WO2019087759A1 - シリコーン粘着剤組成物、粘着テープ、粘着シート、及び両面粘着シート - Google Patents
シリコーン粘着剤組成物、粘着テープ、粘着シート、及び両面粘着シート Download PDFInfo
- Publication number
- WO2019087759A1 WO2019087759A1 PCT/JP2018/038351 JP2018038351W WO2019087759A1 WO 2019087759 A1 WO2019087759 A1 WO 2019087759A1 JP 2018038351 W JP2018038351 W JP 2018038351W WO 2019087759 A1 WO2019087759 A1 WO 2019087759A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- group
- sensitive adhesive
- mass
- pressure
- Prior art date
Links
- 0 CCC(C)(C(C)(C*=C)N(*C)*(C)=C)OC Chemical compound CCC(C)(C(C)(C*=C)N(*C)*(C)=C)OC 0.000 description 2
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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- 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
- C09J2483/00—Presence of polysiloxane
-
- 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
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
Definitions
- the present invention relates to a silicone pressure-sensitive adhesive composition, and more particularly, to a pressure-sensitive adhesive tape and a pressure-sensitive adhesive sheet, and a silicone pressure-sensitive adhesive composition suitable as a double-sided pressure-sensitive adhesive sheet.
- the polysiloxane constituting the silicone adhesive is excellent in heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance because the main skeleton is composed of Si—O bonds having high bonding energy.
- silicone pressure-sensitive adhesives exhibit excellent wettability to various adherends, and silicone resins, polyolefins, fluorocarbon resins, silicone rubbers, and silicone peel-off that are difficult to adhere to organic resin-based pressure-sensitive adhesives such as acrylics and rubbers. It is also sticky on paper.
- the silicone pressure-sensitive adhesive is coated on a support such as a plastic film and cured to improve the pressure-sensitive adhesive properties.
- splicing tapes for connecting silicone release papers are manufactured by applying a silicone adhesive to a heat-resistant substrate, for use as such an adhesive tape.
- Patent Document 1 discloses a double-sided support with silicone adhesive laminated on both sides of a plastic film (support). Adhesive tape is described. However, in the double-sided pressure-sensitive adhesive tape, the total thickness of the tape is increased, which is inconvenient for downsizing, thinning, weight reduction, and visibility of devices. Therefore, a supportless double-sided pressure-sensitive adhesive sheet (especially, an optical pressure-sensitive adhesive sheet (OCA: Optical Clear Adhesive)) is required.
- OCA optical pressure-sensitive adhesive sheet
- the main material of OCA materials is acrylic adhesive.
- acrylic pressure-sensitive adhesives are more susceptible to peeling from adherends because the decrease in transparency and yellowing at high temperatures are large and the change in elastic modulus due to temperature change is large compared to silicone-based pressure-sensitive adhesives. Also have. Therefore, in recent years, attempts have been made to use a silicone pressure-sensitive adhesive in the OCA (Patent Documents 5, 6, and 7).
- silicone pressure-sensitive adhesive By using a silicone pressure-sensitive adhesive, not only a decrease in elastic modulus, weather resistance and stability are expected, but since it is flexible, the impact resistance is further improved. In addition, since silicone has a lower refractive index than acrylic, further improvement in visibility is also expected.
- Patent Document 5 and Patent Document 6 describe that the releasability of two release liners for OCA is improved by using a specific fluorine-containing silicone release agent composition.
- the said patent document 7 describes that the adhesion
- WO2015 / 151221 JP 2002-363523 A JP, 2013-091785, A JP, 2016-180021, A JP, 2013-173944, A JP, 2016-182772, A WO 2010/100024
- the silicone pressure-sensitive adhesives described in Patent Documents 5 and 6 have low adhesion, they are not suitable for permanent adhesion.
- the silicone pressure-sensitive adhesive of Patent Document 7 also has insufficient adhesion and does not mention the peeling force from the peeling film.
- conventional silicone pressure sensitive adhesives for OCA have lower adhesion than acrylic adhesives, and there is a problem that when the composition has an increased adhesion, peeling from the release liner becomes difficult.
- the pressure sensitive adhesive may have different adhesion depending on the peeling rate, and in the application of OCA, a permanent adhesion that is not affected by the change in peeling rate is required.
- the present invention has been made in view of the above circumstances, and it is easy to peel from a release liner, and a pressure-sensitive adhesive composition capable of exhibiting strong adhesive strength without depending on the peeling speed of the silicone pressure-sensitive adhesive after peeling.
- An object of the present invention is to provide a pressure-sensitive adhesive tape having a cured product of the composition, a pressure-sensitive adhesive sheet, and a double-sided pressure-sensitive adhesive sheet comprising the cured product of the composition.
- the present inventor has result of extensive investigations to achieve the above objects, a specific diorganopolysiloxane having a hydroxyl group and / or alkoxy group, the R 1 3 SiO 0.5 units and SiO 2 units, a hydroxyl group and A cured product obtained from a silicone pressure-sensitive adhesive composition containing a condensation reaction product obtained by condensation of an organopolysiloxane having at least one or more alkoxy groups at a specific weight ratio and an organohydrogenpolysiloxane having an average degree of polymerization of 80 or less. It has been found that the object can achieve the above object, and the present invention has been achieved.
- the present invention provides a silicone pressure-sensitive adhesive composition containing the following components (A) to (C).
- a silicon atom Having an acid group or an alkoxy group having 1 to 10 carbon atoms, having a linear or branched diorganopolysiloxane (b) R 1 3 SiO 0.5 units and SiO 2 units, silicon-bonded is an organopolysiloxane having an alkoxy group of a hydroxyl group and / or a silicon atom 1 carbon atoms bound to ⁇ 6, the molar ratio of R 1 3 SiO 0.5 units / SiO 2 units in 0.5-1.5 And the above-mentioned organopolysiloxanes (in the above,
- the present invention further provides a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet having a layer comprising a cured product of the silicone pressure-sensitive adhesive composition, and a double-sided pressure-sensitive adhesive sheet comprising the cured product of the silicone pressure-sensitive adhesive composition.
- the cured product of the pressure-sensitive adhesive composition of the present invention has a high adhesive strength regardless of the peeling rate, so that the adherend can be strongly bonded or fixed. Furthermore, a pressure-sensitive adhesive tape, a pressure-sensitive adhesive sheet, and a double-sided pressure-sensitive adhesive sheet not having a substrate, which exhibit excellent releasability with respect to a release liner formed of a fluorine-containing silicone release agent composition Can be provided.
- Component (A) in the silicone pressure-sensitive adhesive composition of the present invention is a hydroxyl- and / or alkoxy-containing diorganopolysiloxane, an organopolysiloxane having a hydroxyl and / or alkoxy group, and having M units and Q units.
- the component (A) is a condensation product of the following components (a1), (b) and (a2), or the following components (a1) and (b): A condensation reaction product with the component and the component (a2) below, wherein the mass ratio of the component (a1) to the component (a2) is 100/0 to 45/55, and the amount of the component (b) is (a1) And the component (a2) and the component (b) in an amount of 75 to 40 parts by mass.
- R 1 3 SiO 0.5 units and SiO 2 units the number of carbon atoms bonded to a hydroxyl group bonded to a silicon atom and / or silicon atom an organopolysiloxane having an alkoxy group of 1 to 6, the molar ratio of R 1 3 SiO 0.5 units / SiO 2 units is 0.5 to 1.5, Serial organopolysiloxan
- the component (a1) is a linear or branched diorganopolysiloxane having a hydroxyl group bonded to a silicon atom at the end and / or an alkoxy group having 1 to 10 carbon atoms and no alkenyl group.
- R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- R 2 is independently of each other, substituted or unsubstituted, having 1 to 10 carbon atoms having no aliphatic unsaturated bond
- a is an integer of 100 ⁇ a ⁇ 20,000.
- the component (a1) may be used alone or in combination of two or more.
- R 2 include an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. More specifically, it is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or an aralkyl group such as a benzyl group.
- part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with hydroxy group, cyano group, halogen atom, alkoxysilyl group, polyoxyalkylene group, epoxy group, carboxyl group or the like
- the monovalent hydrocarbon group having 1 to 10 carbon atoms can be mentioned. Among them, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.
- the ratio of the total number of aryl groups to the total number of groups bonded to silicon atoms of the diorganopolysiloxane of the formula (1) is preferably 0.1 to 30%.
- the content rate of the aryl group exceeds 30%, the adhesion of the obtained silicone pressure-sensitive adhesive layer may be reduced, or the transparency may be reduced.
- the aryl group means an aryl group bonded to a silicon atom and an aryl group possessed by an aralkyl group bonded to a silicon atom.
- the aryl group possessed by the aralkyl group bonded to the silicon atom is, for example, a phenyl group possessed by a benzyl group (phenylmethyl group) and a phenethyl group (phenylethyl group).
- A is an integer of 100 ⁇ a ⁇ 20,000, preferably an integer of 150 ⁇ a ⁇ 15,000.
- the diorganopolysiloxane may be in the form of oil or gum.
- the viscosity of the component (a1) at 25 ° C. is 300 to 1,000,000 mPa ⁇ s if it is oil-like, and particularly preferably 1,000 to 800,000 mPa ⁇ s.
- the viscosity of the solution dissolved in toluene to a concentration of 30% by mass is preferably 1,000 to 200,000 mPa ⁇ s, particularly 3,000 to 100,000 mPa ⁇ s Is preferred. If the viscosity is less than the above lower limit, it may be difficult to uniformly coat the obtained silicone pressure-sensitive adhesive composition.
- the silicone pressure-sensitive adhesive composition may have too high viscosity, which may make it difficult to stir the composition when it is produced.
- the viscosity is a value measured at 25 ° C. using a BM rotational viscometer (hereinafter the same).
- R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- the hydrocarbon group include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a 6 to 10 aralkyl having 6 carbon atoms.
- R is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.
- the total amount of the hydroxyl group and the alkoxy group is 0.001 to 0.45 mass%, particularly 0.003 to 0.40 mass% in the component (a1) Is preferred.
- the measurement of the SiOH group and the alkoxysilyl group can usually be determined by a known method such as the Glinia method or NMR method (the same applies hereinafter).
- component (a1) More specific examples of the component (a1) include compounds of the following structures, but the present invention is not limited thereto.
- Me is a methyl group and Ph is a phenyl group.
- the bonding order of each siloxane unit shown in the following parentheses is not limited, and may be randomly arranged or may form a block unit.
- the component (a2) is a linear or branched diorganopolysiloxane having two or more alkenyl groups in one molecule.
- the diorganopolysiloxane may have a hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms.
- the component (a2) may be used alone or in combination of two or more.
- R 4 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which has no aliphatic unsaturated bond
- X is an alkenyl group or alkenyl It is a monovalent organic group having a group.
- R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- e is an integer of 0 to 3
- f is an integer of 0 or more
- f ′ is an integer of 2 or more
- g is an integer of 100 or more, 2e + f ⁇ 2, 100 ⁇ f + g ⁇ 20,000, 102 ⁇ f ′ + G ⁇ 20,000.
