WO2018020674A1 - Pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- WO2018020674A1 WO2018020674A1 PCT/JP2016/072394 JP2016072394W WO2018020674A1 WO 2018020674 A1 WO2018020674 A1 WO 2018020674A1 JP 2016072394 W JP2016072394 W JP 2016072394W WO 2018020674 A1 WO2018020674 A1 WO 2018020674A1
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- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- silicone
- adhesive sheet
- adhesive composition
- Prior art date
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Classifications
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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
- 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
- C09J2301/302—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
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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
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet in which the surface of the adhesive layer is not sticky, and when it is pressed with a finger or palm, a stable and appropriate adhesive force is expressed, and positioning, reattachment and re-peeling are easy. .
- Patent Document 1 discloses a pressure-sensitive adhesive sheet that is tack-free at room temperature by providing a core-shell type adhesive layer and that develops an adhesive force by destroying the shell layer by applying a certain pressure or more. It is disclosed.
- a pressure-sensitive adhesive sheet has a complicated process for forming the core-shell adhesive layer, and it is not easy to adjust the pressure at which the shell layer can be broken.
- Patent Document 2 discloses a pressure-sensitive adhesive tape that is substantially tack-free by using a pressure-sensitive adhesive containing a polyester having a polycarbonate structure and a weight average molecular weight of 20,000 or more and a polymer having a specific SP value.
- a pressure-sensitive adhesive may cause an unintended adhesive force in summer or in a high temperature atmosphere, and conversely, it may not adhere sufficiently even when pressed in a winter or low temperature atmosphere.
- Patent Document 3 discloses an acrylic curable pressure-sensitive adhesive that has a low initial tack, has an adhesive strength that can be reattached to an adherend during adhesion, and adheres firmly by a heat curing reaction after adhesion. A composition is disclosed. However, since the adhesive strength due to the curing reaction is generally quite high, it is difficult to re-peel the adhesive tape, so it cannot be used for masking tapes or protective sheet applications. Moreover, it is necessary to store the adhesive tape at a low temperature before use.
- the object of the present invention is that the surface of the pressure-sensitive adhesive layer is not sticky, when it is pressed with a finger or palm, a stable and appropriate pressure-sensitive adhesive force is expressed, and alignment, re-sticking and re-peeling are easy.
- the object is to provide a pressure-sensitive adhesive sheet that is easy to manufacture and store.
- the present invention relates to a silicone pressure-sensitive adhesive composition
- a silicone pressure-sensitive adhesive composition comprising a crosslinked silicone structure, having a gel fraction measured by the following method of 40% or less and a probe tack measured by the following method of 0.9 N or less.
- It is a pressure-sensitive adhesive sheet having an adhesive layer made of a product. (Gel fraction)
- the gel fraction is obtained by the following formula, which is the ratio of insoluble matter when the silicone-based pressure-sensitive adhesive composition is immersed in toluene for 1 day.
- the pressure-sensitive adhesive sheet when the pressure-sensitive adhesive sheet has a large area, first, the pressure-sensitive adhesive sheet is temporarily fixed by lightly pressing the four corners with a finger or palm. If the attachment position is shifted, it is peeled off and temporarily fixed. If the attachment position is correct, press the entire unit to fix it firmly.
- the pressure-sensitive adhesive sheet of the present invention does not have a sticky surface, and when it is pressed with a finger or palm, a stable and appropriate adhesive force is expressed. Even a pressure-sensitive adhesive sheet having a large area can be easily attached to the correct position. Moreover, if the entire corner is pressed uniformly after temporarily fastening the four corners, soot and air traps are less likely to occur.
- the pressure-sensitive adhesive sheet of the present invention uses a silicone-based adhesive for the adhesive layer, for example, it is easier to manufacture than the core-shell adhesive described in Patent Document 1. Moreover, compared with the specific adhesive described in Patent Document 2, the adhesive force is stable. In addition, reattachment and re-peeling are easier than the thermosetting pressure-sensitive adhesive described in Patent Document 3, and storage at room temperature is possible.
- the pressure-sensitive adhesive composition used in the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive as a main component.
- the gel fraction of the pressure-sensitive adhesive composition is 40% or less, preferably 20% or more and 40% or less, more preferably 25% or more and 35% or less.
- the probe tack of the pressure-sensitive adhesive composition is 0.9 N or less, preferably 0.5 N or less, more preferably 0.2 N or less. If the gel fraction and the probe tack are within the specific ranges of the present invention, the surface of the adhesive layer is not sticky, and a stable and appropriate adhesive force appears when pressed with a finger or palm. Specific methods for measuring the gel fraction and probe tack are described in the Examples section described below.
- the swelling degree with respect to toluene of an adhesive composition is not specifically limited, Preferably it is 200% or more and 650% or less, More preferably, it is 300% or more and 550% or less.
- the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition. When the crosslinking density is high, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to spread 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 easy to spread and the degree of swelling is high. This swelling degree is measured by the following method (swelling degree).
- the degree of swelling is obtained by the following formula, which is a swelling ratio due to absorption of toluene when the silicone-based pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
- Swelling degree (%) ((BA) / A) ⁇ 100% A: Initial mass of silicone pressure-sensitive adhesive composition B: Swelling mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene
- silicone adhesive used in the present invention mainly silicone raw rubber (D units long-chain polymer of polydimethylsiloxane having a structure consisting of [(CH 3) 2 SiO] ) and MQ resin (M units And a pressure-sensitive adhesive containing [(CH 3 ) 3 SiO 1/2 ] and a polymer of a three-dimensional silicone resin having a structure consisting of Q units [SiO 4/2 ]).
- a pressure-sensitive adhesive containing a raw silicone rubber and an MQ resin is superior in adhesiveness compared to a single silicone raw rubber.
- basic adhesive properties such as adhesive strength, holding power, and tack can be controlled.
- Silicone pressure-sensitive adhesives are roughly classified into an addition-curing type and a peroxide-curing type depending on the curing mechanism.
- the addition-curable silicone-based pressure-sensitive adhesive includes, for example, a main agent made of silicone raw rubber containing alkenyl groups, MQ resin, and a crosslinking agent made of polyorganosiloxane containing SiH groups. And it hardens
- the silicone raw rubber containing an alkenyl group is typically a polyorganosiloxane having at least two alkenyl groups (for example, vinyl groups) bonded to silicon atoms in one molecule.
- the polyorganosiloxane containing SiH groups is typically a polyorganosiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule.
- the gel fraction decreases when the blending ratio of MQ resin to silicone raw rubber is increased or the content ratio of alkenyl groups in silicone raw rubber (and / or MQ resin) is decreased. Tend to be. In general, when the blending ratio of the MQ resin to the silicone raw rubber is increased or the crosslinking density of the pressure-sensitive adhesive is increased, the probe tack tends to be lowered.
- a method for obtaining a pressure-sensitive adhesive composition having a specific gel fraction and probe tack using an addition-curable silicone-based pressure-sensitive adhesive for example, the blending ratio of MQ resin to silicone raw rubber and silicone raw rubber (and / or MQ)
- the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such an adjustment method.
- the peroxide-curing silicone-based pressure-sensitive adhesive contains, for example, a main agent made of silicone raw rubber not containing an alkenyl group, and MQ resin. And after adding peroxides, such as benzoyl peroxide, as a hardening
- peroxides such as benzoyl peroxide
- curing agent removing a solvent
- the gel fraction tends to decrease when the blending ratio of MQ resin to the raw silicone rubber is increased or the amount of peroxide added is decreased.
- the probe tack tends to be lowered when the blending ratio of the MQ resin to the silicone raw rubber is increased or the crosslinking density of the pressure-sensitive adhesive is increased.
- a method of obtaining a pressure-sensitive adhesive composition having a specific gel fraction and probe tack using a peroxide-curable silicone pressure-sensitive adhesive for example, the blending ratio of MQ resin to silicone raw rubber and the addition of peroxide There is a method of adjusting the amount appropriately.
- the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such an adjustment method.
- the pressure-sensitive adhesive composition used in the present invention preferably contains a cross-linked and cured addition-curable silicone pressure-sensitive adhesive.
- the crosslinking curing reaction of the silicone pressure-sensitive adhesive is usually carried out by heating.
- the crosslinking curing can be performed by a condensation reaction or ultraviolet irradiation.
- the amount of the crosslinking agent made of a polyorganosiloxane containing a SiH group may be appropriately adjusted.
- a pressure-sensitive adhesive composition having a specific gel fraction and probe tack of the present invention using a mixture of two or more types of silicone pressure-sensitive adhesives.
- a silicone adhesive having a relatively high gel fraction and probe tack and a silicone adhesive having a relatively low gel fraction and probe tack are mixed at an appropriate ratio and crosslinked and cured.
- a pressure-sensitive adhesive composition having a gel fraction and probe tack within the scope of the present invention can be obtained.
- the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such a method.
- An additive may be added to the pressure-sensitive adhesive composition for the purpose of improving various properties.
- additives include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane and polydimethylphenylsiloxane; and antioxidants such as phenolic antioxidants and amine antioxidants. Agents; silane coupling agents.
- the type and amount of the additive must be appropriately selected so as not to impair the effects of the invention.
- the pressure-sensitive pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition described above.
- the pressure-sensitive adhesive is made of the pressure-sensitive adhesive composition on at least one side of a substrate.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
- the pressure-sensitive adhesive sheet of the present invention has a double-sided feeling having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a substrate and a pressure-sensitive adhesive layer made of another pressure-sensitive adhesive composition on the other side.
- a pressure-sensitive adhesive sheet may be used.
- the pressure-sensitive adhesive layer can be formed by cross-linking and curing reaction of the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive composition can be applied on a base material and crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the base material.
- the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to crosslinking and curing by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer is applied to one or both sides of the substrate. It can also be combined.
- a solvent may be added.
- the solvent include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, octane and isoparaffin; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate.
- ether solvents such as diisopropyl ether and 1,4-dioxane.
- the coating method is not particularly limited, and a known method may be used. Specific examples thereof include coating using a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater or gravure coater; screen coating; dip coating; cast coating. It is done.
