Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2312/00—Crosslinking
  • C08L2312/04—Crosslinking with phenolic resin

Definitions

• the present invention relates to an epoxy group-containing organopolysiloxane, an ultraviolet curable silicone composition using the same, and a cured film forming method.
• Dimethylorganopolysiloxane is widely used in all industrial fields because of its chemical characteristics.
• reactive group-containing organopolysiloxanes in which various reactive groups are introduced into this dimethylorganopolysiloxane are also widely used.
• the main use of this reactive group-containing organopolysiloxane is as a modifier for organic resins.
• the reactive group-containing organopolysiloxane and organic resin are reacted to form a siloxane chain in the organic resin through a chemical bond.
• Epoxy group-containing organopolysiloxane in which this reactive group is an epoxy group is one of them.
• Epoxy group-containing organopolysiloxanes are used in resin modifiers, plastic additives, fiber treatment agents and the like by taking advantage of the reactivity of epoxy groups.
• resin modifier effects such as lowering the stress of an epoxy resin as a semiconductor sealing material and improving moldability of a thermoplastic resin can be expected.
• the fiber treatment agent has a slimy feeling and gives a smooth and voluminous texture.
• it can be used in combination with an amino-modified silicone oil to impart smooth touch, rebound resilience and durability.
• epoxy group-containing organopolysiloxanes are also used as components of curing compositions and coating agents.
• an epoxy group-containing organopolysiloxane as a curing component of an epoxy resin composition using an acid anhydride-based curing agent, a highly durable and transparent cured product can be obtained.
• a sealing material for the optical semiconductor element of this type its use is being studied (Patent Document 1).
• Patent Documents 2 to 4 For coating applications, many curing methods have been proposed in which an organopolysiloxane containing an epoxy group is cured using an onium salt photoinitiator as a catalyst. This type of curing method has been used as various coating agents because it does not inhibit curing by oxygen as compared with a curing method using radical reaction and proceeds well in the air.
• the ultraviolet (UV) curability of this coating agent tends to depend on the epoxy group content, and it is necessary to increase the epoxy group content (reduce the epoxy equivalent) in order to improve the ultraviolet curability. It was. When the amount of the epoxy group is increased, the UV curability is improved, but the relative amount of the organopolysiloxane portion in the epoxy group-containing organopolysiloxane is reduced, and the effect specific to the organopolysiloxane tends to be reduced. Even when the content is small (even when the epoxy equivalent is large), there has been a demand for an epoxy group-containing organopolysiloxane that can be cured by ultraviolet rays and the hardness of the film after ultraviolet curing is increased.
• Japanese Patent No. 4434841 Japanese Patent Publication No. 02-38602 Japanese Patent Laid-Open No. 3-128975 Japanese Patent Laid-Open No. 2004-068000
• the present invention has been made in view of the above circumstances. Even when the epoxy group content is low (even when the epoxy equivalent is large), an epoxy group-containing organopolysiloxane excellent in ultraviolet curability, and an ultraviolet curable silicone using the epoxy group-containing organopolysiloxane.
• An object is to provide a composition and a method for forming a cured film.
• an epoxy group-containing organopolysiloxane which is represented by the following average composition formula (1) and has an epoxy equivalent of 500 g / mol or more.
• R 1 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an epoxy group-containing group)
• R 2 is an epoxy group-containing substituent
• R 3 is a hydrogen atom or a saturated monovalent hydrocarbon group having 1 to 4 carbon atoms.
• a, b and c are positive numbers
• d is 0 or a positive number
• (a + b) / (c + d) a number satisfying 0.5 to 1.0.
• Such an epoxy group-containing organopolysiloxane of the present invention can be cured by ultraviolet irradiation even when the epoxy group content is low (even when the epoxy equivalent is large).
• the cured film obtained by using the film has transparency.
• the epoxy group-containing organopolysiloxane of the present invention preferably has a weight average molecular weight of 8000 or more and a solid form at 25 ° C.
• Such an epoxy group-containing organopolysiloxane is preferable because it is solid at 25 ° C. (room temperature) and is easy to handle and the hardness of the cured film is sufficiently high.
• the epoxy group-containing organopolysiloxane is (A) Si—H composed of R 1 3 SiO 1/2 units, R 1 2 HSiO 1/2 units, SiO 4/2 units, and R 3 OSiO 3/2 units represented by the following average composition formula (2) An organohydrogenpolysiloxane having a group content of 0.01 to 0.3 mol / 100 g; [Wherein, R 1 , R 3 , a, b, c and d are the same as above. ] (B) An addition reaction product of a compound having both an alkenyl group and an epoxy group is preferable.
