-curable silicone adhesive stock solution (product name: SD-4580, manufactured by Tooli-Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was, and a pressure-sensitive adhesive sheet was produced.
< comparative example 2>
An adhesive liquid (6) was prepared in the same manner as in example 1 except that an addition-curable silicone adhesive stock solution (product name: SD-4570, manufactured by Tooli-Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was, and a pressure-sensitive adhesive sheet was produced.
< comparative example 3>
An adhesive liquid (7) was prepared in the same manner as in example 1 except that an addition-curable silicone adhesive stock solution (product name: SD-4560, manufactured by Tooli-Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it is, and a pressure-sensitive adhesive sheet was produced.
< comparative example 4>
An adhesive liquid (8) was prepared in the same manner as in example 1 except that an addition-curable silicone adhesive stock solution (trade name: KR-3701, manufactured by shin-Etsu chemical industries, Ltd.) having a solid content concentration of 60 mass% was used as it is, and a pressure-sensitive adhesive sheet was produced.
< gel fraction and swelling degree of adhesive composition >
The adhesive liquids (1) to (8) obtained in examples and comparative examples were applied to a release liner so that the thickness after drying became 150 μm, respectively. Then, the adhesive composition was prepared by heating in a drying oven, curing and drying, and used as a sample. The heating temperature was 130 ℃ for 2 minutes.
The obtained sample was cut into 50mm × 50mm, and the release liner was peeled off to obtain a measurement sample formed of a 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) at room temperature (23 ℃) for 24 hours to swell. After the immersion, the measurement sample was taken out, and the swelling mass (B) (═ mass of the adhesive composition after swelling 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) (mass of the adhesive composition after drying). The gel fraction and the swelling degree of the adhesive composition were obtained by the following formulae.
Gel fraction (%) - (C/A). times.100
The degree of swelling (%) ((B-A)/A). times.100%
< Probe tack >
The pressure-sensitive adhesive sheets obtained in examples and comparative examples were measured for the force (probe adhesiveness) required to peel a cylindrical probe having a diameter of 5mm from the adhesive surface in the vertical direction, by using a probe adhesiveness TESTER TE-6001 manufactured by stester industries, according to the probe adhesiveness test method based on JIS Z0237. The load at the time of the measurement was 100gf/cm2The contact time was 1 second, and the peeling speed was 1 cm/sec.
< adhesion to SUS after pressing >
After the pressure-sensitive adhesive sheet cut to a width of 20mm was placed on a polished SUS plate and pressed for 1 minute at the pressures (1) to (5) shown in table 1, the force required to peel the tape at a speed of 300 mm/minute and at an angle of 180 ° was measured within 20 minutes using a tensile tester.
< touch feeling >
The touch feeling on the surface of the adhesive layer of the pressure-sensitive adhesive sheets obtained in examples and comparative examples was evaluated according to the following criteria.
O: and was not sticky.
Δ: slightly tacky.
X: is very sticky.
The results of the above measurements are shown in tables 1 and 2.
[ Table 1]
TABLE 1
[ Table 2]
TABLE 2
< evaluation results >
As shown in Table 1, the pressure-sensitive adhesive sheets of examples 1 to 4 had tack-free adhesive layer surfaces and low initial tack until the pressing pressure was about 10kg/cm2Until then, the adhesive force increased in proportion to the increase in pressing pressure. Therefore, it was found that the pressure-sensitive adhesive sheets of examples 1 to 4 can easily control the adhesive force by the pressing force of the fingers and the palm.
On the other hand, the pressure-sensitive adhesive sheets of comparative examples 1 to 4 had too high gel fraction and probe tackiness, and therefore the surface of the adhesive layer was very tacky. Moreover, the adhesion force is almost fixed regardless of the pressing pressure. Therefore, it was found that the pressure-sensitive adhesive sheets of comparative examples 1 to 4 were difficult to control the adhesive force by the pressing force.
