Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • 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

Definitions

• the present disclosure relates to silsesquioxane derivatives, curable compositions, cured products, hard coating agents, hard coatings, articles, and laminates.
• cycloolefin (co)polymer substrates are used as substrates for optical applications.
• “Cycloolefin (co)polymer substrate” refers to at least one of a substrate containing a cycloolefin copolymer and a substrate containing a cycloolefin polymer.
• the surface of a cycloolefin (co)polymer substrate has a disadvantage of being easily scratched due to its low scratch resistance. To prevent scratches, a hard coat is applied to the surface of the cycloolefin (co)polymer substrate.
• cycloolefin (co)polymer substrates are one of the poorly adhesive substrates that are generally known to have poor adhesion.
• Hard coats for cycloolefin (co)polymer substrates can be obtained, for example, by curing a hard coat agent containing alkoxysilane or its hydrolysate through a sol-gel reaction caused by heating.
• Patent Document 1 discloses that a coating composition (hereinafter also referred to as "hard coat composition”) is coated onto a cycloolefin (co)polymer, and the coating film is cured by a sol-gel method by heating at 140°C for 1 hour.
• the hard coat composition contains an organoalkoxysilane, its hydrolysate or partial hydrolysate, colloidal silica, water, and a hydrophilic organic solvent.
• Patent Document 2 lists norbornene-based resins and cycloolefin-based resins as substrate materials.
• a curable composition hereinafter also referred to as a "hard coat composition”
• the hard coat composition contains a silsesquioxane derivative having a phenyl group and a methyl group, silica particles, and a silane coupling agent.
• Patent Document 1 JP-A-3-122137
• Patent Document 2 WO 2021/060562
• Patent Documents 1 and 2 require high-temperature heating to harden the hard coat composition after it has been coated onto the substrate. Therefore, the substrate needs to be heat-resistant to these heating temperatures. In addition, the curing process takes time, resulting in low productivity and making the method impractical.
• An object of one embodiment of the present disclosure is to provide a silsesquioxane derivative, a curable composition, a cured product, a hard coating agent, a hard coating, an article, and a laminate that have excellent adhesion and weather resistance to poorly adhesive substrates (e.g., cycloolefin (co)polymer substrates, etc.) even in the absence of high-temperature heat treatment.
• poorly adhesive substrates e.g., cycloolefin (co)polymer substrates, etc.
• a silsesquioxane derivative represented by the following formula (1) having a condensation rate of 72.0% or more and a cure shrinkage rate of less than 8.9%.
• 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 an aralkylene group having 7 to 12 carbon atoms;
• R 3 is an alkyl group having 1 to 6 carbon atoms;
• R 4 and R 5 are each independently 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, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms;
• R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenically unsaturated bond and a carbon-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
• ⁇ 2> The silsesquioxane derivative according to ⁇ 1>, in which u is a positive number, and v, x and y each independently are 0 or a positive number.
• ⁇ 3> The silsesquioxane derivative according to ⁇ 1>, wherein u and v are each independently a positive number.
• a curable composition comprising the silsesquioxane derivative according to any one of ⁇ 1> to ⁇ 3> and a polymerization initiator.
• ⁇ 5> A cured product obtained by curing the curable composition according to ⁇ 4>.
• ⁇ 6> A hard coat agent comprising the curable composition according to ⁇ 4>.
• ⁇ 7> A hard coat obtained by curing the hard coat agent according to ⁇ 6>.
• ⁇ 8> An article (preferably a substrate) provided with the hard coat according to ⁇ 7>.
• ⁇ 9> A laminate comprising the hard coat according to ⁇ 7> and a substrate.
• a silsesquioxane derivative a curable composition, a cured product, a hard coating agent, a hard coating, an article, and a laminate that have excellent adhesion and weather resistance to poorly adhesive substrates even without high-temperature heat treatment.
• the numerical ranges indicated using “to” include the numerical values before and after “to” as the minimum and maximum values, respectively.
• the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range.
• the upper or lower limit of the numerical range may be replaced by the values shown in the examples.
• the amount of each component in the composition means the total amount of the corresponding substances present in the composition, unless otherwise specified.
• the term “process” refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.
• “mass %” and “weight %” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
• the "high temperature” in “high-temperature heat treatment” refers, for example, to a temperature applied to promote the sol-gel reaction that hardens the coating agent.
• the high temperature is, for example, 120°C or higher, and preferably 130°C or higher. If the temperature of the high-temperature heat treatment is higher than the softening temperature of the substrate, it is not preferable to use the coating agent to form a hardened product on the substrate.
• silsesquioxane derivative of the present disclosure is represented by the following formula (1), and has a condensation rate of 72.0% or more and a cure shrinkage rate of less than 8.9%.
• 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 an aralkylene group having 7 to 12 carbon atoms;
• R 3 is an alkyl group having 1 to 6 carbon atoms;
• R 4 and R 5 are each independently 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, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms;
• R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenically unsaturated bond and a carbon-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
• the mechanism by which the silsesquioxane derivative of the present disclosure exerts the above-mentioned effects is not clear, but is presumed to be as follows.
• the condensation rate of the silsesquioxane derivative By setting the condensation rate of the silsesquioxane derivative to a predetermined value or more, the hydroxyl group and alkoxy group in the silsesquioxane derivative are present in an appropriate amount. Therefore, the polarity of the silsesquioxane derivative is reduced, and the hydrophobicity is improved. It is presumed that this improves the adhesion between the cured product (hereinafter, simply referred to as "cured product") obtained by curing the silsesquioxane derivative of the present disclosure and a poorly adhesive substrate (e.g., a hydrophobic substrate).
• cured product the cured product obtained by curing the silsesquioxane derivative of the present disclosure and a poorly adhesive substrate (e.g., a hydrophobic substrate).
• the cure shrinkage rate of the silsesquioxane derivative By controlling the cure shrinkage rate of the silsesquioxane derivative to less than a predetermined value, the interfacial stress of the cured product is reduced, and it is presumed that the cured product therefore exhibits excellent adhesion to poorly adhesive substrates and excellent weather resistance.
