Classifications

• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • 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
  • 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
• • 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

Definitions

• the present disclosure relates to a silsesquioxane derivative, a method for producing the same, a curable composition, a hard coat agent, a cured product, a hard coat, and a base material.
• an organosilicon compound having a hydrolyzable group is prepared by adding 50 to 5,000 parts by weight of water to 100 parts by weight of the organosilicon compound without using an organic solvent. It is obtained by hydrolysis of R 1 SiX 3 ( X is a group selected from a hydroxyl group, a hydrolyzable group, and a siloxane residue, and contains 30 to 100 mol% of a unit represented by (at least one of X is a siloxane residue), and A coating whose main component is an organopolysiloxane resin in which 30 to 80 mol% of R 1 SiX 3 is a unit containing one silanol group represented by R 1 Si(OH)Y 2 (Y is a siloxane residue). Agent compositions are disclosed.
• JP-A-10-030068 discloses that after applying a coating agent containing organopolysiloxane resin as a main component to the surface of clean plastic molded objects, wood-based products, ceramics, glass, and metals, high-energy radiation is applied. It is disclosed that an article coated with a cured film having excellent weather resistance etc. can be obtained by irradiating to polymerize and harden (meth)acrylic groups, and then heating to condense and harden silanol groups. .
• the coating agent composition disclosed in JP-A-10-030068 has scratch resistance, adhesion, weather resistance, flame retardance, storage stability, and flexibility, and can be used for plastic molded articles, wood-based products, etc. , it is disclosed that a flexible film can be formed on the surfaces of ceramics, glass, and metals. However, there is no description or suggestion regarding curing shrinkage rate.
• conventional radical polymerization hard coating agents have a problem in that they are not sufficiently cured into a thin film due to polymerization inhibition by oxygen, making it difficult to form a thin film coat.
• the present disclosure has been made in view of the above, and provides a silsesquioxane derivative with a low curing shrinkage rate, a method for producing the same, a curable composition containing the silsesquioxane derivative, and a cured product obtained by curing the same.
• the object of the present invention is to provide a hard coat agent containing the silsesquioxane derivative, a hard coat obtained by curing the same, and a substrate provided with the hard coat.
• Means for solving the above problems include the following aspects. ⁇ 1> A silsesquioxane derivative represented by the following formula (1) and having a curing shrinkage rate of less than 3.0%.
• R CE is each independently a group having a cyclic ether structure
• R 1 is 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 an aralkylene group having 7 to 12 carbon atoms
• R 2 and R 3 are each independently a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms.
• R 4 independently represents a cyclic ether structure.
• R 5 and R 6 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an organic group having 7 to 10 carbon atoms.
• R 3s may be the same or different from each other
• a plurality of R 5s may be the same or different from each other
• a plurality of R 6s may be the same or different from each other
• R 1 to R 6 may each independently have a part of the structure substituted with a substituent or a halogen atom
• v is a positive number
• u, w, x, y and z are each independently 0. Or is a positive number.
• ⁇ 2> The silsesquioxane derivative according to ⁇ 1>, wherein u, y, and z are 0 and satisfy 0 ⁇ x/(v+w) ⁇ 0.5.
• ⁇ 3> The silsesquioxane derivative according to ⁇ 1>, wherein the R CE is a group having an oxetane structure and/or an epoxy structure.
• ⁇ 4> The silsesquioxane derivative according to ⁇ 1>, wherein the R CE is a group having an oxetane structure.
• ⁇ 5> The silsesquioxane derivative according to any one of ⁇ 1> to ⁇ 4>, wherein the cured product obtained after curing has an elastic modulus at 23° C.
• ⁇ 6> A curable composition comprising the silsesquioxane derivative according to any one of ⁇ 1> to ⁇ 5> and a polymerization initiator.
• ⁇ 7> A hard coat agent comprising the curable composition according to ⁇ 6>.
• ⁇ 8> A cured product obtained by curing the curable composition according to ⁇ 6>.
• ⁇ 9> A hard coat obtained by curing the hard coat agent according to ⁇ 7>.
• ⁇ 10> A base material comprising the hard coat according to ⁇ 9>.