- the bonding order of each siloxane unit shown in the above parenthesis is not limited, and may be randomly arranged or may form a block unit)
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 10 carbon atoms.
- the number of carbon atoms in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a hydroxy group, a cyano group, a halogen atom, an alkoxysilyl group, a polyoxyalkylene group, an epoxy group, a carboxyl group or the like 1 to 10 monovalent hydrocarbon groups can be mentioned.
- a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.
- the ratio of the total number of aryl groups to the total number of groups bonded to the silicon atom of each of the diorganopolysiloxanes is preferably 0.1 to 30%.
- the content ratio exceeds 30%, the adhesion of the obtained silicone pressure-sensitive adhesive layer may be reduced, or the transparency may be reduced.
- the aryl group means an aryl group bonded to a silicon atom and an aryl group possessed by an aralkyl group bonded to a silicon atom.
- the aryl group possessed by the aralkyl group bonded to the silicon atom is, for example, a phenyl group possessed by a benzyl group (phenylmethyl group) and a phenethyl group (phenylethyl group).
- X is a monovalent organic group having an alkenyl group or an alkenyl group.
- it is a monovalent hydrocarbon group having an alkenyl group or alkenyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and the monovalent hydrocarbon group may contain an oxygen atom.
- the alkenyl group include a vinyl group, an allyl group, a hexenyl group, and an octenyl group.
- Examples of the monovalent hydrocarbon group having an alkenyl group include cycloalkenylalkyl groups such as a cyclohexenylethyl group.
- alkenyl group-containing monovalent hydrocarbon group which may have an oxygen atom
- examples of the alkenyl group-containing monovalent hydrocarbon group which may have an oxygen atom include (meth) acryloyl alkyl groups such as acryloyl propyl group, acryloyl methyl group, and methacryloyl propyl group.
- the amount of the alkenyl group contained in the component (a2) is preferably 0.0005 mol or more to less than 0.15 mol, more preferably 0.0006 to 0.13 mol, per 100 g of diorganopolysiloxane. 0.10 mol is more preferred. If the amount is less than the above lower limit, the curability may be reduced. If the amount is less than 0.15 mol, the resulting pressure-sensitive adhesive layer does not become hard, and an appropriate adhesive force can be obtained.
- the measurement of the amount of the alkenyl group can be usually obtained by a known method such as an iodinating method (Hanus method or the like) or an NMR method (the same applies hereinafter).
- e is an integer of 0 to 3, preferably 0 or 1
- f is an integer of 0 or more, preferably an integer of 0 to 3,000
- f ′ is 2 or more Is an integer of preferably 2 to 3,000
- g is an integer of 100 or more, preferably 150 to 20,000, 2e + f ⁇ 2, preferably 2 ⁇ 2e + f ⁇ 3,000, 100 ⁇ f + g ⁇ 20,000, preferably 150 ⁇ f + g ⁇ 15,000, and 102 ⁇ f ′ + g ⁇ 20,000, preferably 150 ⁇ e ′ + f ⁇ 15,000.
- the diorganopolysiloxane may be in the form of oil or gum.
- the viscosity of the component (a2) at 25 ° C. is preferably 1,000 to 1,000,000 mPa ⁇ s if it is oil-like, and particularly preferably 5,000 to 800,000 mPa ⁇ s. preferable.
- the viscosity of the solution dissolved in toluene to a concentration of 30 mass% is preferably 1,000 to 200,000 mPa ⁇ s, especially 3,000 to 100,000 mPa ⁇ s Is preferred. If the viscosity is less than the above lower limit value, the curing properties of the silicone pressure-sensitive adhesive composition may be reduced, or uniform coating may be difficult. When the viscosity exceeds the above upper limit value, the silicone pressure-sensitive adhesive composition becomes too high in viscosity, which may make it difficult to stir the composition when it is produced.
- R is a hydrocarbon group having 1 to 10 carbon atoms exemplified above. Among them, a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom is more preferable.
- the component (a2) may have a hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms.
- the total amount of the hydroxyl group and the alkoxy group contained in the component (a2) is preferably 0 to 0.45% by mass, particularly preferably 0 to 0.40% by mass in the component (a2).
- the method of measuring the hydroxyl group and the alkoxy group is as described above.
- the component (a2) is a diorganopolysiloxane having no hydroxyl group or alkoxyl group having 1 to 10 carbon atoms, and is preferably a compound represented by the above formula (3).
- Me is a methyl group
- Vi is a vinyl group
- Ph is a phenyl group.
- the bonding order of each siloxane unit shown in the following parentheses is not limited, and may be randomly arranged or may form a block unit.
- an organopolysiloxane component (b) has an R 1 3 SiO 0.5 units and SiO 2 units, bound hydroxyl groups and / or bonded alkoxy of 1 to 6 carbon atoms to silicon atoms to the silicon atom an organopolysiloxane having a group, independent molar ratio of R 1 3 SiO 0.5 units / SiO 2 units is 0.5 to 1.5, wherein an organopolysiloxane (in the, R 1 is each other And is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms).
- the molar ratio of R 1 3 SiO 0.5 units / SiO 2 units is 0.5 to 1.5, preferably 0.6 to 1.3. When the molar ratio is less than 0.5 or more than 1.5, the adhesive strength of the resulting silicone pressure-sensitive adhesive layer may be reduced, or the peel strength from the release liner may be increased.
- the component (b) may be used alone or in combination of two or more.
- R 1 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbons, a cycloalkyl group having 5 to 8 carbon atoms, Examples thereof include C 6-10 aryl groups, C 7-10 aralkyl groups, and C 2-8 alkenyl groups.
- alkyl group such as methyl group, ethyl group, propyl group, and butyl group
- cycloalkyl group such as cyclohexyl group
- aryl group such as phenyl group and tolyl group
- aralkyl group such as benzyl group
- alkenyl group such as a vinyl group, an allyl group or a hexenyl group.
- a number of monovalent hydrocarbon groups of 1 to 10 can be mentioned. Among them, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.
- the component (b) may have an alkenyl group, but a small amount is preferable. For example, in 100 g of organopolysiloxane, 0.0001 to 0.2 mol is preferable, 0.0005 to 0.15 mol is more preferable, and 0.001 to 0.10 mol is more preferable. If the above upper limit value is exceeded, the resulting pressure-sensitive adhesive layer may become hard, and an appropriate adhesive force may not be obtained.
- the method of measuring the amount of alkenyl groups is as described above.
- (B) component has a R 1 3 SiO 0.5 units and SiO 2 units required.
- R 1 SiO 1.5 units and / or R 1 2 SiO units R 1 are as defined above.
- the total content of R 1 3 SiO 0.5 units and SiO 2 units is not particularly limited as long as the characteristics of the present invention are not impaired, (b Preferably, it is 80 to 100 mol%, more preferably 90 to 100 mol%, based on the total siloxane units of the component).
- the component (b) has a hydroxyl group (SiOH group) bonded to a silicon atom and / or an alkoxy group having 1 to 6 carbon atoms (alkoxysilyl group) bonded to a silicon atom.
- alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a phenoxy group.
- the amount of the siloxane unit having a SiOH group is preferably such that the hydroxyl group content is 0.1 to 5% by mass, preferably 0.2 to 4% by mass of the component (b).
- the hydroxyl group content exceeds 5% by mass, the adhesive strength of the obtained silicone pressure-sensitive adhesive layer may be reduced or the curability may be reduced.
- the hydroxyl group content is less than 0.1% by mass, the condensation reaction between the components (b) and (a) may be insufficient, and the adhesion may be reduced.
- the amount of the siloxane unit having an alkoxysilyl group is preferably such that the content of the alkoxy group is 10% by mass or less, preferably 8% by mass or less of the component (b).
- the adhesive strength of the obtained silicone pressure-sensitive adhesive layer may be reduced or the curability may be reduced.
- the total amount of the siloxane unit having the SiOH group and the siloxane unit having the alkoxysilyl group is 0.1 to 12% by mass, particularly 0% of the component (b), as the sum of the hydroxyl group content and the alkoxy group content.
- the content is preferably 2 to 10% by mass.
- the siloxane unit having a SiOH group, R 1 2 (OH) SiO 0.5 units, R 1 (OH) 2 SiO 0.5 units, R 1 (OH) SiO units, and (OH) SiO 1.5 units and the like can be mentioned .
- siloxane units having an alkoxysilyl group R 1 2 (OR ') SiO 0.5 units, R 1 (OR') 2 SiO 0.5 units, R 1 (OR ') SiO units, and (OR') SiO 1.5
- a unit (OR ′ is, independently of one another, an alkoxy group having 1 to 6 carbon atoms) can be exemplified.
- the component (b) preferably has a weight average molecular weight of 500 to 10,000, more preferably a weight average molecular weight of 1,000 to 8,000.
- the weight average molecular weight can be usually determined as a polystyrene equivalent weight average molecular weight or the like in gel permeation chromatography (GPC) analysis using toluene, tetrahydrosilane (THF) or the like as a developing solvent (the same applies hereinafter).
- the mass ratio of the component (a1) to the component (a2) in the component (A) is 100/0 to 45/55, and the amount of the component (b) It is characterized in that the amount is 40 to 75 parts by mass with respect to a total of 100 parts by mass of the (a1) component, the (a2) component and the (b) component.
- the amount of component (b) is preferably 45 to 70 parts by mass, more preferably 45 to 65 parts by mass, based on 100 parts by mass of components (a1), (a2) and (b). . If the amount of the component (b) is more than the above upper limit value or less than the above lower limit value, the adhesive strength of the obtained silicone pressure-sensitive adhesive layer may be decreased, or the peeling force from the release liner may be increased.
- the mass ratio of (a1) / (a2) is 100/0 to 45/55, preferably 100/0 to 60/40, and more preferably 100/0 to 70/30.
- the component (A) preferably has a low content of alkenyl groups or no alkenyl group. Accordingly, the content of the component (a2) is also preferably small, and in particular, it is most preferable that the component (a2) is not contained.
- the preferable lower limit value of the mass ratio when the component (a2) is contained is 99/1. When the amount of the component (a2) is too large, the crosslink density in the cured product of the resulting silicone pressure-sensitive adhesive composition may be high, and the adhesion may be low.
- the component (A) is a condensation product of the components (a1), (b) and (a2), or a condensation product of the components (a1) and (b) and the component (a2) And a mixture of Component (a1), component (b), and component (a2) are condensation products of hydrolysis condensation reaction of hydroxyl group or alkoxy group of components (a1) and (a2) and hydroxyl group or alkoxy group of component (b) Or obtained by subjecting to a condensation reaction.
- a mixture of the condensation product of the components (a1) and (b) and the component (a2) is subjected to a hydrolysis condensation reaction or a condensation reaction of the components (a1) and (b) to produce a condensation reaction product
- These compounds are obtained by mixing with the component (a2) having neither a hydroxyl group nor an alkoxy group.
- the components (a1), (a2) and (b) be subjected to a condensation reaction before being mixed with the components (B) and (C) described later.