• R 1 to R 8 in formula (1) may each independently be partially substituted with a substituent or a halogen atom.
• R 1 to R 8 may each independently be partially substituted with 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 8 in formula (1) may each independently be unsubstituted.
• 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 of the present disclosure in formula (1), t, u, v, w, x, y, and z are each independently 0 or a positive number, and at least one of u and v is a positive number.
• the silsesquioxane derivative of the present disclosure contains at least one of the structural units (b) and (c) among the structural units (a) to (g) described above, and optionally contains at least one of the structural units (a), (d), (e), (f), and (g).
• t represents the molar ratio of structural unit (a) to 100 moles of structural units (a) to (g) (hereinafter also referred to as "total structural units").
• u represents the molar ratio of structural unit (b) to 100 moles of all structural units.
• v represents the molar ratio of structural unit (c) to 100 moles of all structural units.
• w represents the molar ratio of structural unit (d) to 100 moles of all structural units.
• x represents the molar ratio of structural unit (e) to 100 moles of all structural units.
• y represents the molar ratio of structural unit (f) to 100 moles of all structural units.
• z represents the molar ratio of structural unit (g) to 100 moles of all structural units.
• the molar ratio can be determined from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative of the present disclosure.
• the reaction rate of each raw material of the silsesquioxane derivative is clear or the yield is 100%
• the molar ratio can be determined from the amount of the raw material charged.
• the molar ratio of each of the structural units of the silsesquioxane derivative may be calculated by subjecting a sample dissolved in deuterated chloroform or the like to 1 H-NMR analysis, and, if necessary, further subjecting the sample to 29 Si-NMR analysis.
• the silsesquioxane derivative may be decomposed into its constituent units using an alkali or the like, and the structure of the silsesquioxane derivative may be estimated from the ratio of the constituent units. If necessary, the molar ratio of each of the structural units of the silsesquioxane derivative may be determined by combining known techniques (for example, mass spectrometry, IR (infrared absorption spectroscopy) analysis, etc.).
• 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 derivative. Therefore, the condensation form of the structural units in the silsesquioxane derivative of the present disclosure does not have to be the order of arrangement in formula (1).
• the structural units (a) to (g) will be described in detail below.
• the structural unit (a) of the present disclosure is a Q unit.
• Q unit refers to a unit having four O 1/2 (two oxygen atoms) per silicon atom.
• the proportion of the structural unit (a) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (a) to all structural units (t/(t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of adhesion and weather resistance.
• a molar ratio of 0 means that the corresponding structural unit is not contained, and the same applies below.
• the structural unit (b) of the present disclosure is a T unit in which an acryloyloxy group is bonded to a silicon atom via R 1.
• the term "T unit” refers to a unit having 3 O 1/2 (1.5 oxygen atoms) per 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.
• R 1 is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and 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, and more preferably a cycloalkylene group having 4 to 6 carbon atoms.
• the cycloalkylene group having 3 to 10 carbon atoms may be branched.
• the ratio of the structural unit (b) in the silsesquioxane derivative of the present disclosure 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 preferably 0.20 to 0.99, more preferably 0.30 to 0.90, even more preferably 0.30 to 0.70, and particularly preferably 0.45 to 0.65, from the viewpoints of condensation rate and cure shrinkage rate.
• the molar ratio of the structural unit (b) to all structural units may be 0.
• u>v is satisfied. It is more preferable that 0 ⁇ molar ratio of structural unit (b) (u/(t+u+v+w+x+y+z)) - molar ratio of structural unit (c) (v/(t+u+v+w+x+y+z)) ⁇ 1 is satisfied. It is even more preferable that 0.05 ⁇ molar ratio of structural unit (b) (u/(t+u+v+w+x+y+z)) - molar ratio of structural unit (c) (v/(t+u+v+w+x+y+z)) ⁇ 0.60 is satisfied.
• the structural unit (c) of the present disclosure is a T unit in which an acryloyloxy group (such as a methacryloyloxy group) in which a hydrogen atom is substituted with R3 is bonded to a silicon atom via R2 .
• an acryloyloxy group such as a methacryloyloxy group
• R2 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. Preferred aspects of R2 are the same as those of R1 in the structural unit (b).
• R3 is an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
• a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
• the ratio of the structural unit (c) in the silsesquioxane derivative of the present disclosure 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 0.80, more preferably 0.05 to 0.70, even more preferably 0.20 to 0.70, and particularly preferably 0.35 to 0.55, from the viewpoints of condensation rate and cure shrinkage rate.
• the molar ratio of the structural unit (c) to all structural units may be 0.
• At least one of u and v is a positive number. From the viewpoint of cure shrinkage, it is preferable that u and v are each independently a positive number.
• the total molar ratio ((u+v)/(t+u+v+w+x+y+z)) of the structural units (b) and (c) to all structural units is preferably 0.3 to 1.0, more preferably 0.5 to 1.0, even more preferably 0.7 to 1.0, and particularly preferably 0.9 to 1.0, from the viewpoints of adhesion and weather resistance.
• Constitutional unit (d) of the present disclosure is a T unit in which R4 is bonded to a silicon atom.
• R4 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, an aryl group having 6 to 20 carbon atoms, 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 more preferably a saturated alkyl group having 1 to 10 carbon atoms.
• saturated alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the standpoint of heat resistance and hardness of the cured product, methyl and ethyl groups are preferred, and methyl groups are more preferred.
• Examples of unsaturated alkyl groups having 1 to 10 carbon atoms include vinyl groups, 2-propenyl groups, and ethynyl groups.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may be branched.
• 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.
• the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.
• aryl groups having 6 to 20 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and naphthyl groups. From the standpoint of heat resistance and hardness of the cured product, phenyl groups are preferred.
• the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.
• Examples of aralkyl groups 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 (e.g., a phenyl group, etc.).
• Examples of aralkyl groups having 7 to 20 carbon atoms include a benzyl group or a phenethyl group. From the viewpoints of heat resistance and hardness of the cured product, a benzyl group is preferred.
