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
• • 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
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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

Definitions

• the present invention relates to silsesquioxane compounds, hard coat compositions and hard coat films.
• Patent Document 1 discloses a hard coat composition based on a silsesquioxane compound obtained by condensing an alkoxysilane containing an alicyclic epoxy group in the presence of a base catalyst. Has been done.
• Patent Document 2 discloses a hard coat composition based on a siloxane compound containing an alicyclic epoxy group and having a T-type silane ratio of 80% or more.
• the amount of T-type silane (T3 body) containing an epoxy group and completely condensed is 5 or more equal to or more than 16 with respect to T-type silane (T2 body) which is not partially condensed.
• a hard coat composition based on a siloxane compound contained in less than an equal amount has been disclosed.
• the hard coat layer obtained by curing the silsesquioxane compounds disclosed in Patent Documents 1 to 4 has high hardness, cracks and cracks occur in the hard coat layer when the hard coat film is bent with a small radius of curvature. It tends to occur, and there is a problem in applying it to flexible displays, foldable displays, and the like.
• an object of the present invention is to provide a hard coat film having high hardness and excellent bending resistance, and a curable material for forming a hard coat layer of the hard coat film.
• T3 body which has an alicyclic epoxy group and is completely condensed
• T-type silane (T2 body) which is not partially condensed is within a predetermined range. It has been found that the silsesquioxane compound can achieve both high hardness and bending resistance when a hard coat layer is formed.
• the silsesquioxane compound according to one aspect of the present invention is a condensate of a silane compound represented by the general formula (A).
• the number average molecular weight of the silsesquioxane compound is preferably 500 to 20000.
• R 2 is a hydrogen atom or an alkyl group
• R 3 is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.
• x is an integer of 1 to 3.
• silsesquioxane having a structure represented by the following general formula (5) can be obtained.
• R 2 , R 3 and x are the same as in the general formula (A).
• R 1 is an organic group containing an alicyclic epoxy group.
• the ratio of the structure represented by the general formula (5) to the total number of Si atoms of silsesquioxane is preferably 0.2 to 1.0.
• the silsesquioxane contains a structural unit (T3 body) represented by the general formula (3) and a structural unit (T2 body) represented by the general formula (4).
• the ratio of the contents of the T3 body to the T2 body T3 / T2 is preferably 0.8 or more and less than 5.
• Ra in the general formula (3) and the general formula (4) is the same as that in the general formula (A).
• Z is a hydroxy group or an alkoxy group.
• Sylsesquioxane is obtained by hydrolysis and condensation reaction of the silane compound.
• silsesquioxane having the structure of the formula (5) can be obtained.
• the hydrolysis and condensation reaction of the silane compound may be carried out in the presence of a neutral salt catalyst. Since silsesquioxane obtained by the reaction in the presence of a neutral salt catalyst tends to have a small T3 / T2 ratio, a compound having a T3 / T2 ratio of less than 5 can be easily obtained.
• the neutral salt catalyst includes an ion of an element selected from the group consisting of an alkali metal element and a group 2 element, and a halide ion selected from the group consisting of a chloride ion, a bromide ion, and an iodide ion. Combination salts are preferred.
• the above neutral salt may remain in the silsesquioxane obtained by the hydrolysis and condensation reaction of the silane compound.
• the silsesquioxane may contain about 1 to 10000 ppm of a neutral salt.
• the above silsesquioxane has cationically polymerizable properties and is suitably used for forming a hard coat layer.
• One aspect of the present invention is a hard coat composition containing the above silsesquioxane.
• the hard coat composition may contain a cationic polymerization initiator in addition to silsesquioxane.
• the cationic polymerization initiator may be a photocationic polymerization initiator (photoacid generator).
• One aspect of the present invention is a hard coat film provided with a hard coat layer made of a cured product of the above hard coat composition on at least one main surface of a resin base material.
• the thickness of the hard coat layer may be 0.5 to 100 ⁇ m.
• the resin material of the resin base material include polyester, polycarbonate, polyamide, polyimide, cyclic polyolefin, acrylic resin, and cellulose-based resin.
• a hard coat film is formed by applying the above hard coat composition on a resin base material and irradiating it with active energy rays to cure the hard coat composition (the above silsesquioxane).
• the cured film (hard coat layer) formed by curing the above silsesquioxane compound has high surface hardness and excellent bending resistance.