- the substrate is not particularly limited, but a film-like substrate is preferable. Specific examples thereof include, for example, polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamide imide (PAI), polyether sulfone ( Examples of the resin film include PES), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), and polyethylene (PE). These films can be used as a single layer or a laminated film of two or more layers.
- the thickness of the substrate is not particularly limited, but is preferably 3 to 200 ⁇ m, more preferably 5 to 160 ⁇ m, and particularly preferably 12 to 130 ⁇ m.
- the surface on which the pressure-sensitive adhesive layer of the substrate is provided may be subjected to an easy adhesion treatment as necessary.
- the easy adhesion treatment include primer treatment, corona treatment, etching treatment, plasma treatment, and sandblast treatment.
- the pressure-sensitive adhesive sheet of the present invention may be provided with a release liner.
- the release liner is for protecting the pressure-sensitive adhesive layer of the pressure-sensitive pressure-sensitive adhesive sheet, and is peeled off immediately before application, exposing the pressure-sensitive adhesive and attaching the pressure-sensitive pressure-sensitive adhesive sheet to the adherend.
- the kind of release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include those obtained by subjecting the surface of a base material such as fine paper, glassine paper, and synthetic resin film to a release agent treatment.
- a release agent such as a fluorine-substituted alkyl-modified silicone resin may be used.
- the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer is preferably one obtained by releasing the surface of the polyethylene terephthalate film with a fluorine-substituted alkyl-modified silicone resin.
- a resin film that has not been subjected to a release treatment may be used as a release liner.
- Specific examples thereof include a polyethylene terephthalate (PET) film, a polyethylene (PE) film, and a polypropylene (PP) film.
- the pressure-sensitive adhesive sheet of the present invention has a SUS adhesive strength after pressing for 1 minute at a pressure of 0.03 kg / cm 2 1.9 N / 20 mm or less, preferably 0.15 N / 20 mm or less, more preferably 0.25 N / 20 mm or less.
- This pressure condition of 0.03 kg / cm 2 can serve as an index of the adhesive force generated when the pressure-sensitive adhesive sheet simply contacts the adherend. That is, if the adhesive strength of this test is low, the pressure-sensitive adhesive sheet will not exhibit unnecessary adhesive strength.
- a specific measurement method is described in the column of Examples described later.
- the pressure-sensitive adhesive sheet of the present invention is very useful for applications that do not stick simply by contact with an adherend, and that require stable and appropriate adhesive strength when pressed with a finger or palm. It is. For example, it is useful for applications such as protection, decoration, masking, fixing, etc. Specific examples include affixing to adherends having a large area such as walls, window glass, automobiles, trains, etc. without causing any traps or air pockets. Applications, and applications for fixing precision parts and the like that require accurate positioning.
- part means “part by mass”.
- Example 1 a plurality of prototypes (I to IV) of an addition-curable silicone-based adhesive stock solution were prepared.
- the plurality of prototypes are obtained by appropriately changing the content ratio of the alkenyl group in the silicone raw rubber (and / or MQ resin) in the blending ratio of the MQ resin with respect to the silicone raw rubber, and after crosslinking and curing measured by the method described later. It is a prototype of an adhesive adjusted so that the gel fraction, the degree of swelling, and the probe tack exhibit various values. These prototypes all use a common MQ resin.
- the pressure-sensitive adhesive liquid (1) was applied to one side of a 25 ⁇ m-thick polytetrafluoroethylene (PTFE) film subjected to primer treatment so that the thickness of the pressure-sensitive adhesive layer after drying was 10 ⁇ m.
- PTFE polytetrafluoroethylene
- an untreated PET film having a thickness of 25 ⁇ m was bonded to the pressure-sensitive adhesive layer as a release liner to obtain a pressure-sensitive adhesive sheet.
- Example 2 Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (II) having a gel fraction after cross-linking and curing of 35%, a swelling degree of 358%, and a probe tack of 0.06 N (solid content) A pressure-sensitive adhesive liquid (2) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
- a concentration of 60% by mass was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
- Example 3 Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (III) having a gel fraction after crosslinking and curing of 32%, a swelling degree of 384%, and a probe tack of 0.02 N (solid content) A pressure-sensitive adhesive solution (3) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used in place of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
- Example 4 Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (IV) having a gel fraction after cross-linking and curing of 30%, a swelling degree of 350%, and a probe tack of 0.01 N (solid content) A pressure-sensitive adhesive liquid (4) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
- a pressure-sensitive adhesive liquid (5) was obtained in the same manner as in Example 1, except that an addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4580, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was.
- a pressure-sensitive adhesive sheet was prepared.
- a pressure-sensitive adhesive liquid (6) was obtained in the same manner as in Example 1 except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4570, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was.
- a pressure-sensitive adhesive sheet was prepared.
- a pressure-sensitive adhesive liquid (7) was obtained in the same manner as in Example 1, except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was.
- a pressure-sensitive adhesive sheet was prepared.
- a pressure-sensitive adhesive liquid (8) was prepared in the same manner as in Example 1 except that the addition-curing silicone pressure-sensitive adhesive stock solution (trade name KR-3701, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. Thus, a pressure-sensitive adhesive sheet was produced.
- the addition-curing silicone pressure-sensitive adhesive stock solution (trade name KR-3701, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content concentration of 60% by mass was used as it was.
- the obtained sample was cut into 50 mm ⁇ 50 mm, the release liner was peeled off, and a measurement sample comprising a sheet-like pressure-sensitive adhesive composition was obtained.
- ⁇ Probe tack> Using a probe tack tester TE-6001 manufactured by Tester Sangyo Co., Ltd., a pressure sensitive adhesive sheet obtained in Examples and Comparative Examples was adhered to a cylindrical probe having a diameter of 5 mm according to a probe tack test method according to JIS Z 0237. The force (probe tack) required to peel off from the surface in the vertical direction was measured. The load during this measurement was 100 gf / cm 2 , the contact time was 1 second, and the peeling speed was 1 cm / second.
- ⁇ Tactile sense> The tactile sensation when the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples was touched was evaluated according to the following criteria. ⁇ : There was no stickiness. ⁇ : Slightly sticky. X: It was very sticky.
- the pressure-sensitive adhesive sheets of Examples 1 to 4 are not sticky on the surface of the adhesive layer, have low initial adhesive strength, and are pressed until the press pressure is about 10 kg / cm 2.
- the adhesive force increased in proportion to the increase in pressure. Therefore, it can be seen that the pressure-sensitive adhesive sheets of Examples 1 to 4 can easily control the adhesive force by the pressing force of a finger or palm.
- the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 had a very sticky surface because the gel fraction and probe tack were too high. Moreover, the adhesive strength was almost constant regardless of the press pressure. Therefore, it can be seen that the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 are difficult to control the adhesive force by the pressing force.
- the pressure-sensitive adhesive sheet of the present invention can be applied to an adherend having a large area such as a wall, a window glass, an automobile, and a train without causing any wrinkles or air accumulation, and an accurate position. This is useful for fixing precision parts that need to be aligned.
Abstract
Disclosed is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer comprising a silicone-based adhesive composition containing a crosslinked silicone structure, having a gel fraction, which is the ratio of insoluble content when the silicone-based adhesive composition is immersed in toluene for one day, of 40% or less, and having a probe tack of 0.9 N or less. In this pressure-sensitive adhesive sheet: the surface of the adhesive layer is not tacky; when pressed with a finger or a palm, a stable and appropriate adhesive strength is expressed; positioning, reapplication, and re-peeling are easy; and the production and storage thereof are easy.
Description
本発明は、粘着層の表面がべとついておらず、指や掌で押圧した際には安定した適度な粘着力が発現し、位置合わせ、貼り直し及び再剥離が容易な感圧粘着シートに関する。
The present invention relates to a pressure-sensitive adhesive sheet in which the surface of the adhesive layer is not sticky, and when it is pressed with a finger or palm, a stable and appropriate adhesive force is expressed, and positioning, reattachment and re-peeling are easy. .
従来、物品を固定、保護、マスキング等する際に、指や掌等で貼り付ける感圧粘着シートが広く用いられている。しかし、従来用いられている一般的な感圧粘着シートは粘着層の表面がべとついているので、被着体に接触した際に直ちに接着力が発現し、位置合わせや貼り直しが困難である。また、皺や空気溜まりも生じ易い。
Conventionally, pressure-sensitive adhesive sheets that are pasted with fingers or palms when fixing, protecting, or masking articles have been widely used. However, since the surface of the pressure-sensitive adhesive layer of a general pressure-sensitive pressure-sensitive adhesive sheet that has been used in the past, the adhesive force immediately appears when it comes into contact with the adherend, and it is difficult to align and reattach. . In addition, soot and air accumulation are likely to occur.
そこで、例えば特許文献１には、コアシェル型接着剤層を設けることにより、常温でタックフリーであり、一定以上の圧力を加えてシェル層を破壊することにより接着力を発現する感圧接着シートが開示されている。しかし、このような感圧接着シートは、コアシェル型接着剤層を形成する際の工程が複雑であり、しかもシェル層を破壊できる圧力の調整が簡単ではない。
Therefore, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet that is tack-free at room temperature by providing a core-shell type adhesive layer and that develops an adhesive force by destroying the shell layer by applying a certain pressure or more. It is disclosed. However, such a pressure-sensitive adhesive sheet has a complicated process for forming the core-shell adhesive layer, and it is not easy to adjust the pressure at which the shell layer can be broken.
特許文献２には、粘着剤層にポリカーボネート構造を含む重量平均分子量２万以上のポリエステルと特定のＳＰ値を有するポリマーを含む粘着剤を使用することにより実質的にタックフリーとした粘着テープが開示されている。しかし、このような粘着剤では、夏場や高温雰囲気下では意図しない接着力が発現する恐れがあり、逆に冬場や低温雰囲気下では押圧しても十分に貼着しない恐れがある。
Patent Document 2 discloses a pressure-sensitive adhesive tape that is substantially tack-free by using a pressure-sensitive adhesive containing a polyester having a polycarbonate structure and a weight average molecular weight of 20,000 or more and a polymer having a specific SP value. Has been. However, such a pressure-sensitive adhesive may cause an unintended adhesive force in summer or in a high temperature atmosphere, and conversely, it may not adhere sufficiently even when pressed in a winter or low temperature atmosphere.