- the mass ratio of (a1) / (a2) is 100/0, that is, when the component (a2) is not contained, the component (A) is a condensation product of the components (a1) and (b).
- the condensation reaction may be performed according to a conventionally known method, and may be performed under a solvent such as toluene.
- the components (a1), (a2) and (b) dissolved in a solvent may be reacted with an alkaline catalyst at room temperature (25 ° C.) or heating under reflux, and neutralized as necessary.
- the reaction is preferably carried out so that the amount of hydroxyl groups of the SiOH group (silanol group) remaining in the condensation reaction product is 0.02 to 4.1% by mass, particularly 0.05 to 3.5% by mass.
- alkaline catalysts used for the condensation reaction include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; sodium hydrogencarbonate and potassium hydrogencarbonate Hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organic metals such as butyl lithium; potassium silanolate; ammonia gas, ammonia water, nitrogen compounds such as methylamine, trimethylamine and triethylamine, etc. Gas or ammonia water is preferred.
- metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
- carbonates such as sodium carbonate and potassium carbonate
- metal alkoxides such as sodium methoxide and potassium butoxide
- organic metals such as butyl lithium
- potassium silanolate ammonia gas
- ammonia water nitrogen compounds such as methylamine, trimethylamine and trie
- the temperature of the condensation reaction is not particularly limited, and the reaction can be carried out at 10 to 150 ° C., but usually it may be carried out at room temperature (25 ° C.) to the reflux temperature of the organic solvent.
- the reaction time is not particularly limited, but may be 0.5 to 20 hours, preferably 1 to 16 hours.
- a neutralizing agent for neutralizing the alkaline catalyst may be added.
- the neutralizing agent include acid gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid.
- an inert gas such as nitrogen may be aerated and distilled off.
- the present invention comprises an organohydrogenpolysiloxane having three or more components (A) and (B) SiH groups in one molecule and having an average degree of polymerization of 80 or less, and (C) a platinum group metal catalyst And a silicone pressure-sensitive adhesive composition comprising
- Component (B) is an organohydrogenpolysiloxane containing three or more SiH groups in one molecule and having an average degree of polymerization of 80 or less.
- One organohydrogenpolysiloxane alone or a combination of two or more organohydrogenpolysiloxanes may be used.
- the SiH group present in component (B) and the alkenyl group present in component (a2) and / or component (b) undergo an addition reaction to cure and form a film.
- the SiH groups in the component (B), or the SiH groups in the component (B) and the remaining SiOH groups in the component (A) undergo a dehydrogenation condensation reaction and cure to form a film.
- the present invention reduces the amount of crosslinking due to addition reaction by limiting the amount of alkenyl groups in component (A). As a result, a large amount of diorganopolysiloxane which is not incorporated into the crosslinked structure remains, and the wettability to the adherend is improved. Further, SiH groups in component (B) having a specific average degree of polymerization, or SiH groups in component (B) and residual SiOH groups in component (A) slightly form crosslinks by dehydrogenation condensation reaction Improve the strength of the cured film. Furthermore, the remaining SiH group derived from the component (B) interacts with the functional group present on the surface of the adherend. By these, the hardened
- the component (B) is an organohydrogenpolysiloxane containing 3 or more, preferably 3 to 80, more preferably 3 to 70 SiH groups in one molecule.
- the organohydrogenpolysiloxane may be linear, branched or cyclic.
- the organohydrogenpolysiloxane preferably has a viscosity at 25 ° C. of 1 to 2,000 mPa ⁇ s, more preferably 2 to 1,500 mPa ⁇ s. The method of measuring the viscosity is as described above.
- the component (B) is characterized by having an average degree of polymerization of 80 or less, preferably 70 or less, more preferably 60 or less.
- the adhesive strength may be decreased, or the peel strength from the release liner may be increased.
- the lower limit value is not limited, it is particularly 2 or more, preferably 4 or more.
- the organohydrogenpolysiloxane is represented, for example, by the following formula (5).
- R 5 s independently of each other are a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, at least 3 of which are hydrogen H is an integer of 2 or more, i is an integer of 0 or more, j is an integer of 0 or more, k is an integer of 0 or more, and 2 ⁇ h + i + j + k ⁇ 80)
- h is an integer of 2 or more, preferably 2 to 50
- i is an integer of 0 or more, preferably 0 to 78
- j is an integer of 0 or more, preferably 0 to 50
- k is an integer of 0 or more, preferably 0 to 50 and 2 ⁇ h + i + j + k ⁇ 80, preferably 2 ⁇ h + i + j + k ⁇ 70.
- R 5 s are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which has no aliphatic unsaturated bond.
- the monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, etc. It can be mentioned.
- alkyl group such as methyl group, ethyl group, propyl group and butyl group
- cycloalkyl group such as cyclohexyl group
- aryl group such as phenyl group and tolyl group
- aralkyl group such as benzyl group It is.
- a number of monovalent hydrocarbon groups of 1 to 10 can be mentioned.
- a hydrogen atom, an alkyl group and an aryl group are preferable, and a hydrogen atom, a methyl group, an ethyl group, a propyl group and a phenyl group are more preferable.
- the ratio of the total number of aryl groups to the total number of hydrogen atoms bonded to silicon atoms of the organohydrogenpolysiloxane and the number of substituents is 3 to 40 mol%. Preferably, it is 3 to 30 mol%.
- the aryl group means an aryl group bonded to a silicon atom and an aryl group possessed by an aralkyl group bonded to a silicon atom.
- the aryl group possessed by the aralkyl group bonded to the silicon atom is, for example, a phenyl group possessed by a benzyl group (phenylmethyl group) or a phenethyl group (phenylethyl group).
- the obtained pressure-sensitive adhesive layer and the release layer made of the fluorine-containing silicone release agent composition described later become significantly incompatible. Therefore, the peeling layer and the adhesive layer can be easily peeled, and the rise of the peeling force with time becomes small. Further, when the adhesive layer is bonded to the adherend, the SiH group derived from the component (B) interacts with the functional group present on the adherend surface.
- the adherend is a resin containing an aryl group
- the aryl group in the component (B) and the ⁇ electrons of the aromatic ring of the aryl group in the resin act to cause adhesion due to the stacking effect
- the power can be improved.
- the (B) organohydrogenpolysiloxane is preferably represented by the following formula (2).
- R 3 s independently of one another are a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond
- b is 0 or 1
- d is an integer of 0 or more
- the bonding order of the respective siloxane units shown in the above parenthesis is not limited, and may be randomly arranged or may form block units.
- R 3 examples include monovalent hydrocarbon groups exemplified for R 5 described above. Among them, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a propyl group and a phenyl group are more preferable.
- B is 0 or 1
- c is an integer of 1 or more, preferably an integer of 1 to 70
- d is an integer of 0 or more, preferably an integer of 0 to 70.
- component (B) More specific examples include, but are not limited to, the compounds shown below.
- Me is a methyl group and Ph is a phenyl group.
- the bonding order of each siloxane unit shown in the following parentheses is not limited, and may be randomly arranged or may form a block unit.
- the compounding amount of the component (B) in the silicone pressure-sensitive adhesive composition of the present invention is 0.1 to 5 parts by mass, preferably 0.3 to 4 parts by mass with respect to 100 parts by mass of the component (A). And more preferably 0.5 to 3 parts by mass.
- the amount of the component (B) is less than the above lower limit, the crosslink density in the cured product of the obtained silicone pressure-sensitive adhesive composition becomes low, and the adhesion at low speed becomes low.
- the said upper limit is exceeded, the crosslinking density in the silicone adhesive composition obtained will become high, and when adhesive force becomes low, or the usable time of the process liquid containing this adhesive composition will become short. There is.
- the component (C) is a platinum group metal catalyst, and the addition reaction between the component (a2) and the component (B), the dehydrogenation condensation reaction between the components (B), or the SiH group of the component (B) )
- a catalyst for promoting the dehydrogenation condensation reaction of the remaining SiOH group of the component may be a conventionally known platinum group metal-based catalyst that promotes the reaction.
- platinum system such as chloroplatinic acid, alcohol solution of chloroplatinic acid, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc.
- a catalyst is mentioned.
- catalysts containing metals such as ruthenium, rhodium, palladium or iridium. Among them, platinum-based catalysts are preferred.
- the catalyst may be used alone or in combination of two or more.
- the addition amount of the component (C) may be a catalytic amount.
- the catalytic amount is an effective amount for promoting the above-mentioned reaction.
- the mass of the platinum group metal may be 1 to 5,000 ppm, preferably 5 to 500 ppm, and particularly preferably 10 to 200 ppm, based on the total mass of the components (A) and (B). If the amount is less than the above lower limit, the curability may be reduced, or the crosslink density may be reduced, and the adhesive force may be reduced. If the above upper limit is exceeded, the usable time of the treatment bath may be shortened.
- the silicone pressure-sensitive adhesive composition of the present invention may further contain, as an optional component, a control agent for curing by the addition reaction and condensation reaction described above.
- the component thickens or gels the treatment liquid containing the pressure-sensitive adhesive composition before heat curing, for example, when preparing the silicone pressure-sensitive adhesive composition or applying the pressure-sensitive adhesive composition to a substrate It works to prevent waking up.
- Any known control agent may be used, and examples thereof include various organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds, oxime compounds and organic chloro compounds.
- Acetylene-based alcohols such as 3-methyl-3--1-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne, acetylene-based compounds thereof and alkoxysilanes or siloxanes or Reactants with gensilane, vinyl siloxanes such as tetramethylvinylsiloxane cyclic compounds, organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, organic chromium compounds and the like can be mentioned.
- the reaction control agent may be used alone or in combination of two or more.
- the blending amount of the component (D) is 0 to 8 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
- 0.05 mass parts is preferable. More preferably, it is 0.1 to 5 parts by mass. If the amount of the reaction control agent exceeds the above upper limit, the curability of the resulting composition may be reduced.
- Optional components can be added to the silicone pressure-sensitive adhesive composition of the present invention in addition to the components (A) to (D).
- non-reactive organopolysiloxanes such as polydimethyl siloxane and polydimethyl diphenyl siloxane; phenol type, quinone type, amine type, phosphorus type, phosphorus type, phosphite type, sulfur type, and thioether type antioxidants; triazole type, Light stabilizers such as benzophenone series; flame retardants such as phosphoric acid ester series, halogen series, phosphorus series and antimony series; antistatic agents such as cationic surfactants, anionic surfactants, nonionic surfactants; dyes; pigments; Foaming agent; filler; leveling agent; adhesion improving agent; thickening agent; aromatic hydrocarbon solvents such as toluene and xylene as solvents for lowering viscosity at the time of coating, hex
- the silicone pressure-sensitive adhesive composition of the present invention can be prepared by mixing and dissolving the components (A) to (C) and optionally the component (D) and other additives.
- the preparation method is not limited, the method of adding the component (C) immediately before use after uniformly mixing the component (A), the component (B), and if necessary the component (D) and the optional component beforehand is the pot life Desirable in terms of
- the silicone pressure-sensitive adhesive layer can be obtained by applying the silicone pressure-sensitive adhesive composition of the present invention to various substrates and curing the composition under predetermined conditions.