• a silsesquioxane derivative having a low curing shrinkage rate a method for producing the same, a curable composition containing this silsesquioxane derivative, a cured product obtained by curing the same, and a silsesquioxane derivative having a low curing shrinkage rate, It is possible to provide a hard coat agent containing a sun derivative, a hard coat obtained by curing the same, and a base material provided with the hard coat.
• R CE and R 1 to R 6 in formula (1) may be partially substituted with a substituent or a halogen atom, each independently.
• R CE and R 1 to R 6 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. , 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 6 in formula (1) may each independently be unsubstituted, for example, R CE , R 1 or R 4 to R 6 (preferably R 1 and R 4 to R 6 ). may be unsubstituted.
• silsesquioxane derivative The silsesquioxane derivative of the present disclosure is represented by the following formula (1) and has a curing shrinkage rate of less than 3.0%.
• R 4 independently represents a cyclic ether structure.
• R 5 and R 6 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an organic group having 7 to 10 carbon atoms.
• R 3s may be the same or different from each other
• a plurality of R 5s may be the same or different from each other
• a plurality of R 6s may be the same or different from each other
• R 1 to R 6 may each independently have a part of the structure substituted with a substituent or a halogen atom
• v is a positive number
• u, w, x, y and z are each independently 0. Or is a positive number.
• v in the formula (1) is a positive number, and by adding 2 to 30 molar equivalents of water to the total amount of hydrolyzable groups possessed by the organosilicon compound and performing hydrolysis. It is estimated that a suitable crosslinked structure can be obtained, resulting in low curing shrinkage.
• silsesquioxane derivative of the present disclosure is also excellent in the hardness of the obtained cured product and the indentation modulus of the obtained cured product.
• the curing shrinkage rate of the silsesquioxane derivative of the present disclosure is preferably less than 3.0%, more preferably 2.8% or less, from the viewpoint of hardness and indentation modulus; 2. It is more preferably 6% or less, and may be 2.0% or less. Further, the lower limit of the curing shrinkage rate is 0%.
• the method for measuring the curing shrinkage rate of the silsesquioxane derivative of the present disclosure is as follows.
• the density of the photocured product is measured in accordance with JIS K0061-8 (2001).
• the method for measuring the elastic modulus at 23°C of the cured product of the silsesquioxane derivative of the present disclosure is as follows.
• ⁇ Preparation of photocurable coating agent> When measuring a silsesquioxane derivative whose cyclic ether structure is an epoxy structure, add 0.02 parts by mass of (tolylcumyl)iodonium tetrakis(pentafluorophenyl)borate and propylene glycol to 1 part by mass of the silsesquioxane derivative to be measured.
• a photocurable coating agent is prepared by adding 1 part by mass of monobutyl ether and stirring the mixture with an autorotation-revolution mixer.
• Lamp High pressure mercury lamp (ECS-4011GX manufactured by Eye Graphics Co., Ltd.) Lamp height: 10cm Conveyor speed: 5.75m/min Cumulative light amount per pass: 360 mJ/cm 2 (measured value of UV-A, UV POWER PUCK II manufactured by EIT) Atmosphere: Atmospheric Number of passes: 10 times
• indentation hardness is measured at 23° C. and a strain rate of 0.05/s using a nanoindenter (Nano Indenter G200 manufactured by Agilent Technologies, using a Berkovich indenter).
• the modulus of elasticity is calculated by averaging the Modulus values at an indentation depth of 500 nm to 800 nm.
• structural units (a) to (f) Each structural unit that the silsesquioxane derivative of the present disclosure may contain is referred to as structural units (a) to (f) as follows.
• u, v, w, x, y and z in formula (1) represent the molar ratio of the structural units (a) to (f).
• u, v, w, x, y, and z are relative units (a) to (f) that may be included in the silsesquioxane derivative represented by formula (1).
• the molar ratio can be determined, for example, from NMR (nuclear magnetic resonance) analysis values of the silsesquioxane derivative of the present disclosure. 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 amount of the raw material charged.
• the molar ratio of each constituent unit of a silsesquioxane derivative can be calculated by performing 1 H-NMR analysis on a sample dissolved in deuterated chloroform, etc., and further performing 29 Si-NMR analysis if necessary. You may.