• Such an epoxy group-containing organopolysiloxane can be easily synthesized.
• the (A) organohydrogenpolysiloxane preferably has a weight average molecular weight of 6000 or more and a solid form at 25 ° C.
• Such an (A) organohydrogenpolysiloxane is preferred because it is possible to synthesize a solid epoxy group-containing organopolysiloxane at room temperature (25 ° C.).
• the present invention also provides an ultraviolet curable silicone composition
• an ultraviolet curable silicone composition comprising the epoxy group-containing organopolysiloxane and an onium salt photoinitiator that generates a cationic species by ultraviolet irradiation.
• Such an ultraviolet curable silicone composition of the present invention can be cured by ultraviolet irradiation even when the epoxy group content in the epoxy group-containing organopolysiloxane is small (even when the epoxy equivalent is large), and the cured film is transparent. It will have a sex.
• the present invention provides a cured film forming method characterized in that the cured film is formed by applying the ultraviolet curable silicone composition on a substrate and irradiating with ultraviolet light.
• the ultraviolet curable silicone composition of the present invention is excellent in ultraviolet curable properties, it is possible to form a cured film by irradiating with ultraviolet rays. Moreover, the cured film thus obtained becomes a transparent film.
• the epoxy group-containing organopolysiloxane of the present invention and the ultraviolet curable silicone composition using the epoxy group-containing organopolysiloxane a film cured by ultraviolet irradiation can be obtained even when the epoxy group content is small, and the cured film is transparent. In some cases, because of its high hardness, it can be used as a coating agent for various substrates. In addition, this epoxy group-containing organopolysiloxane can be in a solid form at room temperature (25 ° C.), so it is easy to handle, can be easily mixed with various resins, and can be used as a silicone modifier for various resins. is there.
• the present inventors have conducted extensive studies on an epoxy group-containing organopolysiloxane having novel characteristics.
• the epoxy equivalent is 500 mol / g or more, and SiO 4/2 units, that is, tetrafunctional siloxane.
• an epoxy group-containing organopolysiloxane having a main unit (Q unit) as the main skeleton is used as a component of an ultraviolet curable composition in which an onium salt photoinitiator is blended, even a low content of epoxy group is ultraviolet It was easily cured by (UV) irradiation, and furthermore, the cured film was found to have high hardness in some cases while having transparency, and the present invention was completed.
• the present invention is an epoxy group-containing organopolysiloxane represented by the following average composition formula (1) and having an epoxy equivalent of 500 g / mol or more.
• R 1 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an epoxy group-containing group)
• R 2 is an epoxy group-containing substituent
• R 3 is a hydrogen atom or a saturated monovalent hydrocarbon group having 1 to 4 carbon atoms.
• a, b and c are positive numbers
• d is 0 or a positive number
• (a + b) / (c + d) a number satisfying 0.5 to 1.0.
• Epoxy group-containing organopolysiloxane The epoxy group-containing organopolysiloxane of the present invention is represented by the following average composition formula (1) and has an epoxy equivalent of 500 g / mol or more.
• R 1 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an epoxy group-containing group)
• R 2 is an epoxy group-containing substituent
• R 3 is a hydrogen atom or a saturated monovalent hydrocarbon group having 1 to 4 carbon atoms.
• a, b and c are positive numbers
• d is 0 or a positive number
• (a + b) / (c + d) a number satisfying 0.5 to 1.0.
• R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an epoxy group-containing group) which may be the same or different.
• R 1 includes 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 unsubstituted hydrocarbon group such as an aryl group such as a phenyl group and a tolyl group, Alternatively, a hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, 3, 3 in which part or all of the hydrogen atoms bonded to the carbon atoms of these hydrocarbon groups are substituted with a hydroxy group, a cyano group, a halogen atom, or the like.
• substituted monovalent hydrocarbon groups other than epoxy group-containing groups selected from 1,3-
• R 2 is an epoxy group-containing substituent, and specific examples thereof include the following, but are not particularly limited thereto.
• x, y and z may be 2 to 10, respectively.
• R 3 is a hydrogen atom or a saturated monovalent hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
• a, b, c are positive numbers, d is 0 or a positive number, and a, b, c, d are set so that an epoxy equivalent indicating an epoxy group content in the molecule is 500 g / mol or more.
• it is necessary to satisfy (a + b) / (c + d) 0.5 to 1.0, preferably 0.6 to 0.9.
• (a + b) / (c + d) is larger than 1.0, the hardness of the film is not sufficiently increased when this epoxy group-containing organopolysiloxane is cured with ultraviolet rays.
