Classifications

• • 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
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
  • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • 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
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • 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
  • C08G2150/00—Compositions for coatings

Definitions

• the present invention relates to silsesquioxane derivatives, curable compositions, hard coating agents, cured products, hard coatings and substrates.
• Hard coating agents are used in various places such as displays and housings that require hardness.
• Various curable compositions are known as compositions used for hard coating agents, and for example, polyfunctional acrylates are known.
• organic-inorganic composite compositions in which inorganic fillers are mixed with organic resins
• organic-inorganic hybrid materials in which organic units and inorganic units coexist or chemically bond in nano-order.
• silsesquioxane derivatives are known as such organic-inorganic hybrid materials.
• the applied curable composition is irradiated with an active energy ray such as ultraviolet rays and cured. known to do. If the substrate is in the form of a film, a roll-to-roll coating and curing method can be used. It is known that a nanoimprint method can also be applied to form the hard coat layer.
• Patent Document 1 discloses a composition for forming a hard coat layer containing a polyorganosilsesquioxane having a siloxane structural unit containing an oxetanyl group and a siloxane structural unit containing an epoxy group, and a polymerization initiator. disclosed.
• Patent Document 2 1 to 10 mol% of a dialkoxysilane containing at least one of an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms and a trialkoxysilane containing a (meth)acrylic group
• a polysiloxane comprising 90 to 99 mol % of an alkoxysilane (provided that the sum of dialkoxysilane and trialkoxysilane is 100 mol %) and a hard coating composition containing the polysiloxane are disclosed.
• Patent Document 3 a polymerizable compound having a polymerizable functional group such as a (meth) acryloyl group and having a siloxane bond having a bifunctional silane as a constituent unit more than a trifunctional silane, and a photopolymerizable and an initiator.
• a polymerizable compound having a polymerizable functional group such as a (meth) acryloyl group and having a siloxane bond having a bifunctional silane as a constituent unit more than a trifunctional silane
• Patent Document 1 International Publication 2019/188441 Pamphlet
• Patent Document 2 Japanese Patent Application Laid-Open No. 2013-035918
• Patent Document 3 International Publication 2020/203472 Pamphlet
• curable compositions containing a silsesquioxane derivative or the like When applying a curable composition containing a silsesquioxane derivative or the like to a substrate, it is common to mix the curable composition and a solvent from the viewpoint of improving the coating properties of the curable composition. .
• the curable composition contains a solvent, it is necessary to remove the solvent before curing the coating film, and it is desirable to reduce the amount of solvent used from the viewpoint of reducing environmental load and energy consumption.
• curable compositions that are solvent-free (solvent-free systems) and have low viscosities.
• a solvent-free curable composition preferably has low viscosity, good applicability, curability, and the like, and the cured product obtained by curing the curable composition has high hardness.
• the curability of the curable composition and the hardness of the cured product obtained by curing the curable composition tend to decrease. Therefore, there is generally a trade-off relationship between the viscosity of the solvent-free curable composition, the curability of the curable composition, and the hardness of the cured product.
• Patent Literature 1 describes that a hard coat film was produced as follows. First, a polysilsesquioxane consisting only of T units (units having 3 O 1/2 per silicon atom) obtained by hydrolyzing and polycondensing a trifunctional silane, and a photopolymerization initiator and using methyl isobutyl ketone (MIBK) as a solvent and applying a photocurable composition having a solid concentration of 50% to a substrate. Thereafter, the coating film is heated to remove the solvent, then irradiated with ultraviolet rays, and further heated to cure the coating film, thereby producing a hard coat film having a hard coat layer.
• MIBK methyl isobutyl ketone
• a hard coat containing polysilsesquioxane consisting of only T units as described in Patent Document 1 has high hardness.
• Patent Document 2 describes that a coating film was produced as follows. First, D units obtained by hydrolyzing and polycondensing a dialkoxysilane and a trialkoxysilane containing a (meth)acrylic group (units having two O 1/2 per silicon atom) and A solvent-diluted photocurable composition is prepared comprising a polysiloxane having T units and a photoinitiator. After applying the prepared photocurable composition to a substrate, it is pre-baked, and then a coating film is produced using a high-pressure mercury lamp. A cured coating film using such a silsesquioxane derivative consisting of D units and T units may have low hardness.
• Patent Document 3 describes that a pattern was formed on a base material as follows. First, (1) a polymerizable compound having a siloxane bond having more structural units of a bifunctional silane than a trifunctional silane, and (2) a siloxane bond having more structural units of a bifunctional silane than a trifunctional silane. or (3) a polymerizable compound obtained by reacting a polymerizable compound obtained from a trifunctional silane with chlorotrimethylsilane. and a photopolymerization initiator. A solvent-free photocurable resin composition for imprinting is applied onto a quartz base material, and while being in contact with a quartz imprinting mold, is irradiated with light to produce a photocurable resin composition for imprinting.
• Patent Document 3 when the polymerizable compound described in (1) or (2) above is used, the hardness of the cured product may decrease, and the polymerizable compound described in (3) above may is used, the viscosity is high, and there is room for improvement in that it can be used without a solvent.
• the present invention has been made in view of the above, a silsesquioxane derivative capable of producing a cured product having a low viscosity and excellent hardness, a curable composition containing the silsesquioxane derivative, and the , a hard coating agent containing the silsesquioxane derivative, a hard coating obtained by curing the same, and a substrate containing the hard coating.