- the silicone pressure-sensitive adhesive composition of the present invention is suitably used as, for example, a pressure-sensitive adhesive tape or a pressure-sensitive adhesive sheet having a substrate and a cured product layer composed of a cured product of the composition laminated on at least one surface of the substrate. Can.
- a plastic film made of paper or plastic, glass, metal, cloth or the like is selected.
- paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, kraft paper, Japanese paper, synthetic paper and the like.
- plastic film polyethylene film, polypropylene film, polyester film, polyimide film, polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate Copolymer films, ethylene-vinyl alcohol copolymer films, triacetyl cellulose films, polyetheretherketone films, polyphenylene sulfide films and the like can be mentioned.
- the thickness and type of glass is not particularly limited, and may be chemically strengthened. Glass fibers can also be applied, and glass fibers may be used alone or in combination with other resins. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, nickel foil and the like.
- substrates treated with primer treatment, corona treatment, etching treatment or plasma treatment may be used.
- the coating method to the base material of a silicone adhesive composition should just use a well-known coating system.
- a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a bar coater, a kiss coater, a gravure coater, screen coating, immersion coating, cast coating and the like can be mentioned.
- the coating amount is appropriately set according to the application, but usually, the amount is preferably such that the thickness of the silicone pressure-sensitive adhesive layer after curing is 2 to 2,000 ⁇ m, particularly 3 to 1,000 ⁇ m.
- the curing conditions of the silicone pressure-sensitive adhesive composition may be 70 to 250 ° C. for 10 seconds to 10 minutes, but not limited thereto.
- the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet of the present invention can be produced by directly applying the silicone pressure-sensitive adhesive composition of the present invention to a substrate as described above and curing the composition to form a silicone pressure-sensitive adhesive layer.
- the composition is applied to a release film or release paper on which release coating has been performed and cured to form a silicone pressure-sensitive adhesive layer, and then the silicone pressure-sensitive adhesive layer is produced by a transfer method of bonding to the above substrate May be
- the present invention further provides a substrate, a first release layer formed on the substrate, an adhesive layer laminated on the first release layer, and a second release layer laminated on the adhesive layer. And providing a pressure-sensitive adhesive sheet comprising a laminate.
- the first release layer and the second release layer are each a cured product obtained by curing the fluorine-containing silicone release composition independently, and the pressure-sensitive adhesive layer cures the above-mentioned silicone pressure-sensitive adhesive composition.
- the present invention further provides a substrate-free double-sided pressure-sensitive adhesive sheet comprising a cured product of the silicone pressure-sensitive adhesive composition of the present invention.
- the double-sided pressure-sensitive adhesive sheet not having the substrate is a sheet obtained by removing the substrate and the release layer from the pressure-sensitive adhesive sheet formed of the laminate having the above-described substrate and the release layer. The details will be described below.
- the laminate described above can be obtained by laminating a release layer such as a release liner on both surfaces of an adhesive layer made of a cured product of the silicone adhesive composition of the present invention.
- the form of the laminate may be a sheet or a roll of a long sheet.
- Step 1 A fluorine-containing silicone release agent composition is respectively coated on one surface of each of two substrates and cured to form a first release layer and a second release layer.
- Step 2 The silicone pressure-sensitive adhesive composition is coated on the first release layer obtained in Step 1 and cured to form a pressure-sensitive adhesive layer.
- Step 3 The release agent cured product surface of the second release layer obtained in Step 1 is laminated on the adhesive layer obtained in Step 2.
- Another embodiment is a roll-like laminate produced by the following steps 1 to 3.
- the fluorine-containing silicone release agent composition is coated on both sides of one base material and cured to form a base material having release layers (a first release layer and a second release layer) on both sides.
- the silicone pressure-sensitive adhesive composition is coated on the first release layer obtained in Step 1 and cured to form a pressure-sensitive adhesive layer.
- Step 3) The entire laminate is wound so that the second release layer is stacked on the pressure-sensitive adhesive layer obtained in Step 2.
- the fluorine-containing silicone release agent compositions forming the first release layer and the second release layer may be identical to or different from each other.
- Preferred is a fluorine-containing silicone release agent composition containing the following components (E) to (G).
- the polydiorganosiloxane, wherein the number ratio of the fluorine-containing organic group to the total number is 5% or more and less than 50%.
- the components (E) to (G) will be described in detail.
- the component (E) is an alkenyl group-containing polydiorganosiloxane, which has at least one fluorine-containing organic group in one molecule, and a total of groups bonding a fluorine-containing organic group bonded to a silicon atom to a silicon atom
- the ratio of the total number of the fluorine-containing organic groups to the number is 5% or more and less than 50%. It is preferably 8% to 45%, more preferably 10 to 40%. Even if the content ratio of the fluorine-containing organic group is more than the above upper limit, no further improvement of the releasability can be obtained, and the curability may be reduced, which is not preferable. If it is less than the above lower limit value, the releasability to the silicone pressure sensitive adhesive is reduced.
- the component (E) may be linear or branched.
- the component (E) is preferably a compound represented by the following general formula (6).
- R 6 independently of one another is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which has no aliphatic unsaturated bond
- Y is an alkenyl group having 2 to 10 carbon atoms or It is an alkenyl group containing organic group
- Rf is a fluorine containing organic group.
- the bonding order of the respective siloxane units shown in the above parenthesis is not limited, and may be randomly arranged or may form block units.
- Rf is a fluorine-containing organic group, and is represented by, for example, the following structural formulas (7) to (14).
- m 1 is an integer of 1 to 10
- n is an integer of 1 to 5.
- Y is an alkenyl or alkenyl group-containing organic group having 2 to 10 carbon atoms, and more preferably a monovalent hydrocarbon group having an alkenyl or alkenyl group having 2 to 8 carbon atoms, and the monovalent hydrocarbon The group may contain an oxygen atom.
- the alkenyl group include a vinyl group, an allyl group, a hexenyl group, and an octenyl group.
- Examples of the monovalent hydrocarbon group having an alkenyl group include cycloalkenylalkyl groups such as a cyclohexenylethyl group.
- alkenyl group-containing monovalent hydrocarbon group which may have an oxygen atom
- examples of the alkenyl group-containing monovalent hydrocarbon group which may have an oxygen atom include (meth) acryloyl alkyl groups such as acryloyl propyl group, acryloyl methyl group, and methacryloyl propyl group.
- a vinyl group, an allyl group, a hexenyl group and an octenyl are preferable, and a vinyl group is more preferable.
- R 6 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which has no aliphatic unsaturated bond, preferably an alkyl group having 1 to 6 carbons, carbon Examples include cycloalkyl groups of 5 to 8, aryl groups of 6 to 10 carbon atoms, and aralkyl groups of 7 to 10 carbon atoms.
- alkyl group such as methyl group, ethyl group, propyl group, and butyl group
- cycloalkyl group such as cyclohexyl group
- aryl group such as phenyl group and tolyl group
- aralkyl group such as benzyl group
- alkenyl group such as a vinyl group, an allyl group or a hexenyl group.
- a number of monovalent hydrocarbon groups of 1 to 10 can be mentioned. Among them, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group and a propyl group are more preferable.
- P is an integer of 1 to 3 independently of each other.
- q is an integer of 0 or more
- r is an integer of 1 or more
- s is an integer of 0 or more.
- Me is a methyl group and Vi is a vinyl group.
- Rf, q, r and s are the same as above.
- the bonding order of each siloxane unit shown in the above parentheses is not limited, and block units may be randomly arranged. May be formed.
- the component (E) can be used singly or in combination of two or more.
- the component (F) is an organohydrogenpolysiloxane having at least three SiH groups in one molecule. It acts as a crosslinking agent, and the alkenyl group in the component (E) and the SiH in the component (F) undergo an addition reaction to form a cured film.
- the component (F) has a ratio of the total number of fluorine-containing organic groups to the total number of groups bonded to silicon atoms of 0% to 40%. It is preferred that it is less than.
- the component (F) may be linear, branched or cyclic.
- the component (F) may be used alone or in combination of two or more.
- R 7 is a group independently selected from the options of R 6 in the above formula (6)
- R f is a group selected from the fluorine-containing organic groups defined in the above formula (6)
- t is independently 0 or 1
- u is an integer of 1 or more
- v is an integer of 0 or more
- w is an integer of 0 or more, provided that 3 ⁇ 2t + u, 3 ⁇ u + v + w ⁇ 500, Preferably, 5 ⁇ u + v + w ⁇ 300.
- the bonding order of the respective siloxane units shown in the above parenthesis is not limited, and may be randomly arranged or may form block units.
- component (F) include, but are not limited to, the following compounds. (In the above formulas, Rf, u, v and w are as described above. The bonding order of each siloxane unit shown in the above parentheses is not limited, and block units may be randomly arranged. You may form.)
- the compounding amount of the component (F) is such that the ratio of the number of SiH groups contained in the component (F) to the number of alkenyl groups contained in the component (E) is 0.5 to 10, preferably 0.8 to The amount is five. If the blending amount of the component (F) is too small or too large, the curability of the silicone release agent composition may be reduced or the properties of the cured product may be reduced.
- the component (G) is a platinum group metal catalyst.
- the addition reaction between the component (E) and the component (F) is promoted.
- known hydrosilylation catalysts can be used, and examples thereof include platinum, palladium and rhodium catalysts.
- platinum catalysts are particularly preferable, and examples thereof include chloroplatinic acid, alcohol solutions of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinylsiloxanes.
- the compounding amount of the component (G) is not particularly limited as long as it is an effective amount as a catalyst, but for example, an amount of 1 to 1000 ppm as a mass of platinum group metal with respect to the mass of the component (E) is preferable .
- the silicone release agent composition may further contain other components in addition to the components (E) to (G) described above as long as the objects and effects of the present invention are not impaired.
- non-reactive polyorganosiloxanes such as polydimethylsiloxane, photopolymerization initiators, light stabilizers, antioxidants, flame retardants, reactive diluents, leveling agents, thickeners, and adhesions. These include enhancers, fillers, antistatic agents, antifoams, dyes, pigments and the like.
- an activity control agent such as various organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds, oxime compounds, and organic chloro compounds it can.
- acetylene compounds such as 3-methyl-1-butyn-3-ol and the silylated compounds thereof and silicon compounds such as divinylcyclotetrasiloxane are preferably used. It is preferable that the blending amount of the activity control agent is usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (E).
- the fluorine-containing silicone release agent composition is preferably used by dissolving in a solvent.
- the solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane and isoparaffin, gasoline for industrial use (rubber evaporation Hydrocarbon solvents such as petroleum benzine, solvent naphtha etc., acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone Ketone solvents such as cyclohexanone,
- the amount of the solvent is not particularly limited, it is preferable that the viscosity of the solution of the silicone release agent composition is 100 mPa ⁇ s or less. Thereby, the coating workability of the solution obtained by dissolving the fluorine-containing silicone release agent composition can be improved, and the control of the coating amount and the coating film thickness can be facilitated.