特許文献３には、初期タックが低く、接着時には被着体への貼り直しが可能な程度の粘着力を有し、貼着後は加熱硬化反応により強固に接着するアクリル系の硬化性粘着剤組成物が開示されている。しかし、一般に硬化反応による接着強度はかなり高く粘着テープの再剥離は困難なので、マスキングテープや保護シートの用途には使用できない。しかも、使用前は粘着テープを低温で保管する必要がある。
Patent Document 3 discloses an acrylic curable pressure-sensitive adhesive that has a low initial tack, has an adhesive strength that can be reattached to an adherend during adhesion, and adheres firmly by a heat curing reaction after adhesion. A composition is disclosed. However, since the adhesive strength due to the curing reaction is generally quite high, it is difficult to re-peel the adhesive tape, so it cannot be used for masking tapes or protective sheet applications. Moreover, it is necessary to store the adhesive tape at a low temperature before use.
本発明の目的は、粘着層の表面がべとついておらず、指や掌で押圧した際には安定した適度な粘着力が発現し、位置合わせ、貼り直し及び再剥離が容易であり、しかも製造や保管が容易な感圧粘着シートを提供することにある。
The object of the present invention is that the surface of the pressure-sensitive adhesive layer is not sticky, when it is pressed with a finger or palm, a stable and appropriate pressure-sensitive adhesive force is expressed, and alignment, re-sticking and re-peeling are easy. The object is to provide a pressure-sensitive adhesive sheet that is easy to manufacture and store.
本発明者らは上記目的を達成すべく鋭意検討した結果、特定のゲル分率とプローブタックを有するシリコーン系粘着剤層が非常に効果的であることを見出し、本発明を完成するに至った。
As a result of intensive studies to achieve the above object, the present inventors have found that a silicone-based pressure-sensitive adhesive layer having a specific gel fraction and probe tack is very effective, and have completed the present invention. .
すなわち本発明は、架橋されたシリコーン構造を含み、下記方法により測定されるゲル分率が４０％以下であり、かつ下記方法により測定されるプローブタックが０.９Ｎ以下であるシリコーン系粘着剤組成物からなる粘着剤層を有する感圧粘着シートである。
（ゲル分率）
トルエンにシリコーン系粘着剤組成物を１日間浸漬したときの不溶解分の比率である、下記式によってゲル分率を得る。
ゲル分率（％）＝（Ｃ／Ａ）×１００％
Ａ：シリコーン系粘着剤組成物の初期質量
Ｃ：トルエン浸漬後のシリコーン系粘着剤組成物の乾燥質量（乾燥条件：１３０℃、２時間）
（プローブタック）
ＪＩＳ Ｚ ０２３７に準じたプローブタック試験法に従い、直径５ｍｍの円柱プローブを粘着面から垂直方向に引き剥がすのに要する力（プローブタック）を測定する（荷重１００ｇｆ／ｃｍ２、接触時間１秒、引き剥がし速度１ｃｍ／秒）。 That is, the present invention relates to a silicone pressure-sensitive adhesive composition comprising a crosslinked silicone structure, having a gel fraction measured by the following method of 40% or less and a probe tack measured by the following method of 0.9 N or less. It is a pressure-sensitive adhesive sheet having an adhesive layer made of a product.
(Gel fraction)
The gel fraction is obtained by the following formula, which is the ratio of insoluble matter when the silicone-based pressure-sensitive adhesive composition is immersed in toluene for 1 day.
Gel fraction (%) = (C / A) × 100%
A: Initial mass of silicone-based pressure-sensitive adhesive composition C: Dry mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene (drying conditions: 130 ° C., 2 hours)
(Probe tack)
According to the probe tack test method according to JIS Z 0237, the force (probe tack) required to peel a 5 mm diameter cylindrical probe vertically from the adhesive surface is measured (load 100 gf / cm 2 , contact time 1 second, pull (Peeling speed 1 cm / sec).
（ゲル分率）
トルエンにシリコーン系粘着剤組成物を１日間浸漬したときの不溶解分の比率である、下記式によってゲル分率を得る。
ゲル分率（％）＝（Ｃ／Ａ）×１００％
Ａ：シリコーン系粘着剤組成物の初期質量
Ｃ：トルエン浸漬後のシリコーン系粘着剤組成物の乾燥質量（乾燥条件：１３０℃、２時間）
（プローブタック）
ＪＩＳ Ｚ ０２３７に準じたプローブタック試験法に従い、直径５ｍｍの円柱プローブを粘着面から垂直方向に引き剥がすのに要する力（プローブタック）を測定する（荷重１００ｇｆ／ｃｍ２、接触時間１秒、引き剥がし速度１ｃｍ／秒）。 That is, the present invention relates to a silicone pressure-sensitive adhesive composition comprising a crosslinked silicone structure, having a gel fraction measured by the following method of 40% or less and a probe tack measured by the following method of 0.9 N or less. It is a pressure-sensitive adhesive sheet having an adhesive layer made of a product.
(Gel fraction)
The gel fraction is obtained by the following formula, which is the ratio of insoluble matter when the silicone-based pressure-sensitive adhesive composition is immersed in toluene for 1 day.
Gel fraction (%) = (C / A) × 100%
A: Initial mass of silicone-based pressure-sensitive adhesive composition C: Dry mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene (drying conditions: 130 ° C., 2 hours)
(Probe tack)
According to the probe tack test method according to JIS Z 0237, the force (probe tack) required to peel a 5 mm diameter cylindrical probe vertically from the adhesive surface is measured (load 100 gf / cm 2 , contact time 1 second, pull (Peeling speed 1 cm / sec).
本発明の感圧粘着シートは、例えば感圧粘着シートが広い面積を有する場合、まず指や掌で四隅を軽く押圧することにより仮留めする。そして貼り着け位置がずれている場合は、剥離して仮留めをやり直す。貼り着け位置が正しい場合は、全体を押圧してしっかり固定する。特に、本発明の感圧粘着シートは、粘着層の表面がべとついておらず、しかも指や掌で押圧した際には安定した適度な粘着力が発現するので、このような仮留めを簡単に行うことができ、広い面積を有する感圧粘着シートであっても正しい位置に容易に貼り付けることができる。しかも、四隅を仮留めしてから全体を均一に押圧すれば、皺や空気溜まりも生じにくい。
For example, when the pressure-sensitive adhesive sheet has a large area, first, the pressure-sensitive adhesive sheet is temporarily fixed by lightly pressing the four corners with a finger or palm. If the attachment position is shifted, it is peeled off and temporarily fixed. If the attachment position is correct, press the entire unit to fix it firmly. In particular, the pressure-sensitive adhesive sheet of the present invention does not have a sticky surface, and when it is pressed with a finger or palm, a stable and appropriate adhesive force is expressed. Even a pressure-sensitive adhesive sheet having a large area can be easily attached to the correct position. Moreover, if the entire corner is pressed uniformly after temporarily fastening the four corners, soot and air traps are less likely to occur.
さらに本発明の感圧粘着シートは、粘着剤層にシリコーン系粘着剤を用いているので、例えば特許文献１に記載のコアシェル型接着剤と比較して製造が容易である。また、特許文献２に記載の特定の粘着剤と比較して粘着力が安定している。また、特許文献３に記載の熱硬化性粘着剤と比較して貼り直しや再剥離が容易であり、しかも常温での保管が可能である。
Furthermore, since the pressure-sensitive adhesive sheet of the present invention uses a silicone-based adhesive for the adhesive layer, for example, it is easier to manufacture than the core-shell adhesive described in Patent Document 1. Moreover, compared with the specific adhesive described in Patent Document 2, the adhesive force is stable. In addition, reattachment and re-peeling are easier than the thermosetting pressure-sensitive adhesive described in Patent Document 3, and storage at room temperature is possible.
＜粘着剤組成物＞
本発明に用いる粘着剤組成物は、シリコーン系粘着剤を主成分として含む粘着剤組成物である。粘着剤組成物のゲル分率は４０％以下であり、好ましくは２０％以上４０％以下、より好ましくは２５％以上３５％以下である。粘着剤組成物のプローブタックは０.９Ｎ以下であり、好ましくは０.５Ｎ以下、より好ましくは０.２Ｎ以下である。ゲル分率とプローブタックが本発明の特定の範囲内であれば、粘着層の表面がべとついておらず、指や掌で押圧した際には安定した適度な粘着力が発現する。ゲル分率及びプローブタックの具体的な測定方法は、後述する実施例の欄に記載する。 <Adhesive composition>
The pressure-sensitive adhesive composition used in the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive as a main component. The gel fraction of the pressure-sensitive adhesive composition is 40% or less, preferably 20% or more and 40% or less, more preferably 25% or more and 35% or less. The probe tack of the pressure-sensitive adhesive composition is 0.9 N or less, preferably 0.5 N or less, more preferably 0.2 N or less. If the gel fraction and the probe tack are within the specific ranges of the present invention, the surface of the adhesive layer is not sticky, and a stable and appropriate adhesive force appears when pressed with a finger or palm. Specific methods for measuring the gel fraction and probe tack are described in the Examples section described below.
本発明に用いる粘着剤組成物は、シリコーン系粘着剤を主成分として含む粘着剤組成物である。粘着剤組成物のゲル分率は４０％以下であり、好ましくは２０％以上４０％以下、より好ましくは２５％以上３５％以下である。粘着剤組成物のプローブタックは０.９Ｎ以下であり、好ましくは０.５Ｎ以下、より好ましくは０.２Ｎ以下である。ゲル分率とプローブタックが本発明の特定の範囲内であれば、粘着層の表面がべとついておらず、指や掌で押圧した際には安定した適度な粘着力が発現する。ゲル分率及びプローブタックの具体的な測定方法は、後述する実施例の欄に記載する。 <Adhesive composition>
The pressure-sensitive adhesive composition used in the present invention is a pressure-sensitive adhesive composition containing a silicone-based pressure-sensitive adhesive as a main component. The gel fraction of the pressure-sensitive adhesive composition is 40% or less, preferably 20% or more and 40% or less, more preferably 25% or more and 35% or less. The probe tack of the pressure-sensitive adhesive composition is 0.9 N or less, preferably 0.5 N or less, more preferably 0.2 N or less. If the gel fraction and the probe tack are within the specific ranges of the present invention, the surface of the adhesive layer is not sticky, and a stable and appropriate adhesive force appears when pressed with a finger or palm. Specific methods for measuring the gel fraction and probe tack are described in the Examples section described below.