• Means for solving the above problems include the following aspects. ⁇ 1> A silsesquioxane derivative represented by the following formula (1).
• R 1 and R 2 are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a number of carbon atoms.
• R 3 is an alkyl group of 1 to 6 carbon atoms
• R 4 and R 5 are each independently a hydrogen atom, a saturated or unsaturated alkyl group of 1 to 20 carbon atoms; a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms
• R 6 is an ethylenically unsaturated bond and a carbon an organic group having 2 to 12 carbon atoms having at least one carbon triple bond
• R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon It is an aralkyl group having 7 to 10 atoms, wherein multiple R 5 may be the same or different, multiple R 7 may be the same or different, and multiple R 8 may be the same.
• Each of R 1 to R 8 may be independently partially substituted with a substituent or a halogen atom, y is a positive number, t, u, v, w, x and z are each independently 0 or a positive number, and at least one of u and v is a positive number.
• ⁇ 2> The silsesquioxane derivative according to ⁇ 1>, wherein t, x and z in the formula (1) are 0 and 0.01 ⁇ y/(u+v+w) ⁇ 0.5.
• ⁇ 3> The silsesquioxane derivative according to ⁇ 1> or ⁇ 2>, wherein u and v are each independently a positive number and 0 ⁇ v/u ⁇ 1 in the formula (1).
• ⁇ 4> The silsesquioxane derivative according to any one of ⁇ 1> to ⁇ 3>, which has a viscosity of 10 mPa ⁇ s to 4,000 mPa ⁇ s at 25°C.
• ⁇ 5> A curable composition comprising the silsesquioxane derivative according to any one of ⁇ 1> to ⁇ 4> and a polymerization initiator.
• ⁇ 6> A hard coating agent comprising the curable composition according to ⁇ 5>.
• ⁇ 7> A cured product obtained by curing the curable composition according to ⁇ 5>.
• ⁇ 8> A hard coat obtained by curing the hard coat agent according to ⁇ 6>.
• ⁇ 9> A substrate comprising the hard coat according to ⁇ 8>.
• a silsesquioxane derivative capable of producing a cured product having a low viscosity and excellent hardness, a curable composition containing the silsesquioxane derivative, and a cured product obtained by curing the same, A hard coating agent containing this silsesquioxane derivative, a hard coating obtained by curing the same, and a substrate containing this hard coating can be provided.
• each of R 1 to R 8 in formula (1) may be independently partially substituted with a substituent or a halogen atom.
• R 1 to R 8 each independently represent an alkyl group, an aryl group, an aralkyl group, a vinyl group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, and an ammonium group. , a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxy group, an acid anhydride group, or a halogen atom.
• R 1 to R 8 in formula (1) may each independently be unsubstituted, for example, R 1 to R 3 or R 6 to R 8 (preferably R 1 to R 3 and R 6 to R 8 ) may be unsubstituted.
• silsesquioxane derivative The silsesquioxane derivative of the present invention is represented by the following formula (1).
• R 1 and R 2 are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a number of carbon atoms.
• R 3 is an alkyl group of 1 to 6 carbon atoms
• R 4 and R 5 are each independently a hydrogen atom, a saturated or unsaturated alkyl group of 1 to 20 carbon atoms; a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms
• R 6 is an ethylenically unsaturated bond and a carbon an organic group having 2 to 12 carbon atoms having at least one carbon triple bond
• R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon It is an aralkyl group having 7 to 10 atoms, wherein multiple R 5 may be the same or different, multiple R 7 may be the same or different, and multiple R 8 may be the same.
• Each of R 1 to R 8 may be independently partially substituted with a substituent or a halogen atom, y is a positive number, t, u, v, w, x and z are each independently 0 or a positive number, and at least one of u and v is a positive number.
• structural units (a) to (g) Each structural unit that the silsesquioxane derivative of the present invention may contain is referred to as structural units (a) to (g) as follows.
• the silsesquioxane derivative of the present invention includes at least one of the structural units (b) and (c) among the structural units (a) to (g) described above, and the structural unit (f), At least one of structural unit (a), structural unit (d), structural unit (e), and structural unit (g) is included as necessary.
• the silsesquioxane derivative of the present invention contains at least one of the structural unit (b) and the structural unit (c), and the structural unit (f), so that the cured product has a low viscosity and excellent hardness. manufacturing becomes possible.
• t, u, v, w, x, y and z in formula (1) represent molar ratios of structural units (a) to (g).
• t, u, v, w, x, y and z are the structural units (a) to (g) that may be included in the silsesquioxane derivative represented by the formula (1).
• the molar ratio can be obtained from NMR (nuclear magnetic resonance) analysis values of the silsesquioxane derivative of the present invention. Further, when the reaction rate of each raw material of the silsesquioxane derivative is known, or when the yield is 100%, it can be determined from the charged amount of the raw material.
• the molar ratio of each structural unit of the silsesquioxane derivative is calculated by performing 1 H-NMR analysis on a sample dissolved in deuterated chloroform or the like and, if necessary, further performing 29 Si-NMR analysis. You may The structure of the original silsesquioxane derivative may be estimated from the ratio of the structural units obtained by decomposing the structural units with an alkali or the like. If necessary, known techniques such as mass spectrometry and IR (infrared absorption spectroscopy) analysis may be combined to determine the molar ratio of each structural unit of the silsesquioxane derivative.