• (a + b) / (c + d) is smaller than 0.5, synthesis becomes difficult.
• the epoxy group-containing organopolysiloxane of the present invention has an epoxy equivalent of 500 g / mol or more.
• the upper limit is not particularly limited, but can be 10000 g / mol or less.
• the weight average molecular weight of the epoxy group-containing organopolysiloxane of the present invention is not particularly limited, but is preferably 5000 or more, and more preferably 8000 or more. If the weight average molecular weight is 5000 or more, the hardness of the cured film when the epoxy group-containing organopolysiloxane is UV-cured can be made sufficiently high, and if it is 8000 or more, it becomes a solid at room temperature and is easy to handle. Therefore, it is preferable.
• the epoxy group-containing organopolysiloxane of the present invention is (A) Si—H composed of R 1 3 SiO 1/2 units, R 1 2 HSiO 1/2 units, SiO 4/2 units, and R 3 OSiO 3/2 units represented by the following average composition formula (2) An organohydrogenpolysiloxane having a group content of 0.01 to 0.3 mol / 100 g; Wherein, R 1, R 3, a , b, c, d are as defined above. ] (B) An addition reaction product of a compound having both an alkenyl group and an epoxy group is preferable.
• R 1 , R 3 and a, b, c, d in the average composition formula (2) are the same as those described above. That is, R 1 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an epoxy group-containing group), and R 3 is a hydrogen atom or 1 to 4 carbon atoms.
• the organohydrogenpolysiloxane represented by the above average composition formula (2) contains SiH groups, and the amount thereof is 0.01 to 0.3 mol / 100 g, preferably 0.02 to 0.2 mol / 100 g. It is.
• the weight average molecular weight of the (A) organohydrogenpolysiloxane is not particularly limited, but is preferably 3000 or more, and more preferably 6000 or more.
• a weight average molecular weight of 3000 or more, particularly 6000 or more, is preferable because the epoxy group-containing organopolysiloxane to be synthesized tends to be solid at room temperature (25 ° C.).
• the compound having both an alkenyl group and an epoxy group is not particularly limited as long as it is a compound containing both an alkenyl group and an epoxy group, and examples thereof include allyl glycidyl ether and 1,2-epoxy-4-vinylcyclohexane. However, it is not limited to this.
• the compounding ratio of (A) organohydrogenpolysiloxane and (B) a compound having both an alkenyl group and an epoxy group is usually 0.00 with respect to the number of moles of SiH groups in (A) organohydrogenpolysiloxane. It may be a compound having both 8- to 1.5-fold mol (B) alkenyl group and epoxy group, and more preferably 0.9 to 1.3-fold mol.
• a known addition reaction catalyst can be used as the platinum group metal compound.
• platinum group metal-based catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Of these, platinum-based catalysts are particularly preferably used.
• platinum-based catalyst include chloroplatinic acid, alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinyl siloxane, and the like.
• the amount of the platinum group metal catalyst added is a catalyst amount, but the platinum group metal amount may be in the range of 1 to 50 ppm, and more preferably 5 to 20 ppm.
• the temperature and time for performing the reaction are not particularly limited, but (A) an organohydrogenpolysiloxane and (B) a compound having both an alkenyl group and an epoxy group may be sufficiently reacted.
• the reaction temperature is usually 60 to 140 ° C., preferably Is 80 to 120 ° C., and the reaction time is usually 0.5 to 12 hours, preferably 3 to 12 hours.
• this reaction may be carried out in an organic solvent.
• organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin, diisopropyl ether, 1 And ether solvents such as 1,4-dioxane, or mixed solvents thereof.
• Aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin are particularly preferred.
• After the reaction it may be used while containing the solvent, or it may be used after stripping the solvent to remove the solvent.
• the present invention also provides an ultraviolet curable silicone composition comprising the epoxy group-containing organopolysiloxane of the present invention and an onium salt photoinitiator that generates a cationic species upon irradiation with ultraviolet rays.
• Examples of the onium salt photoinitiator which is contained in the ultraviolet curable silicone composition of the present invention and generates a cationic species by ultraviolet irradiation, include: R 4 2 I + X ⁇ , R 4 3 S + X ⁇ , R 4 3 Se + X ⁇ , R 4 4 P + X ⁇ , R 4 N 2 + X ⁇ (R 4 is an aryl group, X ⁇ is an anion such as SbF 6 ⁇ , AsF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , HSO 4 ⁇ , ClO 4 ⁇ , etc.) , Triarylselenonium salts, tetraarylphosphonium salts, aryldiazonium salts, and the like. From the viewpoint of curing reactivity, diaryl iodonium and triarylsulfonium hexafluoroantimonate are preferred.