粘着剤組成物のトルエンに対する膨潤度は特に限定されないが、好ましくは２００％以上６５０％以下であり、より好ましくは３００％以上５５０％以下である。一般に、膨潤度は粘着剤組成物の架橋密度に依存する。架橋密度が高い場合はトルエンに浸漬しても粘着剤を構成する三次元に架橋されたポリマー鎖が広がりにくく、膨潤度は低くなる。一方、架橋密度が低い場合はポリマー鎖が広がりやすく膨潤度は高くなる。この膨潤度は以下の方法により測定される
（膨潤度）
トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときのトルエンの吸収による膨潤比率である、下記式によって膨潤度を得る。
膨潤度（％）＝（（Ｂ－Ａ）／Ａ）×１００％
Ａ：シリコーン系粘着剤組成物の初期質量
Ｂ：トルエン浸漬後のシリコーン系粘着剤組成物の膨潤質量 Although the swelling degree with respect to toluene of an adhesive composition is not specifically limited, Preferably it is 200% or more and 650% or less, More preferably, it is 300% or more and 550% or less. In general, the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition. When the crosslinking density is high, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to spread 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 easy to spread and the degree of swelling is high. This swelling degree is measured by the following method (swelling degree).
The degree of swelling is obtained by the following formula, which is a swelling ratio due to absorption of toluene when the silicone-based pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
Swelling degree (%) = ((BA) / A) × 100%
A: Initial mass of silicone pressure-sensitive adhesive composition B: Swelling mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene
（膨潤度）
トルエンにシリコーン系粘着剤組成物を常温で１日間浸漬したときのトルエンの吸収による膨潤比率である、下記式によって膨潤度を得る。
膨潤度（％）＝（（Ｂ－Ａ）／Ａ）×１００％
Ａ：シリコーン系粘着剤組成物の初期質量
Ｂ：トルエン浸漬後のシリコーン系粘着剤組成物の膨潤質量 Although the swelling degree with respect to toluene of an adhesive composition is not specifically limited, Preferably it is 200% or more and 650% or less, More preferably, it is 300% or more and 550% or less. In general, the degree of swelling depends on the crosslinking density of the pressure-sensitive adhesive composition. When the crosslinking density is high, the three-dimensionally crosslinked polymer chain constituting the pressure-sensitive adhesive is difficult to spread 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 easy to spread and the degree of swelling is high. This swelling degree is measured by the following method (swelling degree).
The degree of swelling is obtained by the following formula, which is a swelling ratio due to absorption of toluene when the silicone-based pressure-sensitive adhesive composition is immersed in toluene at room temperature for 1 day.
Swelling degree (%) = ((BA) / A) × 100%
A: Initial mass of silicone pressure-sensitive adhesive composition B: Swelling mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene
本発明に用いるシリコーン系粘着剤の具体例としては、主にシリコーン生ゴム（Ｄ単位［(CH3)2SiO］からなる構造を有するポリジメチルシロキサンの長鎖の重合体）とＭＱレジン（Ｍ単位［(CH3)3SiO1/2］とＱ単位［SiO4/2］からなる構造を有する３次元構造のシリコーンレジンの重合体）を含有する粘着剤が挙げられる。このようなシリコーン生ゴムとＭＱレジンを含有する粘着剤は、シリコーン生ゴム単体に比べて粘着性に優れる。また、粘着剤中のシリコーン生ゴムとＭＱレジンの比率を変えることで粘着力・保持力・タック等の基本的な粘着物性をコントロールすることができる。シリコーン系粘着剤は、その硬化機構により、付加硬化型、過酸化物硬化型に大別される。
Specific examples of the silicone adhesive used in the present invention mainly silicone raw rubber (D units long-chain polymer of polydimethylsiloxane having a structure consisting of [(CH 3) 2 SiO] ) and MQ resin (M units And a pressure-sensitive adhesive containing [(CH 3 ) 3 SiO 1/2 ] and a polymer of a three-dimensional silicone resin having a structure consisting of Q units [SiO 4/2 ]). Such a pressure-sensitive adhesive containing a raw silicone rubber and an MQ resin is superior in adhesiveness compared to a single silicone raw rubber. In addition, by changing the ratio of silicone raw rubber and MQ resin in the adhesive, basic adhesive properties such as adhesive strength, holding power, and tack can be controlled. Silicone pressure-sensitive adhesives are roughly classified into an addition-curing type and a peroxide-curing type depending on the curing mechanism.
付加硬化型シリコーン系粘着剤は、例えば、アルケニル基を含有するシリコーン生ゴムからなる主剤と、ＭＱレジンと、ＳｉＨ基を含有するポリオルガノシロキサンからなる架橋剤とを含む。そして、白金触媒下で加熱して架橋反応させることにより硬化する。アルケニル基を含有するシリコーン生ゴムは、代表的には、ケイ素原子に結合したアルケニル基（例えばビニル基）を１分子中に少なくとも２個有するポリオルガノシロキサンである。ＳｉＨ基を含有するポリオルガノシロキサンは、代表的には、ケイ素原子に結合した水素原子を１分子中に少なくとも２個有するポリオルガノシロキサンである。一般に、付加硬化型シリコーン系粘着剤においては、シリコーン生ゴムに対するＭＱレジンの配合比率を高くしたり、あるいはシリコーン生ゴム（及び／又はＭＱレジン）中のアルケニル基の含有比率を低くするとゲル分率が低くなる傾向にある。また一般に、シリコーン生ゴムに対するＭＱレジンの配合比率を高くしたり、粘着剤の架橋密度を高くすると、プローブタックが低くなる傾向にある。したがって、付加硬化型シリコーン系粘着剤を用いて特定のゲル分率及びプローブタックを有する粘着剤組成物を得る方法としては、例えば、シリコーン生ゴムに対するＭＱレジンの配合比率とシリコーン生ゴム（及び／又はＭＱレジン）中のアルケニル基の含有比率を適宜調整する方法がある。ただし、本発明に用いる粘着剤組成物はこのような調整方法で得たものに限定されない。
The addition-curable silicone-based pressure-sensitive adhesive includes, for example, a main agent made of silicone raw rubber containing alkenyl groups, MQ resin, and a crosslinking agent made of polyorganosiloxane containing SiH groups. And it hardens | cures by heating under a platinum catalyst and carrying out a crosslinking reaction. The silicone raw rubber containing an alkenyl group is typically a polyorganosiloxane having at least two alkenyl groups (for example, vinyl groups) bonded to silicon atoms in one molecule. The polyorganosiloxane containing SiH groups is typically a polyorganosiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule. In general, in addition-curable silicone-based pressure-sensitive adhesives, the gel fraction decreases when the blending ratio of MQ resin to silicone raw rubber is increased or the content ratio of alkenyl groups in silicone raw rubber (and / or MQ resin) is decreased. Tend to be. In general, when the blending ratio of the MQ resin to the silicone raw rubber is increased or the crosslinking density of the pressure-sensitive adhesive is increased, the probe tack tends to be lowered. Therefore, as a method for obtaining a pressure-sensitive adhesive composition having a specific gel fraction and probe tack using an addition-curable silicone-based pressure-sensitive adhesive, for example, the blending ratio of MQ resin to silicone raw rubber and silicone raw rubber (and / or MQ) There is a method of appropriately adjusting the content ratio of the alkenyl group in the resin. However, the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such an adjustment method.
過酸化物硬化型シリコーン系粘着剤は、例えば、アルケニル基を含有しないシリコーン生ゴムからなる主剤と、ＭＱレジンとを含む。そして、硬化剤として過酸化ベンゾイル等の過酸化物を添加し、溶媒を除去した後、高温で加熱することで硬化する。一般に、過酸化物硬化型シリコーン系粘着剤においては、シリコーン生ゴムに対するＭＱレジンの配合比率を高くしたり、過酸化物の添加量を少なくするとゲル分率が低くなる傾向にある。また一般に、シリコーン生ゴムに対するＭＱレジンの配合比率を高くしたり、粘着剤の架橋密度を高くするとプローブタックが低くなる傾向にある。したがって、過酸化物硬化型シリコーン系粘着剤を用いて特定のゲル分率及びプローブタックを有する粘着剤組成物を得る方法としては、例えば、シリコーン生ゴムに対するＭＱレジンの配合比率と過酸化物の添加量を適宜調整する方法がある。ただし、本発明に用いる粘着剤組成物はこのような調整方法で得たものに限定されない。
The peroxide-curing silicone-based pressure-sensitive adhesive contains, for example, a main agent made of silicone raw rubber not containing an alkenyl group, and MQ resin. And after adding peroxides, such as benzoyl peroxide, as a hardening | curing agent, removing a solvent, it hardens | cures by heating at high temperature. In general, in a peroxide curable silicone pressure-sensitive adhesive, the gel fraction tends to decrease when the blending ratio of MQ resin to the raw silicone rubber is increased or the amount of peroxide added is decreased. In general, the probe tack tends to be lowered when the blending ratio of the MQ resin to the silicone raw rubber is increased or the crosslinking density of the pressure-sensitive adhesive is increased. Therefore, as a method of obtaining a pressure-sensitive adhesive composition having a specific gel fraction and probe tack using a peroxide-curable silicone pressure-sensitive adhesive, for example, the blending ratio of MQ resin to silicone raw rubber and the addition of peroxide There is a method of adjusting the amount appropriately. However, the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such an adjustment method.