• Each of the structural units (b) to (g) in formula (1) may be of only one type, or may be of two or more types.
• the order of arrangement in formula (1) indicates the composition of the structural units, and does not mean the order of arrangement of the silsesquioxane derivatives. Therefore, the condensed form of the structural units in the silsesquioxane derivative of the present invention does not necessarily have to follow the sequence of formula (1). Details of the structural units (a) to (g) will be described below.
• Structural unit (a) is a Q unit having 4 O 1/2 atoms (2 oxygen atoms) per silicon atom.
• the Q unit means a unit having 4 O 1/2 atoms per silicon atom.
• the proportion of the structural unit (a) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (t/(t+u+v+w+x+y+z)) of the structural unit (a) to all structural units is 0.1 or less from the viewpoint of the viscosity of the silsesquioxane derivative and the hardness of the cured product. is preferred, 0.05 or less is more preferred, and 0 is even more preferred.
• a molar ratio of 0 means that the corresponding structural unit is not included, and the same applies hereinafter.
• Structural unit (b) is a T unit having 3 O 1/2 per silicon atom (1.5 oxygen atoms) and an acryloyloxy group bonded to the silicon atom via R 1 is.
• the T unit means a unit having 3 O 1/2 atoms per 1 silicon atom.
• R 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms. is the base.
• R 1 is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms.
• the alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably a propylene group. .
• the alkylene group having 1 to 10 carbon atoms may be linear or branched.
• the cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, more preferably a cycloalkylene group having 4 to 6 carbon atoms.
• the cycloalkylene group having 3 to 10 carbon atoms may have a branch.
• the ratio of the structural unit (b) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (u/(t+u+v+w+x+y+z)) of the structural unit (b) to all structural units is, from the viewpoint of ultraviolet (hereinafter also referred to as UV) curability, 0.2 to 0.99. It is preferably 0.3 to 0.9, even more preferably 0.35 to 0.8.
• Structural unit (c) is an acryloyloxy group having 3 O 1/2 atoms (1.5 oxygen atoms) per silicon atom, and having a hydrogen atom substituted with R 3 via R 2 is a T unit attached to a silicon atom.
• R 2 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms. is the base. Preferred embodiments of R 2 are the same as R 1 in structural unit (b).
• R 3 is an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms includes, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group, preferably methyl group or ethyl group, more preferably methyl group.
• the ratio of the structural unit (c) in the silsesquioxane derivative of the invention is not particularly limited.
• the molar ratio (v / (t + u + v + w + x + y + z)) of the structural unit (c) to all structural units is preferably 0 to 0.7 from the viewpoint of hardness and UV curability when cured. It is more preferably 0.05 to 0.6, even more preferably 0.1 to 0.5.
• the molar ratio of structural unit (c) to all structural units may be zero.
• At least one of u and v is a positive number, and from the viewpoint of the hardness of the cured product, u and v are preferably independently positive numbers.
• the total molar ratio ((u + v)/(t + u + v + w + x + y + z)) of the structural unit (b) and the structural unit (c) in all structural units is 0.3 to 0.3 from the viewpoint of viscosity and hardness when cured. It is preferably 99, more preferably 0.5 to 0.98, even more preferably 0.7 to 0.95.
• the molar ratio (v/u+v) of the structural unit (c) to the total of the structural unit (b) and the structural unit (c) is 0 to 0.7 from the viewpoint of viscosity and hardness when cured. is preferred, 0.05 to 0.6 is more preferred, and 0.1 to 0.5 is even more preferred.
• Structural unit (d) is a T unit having 3 O 1/2 (1.5 oxygen atoms) per silicon atom and R 4 bonded to the silicon atom.
• R 4 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, or 6 to It is an aryl group of 20 or an aralkyl group of 7 to 20 carbon atoms.
• a saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or branched.
• the saturated or unsaturated alkyl group having 1 to 20 carbon atoms is preferably a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, more preferably a saturated alkyl group having 1 to 10 carbon atoms. more preferred.
• saturated alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. From the viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
• Examples of unsaturated alkyl groups having 1 to 10 carbon atoms include vinyl groups, 2-propenyl groups, and ethynyl groups.
• a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may have a branch.
• a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms is preferably a saturated or unsaturated cycloalkyl group having 4 to 6 carbon atoms.
• the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.
• Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a group in which one or more hydrogen atoms of the phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and a naphthyl group.
• a phenyl group is preferred from the viewpoint of heat resistance and hardness of the cured product.
• the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.
• Examples of the aralkyl group having 7 to 20 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group. Examples thereof include benzyl group and phenethyl group, and benzyl group is preferable from the viewpoint of heat resistance and hardness of the cured product.
• examples of R 4 include a 3-glycidoxypropyl group and a 2-(3,4-epoxycyclohexyl)ethyl group.
• 3-(3-ethyloxetan-3-yl)methoxypropyl group 3-hydroxypropyl group, 3-aminopropyl group, 3-dimethylaminopropyl group, 3-hydroxypropyl group, 3-aminopropyl hydrochloride , hydrochloride of 3-dimethylaminopropyl group, p-styryl group, N-2-(aminoethyl)-3-aminopropyl group, N-phenyl-3-aminopropyl group, N-(vinylbenzyl)-2- Hydrochloride of aminoethyl-3-aminopropyl group, 3-ureidopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, 3-carboxypropyl group and 3-chloropropyl group.