• the hard coat film provided with the cured film on the resin base material is less likely to crack even when bent with a small radius of curvature, and can be suitably used for flexible displays and foldable displays.
• One aspect of the present invention is silsesquioxane having cationically polymerizable properties and a method for producing the same.
• a further aspect of the present invention is a hard coat film comprising a hard coat composition containing the silsesquioxane compound and a hard coat layer composed of a cured product of the hard coat composition, and a method for producing the same.
• preferred forms of the silsesquioxane compound, the hard coat composition for forming the hard coat layer, and the hard coat film will be described in order.
• the components, functional groups, etc. exemplified in this specification may be used alone or in combination (coexistence) of two or more.
• the silsesquioxane compound according to one aspect of the present invention is a condensate of a silane compound represented by the following general formula (A). R a- (Si (OR 2 ) x R 3 3-x ) ... (A)
• R 2 is a hydrogen atom or an alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms.
• Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group and an isobutyl group. Examples thereof include a cyclohexyl group and an ethylhexyl group.
• the silane compound represented by the general formula (A) has 1 to 3 (-OR 2 ) in one molecule. Since Si-OR 2 has hydrolyzability, a silsesquioxane compound can be obtained by condensation of a silane compound. From the viewpoint of hydrolysis resistance, the carbon number of R 2 is preferably 3 or less, and particularly preferably R 2 is a methyl group.
• R 3 is a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aryl group and an aralkyl group.
• the alkyl group preferably has 1 to 16 carbon atoms.
• the aryl group preferably has 6 to 25 carbon atoms.
• the aralkyl group preferably has 7 to 12 carbon atoms.
• hydrocarbons in alkyl groups and aralkyls include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group and cyclohexyl.
• examples thereof include a group, an ethylhexyl group, a benzyl group, a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, a phenethyl group and the like.
• the ratio of the T structure to the total of the 1/2 structure is preferably 0.2 or more, more preferably 0.4 or more, and further preferably 0.6 or more. Preferably, it may be 0.7 or more, 0.8 or more, 0.9 or more, 0.95 or more, or 1.
• Ra is an arbitrary monovalent organic group.
• a silane compound represented by the following general formula (1) i.e., compounds organic group R a is R 1 in the general formula (A) including.
• R 2 , R 3 and x are the same as in the general formula (A).
• R 1 is an organic group containing an alicyclic epoxy group. Since the silane compound contains an alicyclic epoxy group, the silsesquioxane compound obtained by condensation of the silane compound has photocationic polymerizable property.
• Examples of the organic group containing an alicyclic epoxy group include an alicyclic epoxy group, an alkyl group having an alicyclic epoxy group as a substituent, an ethylene glycol group having an alicyclic epoxy group as a substituent, and the like.
• R 1 is preferably an alkyl group having an alicyclic epoxy group as a substituent.
• Specific examples of the alkyl group having an alicyclic epoxy group as a substituent include a (3,4-epoxycyclohexyl) methyl group, a 2- (3,4-epoxycyclohexyl) ethyl group, and a 3- (3,4-epoxy) group.
• Cyclohexyl) propyl group 4- (3,4-epoxycyclohexyl) butyl group, 5- (3,4-epoxycyclohexyl) pentyl group, 6- (3,4-epoxycyclohexyl) hexyl group, 7- (3,4) -Epoxycyclohexyl) heptyl group, 8- (3,4-epoxycyclohexyl) octyl group, 9- (3,4-epoxycyclohexyl) nonyl group, 10- (3,4-epoxycyclohexyl) decyl group, 11- (3) , 4-epoxycyclohexyl) undecyl group, 12- (3,4-epoxycyclohexyl) dodecyl group, 13- (3,4-epoxycyclohexyl) tridecyl group, 14- (3,4-epoxycyclohexyl) tetradecyl
• silane compound (1) Specific examples of the compound represented by the general formula (1) (hereinafter sometimes referred to as “silane compound (1)”) include (3,4-epoxycyclohexyl) trimethoxysilane and (3,4-epoxycyclohexyl).
• silane compound (2) When a silsesquioxane compound is obtained by condensation of a silane compound, another silane compound may be used in addition to the silane compound (1) as the compound represented by the above general formula (A).