シリコーン系粘着剤は２種以上を組み合わせて使用しても良い。特に本発明に用いる粘着剤組成物は、架橋硬化された付加硬化型シリコーン粘着剤を含むことが好ましい。なお、シリコーン粘着剤の架橋硬化反応は通常加熱によって行うが、粘着剤や硬化剤の種類によっては縮合反応や紫外線照射でも架橋硬化が可能である。付加硬化型シリコーン粘着剤を使用する場合においては、ＳｉＨ基を含有したポリオルガノシロキサンからなる架橋剤の量を適宜調整してもよい。
¡Silicon adhesives may be used in combination of two or more. In particular, the pressure-sensitive adhesive composition used in the present invention preferably contains a cross-linked and cured addition-curable silicone pressure-sensitive adhesive. The crosslinking curing reaction of the silicone pressure-sensitive adhesive is usually carried out by heating. However, depending on the type of the pressure-sensitive adhesive or the curing agent, the crosslinking curing can be performed by a condensation reaction or ultraviolet irradiation. In the case of using an addition-curable silicone pressure-sensitive adhesive, the amount of the crosslinking agent made of a polyorganosiloxane containing a SiH group may be appropriately adjusted.
２種以上のシリコーン系粘着剤の混合物を用いて本発明の特定のゲル分率及びプローブタックを有する粘着剤組成物を得ることもできる。具体的には、例えばゲル分率及びプローブタックが比較的高いシリコーン系粘着剤と、ゲル分率及びプローブタックが比較的低いシリコーン系粘着剤とを適当な比率で混合して架橋硬化することにより、ゲル分率及びプローブタックが本発明の範囲内となる粘着剤組成物を得ることができる。ただし、本発明に用いる粘着剤組成物はこのような方法で得たものに限定されない。
It is also possible to obtain a pressure-sensitive adhesive composition having a specific gel fraction and probe tack of the present invention using a mixture of two or more types of silicone pressure-sensitive adhesives. Specifically, for example, a silicone adhesive having a relatively high gel fraction and probe tack and a silicone adhesive having a relatively low gel fraction and probe tack are mixed at an appropriate ratio and crosslinked and cured. A pressure-sensitive adhesive composition having a gel fraction and probe tack within the scope of the present invention can be obtained. However, the pressure-sensitive adhesive composition used in the present invention is not limited to that obtained by such a method.
粘着剤組成物には、各種特性の向上を目的として添加剤を添加しても良い。添加剤の具体例としては、カーボンブラック、シリカ等の無機充填剤；シリコーンレジン、ポリジメチルシロキサン、ポリジメチルフェニルシロキサン等のポリオルガノシロキサン；フェノール系酸化防止剤、アミン系酸化防止剤等の酸化防止剤；シランカップリング剤が挙げられる。ただし添加剤の種類や量は、発明の効果が損なわれないよう適宜選定する必要がある。
An additive may be added to the pressure-sensitive adhesive composition for the purpose of improving various properties. Specific examples of additives include inorganic fillers such as carbon black and silica; polyorganosiloxanes such as silicone resin, polydimethylsiloxane and polydimethylphenylsiloxane; and antioxidants such as phenolic antioxidants and amine antioxidants. Agents; silane coupling agents. However, the type and amount of the additive must be appropriately selected so as not to impair the effects of the invention.
＜感圧粘着シート＞
本発明の感圧粘着シートは、以上説明した粘着剤組成物からなる粘着剤層を有する感圧粘着シートであり、代表的には、基材の少なくとも片面にその粘着剤組成物からなる粘着剤層を有する感圧粘着シートである。また、基材の無いベースレスタイプの感圧粘着シートであってもよい。粘着剤層の厚さは特に限定されないが、好ましくは１～１００μｍ、より好ましくは５～７５μｍ、特に好ましくは１０～５０μｍである。 <Pressure-sensitive adhesive sheet>
The pressure-sensitive pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition described above. Typically, the pressure-sensitive adhesive is made of the pressure-sensitive adhesive composition on at least one side of a substrate. A pressure-sensitive adhesive sheet having a layer. Further, it may be a baseless type pressure-sensitive adhesive sheet having no base material. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 10 to 50 μm.
本発明の感圧粘着シートは、以上説明した粘着剤組成物からなる粘着剤層を有する感圧粘着シートであり、代表的には、基材の少なくとも片面にその粘着剤組成物からなる粘着剤層を有する感圧粘着シートである。また、基材の無いベースレスタイプの感圧粘着シートであってもよい。粘着剤層の厚さは特に限定されないが、好ましくは１～１００μｍ、より好ましくは５～７５μｍ、特に好ましくは１０～５０μｍである。 <Pressure-sensitive adhesive sheet>
The pressure-sensitive pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition described above. Typically, the pressure-sensitive adhesive is made of the pressure-sensitive adhesive composition on at least one side of a substrate. A pressure-sensitive adhesive sheet having a layer. Further, it may be a baseless type pressure-sensitive adhesive sheet having no base material. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 75 μm, and particularly preferably 10 to 50 μm.
本発明の感圧粘着シートは、基材の片面に本発明の粘着剤組成物からなる粘着剤層を有し、もう一方の面に他の粘着剤組成物からなる粘着剤層を有する両面感圧粘着シートであっても良い。
The pressure-sensitive adhesive sheet of the present invention has a double-sided feeling having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention on one side of a substrate and a pressure-sensitive adhesive layer made of another pressure-sensitive adhesive composition on the other side. A pressure-sensitive adhesive sheet may be used.
粘着剤層は、粘着剤組成物を架橋硬化反応させることにより形成できる。例えば、粘着剤組成物を基材上に塗布し、加熱又は縮合反応や紫外線照射により架橋硬化させて基材上に粘着剤層を形成できる。また、粘着剤組成物を離型紙又はその他のフィルム上に塗布し、加熱又は縮合反応や紫外線照射により架橋硬化させて粘着剤層を形成し、この粘着剤層を基材の片面又は両面に貼り合せることもできる。
The pressure-sensitive adhesive layer can be formed by cross-linking and curing reaction of the pressure-sensitive adhesive composition. For example, the pressure-sensitive adhesive composition can be applied on a base material and crosslinked and cured by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer on the base material. In addition, the pressure-sensitive adhesive composition is applied onto a release paper or other film, and is subjected to crosslinking and curing by heating or condensation reaction or ultraviolet irradiation to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer is applied to one or both sides of the substrate. It can also be combined.
塗布の際の粘着剤組成物の粘度を下げる為に、溶剤を添加しても良い。溶剤の具体例としては、トルエン、キシレン等の芳香族系溶剤；ヘキサン、オクタン、イソパラフィン等の脂肪族系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤；酢酸エチル、酢酸イソブチル等のエステル系溶剤；ジイソプロピルエーテル、１,４－ジオキサン等のエーテル系溶剤が挙げられる。
In order to reduce the viscosity of the pressure-sensitive adhesive composition during application, 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 methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and isobutyl acetate. And ether solvents such as diisopropyl ether and 1,4-dioxane.
塗工方法は特に限定されず、公知方法を用いれば良い。その具体例としては、コンマコーター、リップコーター、ロールコーター、ダイコーター、ナイフコーター、ブレードコーター、ロッドコーター、キスコーター又はグラビアコーターを用いた塗工；スクリーン塗工；浸漬塗工；キャスト塗工が挙げられる。
The coating method is not particularly limited, and a known method may be used. Specific examples thereof include coating using a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater or gravure coater; screen coating; dip coating; cast coating. It is done.
基材は特に限定されないが、フィルム状の基材が好ましい。その具体例としては例えば、ポリイミド（ＰＩ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエチレンテレフタラート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリフェニレンサルファイド（ＰＰＳ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルスルフォン（ＰＥＳ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリ塩化ビニル（ＰＶＣ）、ポリエチレン（ＰＥ）の樹脂フィルムが挙げられる。これらのフィルムを単層、または２層以上の積層フィルムとして使用できる。基材の厚さは特に制限されないが、好ましくは３～２００μｍ、より好ましくは５～１６０μｍ、特に好ましくは１２～１３０μｍである。
The substrate is not particularly limited, but a film-like substrate is preferable. Specific examples thereof include, for example, polyimide (PI), polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyamide imide (PAI), polyether sulfone ( Examples of the resin film include PES), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), and polyethylene (PE). These films can be used as a single layer or a laminated film of two or more layers. The thickness of the substrate is not particularly limited, but is preferably 3 to 200 μm, more preferably 5 to 160 μm, and particularly preferably 12 to 130 μm.
基材の粘着剤層を設ける面には、必要に応じて易接着処理を施しても良い。易接着処理としては、例えば、プライマー処理、コロナ処理、エッチング処理、プラズマ処理、サンドブラスト処理などが挙げられる。
The surface on which the pressure-sensitive adhesive layer of the substrate 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, and sandblast treatment.
本発明の感圧粘着シートには剥離ライナーを設けても良い。剥離ライナーとは、感圧粘着シートの粘着剤層を保護する為のものであり、貼り付け直前に剥離し、粘着剤を露出させて被着体に感圧粘着シートを貼り付ける。剥離ライナーの種類は特に限定されず、公知の剥離ライナーを使用できる。その具体例としては、上質紙、グラシン紙、合成樹脂フィルム等の基材の表面に離型剤処理を施したものが挙げられる。離型剤処理には、例えばフッ素置換アルキル変性シリコーン樹脂等の離型剤を用いれば良い。特に、シリコーン系粘着剤層に積層する剥離ライナーとしては、ポリエチレンタレフタレートフィルムの表面をフッ素置換アルキル変性シリコーン樹脂で離型処理したものが好ましい。また、粘着剤層の粘着性が低い場合は、離型処理の施されていない樹脂フィルムを剥離ライナーとして使用しても良い。その具体例としては、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリエチレン（ＰＥ）フィルム、ポリプロピレン（ＰＰ）フィルムが挙げられる。
The pressure-sensitive adhesive sheet of the present invention may be provided with a release liner. The release liner is for protecting the pressure-sensitive adhesive layer of the pressure-sensitive pressure-sensitive adhesive sheet, and is peeled off immediately before application, exposing the pressure-sensitive adhesive and attaching the pressure-sensitive pressure-sensitive adhesive sheet to the adherend. The kind of release liner is not particularly limited, and a known release liner can be used. Specific examples thereof include those obtained by subjecting the surface of a base material such as fine paper, glassine paper, and synthetic resin film to a release agent treatment. For the release agent treatment, a release agent such as a fluorine-substituted alkyl-modified silicone resin may be used. In particular, the release liner to be laminated on the silicone-based pressure-sensitive adhesive layer is preferably one obtained by releasing the surface of the polyethylene terephthalate film with a fluorine-substituted alkyl-modified silicone resin. Moreover, when the adhesiveness of the adhesive layer is low, a resin film that has not been subjected to a release treatment may be used as a release liner. Specific examples thereof include a polyethylene terephthalate (PET) film, a polyethylene (PE) film, and a polypropylene (PP) film.