• the ratio of the structural unit (d) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (w / (t + u + v + w + x + y + z)) of the structural unit (d) to the total structural units is preferably 0.1 or less, and 0.05 or less, from the viewpoint of the hardness of the cured product. It is more preferably 0, and more preferably 0.
• Structural unit (e) is a D unit having two O 1/2 per silicon atom (one oxygen atom) and two R 5 bonds to the silicon atom.
• the D unit means a unit having two O 1/2 atoms per one silicon atom.
• R 5 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, or 6 to It is an aryl group of 20 or an aralkyl group of 7 to 20 carbon atoms.
• multiple R 5 may be the same or different.
• Preferred embodiments of R 5 are the same as R 4 in structural unit (d).
• the ratio of the structural unit (e) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (x/(t + u + v + w + x + y + z)) of the structural unit (e) to the total structural units is preferably 0.1 or less, and 0.05 or less, from the viewpoint of the hardness of the cured product. It is more preferably 0, and more preferably 0.
• Structural unit (f) has one O 1/2 per silicon atom (0.5 oxygen atoms), one R 6 and two R 5 are bonded to the silicon atom M Units.
• the M unit means a unit having one O 1/2 per one silicon atom.
• R 6 is an organic group having 2 to 12 carbon atoms and having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond.
• Examples of the organic group having 2 to 12 carbon atoms and having an ethylenically unsaturated bond include a vinyl group, an orthostyryl group, a methstyryl group, a parastyryl group, an acryloyloxymethyl group, a methacryloyloxymethyl group, and a 2-acryloyloxyethyl group.
• R 7 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (f), multiple R 7 may be the same or different.
• alkyl groups having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. From the viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
• aryl group having 6 to 10 carbon atoms examples include a phenyl group, a group in which one or more hydrogen atoms of the phenyl group are substituted with an alkyl group having 1 to 4 carbon atoms, and a naphthyl group.
• a phenyl group is preferred from the viewpoint of heat resistance and hardness of the cured product.
• Examples of the aralkyl group having 7 to 10 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group. Examples thereof include benzyl group and phenethyl group, and benzyl group is preferable from the viewpoint of heat resistance and hardness of the cured product.
• the proportion of the structural unit (f) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (y/(t + u + v + w + x + y + z)) of the structural unit (f) to all structural units is preferably 0.01 to 0.5 from the viewpoint of viscosity and hardness when cured. It is more preferably 0.02 to 0.4, even more preferably 0.05 to 0.35.
• the molar ratio of the structural unit (b) and the structural unit (c) to the structural unit (f) is the viscosity and the cured product. From the viewpoint of hardness, it is preferably 50:50 to 99:1, more preferably 60:40 to 98:2, even more preferably 65:35 to 95:5.
• Structural unit (g) is an M unit having one O 1/2 (0.5 oxygen atom) per silicon atom and three R 8 bonds to the silicon atom.
• R 8 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (g), multiple R 8 may be the same or different. Preferred embodiments of R 8 are the same as R 7 in structural unit (f).
• the proportion of the structural unit (g) in the silsesquioxane derivative of the present invention is not particularly limited.
• the molar ratio (z / (t + u + v + w + x + y + z)) of the structural unit (g) to all structural units is preferably 0.1 or less, and 0.05 or less, from the viewpoint of the hardness of the cured product. It is more preferably 0, and more preferably 0.
• the silsesquioxane derivative of the present invention may further contain (R 9 O 1/2 ) as a structural unit not containing Si (hereinafter also referred to as structural unit (h)).
• R 9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms may be either an aliphatic group or an alicyclic group, and may be linear or branched. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
• Structural unit (h) is an alkoxy group which is a hydrolyzable group contained in the silicon compound described later, or an alkoxy group formed by substituting the hydrolyzable group of the silicon compound with an alcohol contained in the reaction solvent. It may be a hydroxyl group that remains in the molecule without hydrolysis or polycondensation, or a hydroxyl group that remains in the molecule without polycondensation after hydrolysis.
• t, x and z are preferably 0, w is preferably 0 or a positive number, and t, w, x and z are more preferably 0.
• 0.01 ⁇ y/(u + v + w) ⁇ 0.5 is preferable, 0.02 ⁇ y/(u + v + w) ⁇ 0.4 is more preferable, and 0.05 ⁇ y It is more preferable that /(u+v+w) ⁇ 0.35.
• u and v are each independently positive numbers, preferably 0 ⁇ v/u ⁇ 1, more preferably 0.1 ⁇ v/u ⁇ 1, and 0.1 ⁇ v/u ⁇ 1. 2 ⁇ v/u ⁇ 1 is more preferable, and 0.3 ⁇ v/u ⁇ 1 is particularly preferable.
• the weight average molecular weight (hereinafter also referred to as "Mw") of the silsesquioxane derivative of the present invention is not particularly limited, and may be, for example, 300 to 30,000, or 500 to 15,000. may be from 700 to 10,000, or from 1,000 to 5,000.
• Mw in the present invention means a value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.
• GPC gel permeation chromatography
• the silsesquioxane derivative of the present invention preferably has a viscosity at 25° C. of 10 mPa s to 4,000 mPa s, more preferably 50 mPa s to 2,000 mPa s, and 100 mPa s. More preferably, it is up to 1,600 mPa ⁇ s.
• the viscosity at 25° C. means a value measured using an E-type viscometer (cone and plate type viscometer; for example, Toki Sangyo Co., Ltd. TVE22H-type viscometer).