• silane compound (2) Other silane compounds (that is, silane compounds that do not contain an alicyclic epoxy group, hereinafter may be referred to as "silane compound (2)") are represented by the following general formula (2). R 4 - (Si (OR 2 ) x R 3 3-x) ... (2)
• R 4 is a monovalent organic group containing no alicyclic epoxy group.
• R 4 is a group containing a double bond or a substituted or unsubstituted group containing a substituted or unsubstituted cycloalkyl group, a group containing a substituted or unsubstituted aromatic ring, a substituted or unsubstituted alkyl group, A group having a glycidyl group, a group having an oxetanyl group, or a hydrogen atom.
• Examples of the group containing a substituted or unsubstituted double bond include a vinyl group, an allyl group, and a rocky shore propenyl group.
• Examples of the group containing a substituted or unsubstituted cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclobutylethyl group, a cyclopentylethyl group, a cyclohexylethyl group and the like. Can be mentioned.
• Examples of the group containing a substituted or unsubstituted aromatic ring include a phenyl group, a 4-methylphenyl group, a tolyl group, a naphthyl group and the like.
• Substituentally substituted or unsubstituted alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and tetradecyl group.
• Examples thereof include a group, a pentadecyl group, a hexadecyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, an ethylhexyl group and the like.
• Examples of the group having a glycidyl group include a glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, a 4-glycidyloxybutyl group, a 5-glycidyloxypentyl group, a 6-glycidyloxyhexyl group, and a 7-.
• Examples of the group having an oxetanyl group include an oxetanyl methyl group, a 3-methyl-3-oxetanyl methoxymethyl group, a 3-ethyl-3-oxetanyl methoxymethyl group and the like.
• the ratio of the silane compound (1) to the silane compound represented by the general formula (A) (that is, the sum of the silane compound (1) and the silane compound (2)). Is preferably 20 to 100 mol%, more preferably 33 to 100 mol%, still more preferably 50 to 100 mol%.
• the ratio of the silane compound (1) is substantially equal to the ratio of cycloaliphatic epoxy groups to the total amount of the organic group R a silsesquioxane compound. Since the silsesquioxane compound has an alicyclic epoxy group derived from the silane compound (1), the hardness of the hard coat layer tends to be increased.
• the ratio of the silane compound (1) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.
• ⁇ Characteristics of silsesquioxane compound> (Molecular weight)
• a Si—O—Si bond is formed between the silane compounds, and a silsesquioxane compound is produced.
• the number average molecular weight of the silsesquioxane compound is preferably 500 or more.
• the number average molecular weight of the silsesquioxane compound is preferably 500 or more.
• the molecular weight is excessively large, cloudiness may occur due to a decrease in compatibility with other compositions.
• the number average molecular weight of the silsesquioxane compound is preferably 20000 or less.
• the number average molecular weight of the silsesquioxane compound is more preferably 700 to 18000, further preferably 1000 to 16000, or may be 1200 to 14000 or 1500 to 12000.
• the number average molecular weight of the silsesquioxane compound can be controlled by appropriately selecting the amount of water used in the reaction, the type and amount of the catalyst. For example, the larger the amount of water charged with the catalyst during the hydrolysis reaction, the larger the number average molecular weight tends to be.
• the silsesquioxane compound produced by hydrolysis and condensation of the silane compound of the general formula (A) includes a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).
• Ra is the same as the general formula (A).
• R 4 is an alkoxy group having a hydroxy group or an alkyl group having 1 to 10 carbon atoms.
• the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group and the like.
• the silsesquioxane compound according to the embodiment of the present invention has a ratio of the structure (T3 body) represented by the formula (3) to the structure (T2 body) represented by the formula (4) [T3 body] / [T2 body]. ] Is preferably less than 5.
• T3 / T2 ratio When the ratio of the T3 body to the T2 body (hereinafter, may be referred to as “T3 / T2 ratio”) is less than 5, the bending resistance of the hard coat layer formed by curing the silsesquioxane compound is increased. Tends to improve.
• the T3 / T2 ratio of the silsesquioxane compound is more preferably 4 or less, further preferably 3.5 or less, and may be 3 or less or 2.5 or less.
• the T3 / T2 ratio of the silsesquioxane compound is preferably 0.8 or more, more preferably 1 or more, further preferably 1.5 or more, even if it is 2 or more. good.