本発明の感圧粘着シートは、圧力０.０３ｋｇ／ｃｍ２で１分間プレス後の対ＳＵＳ粘着力が１.９Ｎ/２０ｍｍ以下、好ましくは０.１５Ｎ/２０ｍｍ以下、より好ましくは０.２５Ｎ/２０ｍｍ以下である。この０.０３ｋｇ／ｃｍ２という圧力条件は、感圧粘着シートが単に被着体に接触しただけで生じる粘着力の指標となり得る。すなわち、この試験の粘着力が低ければ、感圧粘着シートが不要な接着力を発現しないようになる。具体的な測定方法は、後述する実施例の欄に記載する。
The pressure-sensitive adhesive sheet of the present invention has a SUS adhesive strength after pressing for 1 minute at a pressure of 0.03 kg / cm 2 1.9 N / 20 mm or less, preferably 0.15 N / 20 mm or less, more preferably 0.25 N / 20 mm or less. This pressure condition of 0.03 kg / cm 2 can serve as an index of the adhesive force generated when the pressure-sensitive adhesive sheet simply contacts the adherend. That is, if the adhesive strength of this test is low, the pressure-sensitive adhesive sheet will not exhibit unnecessary adhesive strength. A specific measurement method is described in the column of Examples described later.
本発明の感圧粘着シートは、単に被着体に接触しただけでは貼り付かず、指や掌で押圧した際には安定した適度な粘着力を発現することが要求される用途に非常に有用である。例えば保護、装飾、マスキング、固定等の用途に有用であり、その具体例としては、壁、窓ガラス、自動車、電車等の広い面積を持つ被着体に皺や空気溜まりを生じることなく貼り付けることが必要な用途、並びに、正確な位置合わせが必要な精密部品等を固定する用途が挙げられる。
The pressure-sensitive adhesive sheet of the present invention is very useful for applications that do not stick simply by contact with an adherend, and that require stable and appropriate adhesive strength when pressed with a finger or palm. It is. For example, it is useful for applications such as protection, decoration, masking, fixing, etc. Specific examples include affixing to adherends having a large area such as walls, window glass, automobiles, trains, etc. without causing any traps or air pockets. Applications, and applications for fixing precision parts and the like that require accurate positioning.
以下、実施例により本発明をさらに詳細に説明する。ただし、本発明はこれら実施例に限定されるものではない。以下の記載において「部」は「質量部」を意味する。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following description, “part” means “part by mass”.
＜実施例１＞
まず、付加硬化型シリコーン系粘着剤原液の複数の試作品（Ｉ～ＩＶ）を用意した。これら複数の試作品は、シリコーン生ゴムに対するＭＱレジンの配合比率のシリコーン生ゴム（及び/又はＭＱレジン）中のアルケニル基の含有比率を適宜変更することによって、後述する方法で測定される架橋硬化後のゲル分率、膨潤度及びプローブタックが様々な値を示すように調整した粘着剤の試作品である。なお、これらの試作品はいずれも共通のＭＱレジンを用いている。そして本実施例においては、これら複数の試作品のうち、架橋硬化後のゲル分率が３７％、膨潤度が３９９％、プローブタックが０.４８Ｎとなる付加硬化型シリコーン系粘着剤原液（Ｉ）を選択し、使用した。具体的には、固形分濃度６０質量％の付加硬化型シリコーン系粘着剤原液（Ｉ）１００部、希釈溶剤としてトルエン１００部、硬化触媒として白金触媒０.９部を均一に混合し、粘着剤液（１）を得た。 <Example 1>
First, a plurality of prototypes (I to IV) of an addition-curable silicone-based adhesive stock solution were prepared. The plurality of prototypes are obtained by appropriately changing the content ratio of the alkenyl group in the silicone raw rubber (and / or MQ resin) in the blending ratio of the MQ resin with respect to the silicone raw rubber, and after crosslinking and curing measured by the method described later. It is a prototype of an adhesive adjusted so that the gel fraction, the degree of swelling, and the probe tack exhibit various values. These prototypes all use a common MQ resin. In this example, among these prototypes, an addition curable silicone pressure-sensitive adhesive stock solution (I) having a gel fraction after cross-linking and curing of 37%, a swelling degree of 399%, and a probe tack of 0.48N. ) Selected and used. Specifically, 100 parts of an addition curable silicone pressure sensitive adhesive stock solution (I) having a solid content concentration of 60% by mass, 100 parts of toluene as a diluting solvent, and 0.9 part of a platinum catalyst as a curing catalyst were mixed uniformly. A liquid (1) was obtained.
まず、付加硬化型シリコーン系粘着剤原液の複数の試作品（Ｉ～ＩＶ）を用意した。これら複数の試作品は、シリコーン生ゴムに対するＭＱレジンの配合比率のシリコーン生ゴム（及び/又はＭＱレジン）中のアルケニル基の含有比率を適宜変更することによって、後述する方法で測定される架橋硬化後のゲル分率、膨潤度及びプローブタックが様々な値を示すように調整した粘着剤の試作品である。なお、これらの試作品はいずれも共通のＭＱレジンを用いている。そして本実施例においては、これら複数の試作品のうち、架橋硬化後のゲル分率が３７％、膨潤度が３９９％、プローブタックが０.４８Ｎとなる付加硬化型シリコーン系粘着剤原液（Ｉ）を選択し、使用した。具体的には、固形分濃度６０質量％の付加硬化型シリコーン系粘着剤原液（Ｉ）１００部、希釈溶剤としてトルエン１００部、硬化触媒として白金触媒０.９部を均一に混合し、粘着剤液（１）を得た。 <Example 1>
First, a plurality of prototypes (I to IV) of an addition-curable silicone-based adhesive stock solution were prepared. The plurality of prototypes are obtained by appropriately changing the content ratio of the alkenyl group in the silicone raw rubber (and / or MQ resin) in the blending ratio of the MQ resin with respect to the silicone raw rubber, and after crosslinking and curing measured by the method described later. It is a prototype of an adhesive adjusted so that the gel fraction, the degree of swelling, and the probe tack exhibit various values. These prototypes all use a common MQ resin. In this example, among these prototypes, an addition curable silicone pressure-sensitive adhesive stock solution (I) having a gel fraction after cross-linking and curing of 37%, a swelling degree of 399%, and a probe tack of 0.48N. ) Selected and used. Specifically, 100 parts of an addition curable silicone pressure sensitive adhesive stock solution (I) having a solid content concentration of 60% by mass, 100 parts of toluene as a diluting solvent, and 0.9 part of a platinum catalyst as a curing catalyst were mixed uniformly. A liquid (1) was obtained.
次に、プライマー処理した厚さ２５μｍのポリテトラフルオロエチレン（ＰＴＦＥ）フィルムの片面に、粘着剤液（１）を乾燥後の粘着剤層の厚さが１０μｍになるように塗布し、乾燥炉内で８０℃、２分及び１３０℃、２分にて硬化・乾燥して粘着剤層を形成した。そして剥離ライナーとして厚さ２５μｍの未処理のＰＥＴフィルムを粘着剤層に貼り合わせ、粘着シートを得た。
Next, the pressure-sensitive adhesive liquid (1) was applied to one side of a 25 μm-thick polytetrafluoroethylene (PTFE) film subjected to primer treatment so that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm. Was cured and dried at 80 ° C. for 2 minutes and 130 ° C. for 2 minutes to form an adhesive layer. Then, an untreated PET film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer as a release liner to obtain a pressure-sensitive adhesive sheet.
＜実施例２＞
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３５％、膨潤度が３５８％、プローブタックが０.０６Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＩ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（２）を調整し、粘着テープを作製した。 <Example 2>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (II) having a gel fraction after cross-linking and curing of 35%, a swelling degree of 358%, and a probe tack of 0.06 N (solid content) A pressure-sensitive adhesive liquid (2) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３５％、膨潤度が３５８％、プローブタックが０.０６Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＩ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（２）を調整し、粘着テープを作製した。 <Example 2>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (II) having a gel fraction after cross-linking and curing of 35%, a swelling degree of 358%, and a probe tack of 0.06 N (solid content) A pressure-sensitive adhesive liquid (2) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
＜実施例３＞
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３２％、膨潤度が３８４％、プローブタックが０.０２Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＩＩ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（３）を調整し、粘着テープを作製した。 <Example 3>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (III) having a gel fraction after crosslinking and curing of 32%, a swelling degree of 384%, and a probe tack of 0.02 N (solid content) A pressure-sensitive adhesive solution (3) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used in place of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３２％、膨潤度が３８４％、プローブタックが０.０２Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＩＩ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（３）を調整し、粘着テープを作製した。 <Example 3>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (III) having a gel fraction after crosslinking and curing of 32%, a swelling degree of 384%, and a probe tack of 0.02 N (solid content) A pressure-sensitive adhesive solution (3) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used in place of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
＜実施例４＞
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３０％、膨潤度が３５０％、プローブタックが０.０１Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＶ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（４）を調整し、粘着テープを作製した。 <Example 4>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (IV) having a gel fraction after cross-linking and curing of 30%, a swelling degree of 350%, and a probe tack of 0.01 N (solid content) A pressure-sensitive adhesive liquid (4) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
先に述べた複数の試作品のうち、架橋硬化後のゲル分率が３０％、膨潤度が３５０％、プローブタックが０.０１Ｎとなる付加硬化型シリコーン系粘着剤原液（ＩＶ）（固形分濃度６０質量％）を選定し、粘着剤原液（Ｉ）の代わりに使用したこと以外は、実施例１と同様の方法で粘着剤液（４）を調整し、粘着テープを作製した。 <Example 4>
Among the plurality of prototypes described above, an addition curable silicone-based adhesive stock solution (IV) having a gel fraction after cross-linking and curing of 30%, a swelling degree of 350%, and a probe tack of 0.01 N (solid content) A pressure-sensitive adhesive liquid (4) was prepared in the same manner as in Example 1 except that a concentration of 60% by mass) was selected and used instead of the pressure-sensitive adhesive stock solution (I) to prepare a pressure-sensitive adhesive tape.