• the silsesquioxane derivative of the present invention can be produced by known methods.
• a method for producing a silsesquioxane derivative is disclosed in detail as a method for producing polysiloxane in WO 2013/031798 pamphlet and the like.
• the silsesquioxane derivative of the present invention can be produced, for example, by the following method.
• the method for producing a silsesquioxane derivative of the present invention comprises a condensation step of hydrolyzing and polycondensing the silicon compound to give the structural unit of formula (1) by condensation in a suitable reaction solvent.
• silicon compound 4" silicon compound 5 (also referred to as “silicon compound 6” or “silicon compound 7").
• silicon compounds 1 to 3 and, if necessary, other silicon compounds may be hydrolyzed and polycondensed.
• a part of the silicon compounds 1 to 3 and, if necessary, other silicon compounds are hydrolyzed and polycondensed to obtain an intermediate silsesquioxane derivative, and then the obtained intermediate product may be further subjected to hydrolysis and polycondensation reactions with the rest of the silicon compounds 1 to 3 and the like.
• the silicon compound 1, the silicon compound 2 and, if necessary, other silicon compounds are hydrolyzed and polycondensed, and then the obtained intermediate product and the silicon compound 3 are combined. may be further subjected to hydrolysis and polycondensation reactions.
• a silicon compound is hydrolyzed and polycondensed in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution are removed. It is preferable to provide a distillation step for distilling off.
• Examples of the silicon compound 1 include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, and (3-acryloyloxypropyl)trichlorosilane. is mentioned.
• Examples of the silicon compound 2 include (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (8-methacryloyloxyoctyl)trimethoxysilane, and (3-methacryloyloxypropyl)trichlorosilane. is mentioned.
• Examples of the silicon compound 3 include 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3 -acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, etc., methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyl oxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, ethynyldimethylmethoxysilane and the like.
• Examples of the silicon compound 4 include tetramethoxysilane, tetraethoxysilane, and the like.
• Silicon compound 5 includes, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltri methoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-
• Examples of the silicon compound 6 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldidiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropy
• Examples of the silicon compound 7 include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, dimethylphenylmethoxysilane, and the like.
• Alcohol may be used as a reaction solvent in the condensation step.
• Alcohol is a narrowly defined alcohol represented by the general formula R--OH, and is a compound having no functional group other than an alcoholic hydroxyl group.
• Alcohol is not particularly limited, and examples include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2- butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, cyclohexanol and the like.
• the reaction solvent used in the condensation step may be alcohol alone, or may be a mixed solvent with at least one sub-solvent.
• the co-solvent may be either a polar solvent, a non-polar solvent, or a combination of both.
• Hydrolysis and polycondensation reactions in the condensation step proceed in the presence of water.
• the amount of water used to hydrolyze the hydrolyzable group contained in the silicon compound is preferably 0.5 to 5 times the amount (mol) of the substance of the hydrolyzable group, more preferably 1 to 2 times the molar amount.
• the hydrolysis and polycondensation reaction of the silicon compound may be carried out without a catalyst or with a catalyst.
• inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid
• acid catalysts exemplified by organic acids such as formic acid, acetic acid, oxalic acid and p-toluenesulfonic acid, ammonia, tetramethylammonium hydroxide, water
• Base catalysts such as sodium oxide, potassium hydroxide, sodium carbonate and potassium carbonate are preferably used, and acid catalysts are more preferably used.
• the amount of the catalyst used is preferably an amount corresponding to 0.01 mol% to 20 mol%, and preferably 0.1 mol% to 10 mol, relative to the total amount (mol) of silicon atoms contained in the silicon compound. % is more preferable.
• an auxiliary agent can be added to the reaction system.
• distillation can be carried out under normal pressure or reduced pressure, can be carried out at room temperature or under heating, and can also be carried out under cooling.
• the method for producing a silsesquioxane derivative can include a neutralization step for neutralizing the catalyst before the distillation step.
• a step of removing salts generated by neutralization by washing with water or the like can also be provided.
• the silsesquioxane derivative represented by formula (1) is a group obtained by adding an acid or the like to an oxetanyl group or an epoxy group to open the ring, among the side chain functional groups derived from the silicon compound used in the production as a raw material. or may contain a hydroxyalkyl group formed by decomposition of an organic group having a (meth)acryloyl group, or a group obtained by adding an acid or the like to an unsaturated hydrocarbon group or the like.
• You can Specific examples thereof include those in which a part of formula (1) includes a structure represented by formula (A) and/or a structure represented by formula (B) below.
• the original organic group having an oxetanyl group or an epoxy group, the original organic group having a (meth)acryloyl group, or the original unsaturated hydrocarbon group derived from the silicon compound as a raw material As long as it is 50 mol % or less with respect to the amount corresponding to the group, there is no problem in carrying out the present invention, and it is preferably 30 mol % or less, more preferably 10 mol % or less.
• the T unit is exemplified, but the same D unit, M unit, etc. may be used.
• the curable composition of the present invention contains the silsesquioxane derivative of the present invention described above and a polymerization initiator.
• the curable composition of the present invention may be used as a hard coating agent.
• the curable composition of the present invention may contain various components (hereinafter also referred to as "other components") as necessary.
• the polymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators and thermal polymerization initiators.
• Photopolymerization initiators include, for example, radical photopolymerization initiators.