• the addition amount of the onium salt photoinitiator is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the ultraviolet curable silicone composition. If it is 0.1 parts by mass or more, the curability of the composition will be sufficient, and if it is 20 parts by mass or less, there is no possibility of adverse effects such as coloring on the surface state of the cured film.
• epoxy group-containing organopolysiloxane other than the epoxy group-containing organopolysiloxane of the present invention
• compounds and resins containing epoxy groups not containing silicone are used. You may use together.
• an epoxy diluent, a vinyl ether diluent, an adhesion improver to a substrate, a leveling agent, an antistatic agent, an antifoaming agent, a pigment, and other types are included as necessary.
• the organopolysiloxane may be added or may be diluted with an organic solvent.
• the present invention also provides a cured film forming method characterized in that the cured film is formed by applying the ultraviolet curable silicone composition of the present invention on a substrate and irradiating with ultraviolet light.
• the material of the substrate to which the ultraviolet curable silicone composition of the present invention is applied examples include glass, plastic, ceramic, metal and the like.
• the shape of a base material is not specifically limited, A plate shape, a film shape, a sheet shape, and a bottle shape are mentioned, Especially, it is preferable that they are a plate shape and a film shape.
• the thickness of the substrate is not particularly limited, but is usually in the range of 5 to 500 ⁇ m in the case of a film or sheet, and in the range of 0.005 to 0.1 m in the case of a thick plate. It is preferable that
• the method of applying (coating) the ultraviolet curable silicone composition of the present invention is not particularly limited.
• flow coating, dip coating, spin coating, spray coating, curtain coating, gravure coating The thin film layer of the ultraviolet curable silicone composition of the present invention can be formed on the surface of various substrates by known methods such as coating, Mayer bar coating, dip coating and the like.
• the surface of the base material before coating is previously subjected to primer treatment with a silane coupling agent or a hydrolyzate thereof; surface activation treatment such as corona treatment; and known anchor treatment using acrylic resin, urethane resin, or the like. May be.
• the coating amount of the ultraviolet curable silicone composition of the present invention is not particularly limited. However, when scratch resistance is required, an amount such that the thickness of the cured product layer of the composition is 0.5 to 30 ⁇ m is preferable. An amount of 1 to 20 ⁇ m is more preferable.
• the thickness of the primer layer after curing is 0.1 to 20 ⁇ m, particularly 0.5.
• the thickness after curing of the hard coat layer is preferably from 0.5 to 30 ⁇ m, particularly preferably from 1 to 20 ⁇ m, and the thickness after curing of the entire resin layer of two or more layers is preferably set to about 0.1 ⁇ m.
• the thickness is preferably 6 to 50 ⁇ m, particularly preferably 1.5 to 30 ⁇ m.
• the ultraviolet light source include a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a mercury arc lamp.
• UV irradiation dose is usually at least 10 mJ / cm 2, preferably 100 ⁇ 3000mJ / cm 2.
• the epoxy group-containing organopolysiloxane of the present invention is easy to handle because it can be made solid at room temperature (25 ° C.), can be easily mixed with various resins, and can be used as a silicone modifier for various resins.
• a film cured by ultraviolet irradiation can be obtained even if the epoxy group content is small, and the cured film has transparency and sometimes has high hardness. Therefore, it can be used as a coating agent for various substrates.
• silicone A corresponding to the epoxy group-containing organopolysiloxane of the present invention was obtained by removing volatile components by stripping. This was a white solid, having an epoxy equivalent of 650 g / mol and a weight average molecular weight of 18,000.
• silicone C corresponding to the epoxy group-containing organopolysiloxane of the present invention was obtained by evaporating volatile components with a strip.
• This was a white solid, having an epoxy equivalent of 6100 g / mol and a weight average molecular weight of 13,500.
• silicone E corresponding to the epoxy group-containing organopolysiloxane of the present invention was obtained by distilling off volatile components with a strip. This was in the shape of a syrup.
• the epoxy equivalent was 650 g / mol and the weight average molecular weight was 6000.
• Example 6 1 part by mass of [bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate] was added to 200 parts by mass of a 50% isododecane solution of silicone A synthesized in Example 1, and stirred well.
• a coating agent which is the ultraviolet curable silicone composition of the present invention was obtained.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic).
• Example 7 1 part by mass of [bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate] was added to 200 parts by mass of a 50% isododecane solution of silicone B synthesized in Example 2 and stirred well.