＜比較例１＞
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（５）を調製し、感圧粘着シートを作製した。 <Comparative Example 1>
A pressure-sensitive adhesive liquid (5) was obtained in the same manner as in Example 1, except that an addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4580, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５８０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（５）を調製し、感圧粘着シートを作製した。 <Comparative Example 1>
A pressure-sensitive adhesive liquid (5) was obtained in the same manner as in Example 1, except that an addition-curing silicone pressure-sensitive adhesive stock solution (trade name SD-4580, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
＜比較例２＞
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５７０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（６）を調製し、感圧粘着シートを作製した。 <Comparative example 2>
A pressure-sensitive adhesive liquid (6) was obtained in the same manner as in Example 1 except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4570, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５７０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（６）を調製し、感圧粘着シートを作製した。 <Comparative example 2>
A pressure-sensitive adhesive liquid (6) was obtained in the same manner as in Example 1 except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4570, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
＜比較例３＞
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（７）を調製し、感圧粘着シートを作製した。 <Comparative Example 3>
A pressure-sensitive adhesive liquid (7) was obtained in the same manner as in Example 1, except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＳＤ－４５６０、東レ・ダウコーニング株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（７）を調製し、感圧粘着シートを作製した。 <Comparative Example 3>
A pressure-sensitive adhesive liquid (7) was obtained in the same manner as in Example 1, except that an addition-curable silicone pressure-sensitive adhesive stock solution (trade name SD-4560, manufactured by Toray Dow Corning Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. A pressure-sensitive adhesive sheet was prepared.
＜比較例４＞
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＫＲ－３７０１、信越化学工業株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（８）を調製し、感圧粘着シートを作製した。 <Comparative example 4>
A pressure-sensitive adhesive liquid (8) was prepared in the same manner as in Example 1 except that the addition-curing silicone pressure-sensitive adhesive stock solution (trade name KR-3701, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. Thus, a pressure-sensitive adhesive sheet was produced.
固形分濃度６０質量％の付加硬化型シリコーン粘着剤原液（商品名ＫＲ－３７０１、信越化学工業株式会社製）をそのまま用いたこと以外は実施例１と同様にして粘着剤液（８）を調製し、感圧粘着シートを作製した。 <Comparative example 4>
A pressure-sensitive adhesive liquid (8) was prepared in the same manner as in Example 1 except that the addition-curing silicone pressure-sensitive adhesive stock solution (trade name KR-3701, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content concentration of 60% by mass was used as it was. Thus, a pressure-sensitive adhesive sheet was produced.
＜粘着剤組成物のゲル分率及び膨潤度＞
実施例及び比較例で得た粘着剤液（１）～（８）をそれぞれ、剥離ライナー上に乾燥後の厚さが１５０μｍになるように塗布した。続いて、乾燥炉で加熱し硬化・乾燥して粘着剤組成物とし、これをサンプルとした。この際の加熱温度は１３０℃、２分である。 <Gel fraction and swelling degree of pressure-sensitive adhesive composition>
The pressure-sensitive adhesive liquids (1) to (8) obtained in Examples and Comparative Examples were each applied on a release liner so that the thickness after drying was 150 μm. Subsequently, it was heated in a drying oven, cured and dried to obtain an adhesive composition, which was used as a sample. The heating temperature at this time is 130 ° C. and 2 minutes.
実施例及び比較例で得た粘着剤液（１）～（８）をそれぞれ、剥離ライナー上に乾燥後の厚さが１５０μｍになるように塗布した。続いて、乾燥炉で加熱し硬化・乾燥して粘着剤組成物とし、これをサンプルとした。この際の加熱温度は１３０℃、２分である。 <Gel fraction and swelling degree of pressure-sensitive adhesive composition>
The pressure-sensitive adhesive liquids (1) to (8) obtained in Examples and Comparative Examples were each applied on a release liner so that the thickness after drying was 150 μm. Subsequently, it was heated in a drying oven, cured and dried to obtain an adhesive composition, which was used as a sample. The heating temperature at this time is 130 ° C. and 2 minutes.
得られたサンプルを５０ｍｍ×５０ｍｍに断裁し、剥離ライナーを剥離し、シート状の粘着剤組成物からなる測定用サンプルを得た。この測定用サンプルの初期質量（Ａ）（＝膨潤前の粘着剤組成物の質量）を測定した。そしてこの測定用サンプルを、初期質量（Ａ）の２５０倍量以上のトルエンに常温（２３℃）で２４時間浸漬し膨潤させた。浸漬後に測定用サンプルを取り出して膨潤質量（Ｂ）（＝トルエンで膨潤した粘着剤組成物の質量）を測定した。さらにこの測定用サンプルを、１３０℃の乾燥機で２時間乾燥させて吸収した溶媒を除去し、乾燥質量（Ｃ）（＝乾燥した粘着剤組成物の質量）を測定した。粘着剤組成物のゲル分率及び膨潤度を下記式によって得た。
ゲル分率（％）＝（Ｃ／Ａ）×１００
膨潤度（％）＝（（Ｂ－Ａ）／Ａ）×１００％ The obtained sample was cut into 50 mm × 50 mm, the release liner was peeled off, and a measurement sample comprising a sheet-like pressure-sensitive adhesive composition was obtained. The initial mass (A) of this measurement sample (= mass of the pressure-sensitive adhesive composition before swelling) was measured. Then, this measurement sample was immersed and swollen in toluene at 250 times the initial mass (A) at room temperature (23 ° C.) for 24 hours. The sample for measurement was taken out after immersion, and swelling mass (B) (= mass of the adhesive composition swollen with toluene) was measured. Further, this measurement sample was dried with a dryer at 130 ° C. for 2 hours to remove the absorbed solvent, and the dry mass (C) (= the mass of the dried pressure-sensitive adhesive composition) was measured. The gel fraction and swelling degree of the pressure-sensitive adhesive composition were obtained by the following formula.
Gel fraction (%) = (C / A) × 100
Swelling degree (%) = ((BA) / A) × 100%
ゲル分率（％）＝（Ｃ／Ａ）×１００
膨潤度（％）＝（（Ｂ－Ａ）／Ａ）×１００％ The obtained sample was cut into 50 mm × 50 mm, the release liner was peeled off, and a measurement sample comprising a sheet-like pressure-sensitive adhesive composition was obtained. The initial mass (A) of this measurement sample (= mass of the pressure-sensitive adhesive composition before swelling) was measured. Then, this measurement sample was immersed and swollen in toluene at 250 times the initial mass (A) at room temperature (23 ° C.) for 24 hours. The sample for measurement was taken out after immersion, and swelling mass (B) (= mass of the adhesive composition swollen with toluene) was measured. Further, this measurement sample was dried with a dryer at 130 ° C. for 2 hours to remove the absorbed solvent, and the dry mass (C) (= the mass of the dried pressure-sensitive adhesive composition) was measured. The gel fraction and swelling degree of the pressure-sensitive adhesive composition were obtained by the following formula.
Gel fraction (%) = (C / A) × 100
Swelling degree (%) = ((BA) / A) × 100%
＜プローブタック＞
実施例及び比較例で得た感圧粘着シートに対して、テスター産業社製プローブタックテスターＴＥ－６００１を使用して、ＪＩＳ Ｚ ０２３７に準じたプローブタック試験法に従い、直径５ｍｍの円柱プローブを粘着面から垂直方向に引き剥がすのに要する力（プローブタック）を測定した。この測定の際の荷重は１００ｇｆ／ｃｍ２、接触時間は１秒、引き剥がし速度は１ｃｍ／秒とした。 <Probe tack>
Using a probe tack tester TE-6001 manufactured by Tester Sangyo Co., Ltd., a pressure sensitive adhesive sheet obtained in Examples and Comparative Examples was adhered to a cylindrical probe having a diameter of 5 mm according to a probe tack test method according to JIS Z 0237. The force (probe tack) required to peel off from the surface in the vertical direction was measured. The load during this measurement was 100 gf / cm 2 , the contact time was 1 second, and the peeling speed was 1 cm / second.
実施例及び比較例で得た感圧粘着シートに対して、テスター産業社製プローブタックテスターＴＥ－６００１を使用して、ＪＩＳ Ｚ ０２３７に準じたプローブタック試験法に従い、直径５ｍｍの円柱プローブを粘着面から垂直方向に引き剥がすのに要する力（プローブタック）を測定した。この測定の際の荷重は１００ｇｆ／ｃｍ２、接触時間は１秒、引き剥がし速度は１ｃｍ／秒とした。 <Probe tack>
Using a probe tack tester TE-6001 manufactured by Tester Sangyo Co., Ltd., a pressure sensitive adhesive sheet obtained in Examples and Comparative Examples was adhered to a cylindrical probe having a diameter of 5 mm according to a probe tack test method according to JIS Z 0237. The force (probe tack) required to peel off from the surface in the vertical direction was measured. The load during this measurement was 100 gf / cm 2 , the contact time was 1 second, and the peeling speed was 1 cm / second.
＜プレス後対ＳＵＳ粘着力＞
２０ｍｍ幅に裁断した感圧粘着シートを研磨したＳＵＳ板に置き、表１に示す圧力（１）～（５）で１分間プレス後、２０分以内に引張試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープを剥離するのに要する力を測定した。 <Post-press vs. SUS adhesive strength>
A pressure-sensitive adhesive sheet cut to a width of 20 mm is placed on a polished SUS plate, pressed for 1 minute at the pressures (1) to (5) shown in Table 1, and then at a speed of 300 mm / min using a tensile tester within 20 minutes. The force required to peel the tape at an angle of 180 ° was measured.
２０ｍｍ幅に裁断した感圧粘着シートを研磨したＳＵＳ板に置き、表１に示す圧力（１）～（５）で１分間プレス後、２０分以内に引張試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープを剥離するのに要する力を測定した。 <Post-press vs. SUS adhesive strength>
A pressure-sensitive adhesive sheet cut to a width of 20 mm is placed on a polished SUS plate, pressed for 1 minute at the pressures (1) to (5) shown in Table 1, and then at a speed of 300 mm / min using a tensile tester within 20 minutes. The force required to peel the tape at an angle of 180 ° was measured.