• examples of R 4 include a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3-ethyloxetan-3-yl)methoxypropyl group, a 3-hydroxypropyl group, a 3-aminopropyl group, a 3-dimethylaminopropyl group, a 3-hydroxypropyl group, a 3-aminopropyl hydrochloride, a 3-dimethylaminopropyl hydrochloride, a p-styryl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-phenyl-3-aminopropyl group, an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl hydrochloride, a 3-ure
• the proportion of the structural unit (d) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (d) to all structural units (w/(t+u+v+w+x+y+z)) is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoints of adhesion and weather resistance.
• the structural unit (e) is a D unit in which two R5 are bonded to a silicon atom.
• the term "D unit” refers to a unit having two O1 /2 (one oxygen atom) per silicon atom.
• R5 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, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• multiple R5s may be the same or different.
• the preferred embodiments of R5 are the same as R4 in the structural unit (d).
• 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 (x/(t+u+v+w+x+y+z)) is preferably 0.4 or less, more preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.1 or less, and even more preferably 0, from the viewpoint of adhesion and weather resistance.
• x is preferably a positive number.
• the structural unit (f) of the present disclosure is an M unit in which one R 6 and two R 5 are bonded to a silicon atom.
• the "M unit” refers to a unit having one O 1/2 (0.5 oxygen atoms) per silicon atom.
• R 6 is an organic group having 2 to 12 carbon atoms and at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond.
• organic groups having 2 to 12 carbon atoms and an ethylenically unsaturated bond include vinyl groups, orthostyryl groups, methstyryl groups, parastyryl groups, acryloyloxymethyl groups, methacryloyloxymethyl groups, 2-acryloyloxyethyl groups, 2-methacryloyloxyethyl groups, 3-acryloyloxypropyl groups, 3-methacryloyloxypropyl groups, 8-acryloyloxyoctyl groups, 8-methacryloyloxyoctyl groups, and 8-methacryloyloxyoctyl groups.
• silsesquioxane derivative examples include octyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 1-phenylethenyl, 2-phenylethenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, and phenylbutynyl. From the viewpoint of hardness when the silsesquioxane derivative is cured, vinyl, 2-propenyl, orthostyryl, metastyryl, and parastyryl groups are preferred, and vinyl is more preferred.
• 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 7s may be the same or different.
• alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the standpoint of heat resistance and hardness of the cured product, methyl and ethyl groups are preferred, and methyl groups are more preferred.
• aryl groups having 6 to 10 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 4 carbon atoms, and naphthyl groups. From the standpoint of heat resistance and hardness of the cured product, phenyl groups are preferred.
• Examples of aralkyl groups 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 (e.g., a phenyl group, etc.).
• Examples of aralkyl groups having 7 to 10 carbon atoms include a benzyl group or a phenethyl group. From the viewpoints of heat resistance and hardness of the cured product, a benzyl group is preferred.
• the proportion of the structural unit (f) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (f) to all structural units (y/(t+u+v+w+x+y+z)) is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less, from the viewpoints of adhesion and weather resistance.
• the structural unit (g) is an M unit in which three R8s are bonded to a silicon atom.
• R8 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 R8s may be the same or different. Preferred aspects of R8 are the same as R7 in the structural unit (f).
• the proportion of the structural unit (g) in the silsesquioxane derivative of the present disclosure is not particularly limited.
• the molar ratio of the structural unit (g) to all structural units (z/(t+u+v+w+x+y+z)) is preferably 0.10 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoints of adhesion and weather resistance.
• the silsesquioxane derivative of the present disclosure may further contain (R 9 O 1/2 ) (hereinafter also referred to as structural unit (h)) as a structural unit not containing Si.
• R9 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. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
• the structural unit (h) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group generated by substitution of the hydrolyzable group of the silicon compound with an alcohol contained in the reaction solvent.
• the structural unit (h) may be one that remains in the molecule without being hydrolyzed or polycondensed.
• the structural unit (h) may be a hydroxyl group that remains in the molecule after hydrolysis without being polycondensed.
• t and z are 0, and w, x and y are each independently 0 or a positive number, and it is more preferable that t, w, x, y and z are 0.
• u is a positive number
• v, x, and y are each independently 0 or a positive number
• u and v are each independently a positive number.
• Each of u and v is independently a positive number, and preferably satisfies 0.1 ⁇ v/u ⁇ 1, more preferably satisfies 0.2 ⁇ v/u ⁇ 1, and further preferably satisfies 0.3 ⁇ v/u ⁇ 1.
• the condensation rate of the silsesquioxane derivative of the present disclosure is 72.0% or more. From the viewpoint of adhesion and weather resistance, the condensation rate is preferably 75.0% or more, and more preferably 78.0% or more. The condensation rate is preferably 98% or less, more preferably 95% or less, and even more preferably 90% or less. If the condensation rate is less than 72.0%, the adhesion is reduced. By having a condensation rate of 98% or less, it is easy to maintain good viscosity, solubility in a solvent, and/or coatability, and the adhesion is more excellent.
• the condensation rate of the silsesquioxane derivative of the present disclosure can be calculated from the ratio of the peak integral values of M1 units, D1 units, D2 units, T1 units, T2 units, T3 units, Q1 units, Q2 units, Q3 units, and Q4 units measured by 29 Si-NMR (nuclear magnetic resonance). Specifically, the condensation rate is calculated according to the following formulas (a) to (c).
• Condensation rate (%) [integral value of silicon corresponding to condensed siloxane bonds / integral value of silicon corresponding to all condensable siloxane bonds] x 100
• an integral value in T3 units is represented as [T3].
• [M0] and [M1] represent the peak integral values of silicon atoms assigned to M0 and M1 below in the 29 Si-NMR spectrum of the silsesquioxane derivative.
• the silicon atoms assigned to M0 and M1 are silicon atoms assigned to a monofunctional organosilicon compound.
• [D0], [D1] and [D2] represent the peak integral values of silicon atoms assigned to D0, D1 and D2 below in the 29 Si-NMR spectrum of the silsesquioxane derivative.