- the solvent is preferably 25 to 100,000 parts by mass, more preferably 400 to 10,000 parts by mass, with respect to a total of 100 parts by mass of the components (E) and (F).
- silicone release agent composition of the present invention it is desirable to add the component (G) immediately before use after uniformly mixing the components (E) and (F) and optional components in advance.
- a release liner having a release layer on one side or both sides can be obtained by applying the above-mentioned fluorine-containing silicone release agent composition on one side or both sides of various substrates and curing the composition under predetermined conditions.
- the release liner having release layers on both sides is obtained by first applying and curing the release agent composition on one side of the substrate and then coating and curing on the other side.
- a plastic film made of paper or plastic, glass, metal, cloth or the like is selected.
- paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, kraft paper, Japanese paper, synthetic paper and the like.
- plastic film polyethylene film, polypropylene film, polyester film, polyimide film, polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate Copolymer films, ethylene-vinyl alcohol copolymer films, triacetyl cellulose films, polyetheretherketone films, polyphenylene sulfide films and the like can be mentioned.
- the thickness and type of glass is not particularly limited, and may be chemically strengthened. Glass fibers can also be applied, and glass fibers may be used alone or in combination with other resins. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, nickel foil and the like.
- a base treated with a primer treatment, a corona treatment, an etching treatment, or a plasma treatment may be used.
- the coating method may be coating using a known coating method, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, bar coater, bar coater, kiss coater, gravure coater, screen coating Construction, dip coating, cast coating and the like.
- the coating amount of the release agent composition can be selected so that the thickness of the release layer after curing becomes 0.03 to 5 ⁇ m, particularly 0.05 to 3.0 ⁇ m.
- the curing conditions may be 30 seconds to 3 minutes at 100 to 180 ° C., but not limited thereto.
- the release agent composition forming the release layer has a fluorine-containing group, while the silicone pressure-sensitive adhesive composition forming the adhesive layer has no fluorine-containing group, Both are incompatible at the interface between the adhesive layer and the release layer. Therefore, the peeling layer and the adhesive layer can be easily peeled, and the heavy peeling with time is small.
- the laminate After peeling one release substrate from the laminate, the laminate is bonded to the adhesive layer surface, and after peeling off the other release substrate from that state, it is opposite to the adhesive layer surface previously bonded.
- the adhesive layer surface By bonding the adhesive layer surface to another object, it can be used as an adhesive sheet which does not have a substrate.
- the pressure-sensitive adhesive sheet which does not have the substrate of the present invention can be advantageously used in miniaturized, thinned or lightened electronic devices and electronic products.
- cover glass and touch panel of electronic terminals such as personal computers and mobile phones, bonding of touch panels and liquid crystal panels, smart phones, tablet terminals, car navigation displays, ticket vending machines, housing game machines, ATMs, operation terminals of Prikra, karaoke It can be used for a remote control, a cash register terminal, and the like.
- each siloxane unit shown in the parentheses in each polysiloxane is not limited, and may be randomly arranged or may form a block unit.
- the viscosity is a value measured at 25 ° C. using a BM rotational viscometer
- the part indicates a part by mass
- the characteristic value indicates a measured value by the following test method.
- Me represents a methyl group
- Vi represents a vinyl group.
- the components (a1), (a2) and (b) used in the following examples and comparative examples are as follows.
- (A1) A dimethylpolysiloxane represented by the following formula (i) and having a viscosity of 70,000 mPa ⁇ s when dissolved in toluene to a concentration of 30% by mass (Where x is a number satisfying the above viscosity)
- (A2) A dimethylpolysiloxane represented by the following formula (ii), which has a viscosity of 48,000 mPa ⁇ s when dissolved in toluene so as to have a concentration of 30% by mass, and a vinyl group content of 0.001 mol / 100 g Have (Here, y and z are numbers satisfying the above viscosity and vinyl group weight)
- (B) A polysiloxane comprising Me 3 SiO 0.5 units and SiO 2 units and having a hydroxyl group bonded to a silicon atom of SiO 2 units (
- the resulting condensation reaction product (solid content: silicon atom-bonded hydroxyl group content: 0.66% by mass) is allowed to cool, and (D) ethynylcyclohexanol (0.2 parts) is added thereto, and the solid content is Toluene was added to be about 50% by mass and mixed to obtain a base mixture A-1.
- Synthesis Example 2 A solution obtained by mixing 50.0 parts of the dimethylpolysiloxane (a1), 83.3 parts of a 60% by mass toluene solution of the polysiloxane (b), 66.7 parts of toluene, and 0.5 parts of aqueous ammonia Stir at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- Synthesis Example 3 30.0 parts of the above dimethylpolysiloxane (a1), 10.0 parts of the above dimethylpolysiloxane (a2), 100.0 parts of a 60% by mass solution of the above polysiloxane (b) in toluene, 60.0 parts of toluene, and ammonia water The solution which mixed 0.5 part was stirred at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- the resulting condensation reaction product (solid content: silicon-bonded hydroxyl group content: 0.92% by mass) is allowed to cool, and then (D) ethynylcyclohexanol (0.2 parts) is added thereto, and the solid content is Toluene was added to be about 50% by mass and mixed to obtain a base mixture A-3.
- Synthesis Example 4 A solution obtained by mixing 40.0 parts of the dimethylpolysiloxane (a1), 100.0 parts of a 60% by mass toluene solution of the polysiloxane (b), 60.0 parts of toluene, and 0.5 parts of aqueous ammonia Stir at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- the resulting condensation reaction product (solid content: silicon-bonded hydroxyl group content: 0.93% by mass) is allowed to cool, and (D) ethynylcyclohexanol (0.2 parts) is added thereto, and the solid content is Toluene was added to be about 50% by mass and mixed to obtain a base mixture A-4.
- Comparative Synthesis Example 5 A solution obtained by mixing 50.0 parts of the dimethylpolysiloxane (a2), 83.3 parts of a 60% by mass toluene solution of the polysiloxane (b), 66.7 parts of toluene, and 0.5 parts of aqueous ammonia Stir at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- Comparative Synthesis Example 6 20.0 parts of the dimethylpolysiloxane (a1), 30.0 parts of the dimethylpolysiloxane (a2), 83.3 parts of a 60% by mass solution of the polysiloxane (b) in toluene, 66.7 parts of toluene, and ammonia water The solution which mixed 0.5 part was stirred at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- the resulting condensation reaction product (solid content: silicon-bonded hydroxyl group content: 0.65% by mass) is allowed to cool, and then (D) ethynylcyclohexanol (0.2 parts) is added thereto, and the solid content is Toluene was added to be about 50% by mass and mixed to obtain a base mixture A-6.
- Comparative Synthesis Example 7 A solution obtained by mixing 40.0 parts of the dimethylpolysiloxane (a2), 100.0 parts of a 60% by mass toluene solution of the polysiloxane (b), 60.0 parts of toluene, and 0.5 parts of aqueous ammonia Stir at room temperature for 12 hours. The mixture was then heated at about 110-125 ° C. for 6 hours while refluxing to distill off ammonia and water.
- the resulting reaction product (solid content: silicon-bonded hydroxyl group content: 0.91% by mass) is allowed to cool, and then (D) ethynylcyclohexanol (0.2 parts) is added thereto, and the solid content is about Toluene was added to be 50% by mass and mixed to synthesize a base mixture A-7.
- Each of the base mixture and the component (B) obtained in the above synthesis example or comparative synthesis example was taken in a flask according to the compounding amount shown in the following Table 1 or 2, and was dissolved by stirring.
- Component (C) was added to the resulting solution in the amounts listed in Tables 1 and 2, and the resulting mixture was stirred and mixed to prepare a silicone pressure-sensitive adhesive composition.
- a pressure-sensitive adhesive sheet was produced by the method described later, and the peel strength of the silicone release liner and the adhesion to the adherend were measured.
- the fluorine-containing silicone release agent composition was prepared by diluting a solution in which hexane and methyl ethyl ketone were mixed at a mass ratio of 1: 1 so that the solid content was 12% by mass.
- first release liner ⁇ Preparation of first release liner>
- the above-mentioned fluorine-containing silicone release agent composition was coated on one side of a polyethylene terephthalate film substrate (thickness 50 ⁇ m) using a wire bar so that the thickness after curing was 1.0 ⁇ m. Then, it was made to heat and harden at 140 ° C and 30 seconds, and the first release liner was produced.
- ⁇ Peeling force 1> The force (N / 25 mm) required to peel off the first release liner from the pressure-sensitive adhesive sheet was measured using a tensile tester at an angle of 180 ° at a speed of 0.3 m / min.
- ⁇ Peeling force 2> The pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet from which the first release liner was peeled off in the peel force test 1 was attached to a polyethylene terephthalate film (thickness: 50 ⁇ m). Thereafter, using a tensile tester, the force (N / 25 mm) required to peel the second release liner from the adhesive sheet was measured at an angle of 180 ° at a speed of 0.3 m / min.
- a double-sided pressure-sensitive adhesive sheet comprising a cured product of the silicone pressure-sensitive adhesive composition of the present invention can be peeled off from the release liners 1 and 2 with a light force.
- the adhesion was measured by peeling the polyethylene terephthalate film at a peeling speed different from 0.3 m / min or 0.05 m / min The forces all showed strong adhesion. That is, the pressure-sensitive adhesive sheet of the present invention is not affected by the peeling speed of the adherend and has high adhesive strength.
- the double-sided pressure-sensitive adhesive sheet (comparative examples 1, 2 and 6) comprising a cured product of a silicone pressure-sensitive adhesive composition having too much content of component (a2) has poor adhesion and has a peeling rate Makes a difference in adhesion.
- the double-sided pressure-sensitive adhesive sheet (comparative examples 4 and 5) comprising a cured product of a silicone pressure-sensitive adhesive composition containing methylhydrogenpolysiloxane having an average degree of polymerization of 80 or more has a large peel force from release liners 1 and 2 It is also inferior.
- the double-sided pressure-sensitive adhesive sheet (comparative example 3) comprising the cured product of the silicone pressure-sensitive adhesive composition not containing the component (B) has a large difference in adhesion depending on the peeling speed of the adherend.
- the cured product of the silicone pressure-sensitive adhesive composition of the present invention has high adhesion regardless of the peeling rate, and therefore, the adherend can be strongly bonded or fixed. Furthermore, a pressure-sensitive adhesive tape and a pressure-sensitive adhesive sheet excellent in releasability and adhesion, and a double-sided pressure-sensitive adhesive sheet not having a substrate, since they exhibit excellent releasability with respect to release liners formed of fluorine-containing silicone release agent compositions. Can be provided.
- the double-sided pressure-sensitive adhesive sheet of the present invention can be advantageously used particularly in miniaturized, thinned or lightened electronic devices and electronic products.
