WO2020121939A1 - Composition adhésive de silicone autocollante et utilisation associée - Google Patents

Composition adhésive de silicone autocollante et utilisation associée Download PDF

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Publication number
WO2020121939A1
WO2020121939A1 PCT/JP2019/047623 JP2019047623W WO2020121939A1 WO 2020121939 A1 WO2020121939 A1 WO 2020121939A1 JP 2019047623 W JP2019047623 W JP 2019047623W WO 2020121939 A1 WO2020121939 A1 WO 2020121939A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
pressure
group
component
composition
Prior art date
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PCT/JP2019/047623
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English (en)
Japanese (ja)
Inventor
智浩 飯村
吉武　誠
尚子 田中
晴彦 古川
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Dow Toray Co Ltd
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Dow Toray Co Ltd
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Application filed by Dow Toray Co Ltd filed Critical Dow Toray Co Ltd
Priority to JP2020560005A priority Critical patent/JP7491655B2/ja
Priority to KR1020217021499A priority patent/KR102782399B1/ko
Priority to CN201980089314.4A priority patent/CN113302255A/zh
Publication of WO2020121939A1 publication Critical patent/WO2020121939A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • 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

Definitions

  • the present invention relates to a silicone pressure sensitive adhesive composition.
  • the present invention also relates to applications such as an adhesive layer or an elastic pressure-sensitive adhesive member obtained by curing the composition, a laminate including the adhesive layer obtained by curing the composition, and the like.
  • polysiloxane-based pressure-sensitive adhesive compositions are superior in electrical insulation, heat resistance, cold resistance, and adhesion to various adherends. It is used for heat-resistant adhesive tape, electrically insulating adhesive tape, heat seal tape, plating masking tape, etc.
  • These polysiloxane-based pressure-sensitive adhesive compositions are classified into addition reaction-curable type, condensation reaction-curable type, peroxide-curable type and the like depending on the curing mechanism. Addition reaction-curable pressure-sensitive adhesive compositions are widely used because they cure rapidly when left at room temperature or heated and do not generate by-products.
  • Such a device has a structure in which a film composed of a plurality of layers including an electrode layer and a display layer is sandwiched between transparent base materials, and is aimed at protecting the electrode layer and the display layer and improving the adhesion between the layers. It is expected that a polysiloxane-based pressure-sensitive adhesive having excellent heat resistance and cold resistance will work effectively.
  • Patent Documents 1 to 4 disclose solvent-free polysiloxane-based pressure-sensitive adhesives, but improvements in various characteristics have been desired as compared with solvent-type polysiloxane-based pressure-sensitive adhesives. ..
  • the present invention has been made to solve the above problems, as a low-solvent type or solvent-free composition, has a viscosity that can be applied substantially without containing a solvent, in curability
  • a silicone pressure-sensitive adhesive composition in which a polyorganosiloxane-based pressure-sensitive adhesive formed by a curing reaction forms an excellent pressure-sensitive adhesive layer having a good balance of adhesive strength, tack, and high temperature holding power.
  • the high-temperature holding power of the pressure-sensitive adhesive means that when the two base materials are adhered using the pressure-sensitive adhesive, the bonding position shifts between the base materials and the separation of the two base materials even at a high temperature.
  • the present invention has an object to provide use of a cured product of the silicone pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer, use as an elastic pressure-sensitive adhesive member in a wide variety of applications, and an apparatus or a device including the same.
  • one of the objects of the present invention is [1] (A) A straight-chain or branched-chain organo having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane polymerization degree of 5 to 250.
  • Polysiloxane (B) a linear organohydrogenpolysiloxane having silicon-bonded hydrogen atoms only at both ends of the molecular chain, (C) a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and SiO 4/2
  • (D) contains an organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule
  • E a hydrosilylation reaction catalyst
  • the ratio of the number of moles of silicon-bonded hydrogen atoms in the component (B) to the number of moles of the aliphatic unsaturated carbon-carbon bond-containing group in the component (A) is in the range of 0.90 to 1.30, The ratio of the number of moles of silicon-bonded hydrogen atoms of the component (B) and the component (D) to the number of moles of the
  • Range of The viscosity of the entire composition at 25° C. is in the range of 1,000 to 300,000 mPa ⁇ s, and The content of the organic solvent is less than 20% by mass of the entire composition, Achieved with a silicone pressure sensitive adhesive composition.
  • the subject of this invention can be suitably solved by the following silicone pressure sensitive adhesive compositions.
  • the total amount of the components (A) to (D) is 100 parts by mass
  • the total amount of the components (A) and (B) is in the range of 10 to 80 parts by mass
  • the amount of component (C) is in the range of 10 to 80 parts by mass
  • the amount of the component (D) is in the range of 0.01 to 10 parts by mass
  • the component (D) is (D1) a cyclic organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule, and (D2) at least 3 silicon-bonded hydrogen atoms having no silicon-bonded hydrogen atoms at the molecular chain terminals. At least one selected from the group consisting of linear or branched organohydrogenpolysiloxanes having atoms,
  • the silicone pressure-sensitive adhesive composition according to [1] or [2].
  • the pressure-sensitive adhesive layer having a thickness of 40 ⁇ m obtained by curing the composition has an adhesive force of 100 on a SUS substrate measured by a 180° peeling test method according to JIS Z 0237 at a pulling speed of 300 mm/min.
  • the silicone pressure-sensitive adhesive composition according to any one of [1] to [3], which is in the range of to 2500 gf/inch. [5] The solvent-free composition according to any one of [1] to [4], wherein the content of the organic solvent is in the range of 0 to 5% by mass based on the whole composition. Silicone pressure sensitive adhesive composition.
  • the problems of the present invention can be suitably solved by using the following pressure-sensitive adhesive layer, laminate, elastic adhesive member and the following applications.
  • the laminate according to [7], which comprises one or more film-shaped substrates, and a release layer for the pressure-sensitive adhesive layer is provided on the film-shaped substrate.
  • a film-shaped substrate A first release layer formed on the film substrate, A pressure-sensitive adhesive layer formed by applying and curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5] on the release layer, and on the pressure-sensitive adhesive layer.
  • An elastic pressure-sensitive adhesive member obtained by curing the silicone pressure-sensitive adhesive composition according to any one of [1] to [5].
  • the silicone pressure-sensitive adhesive composition of the present invention as a low-solvent type or solvent-free type composition, has a viscosity that can be applied substantially without containing a solvent, and is curable by a hydrosilylation reaction. It has excellent adhesiveness, tackiness and high temperature retention after being cured, and it has excellent mechanical strength and elongation of the adhesive layer after curing, and has sufficient adhesiveness for practical use.
  • An adhesive layer can be formed.
  • the cured product of the silicone pressure-sensitive adhesive composition can be suitably used as a pressure-sensitive adhesive layer, an electronic material or a member for a display device, and an electric/electronic component or a display device including the same can be widely used.
  • the viscoelasticity of the adhesive layer is sufficient in the temperature range, it is possible to form a pressure-sensitive adhesive layer that is unlikely to cause a problem of poor adhesion to a substrate such as an electronic component in a temperature range including low temperature to room temperature. It has advantages that industrialization of parts and the like is easy, and that performance improvement of the obtained electronic parts and the like is expected.
  • the silicone pressure-sensitive adhesive composition As a low-solvent type or solvent-free type composition, has practically sufficient coatability even if the composition does not substantially contain an organic solvent, and is rapidly treated by a curing reaction including a hydrosilylation reaction.
  • the pressure-sensitive adhesive layer is hardened to have sufficient tackiness for practical use, and the pressure-sensitive adhesive layer forms a pressure-sensitive adhesive layer excellent in mechanical strength and elongation.
  • the silicone pressure sensitive adhesive composition of the present invention (A) a linear or branched organopolysiloxane having at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule and having a siloxane polymerization degree in the range of 5 to 250, (B) a linear organohydrogenpolysiloxane having silicon-bonded hydrogen atoms only at both ends of the molecular chain, (C) a siloxane unit (M unit) represented by R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and SiO 4/2 An organopolysiloxane resin containing a siloxane unit (Q unit), (D) Organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in the molecule, and (E) hydrosilylation reaction catalyst, wherein the content of the organic solvent is less than 20% by mass of the entire composition. From the viewpoint of handling workability, the composition may further contain (F) a cu
  • the component (A) has at least two aliphatic unsaturated carbon-carbon bond-containing groups in one molecule, and its siloxane polymerization degree is in the range of 5-250.
  • Polysiloxane which is the main ingredient (base polymer) of the present composition.
  • the component (A) having a degree of siloxane polymerization in the range of 5 to 250 the overall viscosity of the composition can be reduced, and a low solvent type or a solventless type composition can be designed and Even if the composition does not contain an organic solvent, practically sufficient coatability can be realized as the entire composition.
  • the component (A) may be a single organopolysiloxane or a mixture of two or more types of organopolysiloxane.
  • the degree of siloxane polymerization of the organopolysiloxane as the component (A) is in the range of 5-250, preferably 5-200, and more preferably 5-180.
  • the component (A) may be an organopolysiloxane having a degree of polymerization of (A1) siloxane in the range of 5 to 50, and a degree of polymerization of the component (A1) and (A2) siloxane in the range of 51 to 250, preferably May be a mixture of organopolysiloxanes ranging from 51 to 200.
  • the siloxane polymerization degree of the component (A) exceeds the above upper limit, the viscosity of the entire composition tends to increase, and coating may be difficult unless a large amount of organic solvent is used. On the other hand, if the siloxane polymerization degree of the component (A) is less than the lower limit, the curability and adhesive performance of the composition may deteriorate. From the viewpoint of the technical effect of the present invention, it is preferable that 50% by mass or more of the component (A) is (A1) an organopolysiloxane having a degree of polymerization of siloxane in the range of 5 to 50. There is an advantage that the viscosity can be reduced.
  • the component (A) has at least two aliphatic unsaturated carbon-carbon bond-containing groups in the molecule.
  • an aliphatic unsaturated carbon-carbon bond-containing group include an alkenyl group, an alkenyloxyalkyl group, an acryloxyalkyl group or a methacryloxyalkyl group, and an alkenyl group is particularly preferable.
  • the alkenyl group is a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group or the like, and a vinyl group or a hexenyl group is particularly preferable.
  • these aliphatic unsaturated carbon-carbon bond-containing groups are preferably bonded to a silicon atom.
  • the aliphatic unsaturated carbon-carbon bond-containing group may be present at either the terminal of the siloxane molecular chain or the side chain of the molecular chain, or may be present at both of them.
  • the content of the aliphatic unsaturated carbon-carbon bond-containing group is preferably 0.001 to 10% by mass, preferably 0.005 to 8.50% by mass, and 0.01 to 10% by mass based on the mass of the component (A). 7.5 mass% is more preferable.
  • the content of the vinyl (CH 2 ⁇ CH—) moiety in the aliphatic unsaturated carbon-carbon bond-containing group (hereinafter referred to as “vinyl content”) is 0.005 to 10.0% by mass.
  • the range of 0.005 to 8.50 mass% is particularly preferable.
  • Component (A) is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group as an organic group other than an aliphatic unsaturated carbon-carbon bond-containing group; a phenyl group; Aryl groups such as tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. May be included. From an industrial point of view, it is particularly preferable to contain a methyl group or a phenyl group.
  • Such a component (A) has a general formula: R 1 3 SiO(R 1 2 SiO) m1 SiR 1 3
  • each R 1 is independently a substituted or unsubstituted monovalent hydrocarbon group, and as the monovalent hydrocarbon group, the aliphatic unsaturated carbon-carbon bond-containing group and other organic groups described above can be used. It is illustrated. However, at least two R 1 's in one molecule are aliphatic unsaturated carbon-carbon bond-containing groups, preferably alkenyl groups, more preferably vinyl groups or hexenyl groups.
  • the siloxane polymerization degree of “m1+2” is preferably in the range of 5 to 230, more preferably in the range of 5 to 200, and more preferably in the range of 5 to 190.
  • “+2” is a sum of siloxane units at both ends of a linear molecule, and further, in the range of 0 to 5, branched siloxane units represented by R 1 SiO 3/2 and SiO 4/ A unit selected from the branched siloxane units represented by 2 may be included. It should be noted that one R 1 SiO 3/2 is a branched siloxane unit, and SiO 4/2 a branched siloxane unit is two R 1 3 SiO 1/2 units. It is added in the molecule to form a chain end corresponding to the branched siloxane unit.
  • R 1 is an aliphatic unsaturated carbon - is preferably an organic group other than carbon bond-containing group, the R 1 in these both ends It is preferably an alkyl group, and from the industrial viewpoint, a methyl group is particularly preferable.
  • the component (A) has an oily property at room temperature, and the component (A) has a viscosity of 1 mPa ⁇ s or more at 25°C.
  • the viscosity of the component (A) at 25° C. is 1 mPa ⁇ s or more. , 100,000 mPa ⁇ s or less is preferable.
  • alkenyl group-containing organopolysiloxanes reduce or remove volatile or low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5), etc.) from the viewpoint of preventing contact failures.
  • octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5), etc. from the viewpoint of preventing contact failures.
  • the degree can be designed as desired, but it may be less than 1% by mass of the entire component (A) and less than 0.1% by mass for each siloxane oligomer, and if necessary, reduced to near the detection limit by gas chromatography. You may.
  • the component (B) is a straight-chain organohydrogenpolysiloxane having silicon-bonded hydrogen atoms only at both ends of the molecular chain, and mainly functions as a chain extender of the component (A) in the hydrosilylation reaction and cures. It is a component that improves the elongation and flexibility of the reaction product (adhesive layer).
  • a molecule is added to a curing reaction product obtained by curing the composition. Since the structure having a stretched chain length is contained in a certain amount or more, the adhesiveness and the holding force as the elastic adhesive member are remarkably improved.
  • the component (B) may be a polyorganosiloxane containing SiH groups at both ends of the molecular chain represented by the formula below.
  • R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms excluding an alkenyl group.
  • n is a number in the range of 0 to 50.
  • the monovalent hydrocarbon group having 1 to 10 carbon atoms bonded to a silicon atom other than the alkenyl group include, for example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group; Aryl groups such as phenyl, tolyl, xylyl, naphthyl, etc.; Aralkyl groups such as benzyl, phenethyl, etc.; Halogenation of chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. Examples thereof include an alkyl group, and a methyl group and a phenyl group are particularly preferable.
  • component (B) examples include, for example, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and dimethylhydrogensiloxy groups at both ends of the molecular chain.
  • dimethylhydrogensiloxy group-blocked dimethylsiloxane/methylphenylsiloxane copolymers at both molecular chain ends dimethylhydrogensiloxy group-blocked dimethylsiloxane/diphenylsiloxane copolymers at both molecular chain ends and organopolysiloxanes thereof
  • a mixture of two or more kinds is exemplified.
  • the component (B) the following organopolysiloxanes are also exemplified.
  • Me and Ph respectively represent a methyl group and a phenyl group
  • m2 is an integer of 1 to 100
  • n2 is an integer of 1 to 50.
  • these components (B) are obtained by reducing or removing volatile or low molecular weight siloxane oligomers (octamethyltetrasiloxane (D4), decamethylpentasiloxane (D5), etc.). Is preferred.
  • the degree can be designed as desired, but it may be less than 1% by mass of the entire component (B) and less than 0.1% by mass for each siloxane oligomer, and may be reduced to near the detection limit, if necessary. ..
  • the content of silicon-bonded hydrogen atoms in the component (B) is not particularly limited, but from the viewpoint of the technical effect of the present invention, the H content in the SiH group is 0.01 to 3.
  • the range of 0 mass% is preferable, and the range of 0.05 to 2.00 mass% is particularly preferable.
  • the component (B) is a linear siloxane having a silicon-bonded hydrogen atom capable of performing a hydrosilylation reaction only at both ends of the molecular chain, and functions as a chain extender in the cured product to extend the cured product. And improve flexibility.
  • the technical effect is the ratio of the number of moles of silicon-bonded hydrogen atoms in the component (B) to the number of moles of an aliphatic unsaturated carbon-carbon bond-containing group such as an alkenyl group in the component (A) (substance ratio).
  • the component (C) is an organopolysiloxane resin, which is a tackifying component that imparts an adhesive force to a base material, and the amount of the component used reduces the adhesive force and pressure-sensitive adhesive performance of the cured product of the present composition. It is possible to adjust from tackiness to strong tackiness.
  • the component (C) is a siloxane unit (M unit) represented by (a) R 3 SiO 1/2 (wherein R independently represents a monovalent organic group) in the molecule, and ( b) An organopolysiloxane resin containing a siloxane unit (Q unit) represented by SiO 4/2 .
  • the molar ratio of M units to Q units is preferably 0.5 to 2.0 (M units/Q units). This is because when the molar ratio is less than 0.5, the adhesive force to the substrate may decrease, and when it is more than 2.0, the cohesive force of the substance forming the adhesive layer decreases.
  • the range of 1.00 to 1.20:1.00 is more preferable, and the range of 0.60:1.00 to 1.10:1.00 is even more preferable.
  • the above molar ratio can be easily measured by 29 Si nuclear magnetic resonance.
  • the component (C) may be composed of only (a) M units and (b) Q units, but R 2 SiO 2/2 units (D units) and/or RSiO 3/2 units (T units). May be included.
  • R's each independently represent a monovalent organic group.
  • the total content of (a) M units and (b) Q units in the component (C) is preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight.
  • the monovalent organic group is not particularly limited, and can be divided into, for example, an aliphatic unsaturated carbon-carbon bond-containing group and an aliphatic unsaturated carbon-carbon bond-free group, (C)
  • the monovalent organic groups of the components can each independently be either.
  • the aliphatic unsaturated carbon-carbon bond-containing group and the aliphatic unsaturated carbon-carbon bond-free group respectively include a monovalent unsaturated hydrocarbon group and an oxygen atom-containing monovalent unsaturated hydrocarbon group, and A monovalent saturated hydrocarbon group and an oxygen atom-containing monovalent saturated hydrocarbon group are included.
  • the monounsaturated or saturated hydrocarbon group is, for example, a substituted or unsubstituted one having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
  • Examples thereof include a valent unsaturated hydrocarbon group and a substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms.
  • Examples of the unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include vinyl group, allyl group and propenyl group. Examples thereof include alkenyl groups such as groups, butenyl groups, pentenyl groups and hexenyl groups. Examples of the substituted monounsaturated hydrocarbon group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms include, for example, these monovalent unsaturated hydrocarbon groups.
  • a group in which a part of the hydrogen atoms of the group is replaced by a halogen atom (fluorine, chlorine, bromine or iodine) and the like can be mentioned.
  • Examples of the unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, pentyl group, hexyl group and octyl group; cyclohexyl group, cycloheptyl group and the like. Examples thereof include a cycloalkyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group, ⁇ -methylstyryl group and 2-phenylethyl group.
  • substituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms for example, a part of hydrogen atoms of these monovalent unsaturated hydrocarbon groups is substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or the like. There are some.
  • fluorinated monovalent saturated hydrocarbon groups such as 3,3,3-trifluoropropyl group, 4,4,5,5,5-pentafluorobutyl group, 3,3,4,4,5 , 5,6,6,6-perfluoroalkyl groups such as nonafluorohexyl groups; chlorinated monovalent saturated hydrocarbon groups such as chloroalkyl groups such as 3-chloropropyl group, chlorophenyl groups such as dichlorophenyl group .
  • a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms is preferable.
  • a methyl group is preferable as the substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
  • a substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferable.
  • the substituted or unsubstituted alkenyl group having 2 to 12 carbon atoms is preferably vinyl group.
  • oxygen atom-containing monovalent unsaturated or saturated hydrocarbon group examples include, for example, substituted or unsubstituted oxygen atom-containing monovalent unsaturated hydrocarbon groups having 2 to 12 carbon atoms, and 1 to 12 carbon atoms. And a substituted or unsubstituted monovalent saturated hydrocarbon group containing an oxygen atom.
  • Examples of the substituted or unsubstituted monovalent unsaturated hydrocarbon group having 2 to 12 carbon atoms include an alkenyloxyalkyl group, an acryloxyalkyl group and a methacryloxyalkyl group.
  • Examples of the alkenyloxyalkyl group include allyloxymethyl group, 3-allyloxypropyl group and the like.
  • Examples of the acryloxyalkyl group include an acryloxymethyl group and a 3-acryloxypropyl group.
  • Examples of the methacryloxyalkyl group include a methacryloxymethyl group and a 3-methacryloxypropyl group.
  • the substituted or unsubstituted monovalent saturated hydrocarbon group having 1 to 12 carbon atoms includes, for example, an alkoxy group having 1 to 12 carbon atoms.
  • alkoxy group having 1 to 12 carbon atoms examples include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and the like.
  • the hydrolyzable group such as a hydroxyl group or an alkoxy group in the component (C) is directly bonded to a silicon atom such as a T unit or a Q unit among the siloxane units in the resin structure, and is derived from silane or silane as a raw material. Is a group generated as a result of hydrolysis, the content of the hydroxyl group or the hydrolyzable group can be reduced by subjecting the synthesized organopolysiloxane resin to a hydrolysis treatment with a silylating agent such as trimethylsilane.
  • a silylating agent such as trimethylsilane.
  • This may prevent the formation of an organopolysiloxane resin structure having a large molecular weight in the cured product, and may further improve the curability of the composition at low temperatures and the storage elastic modulus of the resulting pressure-sensitive adhesive layer. ..
  • At least a part of the component (C) is (C1) in the molecule (Alk)R′ 2 SiO 1/2 (wherein, Alk is independently of each other an aliphatic unsaturated carbon-carbon).
  • a siloxane unit (M unit) represented by a bond-containing group, R'independently of each other represents an aliphatic unsaturated carbon-carbon bond-free group, and a siloxane unit represented by SiO 4/2 It may be a curing-reactive organopolysiloxane resin containing at least (Q units).
  • the aliphatic unsaturated carbon-carbon bond-containing group which is Alk is independently selected from the group consisting of the alkenyl group, the alkenyloxyalkyl group, the acryloxyalkyl group and the methacryloxyalkyl group described above. It is preferably a group.
  • the aliphatic unsaturated carbon-carbon bond-free group which is R′ is preferably a group independently selected from the group consisting of the alkyl group, the aryl group and the aralkyl group described above. Further, some of these groups may be substituted with a halogen atom or the like.
  • the aliphatic unsaturated carbon-carbon bond-containing group which is Alk may be a vinyl group, an allyl group or a hexenyl group, and the aliphatic unsaturated carbon-carbon bond-free group which is R'is It is preferable that they are independently a methyl group, a phenyl group or the like.
  • the component (C) when the component (C) other than the (C1) curing-reactive organopolysiloxane resin is present, the component (C) is preferably non-curing reactive.
  • R of the non-curing reactive component (C) is preferably an aliphatic unsaturated carbon-carbon bond-free group as described above, and more preferably an alkyl group, an aryl group or an aralkyl group. preferable. Further, some of these groups may be substituted with a halogen atom or the like. From an industrial point of view, it is preferable that the aliphatic unsaturated carbon-carbon bond-free group which is R is independently a methyl group, a phenyl group or the like.
  • the proportion of the (C1) curing-reactive organopolysiloxane resin in the component (C) is not particularly limited, but the composition of the present invention or a cured product thereof has an appropriate hardness as a pressure-sensitive adhesive. Therefore, when the total amount of the component (C) is 100% by mass, 50% by weight or less of the component (C) is preferable, 30% by weight or less is more preferable, and 20% by weight or less is even more preferable.
  • the content of the component (C1) in the component (C) is preferably in the range of 0 to 20% by mass, particularly preferably in the range of 0 to 15% by mass, and the composition of the present invention or a cured product thereof.
  • the pressure-sensitive adhesive composed of can have appropriate hardness and flexibility as an adhesive layer for display devices, solar cell modules, and the like.
  • a resin also referred to as MQ resin
  • a component (C) for example, (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (SiO 4/2 ) 0.60 (HO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.52 (SiO 4/2 ) 0.48 (HO 1/2 ) 0.01 (Me 3 SiO 1/2 ) 0.40 (Me 2 ViSiO 1/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.55 (MeO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.25 (Me 2 PhSiO 1/2 ) 0.20 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 ) 0.40 (Me 2 SiO 2/2 ) 0.05 (SiO 4/2 ) 0.55 (HO 1/2 ) 0.05 (Me 3 SiO 1/2 )
  • the total of the subscripts of the silicon atom-containing unit (The quantity is 1, and the subscript of (HO) 1/2 unit indicates the relative quantity.) Can be mentioned. From the standpoint of preventing contact failure, the low molecular weight siloxane oligomer in the component (C) may be reduced or removed.
  • the amount of the component (A) to (D) in the composition is 100 parts by mass in total. In that case, the range of 10 to 80 parts by mass is preferable. If the blending amount of the component (C) is less than the above lower limit, sufficient adhesive force may not be imparted to the silicone pressure-sensitive adhesive composition of the present invention. On the other hand, when the amount of the component (C) compounded exceeds the upper limit, the silicone pressure-sensitive adhesive composition of the present invention becomes too hard, and therefore may not be particularly suitable for use as a pressure-sensitive adhesive. However, when a slightly tacky composition design is required, the content of the component (C) may be suppressed to 10 parts by mass or less.
  • the component (D) is an organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in one molecule, and in the hydrosilylation reaction with the component (A)/the component (D). Is a component that functions as a cross-linking agent and adjusts the hardness of the cured product according to the amount of addition. Generally, three silicon-bonded hydrogen atoms are bonded to different silicon atoms.
  • Such a component (D) includes (D1) a cyclic organohydrogenpolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule and (D2) a silicon-bonded hydrogen atom at the end of the molecular chain, It may be at least one selected from the group consisting of linear or branched organohydrogenpolysiloxanes having at least 3 silicon-bonded hydrogen atoms. Further, the component (D) may be a mixture of two or more kinds of organohydrogenpolysiloxanes belonging to only one of the categories of the component (D1) or the component (D2).
  • the cyclic organohydrogenpolysiloxane which is the component (D1) has, for example, the following formula: [(R 3 HSiO) m3 (R 3 2 SiO) m4 ] It is represented by.
  • m3+m4 is a number in the range of 3 to 20
  • m3 is a number of 3 or more
  • m4 is a number of 0 or more.
  • R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms excluding an alkenyl group, and the same groups as R 2 can be exemplified, and preferably a group independently selected from a methyl group and a phenyl group. ..
  • the siloxane polymerization degree is in the range of 5 to 500, preferably in the range of 5 to 200.
  • 1,3,5,7-tetramethylcyclotetrasiloxane tris(dimethylhydrogensiloxy)methylsilane, tris(dimethylhydrogensiloxy)phenylsilane, 1-(3-gly Sidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-di(3-glycidoxypropyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1-( 3-Glycidoxypropyl)-5-trimethoxysilylethyl-1,3,5,7-tetramethylcyclotetrasiloxane, both ends of the molecular chain trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends of the molecular chain trimethylsiloxy group Blocked dimethyl siloxane/methyl hydrogen siloxane copolymer, molecular chain both ends trimethylsiloxy group blocked methyl hydrogen si
  • the composition of the present invention has, in addition to the SiH/Vi ratio of the component (B) and the component (A), the number of moles of silicon-bonded hydrogen atoms in the component (B) and the component (D) in the entire composition and (A). It is necessary that the ratio (substance amount ratio) to the number of moles of the aliphatic unsaturated carbon-carbon bond-containing group such as the alkenyl group in the component) is in the range of 0.95 to 1.35.
  • the overall crosslink density is appropriately adjusted, the elongation and viscoelasticity are excellent in relation to the component (B), and the appropriate hardness is obtained in relation to the component (D).
  • An adhesive layer having a surface tack within a suitable range can be realized. If the SiH/Vi ratio (the number of moles of silicon-bonded hydrogen atoms/the number of moles of aliphatic unsaturated carbon-carbon bond-containing group) is less than the lower limit, it may cause adhesive residue and the like. Power may be insufficient.
  • the solventless or low solvent type silicone pressure-sensitive adhesive composition according to the present invention contains a hydrosilylation reaction catalyst.
  • the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferable because they can significantly accelerate the curing of the composition. Examples of the platinum-based catalyst include fine powder of platinum, chloroplatinic acid, alcoholic solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, platinum-carbonyl complex, and platinum-alkenylsiloxane complex is particularly preferable. ..
  • the alkenyl siloxane includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Alkenyl siloxanes in which some of the methyl groups of these alkenyl siloxanes are substituted with groups selected from the group consisting of nitriles, amides, dioxolanes, and sulfolanes, ethyl groups, phenyl groups, etc., and vinyls of these alkenyl siloxanes.
  • alkenylsiloxanes examples thereof include alkenylsiloxanes in which the group is substituted with an allyl group, a hexenyl group and the like.
  • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable because the stability of this platinum-alkenylsiloxane complex is good, and it is added in the form of an alkenylsiloxane solution.
  • these hydrosilylation reaction catalysts are catalysts dispersed or encapsulated in a thermoplastic resin such as silicone resin, polycarbonate resin, and acrylic resin.
  • thermoplastic resin fine particle containing a hydrosilylation reaction catalyst may be a thermoplastic resin fine particle containing a hydrosilylation reaction catalyst, particularly a thermoplastic resin fine particle containing a platinum-containing hydrosilylation reaction catalyst.
  • a non-platinum-based metal catalyst such as iron, ruthenium, or iron/cobalt may be used as the catalyst for promoting the hydrosilylation reaction.
  • the content of the hydrosilylation reaction catalyst is not particularly limited, but the amount of the above-mentioned metal, particularly the platinum-based metal is in the range of 0.1 to 200 pm with respect to the total amount of the solid content in the composition.
  • the range may be 0.1 to 150 ppm, 0.1 to 100 ppm, or 0.1 to 50 ppm.
  • the platinum-based metal is a metal element of Group VIII consisting of platinum, rhodium, palladium, ruthenium, and iridium, but in practice, the content of the platinum-based metal excluding the ligand of the hydrosilylation reaction catalyst is above. It is preferably in the range.
  • the solid content means a component (mainly a main component, an adhesion-imparting component, a cross-linking agent, a catalyst and other non-volatile components) which forms a cured layer when the silicone pressure-sensitive adhesive composition according to the present invention is subjected to a curing reaction. ), and does not include volatile components such as a solvent that volatilizes during heat curing and in some cases after heat curing.
  • the content of the platinum-based metal in the silicone pressure-sensitive adhesive composition according to the present invention is 50 ppm or less (45 ppm or less, 35 ppm or less, 30 ppm or less, 25 ppm or less or 20 ppm or less), after curing, heating, ultraviolet rays, etc.
  • the content of the platinum-based metal is 0.1 ppm or more, and if it is less than the lower limit, it may cause curing failure.
  • the component (F) is a curing retarder, which suppresses the cross-linking reaction between the aliphatic unsaturated carbon-carbon bond-containing group and the silicon-bonded hydrogen atom in the composition, prolongs the pot life at room temperature, and preserves it. It is added to improve stability.
  • the curing retarder is preferably used when it is desired to extend the pot life of the curable silicone pressure-sensitive adhesive composition of the present invention. In particular, in practical use, it is generally preferable to use a curing retarder in the solventless or low solvent type silicone pressure-sensitive adhesive composition of the present invention.
  • component (F) examples include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, oxime compounds, and phosphorus compounds.
  • the silicone pressure-sensitive adhesive composition of the present invention has a viscosity increase of 1.5 times or less after 8 hours at room temperature after preparation of the composition and can be cured at 80 to 200° C. Is preferred.
  • the suppression of thickening is important from the viewpoint of handling workability, pot life, and characteristics after curing, and it is possible to secure curability by curing at a certain temperature (80 to 200°C). This is because it can be done.
  • such a composition can be realized by selecting a suitable combination and blending amount of each of the above components and the hydrosilylation catalyst and the component (F).
  • the silicone pressure-sensitive adhesive composition according to the present invention has a relatively low viscosity as its constituent components, it is possible to design a composition of a low solvent type or a solventless type, and the content of the organic solvent is small or substantially. Even if the composition does not contain an organic solvent, practically sufficient coatability can be realized. Specifically, the content of the organic solvent is less than 20% by mass, less than 15% by mass, and it is particularly preferable that the content of the organic solvent is substantially in the range of 0 to 5% by mass.
  • a small amount of the organic solvent is used within the above-mentioned range. It is possible to include.
  • the type and blending amount of the organic solvent are adjusted in consideration of coating workability, etc., but the amount of the organic solvent used is as small as possible from the viewpoint of the composition design of the solventless or low solvent type silicone pressure sensitive adhesive.
  • organic solvent examples include aromatic hydrocarbon solvents such as toluene, xylene and benzene, aliphatic hydrocarbon solvents such as heptane, hexane, octane and isoparaffin, ester solvents such as ethyl acetate and isobutyl acetate, and diisoproprone.
  • aromatic hydrocarbon solvents such as toluene, xylene and benzene
  • aliphatic hydrocarbon solvents such as heptane, hexane, octane and isoparaffin
  • ester solvents such as ethyl acetate and isobutyl acetate
  • diisoproprone examples include ethers, ether solvents such as 1,4-dioxane, chlorinated aliphatic hydrocarbon solvents such as trichloroethylene, perchloroethylene, and methylene chloride, solvent volatile oils, etc., and at least one selected from these is used
  • the silicone pressure-sensitive adhesive composition according to the present invention can optionally contain components other than the above components as long as the technical effects of the present invention are not impaired.
  • adhesion promoters such as polydimethylsiloxane or polydimethyldiphenylsiloxane
  • antioxidants such as phenol-based, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based, or thioether-based Agents: light stabilizers such as triazole-based or benzophenone-based; flame retardants such as phosphate-based, halogen-based, phosphorus-based, or antimony-based; cationic surfactants, anionic surfactants, or nonionic surfactants
  • antistatic agents such as agents may be included.
  • the silicone pressure-sensitive adhesive composition according to the present invention includes a polydimethylsiloxane or polydimethyldiphenylsiloxane containing neither a reactive group containing a carbon-carbon double bond such as an alkenyl group, an acrylic group, a methacrylic group, nor a silicon-bonded hydrogen atom. It is possible to blend a non-reactive organopolysiloxane such as, and to improve the loss coefficient (tan ⁇ ), storage elastic modulus (G′) and loss elastic modulus (G′′) of the pressure-sensitive adhesive layer described later. You may be able to. For example, the use of hydroxyl terminated polydimethylsiloxane or polydimethyldiphenylsiloxane can increase the loss factor of the pressure sensitive adhesive layer and such compositions are within the scope of the present invention.
  • the silicone pressure-sensitive adhesive composition of the present invention has a viscosity of the entire composition at 25° C. in the range of 1,000 to 300,000 mPa ⁇ s, and a viscosity of the entire composition of 1,000 to 250,000 mPa ⁇ s.
  • the range is preferably.
  • the viscosity of the entire composition is preferably in the range of 1,000 to 100,000 mPa ⁇ s.
  • the method for preparing the silicone pressure-sensitive adhesive composition according to the present invention is not particularly limited, and it is carried out by uniformly mixing the respective components. If necessary, a small amount of the organic solvent may be added within the above-mentioned range, or the mixture may be prepared by mixing at a temperature of 0 to 200° C. using a known stirrer or kneader.
  • the organopolysiloxane composition of the present invention is applied on a substrate to form a coating film, and heated under a temperature condition of 80 to 200° C., preferably 90 to 190° C. To obtain a cured product.
  • the coating method include gravure coating, offset coating, offset gravure, roll coating, reverse roll coating, air knife coating, curtain coating, and comma coating.
  • the silicone pressure-sensitive adhesive composition of the present invention is characterized in that the cured layer obtained by curing the composition by a hydrosilylation reaction is pressure-sensitive adhesive. Since the pressure-sensitive adhesive layer of the present invention has the above-mentioned constitution and exhibits a sufficient adhesive force for practical use, it can be used by substituting a known silicone pressure-sensitive adhesive as desired.
  • a pressure-sensitive adhesive layer having a thickness of 40 ⁇ m obtained by curing the silicone pressure-sensitive adhesive composition of the present invention, with respect to a SUS base, using a 180° peeling test method according to JIS Z0237, a tensile speed of 300 mm It is possible to design a pressure-sensitive adhesive layer having an adhesive force measured by /min of 100 to 2500 gf/inch, and a pressure-sensitive adhesive layer of 500 to 2250 gf/inch is preferable.
  • the above-mentioned thickness (40 ⁇ m) is the thickness of the cured layer itself, which is a standard for objectively defining the adhesive strength of the cured layer according to the present invention, and the organopolysiloxane composition of the present invention has a thickness of 40 ⁇ m. Needless to say, it can be used as a hardened layer or a pressure-sensitive adhesive layer having an arbitrary thickness.
  • the cured product of the present invention can be used particularly as a pressure-sensitive adhesive layer. Further, in order to improve the adhesion to the adherend, the surface of the pressure-sensitive adhesive layer or the base material may be subjected to surface treatment such as primer treatment, corona treatment, etching treatment and plasma treatment. However, since the pressure-sensitive adhesive layer of the present invention has excellent adhesion to a substrate such as a display device as described above, these steps are added as necessary to further improve the adhesion to an adherend. It may be improved, and higher production efficiency may be realized by omitting these steps.
  • the silicone pressure-sensitive adhesive composition according to the present invention is applied to a release liner and then cured by heating under the above temperature conditions, and the release liner is peeled off to form a film-shaped substrate, a tape-shaped substrate, or After being attached to a sheet-shaped substrate (hereinafter referred to as "film-shaped substrate") or coated on the film-shaped substrate, it is cured by heating under the above temperature conditions, and the surface of the substrate is sensed.
  • a pressure-adhesive layer can be formed.
  • a cured layer obtained by curing the organopolysiloxane composition according to the present invention on these film-shaped substrates, particularly a laminate provided with a film-shaped pressure-sensitive adhesive layer is an adhesive tape, a plaster, a low-temperature support, It may be used for transfer films, labels, emblems and decorative or descriptive markings. Further, the cured layer obtained by curing the organopolysiloxane composition according to the present invention may be used for assembling automobile parts, toys, electronic circuits, or keyboards. Alternatively, a cured layer obtained by curing the organopolysiloxane composition according to the present invention, particularly a film-like pressure-sensitive adhesive layer, may be used for constructing a laminated touch screen or a flat panel display.
  • the types of base materials include paperboard, cardboard paper, clay coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin film sheet, natural fiber cloth, synthetic fiber cloth, artificial leather cloth, and metal foil.
  • synthetic resin films and sheets are preferable, and examples of synthetic resins include polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, cyclopolyolefin, and nylon (registered trademark).
  • a film of heat resistant synthetic resin such as polyimide, polyether ether ketone, polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamide imide, and polyether sulfone is suitable.
  • transparent materials such as polypropylene, polystyrene, polyvinylidene chloride, polycarbonate, polyethylene terephthalate, and PEN are suitable.
  • the base material is preferably in the form of a film or sheet.
  • the thickness is not particularly limited and can be designed to have a desired thickness depending on the application.
  • a support film that has been subjected to primer treatment, corona treatment, etching treatment, and plasma treatment may be used.
  • the surface of the film-shaped substrate opposite to the pressure-sensitive adhesive layer may be surface-treated such as scratch-proof, stain-proof, fingerprint-proof, anti-glare, anti-reflection and anti-static. ..
  • the coating amount of the silicone pressure-sensitive adhesive composition on the substrate can be designed to have a desired thickness according to the application such as a display device.
  • the thickness of the pressure-sensitive adhesive layer after curing is 1 ⁇ 1,000 ⁇ m, 5-900 ⁇ m, 10-800 ⁇ m, but not limited thereto.
  • the pressure-sensitive adhesive layer according to the present invention may be a single layer or a multi-layer formed by laminating two or more pressure-sensitive adhesive layers depending on the required characteristics.
  • the multi-layer pressure-sensitive adhesive layer may be formed by laminating pressure-sensitive adhesive films prepared one by one, and by coating the pressure-sensitive adhesive layer-forming organopolysiloxane composition on a film substrate having a release layer. The step of working and curing may be performed multiple times.
  • the pressure-sensitive adhesive layer according to the present invention is provided with a function as an adhesion or adhesion function between members and as another functional layer selected from a dielectric layer, a conductive layer, a heat dissipation layer, an insulating layer, a reinforcing layer and the like. Good.
  • the cured layer obtained by curing the solvent-free or low-solvent type silicone pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive layer, particularly a pressure-sensitive adhesive film
  • the cured layer has a release coating ability. It is preferable to handle it as a laminate film which is adhered in a peelable state on the film substrate provided with the release layer.
  • the release layer is sometimes called a release liner, a separator, a release layer or a release coating layer, and is preferably a release coating such as a silicone release agent, a fluorine release agent, an alkyd release agent, or a fluorosilicone release agent. It is a release layer having a function.
  • a pressure-sensitive adhesive layer is formed on the base material itself, which is made of a material that does not easily adhere to the pressure-sensitive adhesive layer of the present invention or the base material on which physical fine irregularities are formed on the base material surface. It may be formed. Particularly, in the laminate according to the present invention, it is preferable to use a release layer obtained by curing a curable fluorosilicone release agent as the release layer.
  • the cured product obtained by curing the solvent-free or low-solvent type silicone pressure-sensitive adhesive composition of the present invention has both viscoelasticity and adhesive force as described above, and therefore, as an elastic adhesive member, various electronic devices or electric It is useful as a member of a mechanical device.
  • the cured product according to the present invention may be transparent or opaque, but a film-shaped cured product, particularly a substantially transparent pressure-sensitive adhesive film, is suitable as a member for a display panel or a display, and particularly, It is particularly useful for so-called touch panel applications in which a device, particularly an electronic device, can be operated by touching the screen with a fingertip or the like.
  • the opaque elastic adhesive layer is not particularly required to be transparent, and is particularly useful for application of a film-like or sheet-like member used for a sensor, a speaker, an actuator, etc. for which the adhesive layer itself requires a certain stretchability or flexibility. Is.
  • the article containing the pressure-sensitive adhesive comprising the silicone pressure-sensitive adhesive composition of the present invention may be a pressure-sensitive adhesive tape, and is made from the above-mentioned synthetic resin film/sheet, metal foil, woven fabric, non-woven fabric, paper or other fiber product. It is characterized in that it is provided with the sheet-shaped member and the above-mentioned adhesive layer.
  • the type of such an adhesive tape is not particularly limited, and it is an insulating tape, a heat-resistant tape, a solder masking tape, a mica tape binder, a temporary fixing tape (including a temporary fixing tape such as a silicone rubber part), a splicing tape (In particular, a splicing tape for silicone release paper is included).
  • the pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition of the present invention can realize the same pressure-sensitive adhesive properties as those of the conventional silicone pressure-sensitive adhesive layer, and also has poor curing or curability. It is possible to improve the adhesion to a substrate such as a display device without causing the problem of deterioration of
  • the laminate of the present invention is a laminate having a pressure-sensitive adhesive layer formed by curing the above silicone pressure-sensitive adhesive composition on the above film-shaped substrate, and preferably these films
  • the strip-shaped substrate is provided with a release layer for the pressure-sensitive adhesive layer.
  • the sheet-shaped base material has at least one release layer, and the release layer is in contact with the pressure-sensitive adhesive layer.
  • the release agent contained in the release layer is not particularly limited, and examples thereof include a silicone release agent, a fluorine release agent, an alkyd release agent, and a fluorosilicone release agent as described above.
  • the laminate of the present invention may be capable of handling the pressure-sensitive adhesive layer separated from the film-shaped substrate alone, and may have two film-shaped substrates.
  • Film substrate A first release layer formed on the film substrate, A pressure-sensitive adhesive layer formed by applying and curing the above silicone pressure-sensitive adhesive composition on the release layer, and a second release layer laminated on the pressure-sensitive adhesive layer. Good.
  • the laminated body of the above-mentioned form has a pressure-sensitive adhesive layer obtained by, for example, applying the above silicone pressure-sensitive adhesive composition onto one release layer formed on a film-shaped substrate and curing it. May be formed, and another release layer may be laminated on the pressure-sensitive adhesive layer.
  • the laminate of the above-described form has, for example, the above silicone pressure-sensitive adhesive composition sandwiched between a first film-shaped base material and a second film-shaped base material, and while being heated, it is uniformly pressed by a press or a roll. It may be produced by molding the composition to a thickness and then curing the composition.
  • the first sheet base material may be provided with a first release layer, or the first sheet base material itself may be provided with a releasability.
  • the second sheet base material may be provided with a second release layer, or the second sheet base material itself may be provided with release properties.
  • the first sheet base material and/or the second sheet base material comprises the first release layer and/or the second release layer
  • the pressure-sensitive adhesive layer is the first release layer and/or the second release layer. It is preferred to contact the release layer.
  • the releasable sheet base material examples include a sheet base material made of a releasable material such as a fluororesin film, or a non-removable or low releasable material such as a polyolefin film such as silicone or fluororesin.
  • the sheet base material examples include a release agent added.
  • examples of the sheet substrate having a release layer include a polyolefin film coated with a release agent such as silicone and fluororesin.
  • the laminate of the present invention can be used, for example, by applying the pressure-sensitive adhesive layer to an adherend and then peeling the pressure-sensitive adhesive layer from the film-shaped substrate adhered to the adherend.
  • the thickness of the pressure-sensitive adhesive layer is preferably 5 to 10000 ⁇ m, more preferably 10 ⁇ m or more or 8000 ⁇ m or less, and particularly preferably 20 ⁇ m or more or 5000 ⁇ m.
  • Disposable panel or display member The cured product obtained by curing the composition of the present invention can be used for the construction of a laminated touch screen or a flat panel display, and its specific usage is as follows. A known method of using the pressure-sensitive adhesive)) can be used without particular limitation.
  • a cured product obtained by curing the composition of the present invention is an optically transparent silicone pressure-sensitive adhesive film or pressure-sensitive adhesive disclosed in the above-mentioned JP-A-2014-522436 or JP-A-2013-512326.
  • a layer it can be used for manufacturing a display device such as a touch panel.
  • the cured product obtained by curing the composition of the present invention can be used as the adhesive layer or the adhesive film described in JP-A-2013-512326 without any particular limitation.
  • the touch panel according to the present invention is a substrate such as a conductive plastic film having a conductive layer formed on one surface thereof, and the present invention attached to the surface on which the conductive layer is formed or the opposite surface thereof. It may be a touch panel including a cured layer formed by curing the composition of.
  • the substrate is preferably a sheet-shaped or film-shaped substrate, and a resin film or a glass plate is exemplified.
  • the base material on which the conductive layer is formed may be a resin film or a glass plate having an ITO layer formed on one surface, particularly a polyethylene terephthalate film.
  • the cured product obtained by curing the silicone pressure-sensitive adhesive composition of the present invention may be used as an adhesive film for a polarizing plate used for manufacturing a display device such as a touch panel, and is described in JP 2013-065009 A. It may be used as a pressure-sensitive adhesive layer used for bonding between the touch panel and the display module.
  • silicone pressure-sensitive adhesive composition of the present invention and the cured product obtained by curing the same is not limited to the above-mentioned ones, and a composition comprising the cured product obtained by curing the composition.
  • Pressure-adhesive films are TV receivers, computer monitors, personal digital assistant monitors, surveillance monitors, video cameras, digital cameras, mobile phones, personal digital assistants, instrument panel displays for automobiles, and various equipment, devices and equipment. It can be used for various display devices for displaying characters, symbols, and images, such as an instrument panel display, an automatic ticket vending machine, an automatic teller machine, an in-vehicle display device, and an in-vehicle transmissive screen.
  • the surface shape of such a display device may be a curved surface shape or a curved shape instead of a flat surface, and in addition to various flat panel displays (FPD), a curved surface display used for automobiles (including electric vehicles) and aircrafts.
  • FPD flat panel displays
  • a curved surface display used for automobiles (including electric vehicles) and aircrafts Alternatively, a curved transmission screen is exemplified.
  • these display devices include various icons such as icons for executing functions or programs on screens and displays, notification displays such as e-mail programs, car navigation devices, membranes for speakers, audio devices, air conditioners, etc.
  • the operation buttons of the device may be displayed, and a touch panel function that enables input operation by touching these icons, notification display, and operation buttons with a finger may be added.
  • the device is a display device such as a CRT display, a liquid crystal display, a plasma display, an organic EL display, an inorganic EL display, an LED display, a surface electrolytic display (SED), a field emission display (FED), or a touch panel using these.
  • a cured product obtained by curing the composition is a film which is a member for a transducer such as a membrane for a speaker (including a sensor, a speaker, an actuator, and a generator) because it has excellent adhesiveness and viscoelasticity.
  • it can be used as a sheet-shaped member, and further can be used as a sealing layer or an adhesive layer used in a secondary battery, a fuel cell or a solar cell module.
  • the pressure-sensitive adhesive layer obtained by curing the silicone pressure-sensitive adhesive composition of the present invention may be substantially transparent, does not cause problems of poor curing and curability, and various display devices and the like.
  • Display device for vehicles that has excellent visibility and operability of display contents for a long period of time due to its excellent adhesion to the base material, and in particular, a display device for vehicles that has a curved screen or curved display and optionally has a touch panel function. It can be suitably used for devices.
  • JP-A-2017-047767, JP-A-2014-182335, JP-A-2014-063064, JP-A-2013-233852, etc. disclose a vehicle display device having a curved display surface.
  • the pressure-sensitive adhesive layer according to the present invention can be suitably applied or replaced as a part or all of the adhesive layer or the pressure-sensitive adhesive layer required to have transparency in these documents. Further, it is needless to say that the silicone pressure-sensitive adhesive composition of the present invention can be used also for other known curved display devices by replacing the currently used transparency-required adhesive layer or pressure-sensitive adhesive layer. In order to further utilize the advantages of the pressure-sensitive adhesive of the present invention, it is preferable to adjust the design of the display device and the member thickness by a known method.
  • the transparent film-like substrate provided with the pressure-sensitive adhesive layer of the present invention is used for the purpose of preventing scratches on the display surface, stains, fingerprints, antistatic, antireflection, peep prevention, etc. You may.
  • silicone pressure-sensitive adhesive composition (Preparation of silicone pressure sensitive adhesive composition) Using the components shown in Table 1 (Examples 1 to 11) and Table 2 (Comparative Examples 1 to 3), silicone pressure-sensitive adhesive compositions shown in Examples and Comparative Examples were prepared. All% in Tables 1 and 2 are% by mass. In each component, Me represents a methyl group and Vi represents a vinyl group. Further, the composition is a substantially solvent-free composition.
  • Adhesive strength (measurement in 20 mm width is indicated in gf unit in gf at a tensile speed of 300 mm/min using a 180° peeling test method according to JIS Z0237 using an RTC-1210 tensile tester manufactured by Orientec Co., Ltd. /Converted to inches).
  • the silicone pressure-sensitive adhesive composition was applied onto a polyimide resin film so as to have a thickness of 40 ⁇ m, and then dried at 150° C. for 3 minutes to prepare an adhesive film.
  • the pressure-sensitive adhesive surface side was attached to a SUS plate, a 200 g weight was hung on the bottom of the SUS plate, and aged in an oven at 200° C. for 30 minutes. The distance that the SUS plate was moving relative to the polyimide resin film after aging was measured.
  • the viscosity (mPa ⁇ s) is a value measured using a rotational viscometer according to JIS K7117-1, and the kinematic viscosity (mm 2 /s) is measured with an Ubbelohde viscometer according to JIS Z8803. It is a value.
  • Table 1 shows the materials of the solventless silicone pressure-sensitive adhesive composition.
  • the viscosity of each component was measured at room temperature (25°C) by the following method. [viscosity]
  • the viscosity (mPa ⁇ s) is a value measured using a rotational viscometer according to JIS K7117-1.
  • the following silicone was used as each component in Table 1.
  • a component obtained by adding the xylene solution of the silicone resin of the component (C) to a mixture of the components (A) and (B) in advance and distilling off the xylene under reduced pressure was used.
  • Alkenyl group-containing polysiloxane represented by the following formula (vinyl group content: 6.3% by mass)
  • SiH group-containing polysiloxane represented by the following formula (silicon atom-bonded hydrogen atom content: 0.124% by mass)
  • (C1 component) MQ silicone resin consisting of (CH 3 ) 3 SiO 1/2 unit, SiO 4/2 unit and hydroxyl group, polystyrene conversion weight average molecular weight (Mw) 6500, OH content 4.5 mol% (1.0% by mass) , Xylene solution (solid content 70% by mass)
  • D2 component Dimethylsiloxane-methylhydrogensiloxane copolymer having both ends of the molecular chain blocked with trimethylsiloxy groups, silicon atom-bonded hydrogen atom content 0.70% by mass
  • D3 component Dimethylsiloxane/methylhydrogensiloxane copolymer having both ends of the molecular chain blocked with trimethylsiloxy groups, weight average molecular weight (Mw) of 1600 in terms of polystyrene, silicon atom-bonded hydrogen atom content of 0.73 mass%
  • the silicone pressure-sensitive adhesive compositions according to Examples 1 to 11 are substantially solventless, but have a practically applicable viscosity range, and the curability and tackiness of the resulting pressure-sensitive adhesive layers. The characteristics were sufficiently excellent in practical use.
  • Comparative Examples 1 and 2 in which the SiH/Vi ratio to the component (B) was less than the lower limit of the present invention, adhesive residue was generated on the adherend of the cured product.
  • Comparative Example 3 in which the SiH/Vi ratio of the entire composition exceeds the upper limit of the present invention, sufficient adhesive strength could not be realized.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne : une composition adhésive de silicone autocollante qui a une viscosité qui rend la composition applicable même lorsqu'elle ne contient sensiblement pas de solvant, et qui présente une excellente aptitude au durcissement et forme des couches adhésives autocollantes ayant des propriétés adhésives satisfaisantes; et une utilisation de la composition adhésive de silicone autocollante. La présente invention concerne une composition adhésive de silicone autocollante qui comprend (A) un organopolysiloxane à chaîne qui comprend un groupe contenant une liaison carbone-carbone insaturée aliphatique et a un degré de polymérisation de siloxane dans la plage de 5 à 250, (B) un organohydrogénopolysiloxane linéaire ayant des atomes d'hydrogène liés au silicium uniquement au niveau des deux extrémités de la chaîne moléculaire, (C) une résine d'organopolysiloxane, et (D) un organohydrogénopolysiloxane ayant au moins trois atomes d'hydrogène liés au silicium dans la molécule, le rapport SiH/Vi sur les groupes SiH contenus dans l'ingrédient (B) se trouvant dans la plage de 0,90 à 1,30, et le rapport de SiH/Vi sur les groupes SiH contenus dans la somme de l'ingrédient (B) et de l' ingrédient (D) se trouvant dans la plage de 0,95 à 1,35. La composition adhésive de silicone autocollante a une viscosité dans la plage de 1 000 à 300 000 mPa·s et une teneur en solvant organique inférieure à 20 % en masse de la composition totale.
PCT/JP2019/047623 2018-12-13 2019-12-05 Composition adhésive de silicone autocollante et utilisation associée Ceased WO2020121939A1 (fr)

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KR1020217021499A KR102782399B1 (ko) 2018-12-13 2019-12-05 실리콘 감압 접착제 조성물 및 그의 용도
CN201980089314.4A CN113302255A (zh) 2018-12-13 2019-12-05 有机硅压敏粘接剂组合物及其用途

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WO2022138345A1 (fr) 2020-12-25 2022-06-30 ダウ・東レ株式会社 Composition adhésive à base de silicones et son utilisation
CN116134093A (zh) * 2020-06-30 2023-05-16 陶氏东丽株式会社 固化性有机硅组合物及其固化物
JP2023080393A (ja) * 2021-11-30 2023-06-09 アイカ工業株式会社 難接着物対応シリコーン系粘着剤組成物
WO2024075661A1 (fr) * 2022-10-05 2024-04-11 ダウ・東レ株式会社 Composition d'organopolysiloxane duricssable pour transducteur, objet durci associé, et transducteur, ou similaire, équipé de cet objet durci

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CN114921192B (zh) * 2022-06-24 2023-03-21 江西昊泽光学膜科技有限公司 一种用于锂电池胶带的有机硅压敏胶及其制备工艺
CN116063979A (zh) * 2023-01-09 2023-05-05 太仓斯迪克新材料科技有限公司 加成型抗静电抗缓冲高粘附有机硅压敏胶及其制备方法

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CN116134093A (zh) * 2020-06-30 2023-05-16 陶氏东丽株式会社 固化性有机硅组合物及其固化物
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