• the silicon atoms assigned to D0, D1 and D2 below are silicon atoms assigned to a bifunctional organosilicon compound.
• [T0], [T1], [T2], and [T3] represent peak integral values of silicon atoms assigned to T0, T1, T2, and T3 below in the 29 Si-NMR spectrum of the silsesquioxane derivative.
• the silicon atoms assigned to T0, T1, T2, and T3 below are silicon atoms assigned to a trifunctional organosilicon compound.
• [Q0], [Q1], [Q2], [Q3] and [Q4] represent peak integral values of silicon atoms assigned to Q0, Q1, Q2, Q3 and Q4 below in the 29 Si-NMR spectrum of the silsesquioxane derivative.
• the silicon atoms assigned to Q0, Q1, Q2, Q3 and Q4 below are silicon atoms assigned to a tetrafunctional organosilicon compound.
• M0 A silicon atom that is not bonded to other silicon atoms through oxygen.
• M1 A silicon atom that is bonded to one silicon atom through oxygen.
• D0 A silicon atom that is not bonded to other silicon atoms through oxygen.
• D1 A silicon atom that is bonded to one silicon atom through oxygen.
• D2 A silicon atom that is bonded to two silicon atoms through oxygen.
• T0 A silicon atom that is not bonded to other silicon atoms through oxygen.
• T1 A silicon atom that is bonded to one silicon atom through oxygen.
• T2 A silicon atom that is bonded to two silicon atoms through oxygen.
• T3 A silicon atom that is bonded to three silicon atoms through oxygen.
• Q0 A silicon atom that is not bonded to other silicon atoms through oxygen.
• Q1 A silicon atom that is bonded to one silicon atom through oxygen.
• Q2 A silicon atom that is bonded to two silicon atoms through oxygen.
• Q3 A silicon atom that is bonded to three silicon atoms through oxygen.
• Q4 A silicon atom that is bonded to four silicon atoms through oxygen.
• the curing shrinkage of the silsesquioxane derivative of the present disclosure is less than 8.9%. From the viewpoint of reducing the interfacial stress, the curing shrinkage is preferably 8.5% or less, more preferably 7.5% or less, and even more preferably 6.5% or less. If the curing shrinkage is 8.9% or more, the adhesion between the cured product and the substrate is reduced.
• the curing shrinkage is not particularly limited, but can be 0%.
• the cure shrinkage of the silsesquioxane derivative is a value calculated according to the following formula (d) after measuring the density in accordance with JIS K0061-8 (2001).
• Cure shrinkage rate (%) [(cured product density - density before curing) / density before curing] x 100
• the "density before curing” indicates the density of the silsesquioxane derivative.
• the method for measuring the cure shrinkage (%) is the same as that described in the Examples.
• the molar ratio (u/(t+u+v+w+x+y+z)) is 0.45 to 0.65
• the molar ratio (v/(t+u+v+w+x+y+z)) is 0.35 to 0.55
• each of the molar ratio (t/(t+u+v+w+x+y+z)), the molar ratio (w/(t+u+v+w+x+y+z)), the molar ratio (x/(t+u+v+w+x+y+z)), the molar ratio (y/(t+u+v+w+x+y+z)) and the molar ratio (z/(t+u+v+w+x+y+z)) is 0, and at least one of the condensation rate being 78.0% or more and the cure shrinkage rate being 7.5% or less is satisfied.
• the silsesquioxane derivative of the present disclosure can form a cured product having excellent adhesion and weather resistance to poorly adhesive substrates, whether by heat treatment other than high-temperature heat treatment (e.g., 110°C) or by active energy ray curing treatment.
• heat treatment other than high-temperature heat treatment (e.g., 110°C) or by active energy ray curing treatment.
• the silsesquioxane derivative of the present disclosure can be produced by a known method.
• the method for producing a silsesquioxane derivative is disclosed in detail in WO 2013/031798 and the like as a method for producing a polysiloxane.
• the method for producing a silsesquioxane derivative according to the present disclosure preferably includes a hydrolysis step in which water is added to a mixture of at least one organosilicon compound and an organic solvent to carry out hydrolysis.
• R represents a group that is bonded to a silicon atom in the silsesquioxane derivative via a carbon atom.
• X represents a hydrolyzable group.
• R examples include groups that are bonded to the silicon atom in the silsesquioxane derivative via a carbon atom (H 2 C ⁇ CHCOO—R 1 —, H 2 C ⁇ C(R 3 )COO—R 2 —, and R 4 to R 8, etc.).
• X is preferably an alkoxy group, a silyloxy group, or a halogen atom, and more preferably an alkoxy group or a silyloxy group.
• the amount of water added is 0.36 to 30 molar equivalents based on the total amount of hydrolyzable groups possessed by the organosilicon compound.
• the hydrolysis step it is preferable to carry out not only hydrolysis of the organosilicon compound but also hydrolysis and polycondensation reaction of the organosilicon compound and, if necessary, other silicon compounds.
• the organosilicon compound and, if necessary, other silicon compounds are subjected to hydrolysis and polycondensation reactions to obtain a silsesquioxane derivative as an intermediate product, and then the obtained intermediate product may be further subjected to hydrolysis and polycondensation reactions with the organosilicon compound and the like.
• the method for producing a silsesquioxane derivative according to the present disclosure preferably further includes a distillation step.
• the organosilicon compound is subjected to hydrolysis and polycondensation reaction in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water, etc. in the reaction liquid are distilled off.
• examples of compounds having an acryloyl group include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, and (3-acryloyloxypropyl)trichlorosilane.
• examples of compounds having a methacryloyl group include (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (8-methacryloyloxyoctyl)trimethoxysilane, and (3-methacryloyloxypropyl)trichlorosilane.
• Organosilicon compounds that give two structural units (f) upon hydrolysis include 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3-acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, and ethynyldimethylmethoxysilane.
• Silicon compounds that give the structural unit (a) upon hydrolysis include, for example, tetramethoxysilane, tetraethoxysilane, etc.