• Thermal polymerization initiators include, for example, thermal radical polymerization initiators. A known compound may be used as the photopolymerization initiator and the thermal polymerization initiator.
• Photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, diethoxyacetophenone, oligo[2-hydroxy-2-methyl-1-[4-(1 -methylvinyl)phenyl]propanone] and acetophenones such as 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl ⁇ -2-methyl-propan-1-one Compound; benzophenone compounds such as benzophenone, 4-phenylbenz
• the thermal radical polymerization initiator is not particularly limited, and examples include peroxides and azo initiators.
• peroxides examples include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate and potassium persulfate; 1,1-bis(t-butylperoxy) 2-methylcyclohexane, 1,1-bis( t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-tri
• Azo initiators include 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, etc., may be used alone, or two or more of them may be used in combination.
• a redox reaction can be achieved by combining with a redox polymerization initiation system using a reducing agent such as iron.
• the content of the polymerization initiator is 0.01 parts by mass to 20 parts by mass with respect to 100 parts by mass of the silsesquioxane derivative represented by formula (1). is preferred, 0.1 to 10 parts by mass is more preferred, and 1 to 5 parts by weight is even more preferred.
• Other components are not particularly limited, and examples include solvents, polymerizable compounds other than the silsesquioxane derivative represented by formula (1), resins, silicones, monomers, fillers, surfactants, antistatic agents ( For example, conductive polymer), leveling agent, photosensitizer, UV absorber, antioxidant, heat resistance improver, stabilizer, lubricant, pigment, dye, plasticizer, suspending agent, adhesion imparting agent, nano Examples include particles, nanofibers, nanosheets, and the like.
• the curable composition of the present invention may contain silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes and disiloxanes.
• silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes and disiloxanes.
• the curable composition of the present invention may or may not contain a solvent.
• the solvent include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents and cellosolve solvents. be done.
• the curable composition of the present invention may contain a polymerizable compound other than the silsesquioxane derivative represented by formula (1) (hereinafter also referred to as "other polymerizable compound"). You don't have to.
• Other polymerizable compounds are not particularly limited as long as they are capable of undergoing a polymerization reaction in the presence of the silsesquioxane derivative represented by formula (1) and the polymerization initiator.
• Other polymerizable compounds include silsesquioxane derivatives other than the silsesquioxane derivative represented by formula (1), (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (having an epoxy group oxetanyl group-containing compounds), compounds having an oxetanyl group (oxetanyl group-containing compounds), and compounds having a vinyl ether group (vinyl ether compounds).
• silsesquioxane derivatives other than the silsesquioxane derivatives represented by formula (1) include silsesquioxane derivatives consisting only of T units, silsesquioxane derivatives containing T units and D units, and the like. .
• (Meth) acrylate compounds are not particularly limited, compounds having one (meth) acryloyl group (hereinafter also referred to as “monofunctional (meth) acrylate”), and compounds having two or more (meth) acryloyl groups (hereinafter also referred to as “polyfunctional (meth)acrylate”).
• Examples of monofunctional (meth)acrylates include Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; monofunctional (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanemethylol (meth)acrylate; Monofunctional (meth)acrylates having aromatic groups of benzyl (meth)acrylate and phenyl (meth)acrylate; (Meth)acrylates of phenol ethylene oxide adducts, (meth) acrylates of phenol propylene oxide adducts, (meth) acrylates of modified nonylphenol ethylene oxide adducts, and (meth) acrylates of non
• polyfunctional (meth)acrylates include Polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate; 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropan
• Urethane (meth)acrylates can also be used as polyfunctional (meth)acrylates.
• urethane (meth)acrylate include a compound obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth)acrylate, and a compound obtained by addition reaction of organic polyisocyanate, polyol and hydroxyl group-containing (meth)acrylate.
• Monofunctional (meth)acrylates, polyfunctional (meth)acrylates, and the like may be used alone, or two or more of them may be used in combination, or different types may be used in combination.
• polyols examples include low-molecular-weight polyols, polyether polyols, polyester polyols and polycarbonate polyols.
• Low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethylol, 3-methyl-1,5-pentanediol, and the like.
• polyether polyols include polypropylene glycol and polytetramethylene glycol.
• polyester polyols reaction products of these low molecular weight polyols and/or polyether polyols with dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or acid components such as anhydrides thereof is mentioned. These may be used alone, or two or more of them may be used in combination, or different types may be used in combination.
• dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or acid components such as anhydrides thereof.
• Organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
• hydroxyl group-containing (meth)acrylates examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; pentaerythritol tri(meth)acrylate; ) acrylates, di(meth)acrylates of isocyanuric acid 3-mol alkylene oxide adducts, and hydroxyl group-containing polyfunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylates. These may be used alone, or two or more of them may be used in combination, or different types may be used in combination.
• the mixing ratio is not particularly limited, for example, 100 mass of the silsesquioxane derivative represented by the formula (1)
• the mixing ratio of the (meth)acrylate compound to 1 part is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, even more preferably 0 to 20 parts by mass. From the viewpoint of adhesion to the inorganic substance layer, the mixing ratio of the (meth)acrylate compound is preferably low.
• a compound having one ethylenically unsaturated group in one molecule other than the (meth)acrylate compound may be added to the curable composition.
• the ethylenically unsaturated group is preferably a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, or a vinyl group.