• the original structure of the silsesquioxane derivative may be deduced from the ratio of the constituent units by decomposing it into constituent units using an alkali or the like.
• the molar ratio of each constituent unit of the silsesquioxane derivative may be determined by combining known techniques such as mass spectrometry and IR (infrared absorption spectroscopy) analysis.
• the structural unit (b) has 3 O 1/2 atoms (1.5 oxygen atoms) per silicon atom, and a group having a cyclic ether structure is bonded to the silicon atom via R 1 .
• the T unit means a unit having three O 1/2 atoms per silicon atom.
• each R CE is preferably a group having an oxetane structure and/or a group having an epoxy structure from the viewpoint of curing shrinkage rate, hardness, and indentation modulus, More preferably, it is a group having an oxetane structure.
• R CE is preferably a group that is independently bonded to R 1 through an oxygen atom from the viewpoint of curing shrinkage rate, hardness, indentation modulus, and ease of synthesis.
• R CE may have only one cyclic ether structure, or may have two or more, but from the viewpoint of curing shrinkage rate, hardness, and indentation modulus, it must have only one. is preferred.
• Specific examples of R CE include 3-ethyl-3-oxetanylmethoxy group, glycidyloxy group, 3-methyl-3-oxetanylmethoxy group, and 3-oxetanylmethoxy group.
• 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. It is the basis. 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 proportion of the structural unit (b) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (b) to all structural units (v/(u+v+w+x+y+z)) is determined from the viewpoint of curing shrinkage rate, hardness, indentation modulus, and ultraviolet (hereinafter also referred to as UV) curability. , preferably from 0.3 to 1, more preferably from 0.5 to 1, even more preferably from 0.7 to 1, particularly preferably from 0.9 to 1.
• the structural unit (c) is a T unit having 3 O 1/2 atoms (1.5 oxygen atoms) per silicon atom, and R 2 bonded to the silicon atom.
• R 2 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 a saturated or unsaturated cycloalkyl group having 6 to 8 carbon atoms. 20 aryl group or an aralkyl group having 7 to 20 carbon atoms.
• the 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, and is preferably a saturated alkyl group having 1 to 10 carbon atoms. More preferred.
• Examples of the saturated alkyl group 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 the unsaturated alkyl group having 1 to 10 carbon atoms include a vinyl group, 2-propenyl group, and ethynyl group.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may have a branch.
• the 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.
• aryl group having 6 to 20 carbon atoms examples include a phenyl group, a group in which one or more of the hydrogen atoms of the phenyl group is substituted with an alkyl group having 1 to 10 carbon atoms, and a naphthyl group. From the viewpoint of heat resistance and hardness of the cured product, phenyl group is preferred.
• 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 a group in which one of the hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl group and phenethyl group, and benzyl group is preferable from the viewpoint of heat resistance and hardness of cured product.
• the proportion of the structural unit (c) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio (w/(u+v+w+x+y+z)) of the structural unit (c) to all structural units is preferably 0.1 or less, and 0.05 or less, from the viewpoint of hardness when formed into a cured product. It is more preferable that it be present, and even more preferable that it be zero.
• the structural unit (d) is a D unit having two O 1/2 atoms (one oxygen atom) per silicon atom, and two R 3 atoms bonded to the silicon atom. Note that the D unit means a unit having two O 1/2 atoms for one silicon atom.
• R 3 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 a saturated or unsaturated cycloalkyl group having 6 to 8 carbon atoms. 20 aryl group or an aralkyl group having 7 to 20 carbon atoms.
• a plurality of R 3 's may be the same or different from each other. Preferred embodiments of R 3 are the same as R 2 in structural unit (c).
• the proportion of the structural unit (d) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio (x/(u+v+w+x+y+z)) of the structural unit (d) to all structural units is preferably 0.1 or less, and 0.05 or less from the viewpoint of hardness when a cured product is obtained. It is more preferable that it be present, and even more preferable that it be zero.
• x is preferably a positive number.
• Structural unit (e) is M in which one silicon atom has one O 1/2 (0.5 oxygen atoms), and one R 4 and two R 5 are bonded to the silicon atom. It is a unit. Note that the M unit means a unit having one O 1/2 for one silicon atom.