• organosilicon compounds in which n is 3 and p is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, ...
• Examples of such compounds include trimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[ ⁇ 3-(trimethoxysilyl)propoxy ⁇ methyl]oxetane, and 3-ethyl-3-[ ⁇ 3-(triethoxysilyl)propoxy ⁇ methyl]oxetane.
• organosilicon compounds in which n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, silane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropy
• organosilicon compound in which n is 1 and p is 3 examples include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and dimethylphenylmethoxysilane.
• the reaction solvent is not particularly limited, but it is preferable to use an alcohol as the organic solvent.
• the alcohol is a compound represented by the general formula R-OH.
• the alcohol is an alcohol in the narrow sense. The alcohol does not have any functional group other than the alcoholic hydroxyl group.
• the alcohol is not particularly limited, and examples thereof 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, and cyclohexanol.
• secondary alcohols are preferred.
• secondary alcohols examples include 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, and cyclohexanol.
• these alcohols may be used alone or in combination of two or more.
• the organic solvent used in the hydrolysis step may be an alcohol alone or a mixed solvent of an alcohol and at least one auxiliary solvent.
• the auxiliary solvent may be either a polar solvent or a non-polar 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 hydrolysis and condensation reactions in the hydrolysis step proceed in the presence of water.
• the amount of water added is, from the viewpoints of the condensation rate and cure shrinkage rate, preferably 0.36 to 30 molar equivalents, more preferably 0.4 to 8 molar equivalents, even more preferably 0.5 to 7 molar equivalents, particularly preferably 0.55 to 6 molar equivalents, and most preferably 0.6 to 4 molar equivalents, relative to the total amount of hydrolyzable groups in the organosilicon compound.
• the hydrolysis and polycondensation reaction of silicon compound may be carried out without catalyst or with catalyst.
• inorganic acid e.g. sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid, etc.
• acid catalyst e.g. formic acid, acetic acid, oxalic acid or paratoluenesulfonic acid, etc.
• base catalyst e.g. ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, etc.
• Acid catalyst is more preferably used.
• the amount of the catalyst used is preferably an amount corresponding to 0.01 mol % to 20 mol %, and more preferably an amount corresponding to 0.1 mol % to 10 mol %, based on the total amount (mol) of silicon atoms contained in the silicon compound.
• an auxiliary can be added to the reaction system.
• the stability of the produced silsesquioxane derivative of the present disclosure can be improved by carrying out the above-mentioned distillation step after carrying out the hydrolysis step.
• the distillation can be carried out under normal pressure or reduced pressure, at room temperature or under heating, or under cooling.
• the method for producing a silsesquioxane derivative may include a neutralization step of neutralizing the catalyst before carrying out the distillation step.
• the method for producing a silsesquioxane derivative may also include a step of removing the salt generated by neutralization by washing with water or the like.
• silsesquioxane derivative represented by formula (1) may contain a group formed by ring-opening by addition of an acid or the like to an oxetanyl group or an epoxy group, among the side chain functional groups derived from the silicon compound used as a raw material in the production.
• the silsesquioxane derivative may contain a hydroxyalkyl group formed by decomposition of an organic group having a (meth)acryloyl group.
• the silsesquioxane derivative may contain a group formed by addition of an acid or the like to an unsaturated hydrocarbon group.
• the content ratio is 50 mol% or less with respect to the amount equivalent to the organic group derived from the silicon compound as a raw material (i.e., the original organic group having an oxetanyl group or an epoxy group, the original organic group having a (meth)acryloyl group, or the original organic group having an unsaturated hydrocarbon group), so long as it is 50 mol% or less, there is no problem in carrying out the present disclosure.
• the content is preferably 30 mol% or less, and more preferably 10 mol% or less.
• T units are exemplified, but similar D units or M units, etc. may also be used.
• the curable composition of the present disclosure includes the silsesquioxane derivative of the present disclosure and a polymerization initiator.
• the curable composition of the present disclosure may further include various components (hereinafter also referred to as "other components") as necessary.
• the polymerization initiator is not particularly limited, and examples thereof include a photopolymerization initiator or a thermal polymerization initiator.
• Examples of the photopolymerization initiator include a photoradical polymerization initiator.
• the thermal polymerization initiator may, for example, be a thermal radical polymerization initiator.
• As each of the photopolymerization initiator and the thermal polymerization initiator a known compound may be used.
• Examples of the photoradical polymerization initiator include Acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, diethoxyacetophenone, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] or 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl ⁇ -2-methyl-propan-1-one; Benzophenone compounds such as benzophenone, 4-phenylbenzoph
• thermal radical polymerization initiator examples include peroxides or azo initiators.
• peroxides include: hydrogen peroxide; Inorganic peroxides such as sodium persulfate, ammonium persulfate, or 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-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclohexane Chlododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylper
• Azo-based initiators include azo compounds.
• azo compounds include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane. These may be used alone or in combination of two or more.
• Reducing agents include ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and ferric chloride.
• the content of the polymerization initiator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the silsesquioxane derivative.
• the curable composition of the present disclosure may contain other components in addition to the polymerization initiator and the silsesquioxane derivative, as long as the effects of the present disclosure are not impaired.
• Other components of the present disclosure are not particularly limited, and examples thereof include solvents, polymerizable compounds other than silsesquioxane derivatives, resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, UV absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion imparting agents, nanoparticles, nanofibers, or nanosheets.
• the curable composition of the present disclosure may contain a silane-based reactive diluent or the like.
• silane-based reactive diluent include tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, or disiloxanes.
• the solvent examples include 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.
• 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.
• the curable compositions of the present disclosure may or may not contain a solvent.
• the other polymerizable compound is not particularly limited as long as it is a compound capable of undergoing a polymerization reaction in the presence of a silsesquioxane derivative and a polymerization initiator.
• the other polymerizable compound include silsesquioxane derivatives other than silsesquioxane derivatives, (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group (compounds containing an oxetanyl group), and compounds having a vinyl ether group (vinyl ether compounds).