• Specific examples of the compound having an ethylenically unsaturated group include (meth)acrylic acid, a Michael addition type dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpho Phosphorus, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These may be used alone or in combination of two or more.
• Examples of epoxy compounds include monofunctional epoxy compounds and polyfunctional epoxy compounds.
• Examples of oxetanyl group-containing compounds include monofunctional oxetane compounds and polyfunctional oxetane compounds.
• Examples of vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. As these compounds, for example, compounds described in JP-A-2011-42755 may be used.
• the silicone is not particularly limited, and known silicones can be used. Examples include polydimethylsilicone, polydiphenylsilicone, polymethylphenylsilicone, etc., which have functional groups at their terminals and/or side chains. things are preferred.
• the functional group is not particularly limited, and examples thereof include (meth)acryloyl group, epoxy group, oxetanyl group, vinyl group, hydroxyl group, carboxy group, amino group, thiol group and the like.
• the content of the other polymerizable compounds is 0.01 per 100 parts by mass of the silsesquioxane derivative represented by formula (1). It is preferably from 0.1 to 50 parts by mass, even more preferably from 1 to 25 parts by mass.
• the cured product of the present invention is obtained by curing the aforementioned curable composition of the present invention.
• the cured product of the present invention can be obtained by irradiating the curable composition of the present invention with an active energy ray or by heating the curable composition of the present invention.
• the curable composition of the present invention When curing the curable composition of the present invention, it may be after applying the curable composition to the substrate.
• the curable composition of the present invention may or may not contain a solvent. When a solvent is included, it is preferable to cure after removing the solvent.
• the method of applying the curable composition is not particularly limited.
• coating methods include ordinary coating methods such as casting, spin coating, bar coating, dip coating, spray coating, roll coating, flow coating and gravure coating.
• the thickness to which the curable composition of the present invention is applied is not particularly limited, and is appropriately set according to the purpose.
• the substrate to which the curable composition of the present invention is applied is not particularly limited, and examples thereof include wood, metal, inorganic materials, plastics, paper, fibers and fabrics. Metals include copper, silver, iron, aluminum, silicon, silicon steel and stainless steel.
• inorganic materials include metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide and gallium oxide; metal nitrides such as aluminum nitride, gallium nitride and silicon nitride; silicon carbide and nitride; Examples include ceramics such as boron, mortar, concrete and glass.
• plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aramid, polyimide resins, polyamideimide resins, 4-fluoro Fluorine resins such as ethylene chloride resins, polyolefin resins such as crosslinked polyethylene resins, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cycloolefin polymers (COP), cycloolefin copolymers (COC) , acetate resins, polyarylates, cellophane, norbornene resins, acetyl cellulose resins such as triacetyl cellulose (TAC), polychloroprene, polyphenylene sulfide, polysulfone
• fibers include natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers and known chemical fibers.
• the fabric may be woven or non-woven, and may be made, for example, using the fibers described above. These materials may be used alone, or two or more of them may be combined, mixed, or composited for use.
• the shape of the substrate is not particularly limited, and examples thereof include plate-like, sheet-like, film-like, rod-like, spherical, fiber-like, powder-like, lens-like and other regular or irregular shapes.
• the curing method and curing conditions are selected depending on whether the curable composition is active energy ray-curable and/or thermosetting. Further, the curing conditions (in the case of active energy ray curing, for example, the type of light source and the amount of light irradiation, and in the case of thermosetting, heating temperature, heating time, etc.) It is appropriately selected depending on the type and amount of the polymerization initiator to be contained, the type of other polymerizable compound, and the like.
• the curing method may be irradiation with an active energy ray using a known active energy ray irradiation device or the like.
• active energy rays include electron beams, and light such as ultraviolet rays, visible rays, and X-rays. Light is preferred, and ultraviolet rays are more preferred from the viewpoint that inexpensive devices can be used.
• Ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). mentioned.
• the intensity of light irradiation to the film coated with the present composition may be selected according to the purpose, application, etc.
• the light irradiation intensity in the light wavelength range effective for polymerization (light with a wavelength of 220 nm to 460 nm is preferably used, although it varies depending on the type of photopolymerization initiator) is 0.1 mW/cm 2 to 1000 mW/cm 2 .
• the irradiation energy should be set as appropriate according to the type of active energy ray, the compounding composition, and the like.
• the light irradiation time to the coating may also be selected according to the purpose, application, etc., and the integrated light amount represented as the product of the light irradiation intensity and the light irradiation time in the light wavelength region is 10 mJ/cm 2 to 7, It is preferable to set the light irradiation time so as to achieve 000 mJ/cm 2 .
• the integrated amount of light is more preferably 200 mJ/cm 2 to 5,000 mJ/cm 2 and even more preferably 500 mJ/cm 2 to 4,000 mJ/cm 2 . When the integrated amount of light is within the above range, curing of the composition proceeds smoothly, and a uniform cured product can be easily obtained.
• heat curing can be appropriately combined before and/or after photocuring.
• the composition is first cured in the portion exposed to light by irradiating light, and then, A two-stage cure can also be performed in which heat is applied to cure the composition in the areas not exposed to light.
• substrates are not particularly limited, and examples thereof include substrates having complex shapes such as fabric, fibrous, powdery, porous, and uneven shapes, and two or more of these shapes. may be combined.
• Thermosetting method When the present composition is a thermosetting composition, its curing method and curing conditions are not particularly limited.
• the curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, even more preferably 110°C to 150°C.