• the ratio of T3 bodies the easier it is to form a dense network-like polysiloxane skeleton that has grown three-dimensionally, and the hardness tends to increase.
• the flexibility of the molecular structure decreases, so the ratio of T3 bodies decreases.
• the bending resistance of the hard coat layer becomes insufficient.
• the surface hardness is high because the excellent balance between the excellent mechanical strength due to the formation of the polysiloxane skeleton and the flexibility (flexibility) due to the T2 body is excellent.
• a hard coat layer having excellent bending resistance is formed.
• the content and ratio of SiO 3/2 and SiO 2/2 in the silsesquioxane compound can be calculated by 29 Si-NMR measurement.
• 29 In Si-NMR the Si atom of SiO 3/2 and the Si atom of SiO 2/2 show different chemical shifts. Therefore, the integrated value of each signal in the NMR spectrum was obtained, and from the ratio of both, T3 / The T2 ratio can be calculated.
• the T3 / T2 ratio can be controlled by adjusting the amount of water used for the hydrolysis / condensation reaction of the silane compound, the type of catalyst, and the amount of catalyst. For example, the larger the amount of catalyst, the larger the T3 / T2 ratio tends to be. As will be described later, the use of a neutral salt catalyst tends to reduce T3 / T2.
• ⁇ Hydrolyzed and condensed silane compounds By reacting the silane compound with water, the Si-OR 2 portion of the silane compound is hydrolyzed, and the hydrolyzate is condensed to obtain a silsesquioxane compound.
• the amount of water required for the hydrolysis and condensation reactions is preferably 0.3 to 3 equivalents, more preferably 0.5 to 2 equivalents, relative to 1 equivalent of the -OR 2 groups bonded to the Si atom.
• the amount of water is excessively small, there are many OR 2 groups remaining without being hydrolyzed, and the molecular weight of the silsesquioxane compound is small, so that the hardness of the hard coat layer tends to be insufficient.
• the amount of water is excessively large, the reaction rate of the hydrolysis and condensation reactions is high, a high molecular weight condensate is produced, and the transparency and flexibility of the hard coat layer tend to decrease.
• the hydrolysis reaction and condensation reaction of the silane compound it is preferable to suppress the deactivation of the alicyclic epoxy group contained in the silane compound (1) due to ring opening. From the viewpoint of suppressing ring opening of the epoxy group, it is preferable to carry out the reaction under neutral or basic conditions. In particular, from the viewpoint of reducing the T3 / T2 ratio of the silsesquioxane compound obtained as a condensate of the silane compound, it is preferable to carry out the hydrolysis and condensation reaction in the presence of a neutral salt catalyst.
• the neutral salt is a positive salt of a strong acid and a strong base, and specifically, an ion (cation) of an element selected from the group consisting of an alkali metal element and a second group element, a chloride ion, and a bromide.
• the neutral salt include lithium chloride, sodium chloride, potassium chloride, beryllium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, beryllium bromide, magnesium bromide, and calcium bromide. , Lithium iodide, sodium iodide, potassium iodide, beryllium iodide, magnesium iodide, calcium iodide and the like.
• a silsesquioxane compound having a small T3 / T2 ratio can be obtained.
• acid catalysts and base catalysts react electrophilically and nucleophilically with various substances, whereas neutral salts are erosive to metal and resin materials in reaction vessels and storage containers. It has the advantage that there are few restrictions on the material of the manufacturing and storage equipment because it is low.
• the acid generated from the photocationic polymerization initiator (photoacid generator) is quenched to carry out the polymerization reaction. May inhibit.
• the neutral salt catalyst may remain in the silsesquioxane compound obtained by condensing the silane compound or the hard coat composition, and steps such as removal and neutralization of the catalyst after the reaction can be omitted.
• the use of a neutral salt catalyst can contribute to simplification of the manufacturing process and improvement of yield.
• the amount of the catalyst used is not particularly limited. The higher the amount of catalyst used, the more the hydrolysis and condensation reactions of the silane compound tend to be promoted. On the other hand, if the amount of the catalyst used is excessively large, the transparency of the condensate may be impaired or purification may become complicated.
• the amount of the neutral salt catalyst used is preferably 0.000001 to 0.1 mol, more preferably 0.000005 to 0.01 mol, based on 1 mol of the hydrolyzable silyl group (-OR 2) of the silane compound. ..
• the neutral salt catalyst may remain in the silsesquioxane compound obtained by the hydrolysis and condensation reaction of the silane compound.
• the amount of the neutral salt (catalyst) remaining in the silsesquioxane compound may be 1 ppm or more, 10 ppm or more, 50 ppm or more, or 100 ppm or more.
• the amount of the basic catalyst remaining in the silsesquioxane compound is preferably 10,000 ppm or less, more preferably 5000 ppm or less, further preferably 3000 ppm or less, and 1000 ppm or less, 800 ppm or less or 500 ppm. It may be as follows.
• the reaction may be carried out while refluxing the diluting solvent, the alcohol generated by the hydrolysis and the like.
• the diluting solvent is preferably one that is compatible with water, and is preferably a water-soluble alcohol or ether compound. Since many silane compounds have low compatibility with neutral salts and water used for hydrolysis, it is preferable to react them as a solution with a diluting solvent as a compatible system.
• the boiling point of the diluting solvent is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and even more preferably 60 ° C. or higher. If the boiling point of the diluting solvent is excessively low, the diluting solvent is refluxed at a low temperature, which may reduce the reaction rate. From the viewpoint of removability of the diluting solvent after the reaction, the boiling point of the diluting solvent is preferably 200 ° C. or lower.
• diluting solvent examples include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether and the like. Can be mentioned.
• the reaction temperature of the hydrolysis and condensation reaction of the silane compound is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and even more preferably 60 ° C. or higher.
• the reaction temperature is preferably 200 ° C. or lower from the viewpoint of suppressing the side reaction of the organic group of the silane compound.
• the silsesquioxane compound obtained by hydrolysis and condensation of the silane compound preferably has a high residual ratio of epoxy groups.
• the residual ratio of epoxy groups that is, the ratio of the number of moles of epoxy groups in the silsesquioxane compound obtained by condensation to the number of moles of epoxy groups contained in the silane compound represented by the general formula (A) as a raw material. , 20% or more is preferable, 40% or more is more preferable, 60% or more is further preferable, 80% or more is particularly preferable, and 90% or more or 95% or more may be used.
• the residual ratio of epoxy groups is determined by 1 1 H-NMR measurement.
• the silsesquioxane compound is obtained by the hydrolysis and condensation reaction of the silane compound represented by the general formula (A).
• the hydrolysis and condensation reaction with the exception of the side reactions of the open ring, the epoxy group, since the monovalent organic group bonded to Si atoms R a does not react, the silsesquioxane compound, [R a in the silane compound -Si] structural part is retained. Therefore, the silsesquioxane compound obtained by condensation of the silane compound (1) has a structure represented by the following general formula (5) (hereinafter, may be referred to as “structure (5)”). [R 1 -Si] ... (5 )
• R 1 in the general formula (5) is the same as that in the general formula (1). That is, the structure (5) is a structure in which an alicyclic epoxy group is bonded to a Si atom with or without another organic group.
• the ratio of the number of structures (5) (that is, the number of alicyclic epoxy groups) to the total number of Si atoms of the silsesquioxane compound is preferably 20% or more, more preferably 33% or more, and further 50% or more. Preferably, it may be 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.
• the silsesquioxane compound produced by the condensation of the silane compound of N molecules contains N Si atoms.
• n structures (5) are formed from n silane compounds (1). Therefore, in the silsesquioxane compound obtained by condensing the silane compound, the ratio (molar ratio: n / N) of the silane compound (1) in the silane compound used as a raw material is the number of Si atoms in the silsesquioxane compound. Is approximately equal to the ratio of structure (5) to.
• the silsesquioxane compound is represented by the following general formula (6) in addition to the above structure (5). It has a structure (hereinafter, may be referred to as “structure (6)”). [R 4 -Si] ... (6 ) R 4 in the general formula (6) is the same as in the general formula (2).
• the hard coat composition according to one aspect of the present invention is a composition containing the above silsesquioxane compound as an essential component.
• the hard coat composition preferably contains a cationic polymerization initiator in addition to the silsesquioxane compound, and may contain other components.
• the content of the silsesquioxane compound in the hard coat composition is 40 parts by weight or more with respect to 100 parts by weight of the total solid content (nonvolatile content). Is preferable, 50 parts by weight or more is more preferable, and 60 parts by weight or more is further preferable.