• the curable composition of the present disclosure may or may not contain a polymerizable compound other than the silsesquioxane derivative (hereinafter also referred to as "other polymerizable compounds").
• silsesquioxane derivatives other than silsesquioxane derivatives include silsesquioxane derivatives consisting of only T units, and silsesquioxane derivatives containing T units and D units.
• (meth)acrylate compound examples 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, or 2-ethylhexyl (meth)acrylate; Monofunctional (meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, or tricyclodecanemethylol (meth)acrylate; Monofunctional (meth)acrylates having an aromatic group, such as benzyl (meth)acrylate or phenyl (meth)acrylate; (meth)acrylates of alkylene oxide adducts of phenol derivatives, such as (meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)acryl
• polyfunctional (meth)acrylate examples include polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, or tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, or tetrapropylene glycol di(meth)acrylate;
• di(meth)acrylate examples include 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, trimethylolpropan
• a urethane (meth)acrylate can also be used.
• the urethane (meth)acrylate include a compound obtained by addition reaction of an organic polyisocyanate with a hydroxyl group-containing (meth)acrylate, and a compound obtained by addition reaction of an organic polyisocyanate with a polyol and a hydroxyl group-containing (meth)acrylate.
• the monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc. may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
• the polyol may include a low molecular weight polyol, a polyether polyol, a polyester polyol, or a polycarbonate polyol.
• low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethylol, and 3-methyl-1,5-pentanediol.
• polyether polyol include polypropylene glycol and polytetramethylene glycol.
• the polyester polyol may be a reaction product of such a low molecular weight polyol and/or polyether polyol with an acid component, such as a dibasic acid or an anhydride thereof, e.g., adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, or terephthalic acid. These may be used alone or in combination of two or more.
• an acid component such as a dibasic acid or an anhydride thereof, e.g., adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, or terephthalic acid.
• 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, or 4-hydroxybutyl (meth)acrylate;
• hydroxyl group-containing polyfunctional (meth)acrylate include pentaerythritol tri(meth)acrylate, di(meth)acrylate of an adduct of 3 moles of alkylene oxide with isocyanuric acid, and dipentaerythritol penta(meth)acrylate. These may be used alone or in combination of two or more.
• the blending ratio is not particularly limited.
• the blending ratio of the (meth)acrylate compound relative to 100 parts by mass of the silsesquioxane derivative is preferably 0 parts by mass to 100 parts by mass, more preferably 0 parts by mass to 50 parts by mass, and even more preferably 0 parts by mass to 20 parts by mass. From the viewpoint of adhesion with the inorganic substance layer, a lower blending ratio of the (meth)acrylate compound is preferable.
• the blending ratio of the (meth)acrylate compound relative to the total amount of the composition is preferably 0 parts by mass to 10 parts by mass, more preferably 0 parts by mass to 5 parts by mass, even more preferably 0 parts by mass to 1 part by mass, and particularly preferably 0 parts by mass.
• 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.
• 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, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more.
• the epoxy compound may be a monofunctional epoxy compound or a polyfunctional epoxy compound.
• the oxetanyl group-containing compound include monofunctional oxetane compounds and polyfunctional oxetane compounds.
• the vinyl ether compound may be a monofunctional vinyl ether compound or a polyfunctional vinyl ether compound. 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 of silicones include polydimethyl silicone, polydiphenyl silicone, and polymethylphenyl silicone. Silicones having functional groups at their ends and/or side chains are preferred.
• the functional groups are not particularly limited, and examples thereof include (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl groups, hydroxyl groups, carboxy groups, amino groups, and thiol groups.
• the content of the other polymerizable compounds is preferably 0.01 parts by mass to 100 parts by mass, more preferably 0.1 parts by mass to 50 parts by mass, and even more preferably 1 part by mass to 25 parts by mass, relative to 100 parts by mass of the silsesquioxane derivative.
• the cured product of the present disclosure is obtained by curing the curable composition of the present disclosure.
• the cured product of the present disclosure can be obtained, for example, by irradiating the curable composition of the present disclosure with active energy rays.
• the cured product of the present disclosure can be obtained, for example, by heating the curable composition of the present disclosure.
• the curable composition may be applied to a substrate, and then the applied product of the curable composition may be cured.
• the elastic modulus at 23° C. of the cured product obtained by curing the curable composition or the hard coat obtained by curing the hard coat agent containing the curable composition is preferably 2.5 GPa or more, more preferably 3.0 GPa or more, and particularly preferably 3.5 GPa or more.
• the elastic modulus is preferably 10.0 GPa or less, more preferably 9.5 GPa or less, and particularly preferably 9.0 GPa or less. If the modulus of elasticity is 2.5 GPa or more, the hardness of the cured product and the hard coat may be increased, whereas if the modulus of elasticity is 10.0 or less, the flexibility of the cured product and the hard coat may be increased.
• Methods for curing the curable composition of the present disclosure include active energy ray curing methods, heat curing methods, etc. Among these, active energy curing methods are preferred from the viewpoints of production efficiency and the range of application of the substrate.
• the curing conditions are not particularly limited.
• the type of light source and the amount of light irradiation can be appropriately changed to obtain a cured product having a desired hardness.
• the heating temperature and heating time can be appropriately changed to obtain a cured product having a desired hardness.
• the type and amount of the polymerization initiator and the type of other polymerizable compound contained in the composition are appropriately selected depending on the curing method.
• the curing method may be to irradiate active energy rays using a known active energy ray irradiation device, etc.
• active energy rays include electron beams, light (e.g., ultraviolet rays, visible light, X-rays, etc.), etc.
• Light is preferred, and ultraviolet rays are more preferred from the viewpoint of being able to use inexpensive equipment.
• ultraviolet irradiation devices include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, extra 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).
• UV ultraviolet
• LEDs light emitting diodes
• the light irradiation intensity of the coating formed by applying the present composition may be selected depending on the purpose and application, and the light irradiation intensity in the light wavelength region effective for activating the active energy ray polymerization initiator (referred to as a photopolymerization initiator in the case of a photocurable type) (which differs depending on the type of photopolymerization initiator, but preferably light with a wavelength of 220 nm to 460 nm is used) is preferably 0.1 mW/cm 2 to 1000 mW/cm 2 .
• the irradiation energy should be appropriately set depending on the type of active energy rays, the compounding composition, etc.
• the light irradiation time of the coating may be selected depending on the purpose and the application. It is preferable that the light irradiation time is set so that the accumulated light amount is 10 mJ/cm 2 to 7,000 mJ/cm 2.
• the accumulated light amount is expressed as the product of the light irradiation intensity in the light wavelength region and the light irradiation time.
• the accumulated light amount 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.
• heat curing Before and/or after the photocuring, heat curing may be appropriately combined.
• Two-stage curing can also be performed.
• the composition is impregnated into a substrate having a portion that is shaded when irradiated with light, and then the substrate is irradiated with light to first cure the composition in the portion exposed to light, and then heat is applied to cure the composition in the portion not exposed to light.
• substrates are not particularly limited, and examples thereof include substrates having complex shapes (e.g., fabric-like, fibrous, powder-like, porous, or uneven, etc.).
• the shape of the substrate may be a combination of two or more of these shapes.
• the curing temperature is preferably 80° C. to 200° C., more preferably 90° C. to 150° C., further preferably 95° C. to 130° C., and particularly preferably 100° C. to 120° C.
• the curing temperature may be constant or may be elevated. A combination of elevated temperature and reduced temperature may also be used.
• the curing time is appropriately selected depending on the type of thermal polymerization initiator, the content ratio of other components, etc., 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 curable composition of the present disclosure can be used, for example, as a hard coating agent, a sealant, a paint, an ink, a resist, or a crosslinking agent.
• the curable composition of the present disclosure can be suitably used as a hard coating agent from the viewpoint of being capable of forming a cured product having high hardness.
• the hard coat agent of the present disclosure includes the curable composition of the present disclosure.
• the hard coat of the present disclosure is obtained by curing the hard coat agent of the present disclosure.
• the curable composition of the present disclosure is used as a hard-coating agent, for example, it is applied to a substrate and dried as necessary to form a coating film made of the hard-coating agent.
• the formed coating film is cured by active energy ray curing treatment or heat curing treatment to form a hard coat in which the hard-coating agent is cured. This provides an article (preferably a substrate) equipped with a hard coat.
• the method for applying the curable composition is not particularly limited.
• the coating method may be a known coating method, such as a casting method, a spin coating method, a bar coating method, a dip coating method, a spray coating method, a roll coating method, a flow coating method, or a gravure coating method.
• the thickness of the curable composition of the present disclosure to be applied is not particularly limited and is, for example, 1 ⁇ m to 20 ⁇ m.
• the article of the present disclosure comprises the hardcoat of the present disclosure described above.
• the article includes those requiring a scratch-resistant surface (for example, a substrate or a molded product).
• the substrate on which the hard coat is formed using the curable composition of the present disclosure is not particularly limited.
• a poorly adhesive substrate is preferable, and a poorly adhesive plastic substrate is more preferable, because the curable composition of the present disclosure exhibits excellent adhesion to poorly adhesive substrates.
• the poorly adhesive plastics include low polar plastics.
• olefin polymers are suitable. Examples of olefin polymers include polyethylene (PE), polypropylene (PP), cycloolefin polymers (COP), and cycloolefin copolymers (COC). Among olefin polymers, COP and COC are particularly preferred.
• the shape of the substrate is not particularly limited, and examples include plate-like, sheet-like, film-like, rod-like, spherical, fibrous, powder-like, lenticular, and other regular or irregular shapes.
• the laminate of the present disclosure has the hard coat of the present disclosure described above and a substrate.
• the details of the substrate are the same as those of the substrate in the above-mentioned article section, and the preferred embodiments are also the same.
• the substrate in the laminate preferably contains an olefin polymer, and the details of the olefin polymer are the same as those of the olefin polymer in the above-mentioned article section, and the preferred embodiments are also the same.
• an aqueous solution was prepared by mixing 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g). The reaction solution was stirred while the prepared aqueous solution was added dropwise from the dropping funnel over a period of about 1 hour, and then allowed to stand overnight at room temperature. The amount of water added was 2.8 molar equivalents relative to the total amount of hydrolyzable groups in the raw organosilicon compound. Thereafter, the reaction solution was heated to 60° C. while the solvent and the like in the reaction solution were distilled off under reduced pressure, obtaining 170 g each of colorless, transparent liquid silsesquioxane derivatives 1 and 5. 1 H-NMR analysis confirmed that each of the structural units in silsesquioxane derivatives 1 and 5 was quantitatively introduced according to the ratio of the raw materials charged.
• Example 2 A silsesquioxane derivative 2 was obtained in the same manner as in Examples 1 and 5, except that the amount of water added during the synthesis of the silsesquioxane derivative was changed to 1.0 molar equivalent.
• the amounts of raw materials charged and the amount of water added during synthesis of the silsesquioxane derivative were changed as shown in Table 1, and the amounts of solvents, etc. were also changed appropriately. Except for the above, the same procedure as in Example 1 was repeated to obtain a silsesquioxane derivative 3.
• Example 4 Only (3-acryloyloxy)propyltrimethoxysilane (structural unit (b)) was used as the raw material for the silsesquioxane derivative 1.
• the amounts of the raw materials and the amount of water added during the synthesis of the silsesquioxane derivative were changed as shown in Table 1, and the amounts of the solvent, etc. were also changed appropriately. Except for the above, the same procedure as in Example 1 was repeated to obtain a silsesquioxane derivative 4.
• Example 6 1,3-divinyltetramethyldisiloxane (structural unit (f)) was used in addition to the raw materials for silsesquioxane derivative 1 in Example 1.
• the amounts of raw materials charged and the amount of water added during synthesis of the silsesquioxane derivative were changed as shown in Table 1, and the amounts of solvents, etc. were also changed appropriately. Except for the above, the same procedure as in Example 1 was repeated to obtain a silsesquioxane derivative 6.
• Comparative Example 2 As the raw material for the silsesquioxane derivative, only (3-acryloyloxy)propyltrimethoxysilane (structural unit (b)) was used. The amounts of the raw materials and the amount of water added during the synthesis of the silsesquioxane derivative were changed as shown in Table 1, and the amounts of the solvent, etc. were also changed appropriately. Except for the above, the same procedure as in Example 1 was repeated to obtain a silsesquioxane derivative c2 for comparison.
• Condensation rate (%) integral value of silicon corresponding to condensed siloxane bonds / integral value of silicon corresponding to all condensable siloxane bonds ⁇ 100
• Formula (b): Integral value of silicon corresponding to condensed siloxane bonds [M1] x 1 + [D1] x 1 + [D2] x 2 + [T1] x 1 + [T2] x 2 + [T3] x 3
• Formula (c): Integral value of silicon corresponding to all condensable siloxane bonds ([M0] + [M1]) x 1 + ([D0] + [D1] + [D2]) x 2 + ([T0] + [T1] + [T2] + [T3]) x 3
• a photocurable composition was poured into a silicone mold on a release polyethylene terephthalate (PET) film, a release PET film was placed on top of the mold, and the resulting mixture was sandwiched between glass plates and fixed in place.
• the fixed photocurable composition was then irradiated with ultraviolet light under the following conditions to be cured, thereby obtaining a photocured product.
• UV irradiation conditions Lamp: High pressure mercury lamp Lamp Height: 10cm Conveyor speed: 5.75 m/min Accumulated light amount per pass: 360 mJ/cm 2 (UV-A) Atmosphere: Air Number of passes: 20
• thermosetting Composition 0.02 parts by mass of dilauroyl peroxide was added to 1 part by mass of the silsesquioxane derivative of Example 5, and the mixture was stirred with a planetary centrifugal mixer to obtain a thermosetting composition.
• thermosetting composition was poured into a silicone mold on a release polyethylene terephthalate (PET) film, and a release PET film was placed on top of it. The resulting mixture was then sandwiched between glass plates and fixed in place. The fixed thermosetting composition was then heated at 110°C for 4 hours to harden it, yielding a thermoset product.
• PET polyethylene terephthalate
• the weather resistance test used photocured films (Examples 1 to 4, Example 6, Comparative Example 1, and Comparative Example 2) and a heat cured film (Example 5).
• the photocured films and heat cured films were prepared as follows.
• a photocurable coating liquid was applied to a cycloolefin copolymer (APL5015AL, manufactured by Mitsui Chemicals, Inc.; APL5014DP, manufactured by Mitsui Chemicals, Inc.) or a cycloolefin polymer (ZEONEX 480R, manufactured by Zeon Corporation) using a No. 8 bar coater, and dried at 60°C for 5 minutes.
• the applied photocurable coating liquid was then irradiated with ultraviolet light under the following conditions to cure the applied photocurable coating liquid. This resulted in a photocured film having a film thickness of about 5 ⁇ m.
• UV irradiation conditions Lamp: High pressure mercury lamp Lamp height: 10cm Conveyor speed: 5.75 m/min Accumulated light amount per pass: 360 mJ/cm 2 (UV-A) Atmosphere: Air Number of passes: 10
• thermosetting Coating Liquid 0.02 parts by mass of dilauroyl peroxide and 1 part by mass of propylene glycol monobutyl ether were added to 1 part by mass of the silsesquioxane derivative to obtain a mixture. The mixture was stirred with a planetary centrifugal mixer to obtain a thermosetting coating liquid.
• thermosetting film A thermosetting coating liquid was applied to a cycloolefin copolymer (APL5015AL manufactured by Mitsui Chemicals, Inc.) using a No. 8 bar coater, and the applied thermosetting coating liquid was cured by heating at 110°C for 4 hours in an air atmosphere. As a result, a thermosetting film having a film thickness of about 5 ⁇ m was obtained. Note that the heating treatment at 110°C is not a high-temperature heating treatment.
• the photocured film and the thermocured film obtained above were subjected to a cross-cut test in accordance with JIS K5600-5-6.
• the results are shown in Table 1 as the results before the weather resistance test.
• the photocured film and the thermocured film were left to stand in an environment of 85°C and 85% RH for 250 hours, and then subjected to a cross-cut test in accordance with JIS K5600-5-6.
• the results are shown in Table 1 as results after a weather resistance test. In Table 1, "-" indicates that the test was not performed.
• the weather resistance was evaluated based on the mass remaining rate, which was calculated according to the following formula (e).
• Remaining square rate (%) (remaining squares) / (number of squares) x 100
• the elastic modulus of the photocured film and the thermocured film obtained above was measured as follows. Indentation hardness was 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 values at indentation depths of 100 nm to 400 nm were averaged to calculate the elastic modulus. The results are shown in Table 1. In Table 1, "-" indicates that the test was not performed.
• the silsesquioxane derivatives of Examples 1 to 6 were shown to have excellent adhesion and weather resistance to poorly adhesive substrates such as cycloolefin copolymers and cycloolefin polymers, even when not subjected to high-temperature heat treatment.
• the silsesquioxane derivatives of Comparative Examples 1 and 2 did not have sufficient adhesion and weather resistance to cycloolefin copolymers and cycloolefin polymers, which are poorly adhesive substrates.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Silicon Polymers (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=93657644

Family Applications (1)

Country Status (5)

Citations (9)

Family Cites Families (2)

• 2024
  • 2024-05-16 WO PCT/JP2024/018229 patent/WO2024247756A1/ja not_active Ceased
  • 2024-05-16 JP JP2025523465A patent/JPWO2024247756A1/ja active Pending
  • 2024-05-16 KR KR1020257042117A patent/KR20260015864A/ko active Pending
  • 2024-05-16 CN CN202480036225.4A patent/CN121399187A/zh active Pending
  • 2024-05-22 TW TW113118877A patent/TW202502913A/zh unknown

Patent Citations (9)

Also Published As

Similar Documents

Legal Events