• the curing temperature may be constant or may be increased. You may combine temperature rise and temperature fall.
• the curing time is appropriately selected according to the type of thermal polymerization initiator and the content of other components, and is preferably 10 minutes to 360 minutes, more preferably 30 minutes to 300 minutes, and even more preferably 60 minutes to 240 minutes.
• the silsesquioxane derivative of the present invention has a low viscosity and can produce a cured product having excellent hardness. Due to the low viscosity, it is excellent in coatability without a solvent, and even when a solvent is used, the amount used can be reduced. Since the silsesquioxane derivative of the present invention has a low viscosity, it can be suitably used for applications requiring low viscosity. For example, it can be applied to adhesive applications, inkjet printing, printing applications such as 3D printing, coating agent applications, nanoprinting applications, and the like.
• the silsesquioxane derivative of the present invention when applied to nanoprinting, has a low viscosity and is therefore excellent in fine transfer properties. Moreover, since the silsesquioxane derivative of the present invention can be used without a solvent, it can be cured as it is after being poured into a mold. The silsesquioxane derivative of the present invention may be used in combination with fillers, other polymerizable compounds and the like. Moreover, since the silsesquioxane derivative of the present invention has a low viscosity, it can be mixed with a large amount of filler. Since the cured product of the present invention is excellent in hardness, it can be applied to hard coats, optical members, and the like.
• a hard coat having excellent hardness can be obtained by curing the hard coat agent comprising the curable composition of the present invention.
• the hard coating agent of the present invention may be provided on a substrate, and for example, a substrate provided with a hard coat can be obtained by curing the hard coating agent applied on the substrate.
• the weight average molecular weight (Mw) of the silsesquioxane derivative in each example and each comparative example was measured as follows. Specifically, by gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8320GPC, hereinafter abbreviated as "GPC"), in a tetrahydrofuran solvent at 40 ° C., a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation ), and the molecular weight in terms of standard polystyrene was calculated from the retention time.
• GPC gel permeation chromatography
• the reaction solution was stirred while the aqueous solution prepared as the mixed solution was added dropwise from the dropping funnel over about 1 hour, and then allowed to stand overnight at room temperature. After that, the solvent and the like in the reaction solution were distilled off under reduced pressure while heating the reaction solution to 60° C. to obtain 145.2 g of a colorless transparent liquid silsesquioxane derivative 1 (S1).
• S1 colorless transparent liquid silsesquioxane derivative 1
• Example 2 to 8 Silsesquioxane derivatives 2 to 8 (S2 to S8 ).
• S2 to S8 3-acryloxypropyltrimethoxysilane (corresponding to structural unit (b)) and 3-methacryloxypropyltrimethoxysilane ( (corresponding to structural unit (c)) was used.
• Table 1 shows the molar ratio of each structural unit in the silsesquioxane derivatives, the viscosity at 25° C. and the weight average molecular weight (Mw).
• photocurable compositions 1 to 13 were prepared as follows. Using the prepared photocurable compositions 1 to 13, evaluation of UV curability and pencil hardness test were carried out. Details are described below.
• Photocurable compositions 1 to 13 (Preparation of photocurable composition) 0.03 part by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one is added to 1 part by mass of the synthesized silsesquioxane derivative 1 to 13, and the mixture is stirred with a rotation/revolution mixer. Photocurable compositions 1 to 13 (P1 to P13) were prepared by doing so. In the photocurable compositions 1 to 13, since the solvent and the like are removed by distillation during the synthesis of the silsesquioxane derivatives 1 to 13, the photocurable compositions 1 to 13 substantially contain a solvent. not
• a high-pressure mercury lamp was used as a UV light source, and each photocurable composition was irradiated with only a short wavelength of 365 nm through a heat ray cut filter, a bandpass filter, and a light reduction filter.
• the UV irradiation intensity at this time was 10 mW/cm 2 .
• UV curability was evaluated according to the following criteria based on the value of storage elastic modulus of each photocurable composition when UV was irradiated for 10 seconds. Excellent UV curability in the order of A>B>C. Table 1 shows the experimental results.
• B 1.0 ⁇ 10 6 Pa or more and less than 5.0 ⁇ 10 6 Pa C: Less than 1.0 ⁇ 10 6 Pa
• Lamp High pressure mercury lamp Height: 10cm Conveyor speed: 5.75m/min Accumulated amount of light per pass: 360 mJ/cm 2 (UV-A) Atmosphere: Atmosphere Number of passes: 10 times
• the photocured film prepared as described above was subjected to a pencil hardness test according to JIS K5600-5-4.
• a pencil hardness test was conducted using a 3H pencil when the PET film was used as the substrate, and an 8H pencil when the SPCC steel plate was used as the substrate.
• the scratch test was performed 10 times for each photocured film, and the number of times the photocured film had no defect was shown in %. The higher the % value, the higher the hardness of the photocured film. Table 1 shows the experimental results.
• the silsesquioxane derivatives obtained in Examples 1-8 had lower viscosities at 25° C. than Comparative Examples 1-3. Furthermore, the silsesquioxane derivatives obtained in Examples 1 to 8 had the same viscosity at 25° C. as compared with Comparative Example 4, and a photocured film having excellent hardness could be produced. . In addition, the silsesquioxane derivatives obtained in Examples 1 to 8 had a lower viscosity at 25° C. than Comparative Example 5, and a photocured film excellent in hardness could be produced.

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