• the hard coat composition preferably contains a thermal cationic polymerization initiator or a photocationic polymerization initiator as a curing catalyst.
• the thermal cationic polymerization initiator is a compound that generates an acid by heating (thermal acid generator)
• the photocationic polymerization initiator is a compound that generates an acid by irradiation with active energy rays (photoacid generator).
• the acid generated from the cationic polymerization initiator promotes ring-opening and polymerization reaction of the epoxy group of the above silsesquioxane compound to form intermolecular crosslinks and cure the hard coat material.
• Photoacid generators include anions (strong acids) such as antimony hexafluoride, boron trifluoride, phosphorus hexafluoride, phosphorus fluoroalkylfluoride, and gallium fluoroalkylfluoride, and sulfonium, ammonium, phosphonium, iodonium, and selenium.
• anions strong acids
• antimony hexafluoride boron trifluoride
• phosphorus hexafluoride phosphorus fluoroalkylfluoride
• gallium fluoroalkylfluoride gallium fluoroalkylfluoride
• sulfonium ammonium, phosphonium, iodonium, and selenium.
• Onium salts that combine cations such as iron-allene complexes; silanol-metal chelate complexes; sulfones such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidesulfonates, benzoinsulfonates, etc. Acid derivatives; organic halogen compounds and the like can be mentioned.
• aromatic sulfonium or aromatic iodonium is preferable because of its high stability in the hard coat composition.
• the counter anion a hard coat layer having high acidity and excellent surface hardness and adhesion to the resin substrate can be easily obtained. Therefore, fluoroantimonate anion, fluoroborate anion, fluorophosphate anion, fluoro A gallium-based anion or the like is preferable.
• the content of the photocationic polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and 0 parts by weight with respect to 100 parts by weight of the silsesquioxane compound. .2 to 2 parts by weight is more preferable.
• the hard coat composition may contain a leveling agent.
• a leveling agent When the hard coat layer contains a leveling agent, it can be expected to reduce surface tension, improve surface smoothness, improve slipperiness, and improve antifouling property (fingerprint resistance, etc.). Further, since the leveling agent has a group having reactivity with an epoxy group and / or a hydrolyzable condensable group, improvement in scratch resistance of the hard coat layer can be expected.
• leveling agent examples include silicone-based leveling agents and fluorine-based leveling agents.
• silicone-based leveling agent examples include leveling agents having a polysiloxane skeleton.
• fluorine-based leveling agent examples include leveling agents having a fluoroaliphatic hydrocarbon skeleton.
• the fluoroaliphatic hydrocarbon skeleton include fluoroC 1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. ..
• fluoroaliphatic hydrocarbon skeleton at least a part of hydrogen atoms of the hydrocarbon may be replaced with fluorine atoms. From the viewpoint of improving the scratch resistance, slipperiness, and antifouling property of the hard coat layer, a perfluoroaliphatic hydrocarbon in which all hydrogen atoms are substituted with fluorine atoms is particularly preferable.
• the content thereof is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and 0, based on 100 parts by weight of the silsesquioxane compound. More preferably, it is 0.05 to 1 part by weight or less.
• the hard coat layer contains a leveling agent, it is preferable that 30% or more of the total amount of the leveling agent is segregated within 100 nm from the surface of the hard coat layer.
• the amount of the leveling agent present within 100 nm from the surface of the hard coat layer is more preferably 50% or more, further preferably 80% or more. The segregation of the leveling agent on the surface tends to increase the water contact angle of the hard coat layer and improve the antifouling property.
• the hard coat composition may contain a reactive additive.
• the reactive diluent may contain, for example, a cationically polymerizable compound other than the above-mentioned silsesquioxane compound.
• a compound having a cationically polymerizable functional group is used as the reactive additive for photocationic polymerization.
• the cationically polymerizable functional group of the reactive diluent include an epoxy group, a vinyl ether group, an oxetane group, and an alkoxysilyl group.
• the reactive additive one having an epoxy group is preferable because of its high compatibility with the silsesquioxane compound and high reactivity with the epoxy group of the silsesquioxane compound.
• the reaction rate is high, the curing rate of the hard coat layer is increased, the tackiness of the surface is reduced (tack-free property is increased), and the sticking (blocking) of the hard coat film tends to be suppressed. Therefore, the reactive additive preferably has a vinyl ether group.
• the content of the reactive additive in the hard coat composition is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, based on 100 parts by weight of the silsesquioxane compound.
• the hard coat composition may contain a photosensitizer for the purpose of improving the photosensitivity of the photocationic polymerization initiator (photoacid generator).
• a photosensitizer for the purpose of improving the photosensitivity of the photocationic polymerization initiator (photoacid generator).
• the photosensitizer it is more efficient that the photoacid generator can absorb light in a wavelength range that cannot be absorbed by itself, and therefore, it is preferable that the photosensitizer has less overlap with the absorption wavelength range of the photoacid generator.
• the photosensitizer include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives and the like.
• the content of the photosensitizer in the hard coat composition is preferably 500 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, based on 100 parts by weight of the photoacid generator.
• the hard coat composition may contain particles for the purpose of adjusting film properties such as surface hardness and bending resistance, suppressing curing shrinkage, and the like.
• the particles organic particles, inorganic particles, organic-inorganic composite particles and the like may be appropriately selected and used.
• the material of the organic particles include poly (meth) acrylic acid alkyl ester, crosslinked poly (meth) acrylic acid alkyl ester, crosslinked styrene, nylon, silicone, crosslinked silicone, crosslinked urethane, and crosslinked butadiene.
• Materials for inorganic particles include metal oxides such as silica, titania, alumina, tin oxide, zirconia, zinc oxide, and antimony oxide; metal nitrogenous products such as silicon nitride and boron nitride; calcium carbonate, calcium hydrogen phosphate, calcium phosphate, etc.
• metal salts such as aluminum phosphate.
• Examples of the organic-inorganic composite filler include those having an inorganic layer formed on the surface of organic particles and those having an organic layer or organic fine particles formed on the surface of the inorganic particles.
• Examples of the particle shape include spherical, powdery, fibrous, needle-like, and scaly-like. Since the spherical particles have no anisotropy and stress is unlikely to be unevenly distributed, the occurrence of strain can be suppressed, which can contribute to the suppression of warpage of the film due to curing shrinkage or the like.
• the average particle size of the particles is, for example, about 5 nm to 10 ⁇ m. From the viewpoint of enhancing the transparency of the hard coat layer, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, further preferably 300 nm or less, and particularly preferably 100 nm or less.
• the particle size can be measured by a laser diffraction / scattering type particle size distribution measuring device, and the volume-based median size is taken as the average particle size.
• the hard coat composition may contain surface-modified particles.
• Surface modification of the particles tends to improve the dispersibility of the particles in the silsesquioxane compound.
• the particle surface is modified with a polymerizable functional group capable of reacting with an epoxy group, the functional group on the particle surface reacts with the epoxy group of the silsesquioxane compound to form a chemical crosslink. Therefore, improvement in film strength can be expected.
• Examples of the polymerizable functional group capable of reacting with the epoxy group include a vinyl group, a (meth) acrylic group, a hydroxyl group, a phenolic hydroxyl group, a carboxy group, an acid anhydride group, an amino group, an epoxy group, an oxetane group and the like.
• an epoxy group is preferable.
• particles surface-modified with an epoxy group are preferable because chemical crosslinks can be formed between the particles and the silsesquioxane compound when the hard coat composition is cured by photocationic polymerization.
• Examples of particles having a reactive functional group on the surface include surface-modified inorganic particles and core-shell polymer particles.
• the hard coat composition may be a solvent-free type or may contain a solvent.
• a solvent it is preferable that the resin base material is not dissolved.
• the content of the solvent is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 100 parts by weight or less, based on 100 parts by weight of the silsesquioxane compound.
• the hard coat composition may contain additives such as an inorganic pigment, an organic pigment, a surface conditioner, a surface modifier, a plasticizer, a dispersant, a wetting agent, a thickener, and an antifoaming agent. Further, the hard coat composition may contain a thermoplastic or thermosetting resin material other than the above-mentioned silsesquioxane compound. When the resin material other than the silsesquioxane compound and / or the silsesquioxane compound has radical polymerization property, the hard coat composition may contain a radical polymerization initiator in addition to the cationic polymerization initiator.
• a hard coat film is obtained by applying a hard coat composition on a resin base material, drying and removing a solvent if necessary, and then irradiating with active energy rays to cure the hard coat composition.