• each R 4 is independently an organic group having 2 to 12 carbon atoms and having a cyclic ether structure.
• R 4 is preferably R CE -R 1 - in the structural unit (b). Further, preferred embodiments are also the same as those of R CE and R 1 in the structural unit (b).
• R 5 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.
• a plurality of R 5s may be the same or different from each other.
• alkyl group 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 of the hydrogen atoms of the phenyl group is substituted with an alkyl group having 1 to 4 carbon atoms, and a naphthyl group. From the viewpoint of heat resistance and hardness of the cured product, phenyl group is preferred.
• Examples of the aralkyl group having 7 to 10 carbon atoms include a group in which one of the hydrogen atoms of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl group and phenethyl group, and benzyl group is preferable from the viewpoint of heat resistance and hardness of cured product.
• the proportion of the structural unit (e) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (e) to all structural units (y/(u+v+w+x+y+z)) should be 0.5 or less from the viewpoint of curing shrinkage rate, hardness, storage stability, and UV curability. is preferable, more preferably 0.3 or less, and still more preferably 0.1 or less.
• the molar ratio (y/(u+v+w+x+y+z)) of the structural unit (e) to all structural units may be 0 or 0.01 or more.
• the structural unit (f) is an M unit having one O 1/2 (0.5 oxygen atom) per silicon atom and three R 6 bonded to the silicon atom.
• R 6 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.
• a plurality of R 6 's may be the same or different from each other.
• Preferred embodiments of R 6 are the same as R 5 in structural unit (e).
• the proportion of the structural unit (f) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio (z/(u+v+w+x+y+z)) of the structural unit (f) to all structural units is preferably 0.1 or less, and 0.05 or less from the viewpoint of hardness when formed into a cured product. It is more preferable that it be present, and even more preferable that it be zero.
• the silsesquioxane derivative of the present disclosure may further contain (R 7 O 1/2 ) as a Si-free structural unit (hereinafter also referred to as structural unit (g)).
• R 7 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 either linear or branched. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.
• u, y, and z are 0, and w and x are each independently 0 or a positive number. , u, w, x, y and z are more preferably 0. Further, in formula (1), from the viewpoint of curing shrinkage rate, hardness, and indentation modulus, it is preferable that 0 ⁇ x/(v+w) ⁇ 0.5, and 0 ⁇ x/(v+w) ⁇ 0. It is more preferable that 0 ⁇ x/(v+w) ⁇ 0.1 be satisfied.
• the viscosity at 25° C. is preferably 10 mPa ⁇ s to 50,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 40,000 mPa ⁇ s, and 1,000 mPa ⁇ s. - It is more preferably from s to 30,000 mPa ⁇ s, and particularly preferably from 2,000 mPa ⁇ s to 25,000 mPa ⁇ s.
• the viscosity at 25° C. means a value measured using an E-type viscometer (cone-plate viscometer; for example, TVE22H-type viscometer manufactured by Toki Sangyo Co., Ltd.).
• R examples include groups that bond to the silicon atom of the silsesquioxane derivative via a carbon atom (such as R CE -R 1 - and R 2 to R 6 ).
• X is preferably an alkoxy group, a silyloxy group, or a halogen atom, and more preferably an alkoxy group or a silyloxy group.
• n 3 in the obtained intermediate product and the organosilicon compound.
• Hydrolysis and polycondensation reactions with a compound in which p is 1 may further be performed.
• a silsesquioxane derivative whose terminal portion is capped with the structural unit (e) derived from a compound in which n is 3 and p is 1 in the organosilicon compound. Increase in viscosity of the oxane derivative is suppressed, and storage stability is improved.
• organosilicon compounds examples of those having an epoxy group include (glycidyloxypropyl)trimethoxysilane, (glycidyloxypropyl)triethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Can be mentioned.
• Examples include silane and ethynyldimethylmethoxysilane.
• organosilicon compound in which n is 3 and p is 1 examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyl
• Examples of the organic silicon compound in which n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldidiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, and diphenyldiethoxysilane.
• the organic solvent used in the hydrolysis step may be only alcohol, or may be a mixed solvent with at least one type of subsolvent.
• the subsolvent may be either a polar solvent or a nonpolar solvent, or a combination of both.