Industrial applicability of the invention
The pressure-sensitive adhesive sheet of the present invention is useful, for example, in applications requiring attachment to an object to be attached having a large area such as a wall, window glass, automobile, train, etc. without generating wrinkles or air bubbles, and applications requiring fixing of precision parts, etc. requiring accurate positioning.
Claims (5)
1. A pressure-sensitive adhesive sheet having an adhesive layer containing a silicone-based adhesive composition,
the silicone adhesive composition contains a crosslinked silicone structure, and has a gel fraction of 20% to 40% as measured by the following method, and a probe adhesion of 0.5N or less as measured by the following method;
gel fraction:
the gel fraction, which is the ratio of insoluble components when the silicone adhesive composition is immersed in toluene for 1 day, 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;
probe adhesion:
the force required for peeling a cylindrical probe having a diameter of 5mm from the adhesive surface in the vertical direction was measured in accordance with the probe adhesion test method based on JIS Z0237, the force being the probe adhesion and the load being 100gf/cm2The contact time was 1 second, the peeling speed was 1 cm/sec,
the silicone-based adhesive composition contains a silicone raw rubber which is a long-chain polymer of polydimethylsiloxane having a structure containing a D unit of (CH) and an MQ resin3)2SiO, the MQ resin is a polymer of a three-dimensional structure organic silicon resin with a structure containing M units and Q units, and the M units are (CH)3)3SiO1/2The unit of Q is SiO4/2。
2. The pressure-sensitive adhesive sheet according to claim 1, wherein the silicone-based adhesive composition comprises an addition-curable silicone adhesive that is cured by crosslinking.
3. The pressure-sensitive adhesive sheet according to claim 1, wherein the substrate has an adhesive layer on at least one surface thereof.
4. The pressure-sensitive adhesive sheet according to claim 3, wherein the substrate is a resin film.
5. The pressure-sensitive adhesive sheet according to claim 1, wherein the pressure is 0.03kg/cm as measured by the following method2The adhesion to SUS after pressing for 1 minute was 1.9N/20mm or less,
adhesion to SUS after pressing:
the pressure-sensitive adhesive sheet cut to a width of 20mm was placed on a ground SUS plate at a pressure of 0.03kg/cm2After pressing for 1 minute, the force required to peel the tape at a speed of 300 mm/minute at an angle of 180 ° was measured within 20 minutes using a tensile tester.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/072394 WO2018020674A1 (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109476962A CN109476962A (en) | 2019-03-15 |
| CN109476962B true CN109476962B (en) | 2021-12-10 |
Family
ID=61017240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680087979.8A Active CN109476962B (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6677812B2 (en) |
| KR (2) | KR102422197B1 (en) |
| CN (1) | CN109476962B (en) |
| WO (1) | WO2018020674A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021199355A1 (en) * | 2020-03-31 | 2021-10-07 | 株式会社寺岡製作所 | Resin composition and adhesive tape |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093719A (en) * | 2010-12-27 | 2011-06-15 | 东莞市阿比亚能源科技有限公司 | High-power light emitting diode (LED) chip packaging soft gel |
| JP4809988B2 (en) * | 2001-03-21 | 2011-11-09 | 日東電工株式会社 | Silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using the same |
| CN104093809A (en) * | 2011-12-08 | 2014-10-08 | 莫门蒂夫性能材料股份有限公司 | Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof |
| CN104877622A (en) * | 2014-02-27 | 2015-09-02 | 信越化学工业株式会社 | Silicone pressure-sensitive adhesive composition having improved substrate adhesion and pressure-sensitive adhesive article |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07216338A (en) | 1994-02-04 | 1995-08-15 | Toyo Ink Mfg Co Ltd | Hardenable pressure-sensitive composition and sheet or tape coated therewith |
| JP3874498B2 (en) | 1997-08-21 | 2007-01-31 | 日東電工株式会社 | Fastening system |
| JP3751186B2 (en) * | 2000-06-14 | 2006-03-01 | 信越化学工業株式会社 | Silicone adhesive composition |
| JP2004091703A (en) * | 2002-09-02 | 2004-03-25 | Shin Etsu Chem Co Ltd | Conductive silicone self-adhesive composition and self-adhesive tape |
| JP5234064B2 (en) * | 2010-08-23 | 2013-07-10 | 信越化学工業株式会社 | Solvent-free addition-type silicone adhesive composition and adhesive article |
| KR20120102207A (en) | 2011-03-08 | 2012-09-18 | 디에스환경기술 주식회사 | Coagulant throwing apparatus for waste water treatment device |
| 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 |
-
2016
- 2016-07-29 KR KR1020217012458A patent/KR102422197B1/en active IP Right Grant
- 2016-07-29 WO PCT/JP2016/072394 patent/WO2018020674A1/en active Application Filing
- 2016-07-29 KR KR1020187038076A patent/KR20190012228A/en active Application Filing
- 2016-07-29 CN CN201680087979.8A patent/CN109476962B/en active Active
- 2016-07-29 JP JP2018529330A patent/JP6677812B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4809988B2 (en) * | 2001-03-21 | 2011-11-09 | 日東電工株式会社 | Silicone pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using the same |
| CN102093719A (en) * | 2010-12-27 | 2011-06-15 | 东莞市阿比亚能源科技有限公司 | High-power light emitting diode (LED) chip packaging soft gel |
| CN104093809A (en) * | 2011-12-08 | 2014-10-08 | 莫门蒂夫性能材料股份有限公司 | Self-crosslinking silicone pressure sensitive adhesive compositions, process for making and articles made thereof |
| CN104877622A (en) * | 2014-02-27 | 2015-09-02 | 信越化学工业株式会社 | Silicone pressure-sensitive adhesive composition having improved substrate adhesion and pressure-sensitive adhesive article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109476962A (en) | 2019-03-15 |
| WO2018020674A1 (en) | 2018-02-01 |
| JP6677812B2 (en) | 2020-04-08 |
| KR20210049195A (en) | 2021-05-04 |
| KR102422197B1 (en) | 2022-07-20 |
| KR20190012228A (en) | 2019-02-08 |
| JPWO2018020674A1 (en) | 2019-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0662995B1 (en) | Cationically co-curable polysiloxane release coatings | |
| KR101186709B1 (en) | Silicone rubber based pressure sensitive adhesive sheet | |
| JP5130995B2 (en) | Solvent-free silicone adhesive composition | |
| JP2006052384A (en) | Silicone rubber based adhesive sheet | |
| KR102088105B1 (en) | Reusable release film | |
| JP6378516B2 (en) | Silicone adhesive tape | |
| CN108690528B (en) | Protective sheet | |
| CN109196070B (en) | Adhesive composition and adhesive tape | |
| KR20170056051A (en) | Release film prevention peel defects | |
| WO2021029414A1 (en) | Organopolysiloxane composition having pressure-sensitive adhesive layer formation properties, and use of said composition | |
| JP6626125B2 (en) | Adhesive composition and adhesive tape | |
| CN109476962B (en) | Pressure-sensitive adhesive sheet | |
| CN113631376A (en) | Release sheet | |
| CN114269875B (en) | Pressure-sensitive adhesive layer-forming polyorganosiloxane composition and use thereof | |
| CN115362218B (en) | Resin composition and adhesive tape | |
| KR102469375B1 (en) | Silicone based adhesive protective film and optical member comprising the same | |
| KR20200044082A (en) | Silicone adhesive composition and adhesive tape | |
| JP2019151043A (en) | Silicone rubber molded body and manufacturing method therefor | |
| JP2020116888A (en) | Peeling sheet | |
| CN113613897A (en) | Release sheet | |
| TW201335318A (en) | Pressure sensitive adhesive sheet and method of producing thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |