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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—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
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular 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
  • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2483/00—Presence of polysiloxane
  • C09J2483/003—Presence of polysiloxane in the primer coating

Definitions

• the present invention relates to a primer composition for a silicone pressure-sensitive adhesive.
• Adhesive labels and adhesive tapes are used by applying an adhesive to the base material and then curing it, and are used in various industrial situations. Paper, plastic film, and the like are used as the base material, and adhesive labels and the like on the paper base material are indispensable for identifying products in stores and can be seen in every scene of daily life.
• the adhesive material there are rubber type, acrylic type, silicone type, etc., but among these, the silicone type is considered to have the best durability. Specifically, heat resistance, cold resistance, weather resistance, chemical resistance, electrical insulation, and the like are good, and a silicone adhesive is used in cases where these characteristics are required. Although it is expensive compared to other organic adhesives, it is used as a material for industrial high-performance adhesive products that cannot be handled by their performance.
• silicone due to the structure of the material, silicone has excellent wettability to the surface, and has the feature that it is difficult for air bubbles to get caught when it is attached. Taking advantage of this feature, it has recently been used as an adhesive for adhesive films that protect displays such as mobile phones. In addition, since smartphones and tablet terminals with a touch panel structure are liable to get dirty when a finger comes into direct contact with the screen, it is widely used to attach an antifouling coated film to the screen. Is increasing.
• silicone adhesives are often used with a plastic film as the base material.
• the plastic film has poorer adhesion to the resin to be coated than the paper base material. Poor adhesion causes problems such as set-off when wound with a roll, and the adhesive layer is transferred to the adherend when it is attached to the adherend and then peeled off after a lapse of time. I have something to do.
• the primer composition As for the primer composition, a material based on silicone and forming a cured film by heating has been proposed for a long time, and a condensed type using a base material having a silanol group or a base having an alkenyl group has been proposed. A type that cures by hydrosilylation with a hydrosilyl group-containing siloxane has been proposed (Patent Documents 1 to 4).
• condensation type primer when the silicone adhesive is an addition type, the primer effect may not be sufficiently exhibited in some compositions.
• addition type primer since the addition type primer has poor curability, there is a problem that silicone is transferred to the back surface when the primer-treated base material is wound up, and there is much room for improvement in any type.
• the present invention has been made to solve the above problems, and an object of the present invention is to provide a primer composition capable of improving the adhesion between a silicone pressure-sensitive adhesive and a substrate.
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond, which may be the same or different, and 100 ⁇ a ⁇ 10,000. is there.
• a primer composition for a silicone pressure-sensitive adhesive which comprises (C) 50 to 300 parts by mass of a silicon compound containing an alkenyl group-containing organic group, and (D) 0.1 to 10 parts by mass of a Lewis acid catalyst. provide.
• the primer composition for a silicone pressure-sensitive adhesive may further contain (E) an organic solvent in an amount of 0 to 10,000 parts by mass with respect to 100 parts by mass of the component (A).
• the component (C) is a silicon compound represented by the following general formula (2).
• R 2 b -Si- (OR 3 ) 4-b (2) (In the formula, R 2 is an alkenyl group-containing organic group independently, R 3 is an alkyl group having 1 to 5 carbon atoms independently, and b is 1, 2 or 3).
• the component (D) can be a metal catalyst.
• the primer composition for a silicone adhesive can be cured satisfactorily.
• the present invention also provides an article having a cured product of the above-mentioned primer composition for a silicone adhesive on one side or both sides of a base material.
• the present invention also provides an adhesive article having a cured product of a silicone adhesive on a surface (primer-treated surface) of the article having the cured product.
• the silicone pressure-sensitive adhesive is a hydrosilylation-curable pressure-sensitive adhesive.
• Such a silicone pressure-sensitive adhesive has more preferable adhesion between the silicone pressure-sensitive adhesive and the base material.
• the primer composition for a silicone pressure-sensitive adhesive of the present invention it is possible to provide an adhesive article using a silicone pressure-sensitive adhesive having good adhesion to a base material.
• the present inventor has made it difficult with the conventional condensation type primer composition by adding a silicon material having an alkenyl group to the condensation type primer composition. It has been found that the adhesion to the substrate can be significantly improved in a part of the composition of the additional type silicone pressure-sensitive adhesive, and the present invention has been made.
• It is a primer composition for a pressure-sensitive adhesive.
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond, which may be the same or different, and 100 ⁇ a ⁇ 10,000. is there.
• the primer composition for a silicone pressure-sensitive adhesive of the present invention contains (A) 100 parts by mass of a specific organopolysiloxane, and (B) 1 to 1 to an organohydrogenpolysiloxane having at least 3 Si—H groups in one molecule.
• a condensed primer composition containing 20 parts by mass, (C) 50 to 300 parts by mass of a silicon compound containing an alkenyl group-containing organic group, and (D) 0.1 to 10 parts by mass of a Lewis acid catalyst.
• the primer composition for a silicone pressure-sensitive adhesive may further contain other components such as (E) an organic solvent, if necessary.
• the primer composition of the present invention is intended to improve the adhesion to a base material by applying it to a base material and then applying a silicone pressure-sensitive adhesive on the base material.
• a silicone pressure-sensitive adhesive on the base material.
• each component constituting the composition of the present invention will be described.
• the component (A) is an organopolysiloxane represented by the following average composition formula (1).
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond, which may be the same or different, and 100 ⁇ a ⁇ 10,000. is there.
• R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated bond.
• an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cyclohexyl group or the like.
• a cycloalkyl group, an aryl group such as a phenyl group, or the like, and a part or all of the hydrogen atom bonded to the carbon atom of these groups may be substituted with a halogen atom or another group.
• a saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are particularly preferable.
• a in the formula (1) 100 ⁇ a ⁇ 10,000, preferably 200 ⁇ a ⁇ 8,000, and more preferably 500 ⁇ a ⁇ 6,000. If a is 100 or less, the cured film may become too hard to exert a sufficient primer effect, and if it is 10,000 or more, the reactivity deteriorates due to a decrease in molecular motility, and the film is sufficiently cured. There is a concern that the film cannot be formed well without progressing.
• (A) is usually produced by ring-opening polymerization of a cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane using a small amount of water and a catalyst to form a terminal silanol group, but after the polymerization, it is a raw material. Since it contains cyclic low-molecular-weight siloxane, it is preferable to use the one obtained by distilling off the cyclic low-molecular-weight siloxane while aerating the inert gas through the reaction product under heating and reduced pressure.
• a cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane
• Examples of the specific structure of (A) include, but are not limited to, those shown below.
• Me and Ph in the following formula indicate a methyl group and a phenyl group, respectively. (100 ⁇ c ⁇ 10,000, 100 ⁇ d + e ⁇ 10,000, 0 ⁇ e ⁇ 500)
• the component (B) is an organohydrogenpolysiloxane having at least 3 Si—H groups in one molecule, and is not particularly limited, but can be represented by, for example, the following average composition formula (3).
• R 4 f H g SiO (4-f-g) / 2 (3) (In the formula, R 4 independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, f> 0, g> 0, and 0 ⁇ f + g ⁇ 3).
• the monovalent hydrocarbon group having 1 to 10 carbon atoms R 4 for example, a methyl group, an ethyl group, a propyl group, an alkyl group such as butyl group, cycloalkyl groups such as cyclohexyl group, a vinyl group, an allyl group, hexenyl Examples thereof include an alkenyl group such as a group and an octenyl group, and an aryl group such as a phenyl group.
• a part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and trifluoromethyl groups, 3,3,3-trifluoropropyl groups and the like may be substituted. Illustrated. Of these, a saturated aliphatic group or aromatic group is preferable, and a methyl group and a phenyl group are more preferable.
• R 5 3 Si-O- (R 6 2 Si-O) h- (R 7 HSi-O) i -SiR 8 3 (4)
• R 5 and R 8 represent monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms
• R 6 and R 7 represent monovalent hydrocarbon groups having 1 to 10 carbon atoms
• h is 0.
• i is 3 ⁇ i ⁇ 80
• Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R 6 and R 7 include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group and an allyl group.
• Examples thereof include an alkenyl group such as a group, a hexenyl group and an octenyl group, and an aryl group such as a phenyl group.
• R 5 and R 8 are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms of R 5 and R 8 are the same as those described above.
• h is 0 ⁇ h ⁇ 100, preferably 0 ⁇ h ⁇ 80 or 0 ⁇ h ⁇ 80, i is 3 ⁇ i ⁇ 80, and 5 ⁇ i ⁇ 70 is preferable.
• the component (B) is usually produced by ring-opening polymerization of a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane and a Si—H-containing siloxane such as tetramethylcyclotetrasiloxane using an acid catalyst. Since it contains cyclic low-molecular-weight siloxane as a raw material after polymerization, it is preferable to use the one obtained by distilling it under heating and reduced pressure while allowing an inert gas to be aerated in the reaction product.
• a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane and a Si—H-containing siloxane such as tetramethylcyclotetrasiloxane
• an acid catalyst Since it contains cyclic low-molecular-weight siloxane as a raw material after polymerization, it is preferable to use the one obtained by distilling it under heating
• the blending amount of the component (B) is 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 1 part by mass, the composition may not be sufficiently cured, and if it is more than 20 parts by mass, the reaction point with the pressure-sensitive adhesive layer that is applied and cured on the cured film of the primer is If it is too much, the curability of the adhesive may be deteriorated.
• the component (C) is a silicon compound containing an alkenyl group-containing organic group, and is not particularly limited, but preferably, a compound represented by the following general formula (2) can be mentioned.
• R 2 b -Si- (OR 3 ) 4-b (2) (In the formula, R 2 is an alkenyl group-containing organic group independently, R 3 is an alkyl group having 1 to 5 carbon atoms independently, and b is 1, 2 or 3).
• R 2 is an alkenyl group-containing organic group, and the alkenyl group-containing organic group preferably has 2 to 10 carbon atoms, and examples thereof include an alkenyl group such as a vinyl group, an allyl group, a hexenyl group, and an octenyl group. ..
• R 3 is an alkyl group having 1 to 5 carbon atoms independently, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.
• a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
• the component (C) is 50 to 300 parts by mass, preferably 70 to 280 parts by mass, and more preferably 80 to 250 parts by mass with respect to 100 parts by mass of the component (A). If it is less than 50 parts by mass, the primer effect may not be sufficiently exhibited and the adhesion of the adhesive to the substrate may not be improved. If it is more than 300 parts by mass, it is applied onto the cured film of the primer and cured. If there are too many reaction points with the pressure-sensitive adhesive layer, the curability of the pressure-sensitive adhesive may deteriorate.
• Examples of the specific structure of the component (C) include those shown below, but are not limited thereto.
• Me and Et in the following formula indicate a methyl group and an ethyl group, respectively.
• the component (D) is a Lewis acid catalyst and functions as a curing catalyst.
• the component (D) can be a metal catalyst (metal compound catalyst).
• metal catalyst metal compound catalyst
• Various examples include tin compounds, aluminum compounds, titanium compounds, zirconium compounds, scandium compounds, vanadium compounds, iron compounds, cobalt compounds, nickel compounds, copper compounds, zinc compounds, lanthanum compounds, cerium compounds, etc.
• a metal compound is preferable, a tin compound, an aluminum compound, and a titanium compound are particularly preferable, and a tin compound is more preferable.
• halogenated compounds such as chlorides, bromides and iodides, nitrates, sulfates, carbonates, sulfonates, trifluoromethanesulfonates, carboxylates and the like are preferably used.
• the component (D) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A), and if it is less than 0.1 parts by mass, the composition may not be sufficiently cured, and the composition may not be sufficiently cured. If there are too many, the reaction site where the component (A) and the component (B) react excessively to form a chemical bond with the pressure-sensitive adhesive may be reduced, and a sufficient primer effect may not be obtained.
• component (D) examples include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin diacetate, tin octoate, aluminum chloride, aluminum acetylacetate, titanium acetylacetonate, tetraethoxytitanium and the like. However, it is not limited to these.
• an organic solvent may be used as the component (E) in order to lower the viscosity to improve workability or to improve the wettability when applied to a substrate.
• the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane and isoparaffin, and industrial gasoline (rubber volatile oil, etc.).
• Petroleum benzine such as solvent naphtha, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methylisobutylketone, diisobutylketone, acetonylacetone, cyclohexanone.
• hydrocarbon solvents such as solvent naphtha, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methylisobutylketone, diisobutylketone, acetonylacetone, cyclohexanone.
• Ketone solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate and other ester solvents, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,4- Ether-based solvents such as dioxane, solvents having an ester and ether moiety such as 2-methoxyethyl acetylate, 2-ethoxyethyl acetylate, propylene glycol monomethyl ether acetylate, 2-butoxyethyl acetylate, hexamethyldisiloxane, octa Siloxane-based solvents such as methyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris (trimethylsiloxy)
• the amount of the component (E) added is 0 to 10,000 parts by mass (more than 0 and 10,000 parts by mass or less) with respect to 100 parts by mass of the component (A), preferably 0 to 5,000 parts by mass. , More preferably 0 to 3,000 parts by mass. If it is 10,000 parts by mass or less, there is no possibility that the coatability is deteriorated.
• silicone pressure-sensitive adhesive used together with the primer composition of the present invention
• the silicone pressure-sensitive adhesive is not particularly limited, and examples thereof include those containing the components described below.
• a pressure-sensitive adhesive that cures by hydrosilylation is preferable.
• the silicone pressure-sensitive adhesive may be referred to as a "silicone pressure-sensitive adhesive composition”.
• the component (F) is an organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule.
• the component (F) is an organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule.
• R 9 is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different, and at least 2 of R 9 contains an alkenyl group-containing organic group having 2 to 10 carbon atoms.
• L is 2.
• the above integer, m is an integer of 1 or more, n and o are integers of 0 or more, and 50 ⁇ l + m + n + o ⁇ 12,000.
• R 9 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and two or more of them are alkenyl group-containing organic groups.
• the monovalent hydrocarbon group examples include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like.
• a part or all of the hydrogen atom bonded to the carbon atom of these groups may be substituted with a halogen atom or another group, and examples thereof include a trifluoromethyl group, a 3,3,3-trifluoropropyl group and the like. Will be done. Saturated aliphatic groups or aromatic groups are preferable, and methyl groups and phenyl groups are particularly preferable.
• the alkenyl group-containing organic group preferably has 2 to 10 carbon atoms, and examples thereof include an alkenyl group such as a vinyl group, an allyl group, a hexenyl group and an octenyl group, an acryloylpropyl group, an acryloylmethyl group and a methacryloylpropyl group.
• examples thereof include a cycloalkenylalkyl group such as an acryloylalkyl group and a methacryloylalkyl group, a cyclohexenylethyl group, and an alkenyloxyalkyl group such as a vinyloxypropyl group.
• vinyl groups are particularly preferred.
• the amount of the alkenyl group contained in (F) is 0.0005 to 0.05 mol, preferably 0.0006 to 0.04 mol, and 0.0007 to 0.03 mol per 100 g of the organopolysiloxane. Is more preferable. If it is 0.0005 mol or more, the crosslink density becomes small and the adhesive layer does not coagulate and break, and if it is 0.05 mol or less, the adhesive layer does not become too hard and appropriate adhesive strength and tack are obtained. Be done.
• l is an integer of 2 or more
• m is an integer of 1 or more
• n and o are integers of 0 or more
• the component (F) is usually produced by ring-opening polymerization of cyclic low-molecular-weight siloxane such as octamethylcyclotetrasiloxane using a catalyst, but after polymerization, it contains cyclic low-molecular-weight siloxane as a raw material. It is preferable to use the one obtained by distilling off the inert gas under heating and reduced pressure while aerating the inert gas through the reaction product.
• Examples of the component (F) include, but are not limited to, those represented by the following general formula.
• R 9-1 and R 9-2 examples include those exemplified in R 9 above. It should be noted that 48 ⁇ p ⁇ 11,998 is preferable, 1 ⁇ q ⁇ 1,000 is preferable, and 2 ⁇ q ⁇ 800 is more preferable.
• More specific component (F) includes, but is not limited to, those represented by the following general formula.
• Me, Vi, and Ph in the following formula represent a methyl group, a vinyl group, and a phenyl group, respectively.
• the component (G) is R 10 3 SiO 1/2 unit (in the formula, R 10 is a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl having 2 to 6 carbon atoms which does not independently have an aliphatic unsaturated bond.
• the molar ratio is 0.5 to 1.0, which contains 4/2 units of (R) and SiO 4/2 units and is represented by (R 10 3 SiO 1/2 units) / (SiO 4/2 units). It is a polyorganosiloxane. If the molar ratio is 0.5 or more, the adhesive strength and tack are not likely to decrease, and if it is 1.0 or less, the adhesive strength and holding power are not likely to decrease.
• the molar ratio is preferably 0.6 to 0.9.
• R 10 independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not independently have an aliphatic unsaturated bond, and is used as a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• An alkyl group having 2 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group, and an aryl group having 6 to 10 carbon atoms such as a phenyl group and a tolyl group are preferable.
• the alkenyl group having 2 to 6 carbon atoms a vinyl group, an allyl group, a butenyl group and the like are preferable.
• Component (G) may contain a silanol group or a hydrolyzable alkoxy group other than R 10, the content that becomes 0.01 to 4.0 mass% of the total mass of the component (G) It is preferably 0.05 to 3.5% by mass, more preferably 0.05 to 3.5% by mass. If the content is 0.01% by mass or more, the cohesive force of the pressure-sensitive adhesive is not likely to decrease, and if it is 4.0% by mass or less, the tack of the pressure-sensitive adhesive is not likely to decrease.
• the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a phenoxy group and the like, and a methoxy group is preferable when used.
• Two or more kinds of the component (G) may be used in combination. Further, if necessary, it is possible to contain R 10 2 SiO 2/2 unit and R 10 SiO 3/2 unit.
• the component (G) may be obtained by a condensation reaction in the presence of a catalyst. This is to react the hydrolyzable groups existing on the surface with each other, and is expected to have effects such as improvement of adhesive strength. It may be reacted at room temperature to reflux using an alkaline catalyst and neutralized if necessary. Further, this reaction may be carried out in the coexistence of the component (F).
• the alkaline catalyst examples include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Metal alkoxides such as sodium methoxydo and potassium butoxide; Organic metals such as butyl lithium; Potassium silanolate; Ammonia gas, aqueous ammonia, nitrogen compounds such as methylamine, trimethylamine and triethylamine, etc., but ammonia gas or aqueous ammonia preferable.
• the temperature of the condensation reaction may be from room temperature 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 that neutralizes the alkaline catalyst may be added, if necessary.
• the neutralizing agent include acid gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octyl 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 blending amount of the component (F) may be 100 to 30 parts by mass, the blending amount of the component (G) may be 70 to 0 parts by mass, and the component (G) may not be contained.
• the silicone pressure-sensitive adhesive composition also contains a compound similar to the above-mentioned component (B).
• the blending amount of the (B') component (polyorganohydrogensiloxane having three or more Si—H groups in one molecule) used in the silicone pressure-sensitive adhesive composition is (B') with respect to the alkenyl group in the (F) component.
• the molar ratio of Si—H groups (Si—H group / alkenyl group) in the component may be 0.5 to 30, and it is preferable to mix in the range of 1 to 25. If it is 0.5 or more, the crosslink density is sufficient and the adhesive properties are sufficiently obtained, and if it is 30 or less, the adhesive strength and tack are sufficient, and the pot life of the treatment bath is not shortened.
• the component (H) is a platinum group metal-based catalyst for hydrosilylating and adding the alkenyl group in the component (F) and the Si—H group in the component (B') to cure them, and the central metal is platinum.
• platinum examples include palladium, iridium, rhodium, osmium, ruthenium and the like, with platinum being preferred.
• the platinum catalyst include platinum chloride acid, an alcohol solution of platinum chloride acid, a reaction product of platinum chloride acid and alcohol, a reaction product of platinum chloride acid and an olefin compound, and a reaction product of platinum chloride acid and a vinyl group-containing siloxane. Examples thereof include a complex of platinum and a vinyl group-containing siloxane.
• the content of the component (H) is preferably such that the amount of metal is 1 to 500 ppm with respect to the total amount of the components (F), (G), and (B'), and more preferably 2 to 450 ppm. If it is 1 ppm or more, the reaction is sufficiently fast, the curing is sufficient, and various characteristics such as adhesive strength and holding power are sufficiently exhibited. If it is 500 ppm or less, the flexibility of the cured product will not be reduced.
• the component (I) is a control agent, which causes an addition reaction to start before heat curing when the silicone pressure-sensitive adhesive composition is prepared or applied to a base material, causing the treatment liquid to thicken or gel. It is added to prevent it from occurring.
• the reaction control agent is coordinated with a platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when it is heat-cured, the coordination is deviated and catalytic activity is exhibited. Any reaction control agent conventionally used in the addition reaction curable silicone composition can be used.
• Specific examples include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexin, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl -1,3-Divinyldisiloxane, maleic acid ester, adipic acid ester and the like can be mentioned.
• the blending amount of the component (I) is preferably 0.01 to 5 parts by mass, preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total of the components (F), (G) and (B'). More preferred. If it is 0.01 part by mass or more, the reaction can be sufficiently suppressed, the composition is not cured before the work, and if it is 5 parts by mass or less, the reaction is sufficiently fast and the curing is sufficient.
• the silicone pressure-sensitive adhesive containing the above When the silicone pressure-sensitive adhesive containing the above is highly viscous and difficult to handle, it can be diluted by using an appropriate organic solvent as the (E') component.
• the (E') organic solvent the same solvent as the above-mentioned component (E) can be used.
• the blending amount is 0 to 2,000 parts by mass, preferably 0 to 1,500 parts by mass, and more preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the component (F). If it is 2,000 parts by mass or less, the coatability does not deteriorate.
• the silicone pressure-sensitive adhesive composition can be prepared by uniformly mixing each of the above components. Generally, the silicone pressure-sensitive adhesive composition is used by uniformly mixing the catalyst immediately before use.
• the silicone pressure-sensitive adhesive composition may be applied to the substrate by using a known coating method, for example, a wire bar, a comma coater, a lip coater, a roll coater, a die coater, a knife coater, and a blade.
• a known coating method for example, a wire bar, a comma coater, a lip coater, a roll coater, a die coater, a knife coater, and a blade.
• Examples include coaters, rod coaters, kiss coaters, gravure coaters, screen coatings, immersion coatings, cast coatings and the like.
• the thickness of the adhesive layer after curing can be 1 to 500 ⁇ m, but this is not the case.
• heating may be performed at 80 to 180 ° C., particularly 100 to 160 ° C. for 10 seconds to 10 minutes, particularly 30 seconds to 8 minutes, but this is not the case.
• the primer composition for a silicone pressure-sensitive adhesive of the present invention is obtained by applying the primer composition for a silicone pressure-sensitive adhesive to at least one surface of a base material and curing the cured product of the primer composition for a silicone pressure-sensitive adhesive. It is possible to obtain an article having at least one side of the above. Then, by applying and curing the silicone adhesive on the surface (primer-treated surface) of the article having the cured product, the adhesive article having the cured product of the adhesive can be obtained.
• the silicone pressure-sensitive adhesive is preferably a hydrosilylation-curable pressure-sensitive adhesive.
• the primer composition for a silicone pressure-sensitive adhesive of the present invention is an article such as a surface-treated base material capable of improving the adhesion to the silicone pressure-sensitive adhesive by coating and curing the composition on the base material. Can be provided.
• the base material on which the above composition is applied is not particularly limited as long as it is a flat member such as a sheet, film, plate, woven fabric, or foil, and for example, paper, plastic film, glass, or metal is selected.
• the paper include high-quality paper, coated paper, art paper, glassin paper, polyethylene laminated paper, kraft paper and the like.
• Plastic films include polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate copolymer.
• Examples thereof include films, ethylene-vinyl alcohol copolymer films, triacetyl cellulose films, polyether ether ketone films, and polyphenylene sulfide films.
• the glass is not particularly limited in thickness and type, and may be chemically strengthened. Further, glass fiber can also be applied, and the glass fiber may be used alone or in combination with another resin. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, nickel foil and the like. When the above composition is coated and cured, and then a silicone adhesive is applied and used, a polyester film or a polyimide film is preferable.
• the coating method for the substrate of the composition may be a known coating method, for example, a wire bar, a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, and the like.
• Examples include rod coater, knife coater, gravure coater, screen coating, immersion coating, cast coating and the like.
• the amount of the composition applied to the substrate is preferably in the range of 0.1 to 2 g / m 2 in terms of solid content, particularly preferably in the range of 0.2 to 1.8 g / m 2 , and the curing conditions are 80 to 180. It may be heated at ° C., particularly 100 to 160 ° C. for 10 seconds to 10 minutes, particularly 30 seconds to 8 minutes, but this is not the case.
• an adhesive article having good adhesion to the base material By applying a silicone adhesive on the surface treated with the above composition and curing it, an adhesive article having good adhesion to the base material can be obtained.
• a silicone pressure-sensitive adhesive composition an addition-curing type organopolysiloxane composition that is cured by a platinum-based catalyst is preferable, and specifically, a composition containing the above-mentioned various components is preferably used.
• Me represents a methyl group
• Vi represents a vinyl group
• Et represents an ethyl group.
• the viscosity is a value at 25 ° C. measured by a rotational viscometer.
• the component (A) has a viscosity of 1,400 mPa ⁇ s when dissolved in toluene so as to have a concentration of 30% by mass, and is represented by the following formula (a-1) in which the molecular end is sealed with an OH group.
• a-1 100 parts by mass of dimethylpolysiloxane
• B 1 part by mass of polyorganohydrogensiloxane represented by the following average composition formula (b-1).
• Toluene was added as a component (E) in an amount of 1,900 parts by mass to prepare a silicone solution.
• a primer composition for a silicone pressure-sensitive adhesive was prepared by mixing 5 parts by mass of dioctyltin diacetate as a component (D).
• component (F) 35 parts by mass of polysiloxane represented by the following average composition formula (f-1) was added.
• component (G) Me 3 containing SiO 1/2 units and SiO 2 units, (Me 3 SiO 1/2 units) / methylpolysiloxane (g mole ratio of (SiO 2 units) of 0.85 -1) 65 parts by mass of the 60% by mass toluene solution as the non-volatile content,
• component (B') 0.35 parts by mass of methylhydrogenpolysiloxane represented by the above average composition formula (b-1), (I) 0.25 parts by mass of ethynylcyclohexanol as a component, 0.5 parts by mass of a toluene solution containing 0.5% by mass of the platinum content of the 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex as the component (H).
• Example 2 The procedure was the same as in Example 1 except that the component (c-1) (C-1) was 80 parts by mass.
• Example 3 The same procedure as in Example 1 was carried out except that the component (c-1) (C-1) was 200 parts by mass.
• Example 4 instead of the component (a-1) (a-1), the viscosity when dissolved in toluene so as to have a concentration of 30% by mass is 350 mPa ⁇ s, and the molecular end is sealed with an OH group according to the following formula.
• Y is a value that satisfies the above viscosity and satisfies 100 ⁇ Y ⁇ 10,000.
• Example 5 instead of the component (a-1) (a-1), the viscosity when dissolved in toluene so as to have a concentration of 30% by mass is 5,000 mPa ⁇ s, and the molecular end is sealed with an OH group as follows. The procedure was the same as in Example 1 except that the dimethylpolysiloxane (a-3) represented by the formula was used. (Z is a value that satisfies the above viscosity, and satisfies 100 ⁇ Z ⁇ 10,000.)
• Example 6 The same procedure as in Example 1 was carried out except that the silicon compound represented by the following formula (c-2) was used instead of the component (c-1).
• Example 7 The same procedure as in Example 1 was carried out except that the silicon compound represented by the following formula (c-3) was used instead of the component (c-1).
• Example 8 In the silicone pressure-sensitive adhesive composition, the component (F) (f-1) is 40 parts by mass, the component (G) (g-1) is 60 parts by mass, and the component (B') is (b-1). ) was 0.40 parts by mass in the same manner as in Example 1.
• Example 9 The component (F-1) in the silicone pressure-sensitive adhesive composition is 45 parts by mass, the component (G) is 55 parts by mass, and the component (B') is (b-1). ) was 0.45 parts by mass in the same manner as in Example 1.
• Example 10 instead of component (f-1) in the silicone pressure-sensitive adhesive composition, 35 parts by mass of polysiloxane represented by the following average composition formula (f-2) is component (G).
• component (G) 35 parts by mass of polysiloxane represented by the following average composition formula (f-2) is component (G).
• the Si—H group in the B') component is 5.6 times the molar ratio of the vinyl group in the (F) component).
• Example 11 It is a (G) component of the silicone pressure-sensitive adhesive composition (g-1) in place of, containing Me 3 SiO 1/2 units and SiO 2 units, (Me 3 SiO 1/2 units) / (SiO 2 The same as in Example 1 except that a 60 mass% toluene solution of methyl polysiloxane (g-2) having a molar ratio of (unit) of 0.76 was used as a non-volatile content in an amount of 65 parts by mass.
• Example 1 The same procedure as in Example 1 was carried out except that the component (c-1) (C) was not blended.
• Example 2 The same procedure as in Example 1 was carried out except that 100 parts by mass of the silicon compound represented by the following formula (c-4) was used instead of the component (c-1) (C-1).
• Example 3 The same procedure as in Example 1 was carried out except that 100 parts by mass of the silicon compound represented by the following formula (c-5) was used instead of the component (c-1) (C-1).
• the primer composition for silicone adhesive is coated on polyethylene terephthalate (PET) having a thickness of 25 ⁇ m and a width of 25 mm so that the solid content after curing is 0.5 g / m 2 using a wire bar at 120 ° C./30. Air dried in seconds.
• the silicone pressure-sensitive adhesive composition was applied onto the primer-treated surface of this base material using an applicator and cured at 130 ° C./1 minute, and 2 mm of the side of the obtained tape was cut. After that, it was torn and pulled from both sides, and it was visually confirmed whether or not the adhesive layer was lifted from the base material, and evaluated as follows. ⁇ : Does not rise ⁇ : Lifts
• the primer curability was sufficient, the primer effect was sufficiently exhibited, and the adhesion between the silicone adhesive and the base film was good. It was confirmed that the addition of the silicon compound having an alkenyl group as the component (C) was effective, because the alkenyl group was introduced into the primer and it reacted with the Si—H group in the silicone pressure-sensitive adhesive. It is presumed that good substrate adhesion was achieved.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

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