＜触感＞
実施例及び比較例で得た感圧粘着シートの粘着剤層の表面を触った時の触感を、以下の基準で評価した。
○：べとつきが無かった。
△：ややべとつきが有った。
×：非常にべとついていた。 <Tactile sense>
The tactile sensation when the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples was touched was evaluated according to the following criteria.
○: There was no stickiness.
Δ: Slightly sticky.
X: It was very sticky.
実施例及び比較例で得た感圧粘着シートの粘着剤層の表面を触った時の触感を、以下の基準で評価した。
○：べとつきが無かった。
△：ややべとつきが有った。
×：非常にべとついていた。 <Tactile sense>
The tactile sensation when the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples was touched was evaluated according to the following criteria.
○: There was no stickiness.
Δ: Slightly sticky.
X: It was very sticky.
以上の各測定の結果を表１及び２に示す。
The results of the above measurements are shown in Tables 1 and 2.
＜評価結果＞
表１及び図１に示すように、実施例１～４の感圧粘着シートは粘着層の表面がべとついておらず、且つ初期粘着力が低く、プレス圧が約１０ｋｇ／ｃｍ２まではプレス圧の上昇に比例して粘着力が高くなった。したがって、実施例１～４の感圧粘着シートは指や掌の押圧力により粘着力を容易に制御できることが分かる。 <Evaluation results>
As shown in Table 1 and FIG. 1, the pressure-sensitive adhesive sheets of Examples 1 to 4 are not sticky on the surface of the adhesive layer, have low initial adhesive strength, and are pressed until the press pressure is about 10 kg / cm 2. The adhesive force increased in proportion to the increase in pressure. Therefore, it can be seen that the pressure-sensitive adhesive sheets of Examples 1 to 4 can easily control the adhesive force by the pressing force of a finger or palm.
表１及び図１に示すように、実施例１～４の感圧粘着シートは粘着層の表面がべとついておらず、且つ初期粘着力が低く、プレス圧が約１０ｋｇ／ｃｍ２まではプレス圧の上昇に比例して粘着力が高くなった。したがって、実施例１～４の感圧粘着シートは指や掌の押圧力により粘着力を容易に制御できることが分かる。 <Evaluation results>
As shown in Table 1 and FIG. 1, the pressure-sensitive adhesive sheets of Examples 1 to 4 are not sticky on the surface of the adhesive layer, have low initial adhesive strength, and are pressed until the press pressure is about 10 kg / cm 2. The adhesive force increased in proportion to the increase in pressure. Therefore, it can be seen that the pressure-sensitive adhesive sheets of Examples 1 to 4 can easily control the adhesive force by the pressing force of a finger or palm.
一方、比較例１～比較例４の感圧粘着シートは、ゲル分率及びプローブタックが高過ぎるので、粘着層の表面が非常にべとついていた。しかも、プレス圧にかかわらず粘着力がほぼ一定であった。したがって、比較例１～４の感圧粘着シートは押圧力により粘着力を制御するのは困難であることが分かる。
On the other hand, the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 had a very sticky surface because the gel fraction and probe tack were too high. Moreover, the adhesive strength was almost constant regardless of the press pressure. Therefore, it can be seen that the pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 are difficult to control the adhesive force by the pressing force.
本発明の感圧粘着シートは、例えば、壁、窓ガラス、自動車、電車等の広い面積を持つ被着体に皺や空気溜まりを生じることなく貼り付けることが必要な用途、並びに、正確な位置合わせが必要な精密部品等を固定する用途に有用である。
The pressure-sensitive adhesive sheet of the present invention can be applied to an adherend having a large area such as a wall, a window glass, an automobile, and a train without causing any wrinkles or air accumulation, and an accurate position. This is useful for fixing precision parts that need to be aligned.
Claims (7)
- 架橋されたシリコーン構造を含み、下記方法により測定されるゲル分率が４０％以下であり、かつ下記方法により測定されるプローブタックが０.９Ｎ以下であるシリコーン系粘着剤組成物からなる粘着剤層を有する感圧粘着シート。
（ゲル分率）
トルエンにシリコーン系粘着剤組成物を１日間浸漬したときの不溶解分の比率である、下記式によってゲル分率を得る。
ゲル分率（％）＝（Ｃ／Ａ）×１００％
Ａ：シリコーン系粘着剤組成物の初期質量
Ｃ：トルエン浸漬後のシリコーン系粘着剤組成物の乾燥質量（乾燥条件：１３０℃、２時間）
（プローブタック）
ＪＩＳ Ｚ ０２３７に準じたプローブタック試験法に従い、直径５ｍｍの円柱プローブを粘着面から垂直方向に引き剥がすのに要する力（プローブタック）を測定する（荷重１００ｇｆ／ｃｍ２、接触時間１秒、引き剥がし速度１ｃｍ／秒）。 A pressure-sensitive adhesive comprising a silicone-based pressure-sensitive adhesive composition comprising a crosslinked silicone structure, having a gel fraction measured by the following method of 40% or less and a probe tack measured by the following method of 0.9 N or less A pressure-sensitive adhesive sheet having a layer.
(Gel fraction)
The gel fraction is obtained by the following formula, which is the ratio of insoluble matter when the silicone-based pressure-sensitive adhesive composition is immersed in toluene for 1 day.
Gel fraction (%) = (C / A) × 100%
A: Initial mass of silicone-based pressure-sensitive adhesive composition C: Dry mass of silicone-based pressure-sensitive adhesive composition after immersion in toluene (drying conditions: 130 ° C., 2 hours)
(Probe tack)
According to the probe tack test method according to JIS Z 0237, the force (probe tack) required to peel a 5 mm diameter cylindrical probe vertically from the adhesive surface is measured (load 100 gf / cm 2 , contact time 1 second, pull (Peeling speed 1 cm / sec). - シリコーン系粘着剤組成物のゲル分率が２０％以上４０％以下である請求項１記載の感圧粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, wherein the silicone pressure-sensitive adhesive composition has a gel fraction of 20% to 40%.
- シリコーン系粘着剤組成物のプローブタック０.５Ｎ以下である請求項１記載の感圧粘着シート。 2. The pressure-sensitive adhesive sheet according to claim 1, which has a probe tack of 0.5 N or less of the silicone-based adhesive composition.
- シリコーン系粘着剤組成物が架橋硬化された付加硬化型シリコーン粘着剤を含む請求項１記載の感圧粘着シート。 The pressure-sensitive adhesive sheet according to claim 1, comprising an addition-curable silicone adhesive obtained by crosslinking and curing the silicone-based adhesive composition.
- 基材の少なくとも片面に粘着剤層を有する請求項１記載の感圧粘着シート。 2. The pressure-sensitive adhesive sheet according to claim 1, which has an adhesive layer on at least one side of the substrate.
- 基材が樹脂フィルムである請求項６記載の感圧粘着シート。 The pressure-sensitive adhesive sheet according to claim 6, wherein the substrate is a resin film.
- 下記方法により測定される圧力０.０３ｋｇ／ｃｍ２で１分間プレス後の対ＳＵＳ粘着力が１.９Ｎ/２０ｍｍ以下である請求項１記載の感圧粘着シート。
（プレス後対ＳＵＳ粘着力）
２０ｍｍ幅に裁断した感圧粘着シートを研磨したＳＵＳ板に置き、圧力０.０３ｋｇ／ｃｍ２で１分間プレス後、２０分以内に引張試験機を用いて３００ｍｍ／分の速度で１８０°の角度でテープを剥離するのに要する力を測定する。 The pressure-sensitive adhesive sheet according to claim 1, wherein the adhesive strength against SUS after pressing for 1 minute at a pressure of 0.03 kg / cm 2 measured by the following method is 1.9 N / 20 mm or less.
(After pressing vs. SUS adhesive strength)
A pressure-sensitive adhesive sheet cut to a width of 20 mm is placed on a polished SUS plate, pressed at a pressure of 0.03 kg / cm 2 for 1 minute, and then at an angle of 180 ° at a speed of 300 mm / minute using a tensile tester within 20 minutes. Measure the force required to peel the tape.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018529330A JP6677812B2 (en) | 2016-07-29 | 2016-07-29 | Pressure sensitive adhesive sheet |
| KR1020187038076A KR20190012228A (en) | 2016-07-29 | 2016-07-29 | Pressure sensitive adhesive sheet |
| CN201680087979.8A CN109476962B (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
| KR1020217012458A KR102422197B1 (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
| PCT/JP2016/072394 WO2018020674A1 (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/JP2016/072394 WO2018020674A1 (en) | 2016-07-29 | 2016-07-29 | Pressure-sensitive adhesive sheet |
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| WO2018020674A1 true WO2018020674A1 (en) | 2018-02-01 |
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| JP (1) | JP6677812B2 (en) |
| KR (2) | KR20190012228A (en) |
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| WO2021199355A1 (en) * | 2020-03-31 | 2021-10-07 | 株式会社寺岡製作所 | Resin composition and adhesive tape |
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2016
- 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 KR KR1020217012458A patent/KR102422197B1/en active IP Right Grant
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|---|---|---|---|---|
| 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 |
| JP2004091703A (en) * | 2002-09-02 | 2004-03-25 | Shin Etsu Chem Co Ltd | Conductive silicone self-adhesive composition and self-adhesive tape |
| JP2015199878A (en) * | 2014-04-10 | 2015-11-12 | フジコピアン株式会社 | Double-sided adhesive film and protective member for information display screen using the same |
Cited By (3)
| 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 |
| CN115362218A (en) * | 2020-03-31 | 2022-11-18 | 株式会社寺冈制作所 | Resin composition and adhesive tape |
| CN115362218B (en) * | 2020-03-31 | 2023-09-19 | 株式会社寺冈制作所 | Resin composition and adhesive tape |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102422197B1 (en) | 2022-07-20 |
| KR20190012228A (en) | 2019-02-08 |
| JPWO2018020674A1 (en) | 2019-04-18 |
| CN109476962A (en) | 2019-03-15 |
| JP6677812B2 (en) | 2020-04-08 |
| KR20210049195A (en) | 2021-05-04 |
| CN109476962B (en) | 2021-12-10 |
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