Abstract
Description
(A)下記(a1)成分と、下記(b)成分と、及び下記(a2)成分との縮合反応物であり、又は、下記(a1)成分と下記(b)成分との縮合反応物及び下記(a2)成分から成り、(a1)成分/(a2)成分の質量比が100/0~45/55であり、且つ、(b)成分の量が、(a1)成分、(a2)成分及び(b)成分の合計100質量部に対し75~40質量部である
(a1)ケイ素原子に結合した水酸基及び/又は炭素原子数1~10のアルコキシ基を末端に有し、アルケニル基を有さない直鎖状又は分岐状のジオルガノポリシロキサン
(a2)1分子中に2個以上のアルケニル基を有し、アルケニル基含有量が0.0005mol/100g以上から0.15mol/100g未満であり、任意でケイ素原子に結合した水酸基又は炭素原子数1~10のアルコキシ基を有する、直鎖状又は分岐状のジオルガノポリシロキサン
(b)R1 3SiO0.5単位及びSiO2単位を有し、ケイ素原子に結合した水酸基及び/又はケイ素原子に結合した炭素原子数1~6のアルコキシ基を有するオルガノポリシロキサンであり、R1 3SiO0.5単位/SiO2単位のモル比が0.5~1.5である、前記オルガノポリシロキサン(前記において、R1は互いに独立に、置換又は非置換の、炭素原子数1~10の1価炭化水素基である)
(B)SiH基を1分子中に3個以上有し、平均重合度80以下を有するオルガノハイドロジェンポリシロキサン (A)成分100質量部に対して0.1~5質量部、及び
(C)白金族金属系触媒 触媒量。
本発明はさらに、上記シリコーン粘着剤組成物の硬化物から成る層を有する、粘着テープ又は粘着シート、並びに、上記シリコーン粘着剤組成物の硬化物からなる両面粘着シートを提供する。
本発明のシリコーン粘着剤組成物において(A)成分は、水酸基及び/又はアルコキシ基含有ジオルガノポリシロキサンと、水酸基及び/又はアルコキシ基を有し、且つM単位及びQ単位を有するオルガノポリシロキサンとの縮合反応物である。詳細には、(A)成分は、下記(a1)成分と、下記(b)成分と、及び下記(a2)成分との縮合反応物であり、又は、下記(a1)成分と下記(b)成分との縮合反応物及び下記(a2)成分から成り、(a1)成分/(a2)成分の質量比が100/0~45/55であり、且つ、(b)成分の量が、(a1)成分、(a2)成分及び(b)成分の合計100質量部に対し75~40質量部となる量であることを特徴とする。
(a1)ケイ素原子に結合した水酸基及び/又は炭素原子数1~10のアルコキシ基を末端に有し、アルケニル基を有さない直鎖状又は分岐状のジオルガノポリシロキサン
(a2)1分子中に2個以上のアルケニル基を有し、アルケニル基含有量が0.0005mol/100g以上から0.15mol/100g未満であり、任意でケイ素原子に結合した水酸基又は炭素原子数1~10のアルコキシ基を有する、直鎖状又は分岐状のジオルガノポリシロキサン
(b)R1 3SiO0.5単位及びSiO2単位を有し、ケイ素原子に結合した水酸基及び/又はケイ素原子に結合した炭素原子数1~6のアルコキシ基を有するオルガノポリシロキサンであり、R1 3SiO0.5単位/SiO2単位のモル比が0.5~1.5である、前記オルガノポリシロキサン(前記において、R1は互いに独立に、置換又は非置換の、炭素原子数1~10の1価炭化水素基である)
(b)成分は、R1 3SiO0.5単位及びSiO2単位を有し、ケイ素原子に結合した水酸基及び/又はケイ素原子に結合した炭素原子数1~6のアルコキシ基を有するオルガノポリシロキサンであり、R1 3SiO0.5単位/SiO2単位のモル比が0.5~1.5である、前記オルガノポリシロキサンである(前記において、R1は互いに独立に、置換又は非置換の、炭素原子数1~10の1価炭化水素基である)。R1 3SiO0.5単位/SiO2単位のモル比は0.5~1.5であり、好ましくは0.6~1.3である。該モル比が0.5未満または1.5を超えると、得られるシリコーン粘着剤層の粘着力が低下する場合や、剥離ライナーからの剥離力が高くなる場合がある。(b)成分は、1種単独であっても2種以上の併用であってもよい。
なお、SiOH基を有するシロキサン単位とは、R1 2(OH)SiO0.5単位、R1(OH)2SiO0.5単位、R1(OH)SiO単位、及び(OH)SiO1.5単位等が例示できる。また、アルコキシシリル基を有するシロキサン単位とは、R1 2(OR’)SiO0.5単位、R1(OR’)2SiO0.5単位、R1(OR’)SiO単位、及び(OR’)SiO1.5単位(OR’は、互いに独立に炭素原子数1~6のアルコキシ基である)等が例示できる。
(B)成分は、SiH基を1分子中に3個以上含有し、平均重合度80以下を有するオルガノハイドロジェンポリシロキサンである。1種のオルガノハイドロジェンポリシロキサン単独でも2種以上のオルガノハイドロジェンポリシロキサンの組合せでもよい。
(C)成分は白金族金属系触媒であり、上記(a2)成分と(B)成分との付加反応、(B)成分同士の脱水素縮合反応、または(B)成分のSiH基と(A)成分の残存SiOH基の脱水素縮合反応を促進させるための触媒である。該触媒としては、前記反応を促進させる従来公知の白金族金属系触媒であればよい。例えば、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコールとの反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサンとの反応物などの白金系触媒が挙げられる。さらには、ルテニウム、ロジウム、パラジウム、またはイリジウムなどの金属を含有する触媒も挙げられる。中でも白金系触媒が好ましい。触媒は1種単独であっても2種以上の併用であってもよい。
本発明のシリコーン粘着剤組成物は任意成分として、上述した付加反応及び縮合反応による硬化の制御剤を更に含んでいてよい。該成分は、加熱硬化の前、例えば、シリコーン粘着剤組成物の調合時又は該粘着剤組成物の基材への塗工時に、該粘着剤組成物を含む処理液が増粘又はゲル化を起こさないようにするために機能する。従来公知の制御剤であればよく、例えば、各種有機窒素化合物、有機リン化合物、有機ケイ素化合物、アセチレン系化合物、オキシム化合物、及び有機クロロ化合物などが挙げられる。
本発明のシリコーン粘着剤組成物には、上記(A)~(D)成分以外に任意成分を添加することができる。例えば、ポリジメチルシロキサン、ポリジメチルジフェニルシロキサンなどの非反応性のオルガノポリシロキサン;フェノール系、キノン系、アミン系、リン系、ホスファイト系、イオウ系、チオエーテル系などの酸化防止剤;トリアゾール系、ベンゾフェノン系などの光安定剤;リン酸エステル系、ハロゲン系、リン系、アンチモン系などの難燃剤;カチオン活性剤、アニオン活性剤、非イオン系活性剤などの帯電防止剤;染料;顔料;消泡剤;充填剤;レベリング剤;密着向上剤;増粘剤;塗工時に粘度を下げるための溶剤として、トルエン、キシレン等の芳香族炭化水素系溶剤、ヘキサン、ヘプタン、オクタン、イソオクタン、デカン、シクロヘキサン、メチルシクロヘキサン、イソパラフィン等の脂肪族炭化水素系溶剤、工業用ガソリン、石油ベンジン、ソルベントナフサ等の炭化水素系溶剤、アセトン、メチルエチルケトン、2-ペンタノン、3-ペンタノン、2-ヘキサノン、2-ヘプタノン、4-ヘプタノン、メチルイソブチルケトン、ジイソブチルケトン、アセトニルアセトン、シクロヘキサノン等のケトン系溶剤、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル等のエステル系溶剤、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、1,2-ジメトキシエタン、1,4-ジオキサン等のエーテル系溶剤、2-メトキシエチルアセタート、2-エトキシエチルアセタート、プロピレングリコールモノメチルエーテルアセタート、2-ブトキシエチルアセタート等のエステルとエーテル部分を有する溶剤、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、トリス(トリメチルシロキシ)メチルシラン、テトラキス(トリメチルシロキシ)シラン等のシロキサン系溶剤、又はこれらの混合溶剤などが使用できる。これらは1種単独で又は2種以上を適宜組み合わせて用いることができる。
(工程1)2つの基材の各片面に含フッ素シリコーン剥離剤組成物を各々塗工し、硬化させて、第1剥離層および第2剥離層を形成する。
(工程2)工程1で得た第1剥離層上にシリコーン粘着剤組成物を塗工し、硬化させて粘着層を形成する。
(工程3)工程2で得た粘着層上に工程1で得た第2剥離層の剥離剤硬化物面を積層させる。
(工程1)1つの基材の両面に含フッ素シリコーン剥離剤組成物を塗工し、硬化させて、両面に剥離層(第1剥離層及び第2剥離層)を有する基材を形成する。
(工程2)工程1で得た第1剥離層上にシリコーン粘着剤組成物を塗工し、硬化させて粘着層を形成する。
(工程3)工程2で得た粘着層の上に第2剥離層が積層するように積層体全体を巻き取る。
(E)ケイ素原子に結合したアルケニル基を1分子中に2個以上有し、及び、ケイ素原子に結合したフッ素含有有機基を1分子中に1個以上有し、ケイ素原子に結合する基の合計個数に対する該フッ素含有有機基の個数割合が5%以上50%未満である、ポリジオルガノシロキサン、
(F)1分子中にSiH基を3個以上有するポリオルガノシロキサン (E)成分中のアルケニル基に対する(F)成分中のSiH基の個数比が0.5~10となる量 及び
(G)白金族金属系触媒 触媒量。
以下、(E)~(G)成分について、詳細に説明する。
(E)成分は、1種単独でも2種以上を組み合わせても使用することができる。
下記において粘度はBM型回転粘度計を用いて25℃で測定した値であり、部は質量部を示し、特性値は下記の試験方法による測定値を示す。また、各例中、Meはメチル基、Viはビニル基を表す。
(a1)下記式(i)で示されるジメチルポリシロキサンであり、30質量%の濃度となるようにトルエンで溶解したときの粘度70,000mPa・sを有する
(a2)下記式(ii)で示されるジメチルポリシロキサンであり、30質量%の濃度となるようにトルエンで溶解したときの粘度が48,000mPa・sであり、ビニル基量0.001mol/100gを有する
(b)Me3SiO0.5単位及びSiO2単位からなり、SiO2単位のケイ素原子に結合した水酸基を有するポリシロキサン(Me3SiO0.5単位/SiO2単位(モル比)=0.85、ケイ素原子結合水酸基含有量2.2質量%、重量平均分子量3,000)
[合成例1]
上記ジメチルポリシロキサン(a1)37.5部、上記ジメチルポリシロキサン(a2)12.5部、上記ポリシロキサン(b)の60質量%トルエン溶液83.3部、トルエン66.7部、及びアンモニア水0.5部を混合して成る溶液を、室温(25℃、以下同じ)で12時間撹拌した。次いで、還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた縮合反応生成物(固形分のケイ素原子結合水酸基含有量0.66質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合して、ベース混合物A-1を得た。
上記ジメチルポリシロキサン(a1)50.0部、上記ポリシロキサン(b)の60質量%トルエン溶液83.3部、トルエン66.7部、及びアンモニア水0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた縮合反応生成物(固形分のケイ素原子結合水酸基含有量0.68質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合して、ベース混合物A-2を得た。
上記ジメチルポリシロキサン(a1)30.0部、上記ジメチルポリシロキサン(a2)10.0部、上記ポリシロキサン(b)の60質量%トルエン溶液100.0部、トルエン 60.0部、及びアンモニア水 0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた縮合反応生成物(固形分のケイ素原子結合水酸基含有量0.92質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合して、ベース混合物A-3を得た。
上記ジメチルポリシロキサン(a1)40.0部、上記ポリシロキサン(b)の60質量%トルエン溶液100.0部、トルエン60.0部、及びアンモニア水 0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた縮合反応生成物(固形分のケイ素原子結合水酸基含有量0.93質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合して、ベース混合物A-4を得た。