• a coating agent which is the ultraviolet curable silicone composition of the present invention was obtained.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic).
• Example 8 1 part by mass of [bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate] was added to 200 parts by mass of a 50% isododecane solution of silicone C synthesized in Example 3, and stirred well.
• a coating agent which is the ultraviolet curable silicone composition of the present invention was obtained.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic).
• Example 9 1 part by mass of [bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate] was added to 200 parts by mass of a 50% isododecane solution of silicone D synthesized in Example 4 and stirred well.
• a coating agent which is the ultraviolet curable silicone composition of the present invention was obtained.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic).
• Example 10 100 parts by mass of a 50% isododecane solution of silicone A synthesized in Example 1, and 2,4,6,8-tetramethyl-2,4-bis [2- (7-oxabicyclo [4.1.0] heptane -3-yl) ethyl] -6,8-dipropylcyclotetrasiloxane and 2,4,6,8-tetramethyl-2,6-bis [2- (7-oxabicyclo [4.1.0] heptane 1) [Bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate] is added to 50 parts by mass of a mixture of -3-yl) ethyl] -4,8-dipropylcyclotetrasiloxane.
• a coating agent which is an ultraviolet curable silicone composition of the present invention.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic). ) was irradiated into a high-pressure mercury lamp (ultraviolet irradiation apparatus manufactured by Eyegraphic Co., Ltd.) having a 365 nm region irradiation energy measured in step) and cured to prepare a test piece. The obtained film was transparent and free from tack.
• Example 11 50 parts by mass of 50% isododecane solution of silicone A synthesized in Example 1 and 2,4,6,8-tetramethyl-2,4-bis [2- (7-oxabicyclo [4.1.0] heptane -3-yl) ethyl] -6,8-dipropylcyclotetrasiloxane and 2,4,6,8-tetramethyl-2,6-bis [2- (7-oxabicyclo [4.1.0] heptane [3- (yl) ethyl] -4,8-dipropylcyclotetrasiloxane is mixed with 75 parts by mass of [bis [4-n-alkyl (C 10 -C 13 ) phenyl] iodonium hexafluoroantimonate].
• a coating agent which is an ultraviolet curable silicone composition of the present invention.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and isododecane was volatilized with a dryer at 60 ° C., and then the irradiation energy was 400 mJ / cm 2 (UV meter (UVPF-A1 manufactured by Eye Graphic). ) was irradiated into a high-pressure mercury lamp (ultraviolet irradiation apparatus manufactured by Eyegraphic Co., Ltd.) having a 365 nm region irradiation energy measured in step) and cured to prepare a test piece. The obtained film was transparent and free from tack.
• This coating agent was applied to a glass plate so that the cured coating film had a thickness of 20 ⁇ m, and a high-pressure mercury lamp with an irradiation energy of 400 mJ / cm 2 (irradiation energy in the 365 nm region measured with a UV meter (UVPF-A1) manufactured by Eye Graphic).
• a test piece was prepared by placing in (Igraphic Ultraviolet irradiation device) and curing. The obtained film was transparent and free from tack.
• Epoxy equivalent was calculated by back titrating a sample having a predetermined mass dissolved in 1,4-dioxane using hydrochloric acid and sodium hydroxide. For titration, an automatic titrator (COM-1750 manufactured by Hiranuma Sangyo Co., Ltd.) was used. For the solid sample, the epoxy equivalent was measured by diluting with various solvents, and the target numerical value was obtained by calculating from the diluted concentration.
• an automatic titrator COM-1750 manufactured by Hiranuma Sangyo Co., Ltd.
• the silicone compositions containing the epoxy group-containing organopolysiloxane of the present invention were excellent in ultraviolet curability and the cured film was transparent.
• the epoxy group-containing organopolysiloxane (3) used in Comparative Example 2 was not sufficiently cured by ultraviolet irradiation, and a film having a part of tack was obtained.
• the epoxy group-containing organopolysiloxane of the present invention is UV-cured even when the epoxy equivalent is larger than the epoxy group-containing organopolysiloxane (3), such as silicone B and silicone C used in Examples 7 and 8. A transparent film was obtained.
• Example 6 when Comparative Example 1 and Example 6 are compared, the epoxy equivalent of silicone A used in Example 6 is larger than the epoxy equivalent of the epoxy group-containing organopolysiloxane used in Comparative Example 1, but the cured film thereof. Example 6 was harder than Comparative Example 1, and even if the epoxy equivalent was large, high hardness could be achieved.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

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