• organic solvents other than alcohol include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.
• the amount of the catalyst used is preferably an amount corresponding to 0.01 mol% to 20 mol%, and 0.1 mol% to 10 mol%, based on the total amount (mol) of silicon atoms contained in the silicon compound. More preferably, the amount corresponds to %.
• an auxiliary agent can be added to the reaction system.
• the above-mentioned iodonium salt can be a commercially available product. Specifically, for example, “UV9380C” (trade name) manufactured by Mentive Performance Materials Japan, “PHOTOINITIATOR 2074” (trade name) manufactured by Solvay Japan, Inc. ), manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., "WPI-116" (trade name) and “WPI-113” (trade name).
• thermal cationic polymerization initiator examples include sulfonium salts, phosphonium salts, and quaternary ammonium salts. Among these, sulfonium salts are preferred.
• the counter anion in the thermal cationic polymerization initiator include AsF 6 - , SbF 6 - , PF 6 - , B(C 6 F 5 ) 4 - , and the like.
• the sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, tri(4-methoxyphenyl)sulfonium arsenic hexafluoride, and diphenyl(4-phenylthio). phenyl)sulfonium, arsenic hexafluoride, and the like.
• the sulfonium salt can be a commercially available product, and specifically, for example, "ADEKA Opton CP-66” (trade name) and “ADEKA Opton CP-77” (trade name) manufactured by ADEKA Co., Ltd.
• Examples include “Sun Aid SI-60L” (trade name), “Sun Aid SI-80L” (trade name), and “Sun Aid SI-100L” (trade name) manufactured by Shin Kagaku Kogyo Co., Ltd.
• the polymerization initiators may be used alone or in combination of two or more.
• the content of the polymerization initiator is 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the silsesquioxane derivative represented by formula (1).
• the amount is preferably 0.1 parts by weight to 10 parts by weight, and even more preferably 1 part to 5 parts by weight.
• Other components are not particularly limited, and include, for example, a solvent, a polymerizable compound other than the silsesquioxane derivative represented by formula (1), a resin, a silicone, a monomer, a filler, a surfactant, an antistatic agent ( For example, conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion agents, nano Examples include particles, nanofibers, nanosheets, and the like.
• the curable composition of the present disclosure may contain a silane-based reactive diluent such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.
• a silane-based reactive diluent such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.
• the curable composition of the present disclosure 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. It will be done.
• the curable composition of the present disclosure may or may not contain a polymerizable compound (hereinafter also referred to as "other polymerizable compound") other than the silsesquioxane derivative represented by formula (1). You don't have to be there.
• Other polymerizable compounds are not particularly limited as long as they are compounds that can undergo a polymerization reaction in the presence of the silsesquioxane derivative represented by formula (1) and a polymerization initiator.
• Other polymerizable compounds include silsesquioxane derivatives other than the silsesquioxane derivative represented by formula (1), epoxy compounds (compounds having an epoxy group), and compounds having an oxetanyl group (compounds containing an oxetanyl group).
• the curable composition has a higher cure shrinkage rate, hardness, and indentation modulus than an epoxy compound and a compound having an oxetanyl group. It is preferable to contain a compound having at least one selected from the group consisting of: more preferably an epoxy compound; and particularly preferably a polyfunctional epoxy compound.
• silsesquioxane derivatives other than the silsesquioxane derivative represented by formula (1) examples include silsesquioxane derivatives consisting only of T units, silsesquioxane derivatives containing T units and D units, etc. .
• Examples of the epoxy compound include monofunctional epoxy compounds and polyfunctional epoxy compounds.
• Examples of the oxetanyl group-containing compound include monofunctional oxetane compounds and polyfunctional oxetane compounds.
• Examples of the vinyl ether compound include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. As these compounds, for example, compounds described in JP-A No. 2011-42755 may be used.
• polyfunctional epoxy compounds include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexylcarboxylate (for example, manufactured by Daicel Corporation) "Celoxide 2021P" (trade name)), di(3,4-epoxycyclohexyl) adipate, bisphenol A epoxy resin, halogenated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S diglycidyl ether, bisphenol F-type epoxy resin, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, compound in which both ends of polybutadiene are glycidyl etherified, o-cresol novolac type epoxy resin, m-cresol novolac type epoxy resin , p-cresol novolak type epoxy resin, phenol novolac
• a block comprising an ethylene-butylene copolymer part and an isoprene polymer part, such as a compound in which the double bond in a styrene-butadiene copolymer is partially epoxidized, such as "L-207" (trade name) manufactured by KRATON.
• a copolymer a part of the isoprene polymer part is epoxidized, and in a ring-opening polymer of 4-vinylcyclohexene oxide such as "EHPE3150" (trade name) manufactured by Daicel Corporation, the vinyl group is epoxidized.
• Compounds with a structure of Examples thereof include alicyclic type cage-shaped silsesquioxanes having groups, epoxy group-containing silsesquioxane compounds, and epoxidized vegetable oils.
• Examples of monofunctional epoxy compounds include ⁇ -olefin epoxides such as 1,2-epoxyhexadecane, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, and glycidyl methacrylate.
• polyfunctional oxetane compounds include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene (XDO), di[2-(3-oxetanyl)butyl]ether (DOX), 1, 4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[ (3-ethyloxetan-3-yl)methoxy]benzene (CTOX), 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl(2,2'-BPOX),3,3',5,5'-tetramethyl[
• silicone there are no particular restrictions on the silicone, and known silicones can be used, such as polydimethyl silicone, polydiphenyl silicone, and polymethylphenyl silicone, which have functional groups at their terminals and/or side chains.
• 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, and thiol group.
• (Meth)acrylate compounds are not particularly limited, and include 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)acrylate of phenol ethylene oxide adduct, (meth)acrylate of phenol propylene oxide adduct, (meth)acrylate of modified nonylphenol ethylene oxide adduct, (meth)acrylate of nonylphenol propylene
• polyfunctional (meth)acrylates include: Polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylate 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)acrylate can also be used as the polyfunctional (meth)acrylate.
• urethane (meth)acrylate include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth)acrylate, compounds obtained by addition reaction of organic polyisocyanate, polyol, and hydroxyl group-containing (meth)acrylate, etc. .
• Monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc. may be used alone, in combination of two or more, or in combination of different types.
• examples of polyols include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols.
• examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, and 3-methyl-1,5-pentanediol.
• examples of polyether polyols include polypropylene glycol, polytetramethylene glycol, and the like.
• organic polyisocyanate examples 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 include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; pentaerythritol tri(meth)acrylate; ) acrylate, di(meth)acrylate of 3 moles of alkylene oxide adduct of isocyanuric acid, and hydroxyl group-containing polyfunctional (meth)acrylate such as dipentaerythritol penta(meth)acrylate. These may be used alone, or two or more types may be used in combination, or different types may be used in combination.
• 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, and acryloyl morphocarbon. Examples include phosphorus, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more.
• the light irradiation intensity in the light wavelength range effective for photopolymerization (depending on the type of photopolymerization initiator, but preferably light with a wavelength of 220 nm to 460 nm is used) is 0.1 mW/cm 2 to 1000 mW/cm 2 . It is preferable that there be. Further, the irradiation energy should be appropriately set depending on the type of active energy ray, the composition, etc.
• the cured product of the present disclosure Since the cured product of the present disclosure has excellent hardness, it can be applied to hard coats, optical members, etc. Further, by curing a hard coat agent containing the curable composition of the present disclosure, a hard coat with excellent hardness can be obtained.
• the hard coat agent of the present disclosure may be provided on a base material, and for example, a base material provided with a hard coat can be obtained by curing the hard coat agent applied on the base material.
• the hard coat agent of the present disclosure may contain various components as necessary.
• the silsesquioxane derivative of the present disclosure can produce a cured product that has low viscosity and excellent hardness.
• the silsesquioxane derivatives obtained in Examples 1 to 3 had lower cure shrinkage rates than Comparative Examples 1 to 3. Furthermore, the silsesquioxane derivatives obtained in Examples 1 to 3 were excellent in the hardness of the obtained cured products and the indentation modulus of the obtained cured products.

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  • 2023-06-05 WO PCT/JP2023/020904 patent/WO2023238836A1/ja not_active Ceased
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