上記ジメチルポリシロキサン(a2)50.0部、上記ポリシロキサン(b)の60質量%トルエン溶液83.3部、トルエン66.7部、及びアンモニア水 0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた反応生成物(固形分のケイ素原子結合水酸基含有量0.64質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合し、ベース混合物A-5を得た。
上記ジメチルポリシロキサン(a1)20.0部、上記ジメチルポリシロキサン(a2)30.0部、上記ポリシロキサン(b)の60質量%トルエン溶液 83.3部、トルエン66.7部、及びアンモニア水 0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた縮合反応生成物(固形分のケイ素原子結合水酸基含有量0.65質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合して、ベース混合物A-6を得た。
上記ジメチルポリシロキサン(a2)40.0部、上記ポリシロキサン(b)の60質量%トルエン溶液100.0部、トルエン60.0部、及びアンモニア水 0.5部を混合してなる溶液を、室温で12時間撹拌した。次いで還流させながら約110~125℃で6時間加熱し、アンモニアと水を留去した。得られた反応生成物(固形分のケイ素原子結合水酸基含有量0.91質量%)を放冷したのち、これに(D)エチニルシクロヘキサノール(0.2部)を添加し、固形分が約50質量%となるようにトルエンを加えて混合し、ベース混合物A-7を合成した。
シリコーン粘着剤組成物の調製
シリコーン粘着剤組成物にて使用した(B)及び(C)成分は以下の通りである。
(B)成分
(B-1)下記式で示されるメチルハイドロジェンポリシロキサン
また、実施例及び比較例で調製したシリコーン剥離剤組成物にて使用した(E)及び(F)成分は以下の通りである。
(E-1)下記式で示されるジメチルポリシロキサン
上記含フッ素シリコーン剥離剤組成物を、ポリエチレンテレフタレートフィルム基材(厚み50μm)の片面に硬化後の厚みが1.0μmとなるようにワイヤーバーを用いて塗工した。その後、140℃及び30秒にて加熱して硬化させて、第一の剥離ライナーを作製した。
上記含フッ素シリコーン剥離剤組成物を、ポリエチレンテレフタレートフィルム基材(厚み50μm)の片面に硬化後の厚みが0.6μmとなるようにワイヤーバーを用いて塗工した。その後、140℃及び30秒にて加熱して硬化させて、第二の剥離ライナーを作製した。
実施例及び比較例で得たシリコーン粘着剤組成物の各々について、第二の剥離ライナーの剥離処理面に硬化後の厚みが50μmとなるようにアプリケータを用いて塗工した後、130℃、2分にて加熱して粘着剤組成物を硬化させた。次いで、この粘着面の上に第一の剥離ライナーの剥離処理面を貼り合わせて積層体を作製した。この粘着シートを、ゴム層で被覆された重さ2kgのローラーを1往復させることにより圧着し、25℃で1日静置してエージングさせて、粘着シートを得た。各粘着シートについて以下の評価試験を行った。結果を表1及び2に示す。
引っ張り試験機を用いて0.3m/分の速度で180゜の角度にて、上記粘着シートから第一の剥離ライナーを引き剥がすのに要する力(N/25mm)を測定した。
上記剥離力1試験にて第一の剥離ライナーを剥がした粘着シートの粘着面をポリエチレンテレフタレートフィルム(厚み50μm)に貼りつけた。その後、引っ張り試験機を用いて0.3m/分の速度で180゜の角度にて、粘着シートから第二の剥離ライナーを引き剥がすのに要する力(N/25mm)を測定した。
上記剥離力2試験にて第二の剥離ライナーを剥がした後の粘着層面をガラス板に貼りつけ、ゴム層で被覆された重さ2kgのローラーを1往復させることにより圧着した。室温で約2時間放置した後、引っ張り試験機を用いて0.3m/分の速度で180゜の角度にて、ポリエチレンテレフタレートフィルムを粘着層面から引き剥がすのに要する力(N/25mm)を測定した。
上記剥離力2試験にて第二の剥離ライナーを剥がした後の粘着層面をガラス板に貼りつけ、ゴム層で被覆された重さ2kgのローラーを1往復させることにより圧着した。室温で約2時間放置した後、引っ張り試験機を用いて0.05m/分の速度で180゜の角度にて、ポリエチレンテレフタレートフィルムを粘着層面から引き剥がすのに要する力(N/25mm)を測定した。
一方、表2に示す通り、(a2)成分の含有量が多すぎるシリコーン粘着剤組成物の硬化物からなる両面粘着シート(比較例1、2および6)は、粘着力が劣り、また剥離速度により粘着力に差が出る。平均重合度80超を有するメチルハイドロジェンポリシロキサンを含むシリコーン粘着剤組成物の硬化物からなる両面粘着シート(比較例4及び5)は剥離ライナー1及び2からの剥離力が大きく、また粘着力にも劣る。さらに(B)成分を含まないシリコーン粘着剤組成物の硬化物からなる両面粘着シート(比較例3)は被着体の剥離速度によって粘着力に大きな差がある。
Claims (12)
- 下記(A)~(C)成分を含有するシリコーン粘着剤組成物
(A)下記(a1)成分と、下記(b)成分と、及び下記(a2)成分との縮合反応物であり、又は、下記(a1)成分と下記(b)成分との縮合反応物及び下記(a2)成分から成り、(a1)成分/(a2)成分の質量比が100/0~45/55であり、且つ、(b)成分の量が、(a1)成分、(a2)成分及び(b)成分の合計100質量部に対し75~40質量部である
(a1)ケイ素原子に結合した水酸基及び/又は炭素原子数1~10のアルコキシ基を末端に有し、アルケニル基を有さない直鎖状又は分岐状のジオルガノポリシロキサン
(a2)1分子中に2個以上のアルケニル基を有し、アルケニル基含有量が0.0005mol/100g以上から0.15mol/100g未満であり、任意でケイ素原子に結合した水酸基又は炭素原子数1~10のアルコキシ基を有する、直鎖状又は分岐状のジオルガノポリシロキサン
(b)R1 3SiO0.5単位及びSiO2単位を有し、ケイ素原子に結合した水酸基及び/又はケイ素原子に結合した炭素原子数1~6のアルコキシ基を有するオルガノポリシロキサンであり、R1 3SiO0.5単位/SiO2単位のモル比が0.5~1.5である、前記オルガノポリシロキサン(前記において、R1は互いに独立に、置換又は非置換の、炭素原子数1~10の1価炭化水素基である)
(B)SiH基を1分子中に3個以上有し、平均重合度80以下を有するオルガノハイドロジェンポリシロキサン (A)成分100質量部に対して0.1~5質量部、及び
(C)白金族金属系触媒 触媒量。 - さらに(D)反応制御剤を(A)成分及び(B)成分の合計100質量部に対して0.05~8質量部含む、請求項1に記載のシリコーン粘着剤組成物。
- (B)成分が、炭素数6~10のアリール基又はアリール基を含む炭素数6~10のアラルキル基を有し、ケイ素原子に結合する水素原子及びケイ素原子に結合する置換基の合計個数に対する該アリール基の合計個数の割合が3%~40%である、請求項1~4のいずれか1項に記載のシリコーン粘着剤組成物。
- 上記(A)成分において(a1)/(a2)の質量比が100/0~60/40である、請求項1~5のいずれか1項に記載のシリコーン粘着剤組成物。
- 上記(A)成分において(a1)/(a2)の質量比が100/0であり、上記(A)成分が(a1)成分及び(b)成分の縮合反応物であり(a2)成分を含まない、請求項1~6のいずれか1項に記載のシリコーン粘着剤組成物。
- 基材と、該基材の少なくとも片面に積層された請求項1~7のいずれか1項に記載のシリコーン粘着剤組成物の硬化物からなる層とを有する粘着テープ。
- 基材と、該基材の少なくとも片面に積層された請求項1~7のいずれか1項に記載のシリコーン粘着剤組成物の硬化物からなる層とを有する粘着シート。
- 基材及び、該基材の一方の面上に形成された第1剥離層と、該第1剥離層上に積層された粘着層と、及び該粘着層上に積層された第2剥離層とを有する積層体から成る粘着シート又はテープであって、第1剥離層及び第2剥離層が互いに独立に、含フッ素シリコーン剥離剤組成物を硬化して成る硬化物であり、前記粘着層が、請求項1~7のいずれか1項に記載のシリコーン粘着剤組成物を硬化してなる硬化物である、前記粘着シート又はテープ。
- 請求項1~7のいずれか1項に記載のシリコーン粘着剤組成物の硬化物からなる、基材を有さない両面粘着シート。
- 請求項10記載の粘着シートであって、前記含フッ素シリコーン剥離剤組成物が
(E)ケイ素原子に結合したアルケニル基を1分子中に2個以上有し、及び、ケイ素原子に結合したフッ素含有有機基を1分子中に1個以上有し、ケイ素原子に結合した基の合計個数に対する該フッ素含有有機基の個数割合が5%以上50%未満である、ポリジオルガノシロキサン、
(F)1分子中にSiH基を3個以上有するポリオルガノシロキサン (E)成分中のアルケニル基に対する(F)成分中のSiH基の個数比が0.5~10となる量 及び
(G)白金族金属系触媒 触媒量
を含有する、前記粘着シート又はテープ。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020207014507A KR102576481B1 (ko) | 2017-11-02 | 2018-10-15 | 실리콘 점착제 조성물, 점착 테이프, 점착 시트 및 양면 점착 시트 |
EP18873535.1A EP3705548A4 (en) | 2017-11-02 | 2018-10-15 | SILICONE ADHESIVE COMPOSITION, ADHESIVE TAPE, ADHESIVE FILM AND DOUBLE SIDED ADHESIVE FILM |
US16/760,023 US11732169B2 (en) | 2017-11-02 | 2018-10-15 | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet |
CN201880071133.4A CN111315840B (zh) | 2017-11-02 | 2018-10-15 | 硅酮粘着剂组合物、粘着带、粘着片及双面粘着片 |
JP2019551019A JP6997794B2 (ja) | 2017-11-02 | 2018-10-15 | シリコーン粘着剤組成物、粘着テープ、粘着シート、及び両面粘着シート |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017212580 | 2017-11-02 | ||
JP2017-212580 | 2017-11-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019087759A1 true WO2019087759A1 (ja) | 2019-05-09 |
Family
ID=66333014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/038351 WO2019087759A1 (ja) | 2017-11-02 | 2018-10-15 | シリコーン粘着剤組成物、粘着テープ、粘着シート、及び両面粘着シート |
Country Status (7)
Country | Link |
---|---|
US (1) | US11732169B2 (ja) |
EP (1) | EP3705548A4 (ja) |
JP (1) | JP6997794B2 (ja) |
KR (1) | KR102576481B1 (ja) |
CN (1) | CN111315840B (ja) |
TW (1) | TWI774862B (ja) |
WO (1) | WO2019087759A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020017142A1 (ja) * | 2018-07-17 | 2020-01-23 | 信越化学工業株式会社 | 皮膚貼付用付加反応硬化型シリコーン粘着剤組成物及び皮膚貼付用粘着テープ |
WO2020026844A1 (ja) * | 2018-08-01 | 2020-02-06 | 信越化学工業株式会社 | シリコーン粘着剤組成物及びこれを用いた粘着テープ又は粘着フィルム |
JP2021059697A (ja) * | 2019-10-09 | 2021-04-15 | 日東電工株式会社 | フッ素樹脂シート及び粘着テープ |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112574682B (zh) * | 2020-11-12 | 2022-12-06 | 苏州赛伍应用技术股份有限公司 | 一种用于MiniLED巨量转移的多层结构胶带及其制备方法 |
TW202221082A (zh) * | 2020-11-17 | 2022-06-01 | 明基材料股份有限公司 | 一種矽膠阻氣膜 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0718185A (ja) * | 1993-06-30 | 1995-01-20 | Shin Etsu Chem Co Ltd | 剥離剤用シリコーン組成物 |
JP2002363523A (ja) | 2001-06-13 | 2002-12-18 | Nitto Denko Corp | 感圧性接着剤組成物、感圧性接着シート及び光学フィルム |
WO2010100024A1 (de) | 2009-03-04 | 2010-09-10 | Tesa Se | Haftklebemasse |
JP2011001448A (ja) * | 2009-06-18 | 2011-01-06 | Shin-Etsu Chemical Co Ltd | 付加反応硬化型シリコーン粘着剤組成物および粘着テープ |
JP2012041505A (ja) * | 2010-08-23 | 2012-03-01 | Shin-Etsu Chemical Co Ltd | 無溶剤型付加型シリコーン粘着剤組成物及び粘着性物品 |
JP2013091785A (ja) | 2011-10-08 | 2013-05-16 | Mitsubishi Plastics Inc | 基材レス両面粘着シート |
JP2013173944A (ja) | 2013-04-18 | 2013-09-05 | Shin-Etsu Chemical Co Ltd | シリコーン粘着層を含む積層体 |
WO2015151221A1 (ja) | 2014-03-31 | 2015-10-08 | リンテック株式会社 | 両面粘着シート |
JP2016180021A (ja) | 2015-03-23 | 2016-10-13 | 三菱樹脂株式会社 | 基材レス両面粘着シート |
JP2016182772A (ja) | 2015-03-26 | 2016-10-20 | 信越化学工業株式会社 | 積層体、その作製方法、基材レス粘着シートの使用方法及び物品 |
JP2017222819A (ja) * | 2016-06-17 | 2017-12-21 | 信越化学工業株式会社 | 付加反応硬化型シリコーン粘着剤組成物及び粘着テープ |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5696209A (en) * | 1996-10-09 | 1997-12-09 | Dow Corning Corporation | Dual-cure flowable adhesive |
US6387487B1 (en) * | 2000-08-11 | 2002-05-14 | General Electric Company | Dual cure, low-solvent silicone pressure sensitive adhesives |
JP5534640B2 (ja) * | 2007-12-27 | 2014-07-02 | 東レ・ダウコーニング株式会社 | シリコーン系感圧接着剤組成物、感圧接着シートおよびシリコーンゴム積層体 |
WO2011087146A1 (ja) | 2010-01-13 | 2011-07-21 | 東レ・ダウコーニング株式会社 | シリコーン系再剥離性粘着剤組成物、該組成物を硬化させてなる再剥離粘着層を有するシート状基材、その保護フィルムまたは固定シートとしての使用 |
JP6348434B2 (ja) * | 2014-03-28 | 2018-06-27 | 信越化学工業株式会社 | シリコーン粘着剤組成物、その製造法及び粘着フィルム |
EP3536757A1 (en) | 2015-03-26 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Release agent composition for silicone adhesive and release liner |
JP6803246B2 (ja) * | 2016-07-11 | 2020-12-23 | 信越化学工業株式会社 | シリコーン組成物、剥離紙及び剥離フィルム |
WO2018012296A1 (ja) * | 2016-07-11 | 2018-01-18 | 信越化学工業株式会社 | シリコーン組成物、剥離紙及び剥離フィルム |
-
2018
- 2018-10-15 JP JP2019551019A patent/JP6997794B2/ja active Active
- 2018-10-15 EP EP18873535.1A patent/EP3705548A4/en active Pending
- 2018-10-15 CN CN201880071133.4A patent/CN111315840B/zh active Active
- 2018-10-15 US US16/760,023 patent/US11732169B2/en active Active
- 2018-10-15 KR KR1020207014507A patent/KR102576481B1/ko active IP Right Grant
- 2018-10-15 WO PCT/JP2018/038351 patent/WO2019087759A1/ja unknown
- 2018-10-17 TW TW107136435A patent/TWI774862B/zh active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0718185A (ja) * | 1993-06-30 | 1995-01-20 | Shin Etsu Chem Co Ltd | 剥離剤用シリコーン組成物 |
JP2002363523A (ja) | 2001-06-13 | 2002-12-18 | Nitto Denko Corp | 感圧性接着剤組成物、感圧性接着シート及び光学フィルム |
WO2010100024A1 (de) | 2009-03-04 | 2010-09-10 | Tesa Se | Haftklebemasse |
JP2011001448A (ja) * | 2009-06-18 | 2011-01-06 | Shin-Etsu Chemical Co Ltd | 付加反応硬化型シリコーン粘着剤組成物および粘着テープ |
JP2012041505A (ja) * | 2010-08-23 | 2012-03-01 | Shin-Etsu Chemical Co Ltd | 無溶剤型付加型シリコーン粘着剤組成物及び粘着性物品 |
JP2013091785A (ja) | 2011-10-08 | 2013-05-16 | Mitsubishi Plastics Inc | 基材レス両面粘着シート |
JP2013173944A (ja) | 2013-04-18 | 2013-09-05 | Shin-Etsu Chemical Co Ltd | シリコーン粘着層を含む積層体 |
WO2015151221A1 (ja) | 2014-03-31 | 2015-10-08 | リンテック株式会社 | 両面粘着シート |
JP2016180021A (ja) | 2015-03-23 | 2016-10-13 | 三菱樹脂株式会社 | 基材レス両面粘着シート |
JP2016182772A (ja) | 2015-03-26 | 2016-10-20 | 信越化学工業株式会社 | 積層体、その作製方法、基材レス粘着シートの使用方法及び物品 |
JP2017222819A (ja) * | 2016-06-17 | 2017-12-21 | 信越化学工業株式会社 | 付加反応硬化型シリコーン粘着剤組成物及び粘着テープ |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020017142A1 (ja) * | 2018-07-17 | 2020-01-23 | 信越化学工業株式会社 | 皮膚貼付用付加反応硬化型シリコーン粘着剤組成物及び皮膚貼付用粘着テープ |
WO2020026844A1 (ja) * | 2018-08-01 | 2020-02-06 | 信越化学工業株式会社 | シリコーン粘着剤組成物及びこれを用いた粘着テープ又は粘着フィルム |
JPWO2020026844A1 (ja) * | 2018-08-01 | 2021-08-02 | 信越化学工業株式会社 | シリコーン粘着剤組成物及びこれを用いた粘着テープ又は粘着フィルム |
JP7092196B2 (ja) | 2018-08-01 | 2022-06-28 | 信越化学工業株式会社 | シリコーン粘着剤組成物及びこれを用いた粘着テープ又は粘着フィルム |
JP2021059697A (ja) * | 2019-10-09 | 2021-04-15 | 日東電工株式会社 | フッ素樹脂シート及び粘着テープ |
Also Published As
Publication number | Publication date |
---|---|
EP3705548A4 (en) | 2021-08-11 |
TWI774862B (zh) | 2022-08-21 |
KR20200079504A (ko) | 2020-07-03 |
CN111315840A (zh) | 2020-06-19 |
US11732169B2 (en) | 2023-08-22 |
KR102576481B1 (ko) | 2023-09-07 |
CN111315840B (zh) | 2022-11-15 |
EP3705548A1 (en) | 2020-09-09 |
JPWO2019087759A1 (ja) | 2020-11-26 |
JP6997794B2 (ja) | 2022-01-18 |
US20210024797A1 (en) | 2021-01-28 |
TW201923013A (zh) | 2019-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2423289B1 (en) | Solventless addition-curable pressure sensitive silicone adhesive composition and adhesive article | |
JP4850931B2 (ja) | 付加反応硬化型シリコーン粘着剤組成物および粘着テープ | |
JP6997794B2 (ja) | シリコーン粘着剤組成物、粘着テープ、粘着シート、及び両面粘着シート | |
KR102306232B1 (ko) | 실리콘 점착제용 박리제 조성물, 박리 필름 및 적층체 | |
KR20080089268A (ko) | 무용제형 실리콘 감압 접착제 조성물 | |
JP4648011B2 (ja) | 芳香族溶剤を含まないシリコーン粘着剤組成物およびそれを塗工した粘着テープ、シートまたはラベル | |
WO2019142779A1 (ja) | シリコーン粘着剤組成物、粘着フィルムおよび粘着テープ | |
JP6515876B2 (ja) | 付加反応硬化型シリコーン粘着剤組成物及び粘着テープ | |
JP6413878B2 (ja) | シリコーン粘着剤用剥離剤組成物及び剥離フィルム | |
JP6471579B2 (ja) | 積層体、その作製方法、基材レス粘着シートの使用方法及び物品 | |
WO2018190047A1 (ja) | シリコーン粘着剤用プライマー組成物及び物品 | |
JP7153015B2 (ja) | シリコーン粘着剤用剥離剤組成物および剥離フィルム | |
JP4123349B2 (ja) | シリコーン剥離層とシリコーン粘着層の積層物品及びその製造方法 | |
JP7321954B2 (ja) | シリコーン粘着剤組成物 | |
JP7358174B2 (ja) | シリコーン粘着剤用プライマー組成物 | |
WO2023195390A1 (ja) | シリコーン粘着剤組成物、粘着テープおよび粘着フィルム | |
CN116998005A (zh) | 压敏粘合剂组合物及其制备方法和在柔性有机发光二极管应用中的用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18873535 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019551019 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20207014507 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2018873535 Country of ref document: EP Effective date: 20200602 |