• the hard coat layer may be formed on only one main surface of the resin base material, or may be formed on both main surfaces of the resin base material.
• the resin base material is a film base material that serves as a base for forming the hard coat layer.
• the resin base material is preferably transparent, and its total light transmittance is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
• the haze of the resin base material is preferably 2% or less, more preferably 1% or less.
• the thickness of the resin base material is not particularly limited, and is, for example, 1 to 1000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, and even more preferably 15 to 150 ⁇ m.
• the resin material constituting the resin base material is preferably a transparent resin.
• the transparent resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polycarbonate, polyamide, transparent polyimide, cyclic polyolefin, polymethylmethacrylate (PMMA), and triacetyl cellulose (TAC).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• acrylic resins such as polycarbonate, polyamide, transparent polyimide, cyclic polyolefin, polymethylmethacrylate (PMMA), and triacetyl cellulose (TAC).
• TAC triacetyl cellulose
• examples include cellulose-based resins.
• polyester such as PET and transparent polyimide are preferable because of their high mechanical strength.
• a transparent polyimide is particularly preferable as a resin material of the resin base material because the film base material is required to have excellent heat resistance and mechanical strength. While general all-aromatic polyimide is colored yellow or brown, transparent polyimide with high visible light transmittance is available due to the introduction of alicyclic structure, bending structure, fluorine substituent, etc. can get.
• the resin base material may be a single layer or a multi-layer structure.
• the resin base material may be a laminate in which a plurality of films are bonded together, and an easy-adhesion layer, an antistatic layer, and an antireflection layer may be formed on the hard coat layer forming surface and / or the hard coat layer non-forming surface of the film base material. It may be provided with a functional layer such as a layer.
• the resin base material may be provided with a hard coat layer formed of a material other than the above-mentioned silsesquioxane compound on one main surface.
• the hard coat layer is formed by applying the hard coat composition on the resin base material and curing the hard coat composition.
• the surface of the resin base material may be subjected to surface treatment such as corona treatment or plasma treatment.
• an easy-adhesion layer (primer layer) or the like may be provided on the surface of the resin base material.
• the hard coat layer formed by curing the hard coat composition containing the above silsesquioxane compound does not need to be provided with an easy-adhesion layer or the like because it exhibits high adhesion to the resin substrate. That is, in the hard coat film, the resin base material and the hard coat layer may be in contact with each other.
• the hard coat composition By irradiating the hard coat composition with active energy rays or by heating, an acid is generated from the cationic polymerization initiator, and the epoxy group of the silsesquioxane compound is ring-opened and cationically polymerized to cure the composition. proceed.
• the hard coat composition contains a reactive additive, in addition to the polymerization reaction between the silsesquioxane compounds, a polymerization reaction between the epoxy group of the silsesquioxane compound and the reactive additive also occurs.
• the hard coat composition contains particles having a reactive functional group on the surface, the functional group on the surface of the particles may react with the epoxy group of the silsesquioxane compound to form a chemical crosslink.
• Examples of the active energy rays irradiated during photocuring include visible rays, ultraviolet rays, infrared rays, X-rays, ⁇ -rays, ⁇ -rays, ⁇ -rays, and electron beams.
• Ultraviolet rays are preferable as the active energy rays because the curing reaction rate is high and the energy efficiency is excellent.
• the integrated irradiation amount of the active energy rays is, for example, about 50 to 10000 mJ / cm 2 , and may be set according to the type and blending amount of the photocationic polymerization initiator, the thickness of the hard coat layer, and the like.
• the curing temperature is not particularly limited, but is usually 150 ° C. or lower.
• the thickness of the hard coat layer is preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more, further preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, and may be 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more.
• the thickness of the hard coat layer is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and may be 70 ⁇ m or less.
• the total thickness of the hard coat film is, for example, 1 to 1000 ⁇ m, preferably 10 to 500 ⁇ m, more preferably 15 to 250 ⁇ m, and even more preferably 20 to 200 ⁇ m.
• the ratio of the thickness of the hard coat layer to the thickness of the resin base material (hard coat layer thickness / resin base material thickness) in the hard coat film is not particularly limited, and is appropriately from 1/10 to 10/1, for example. You can select it.
• the hard coat layer formed by curing the above hard coat composition has excellent adhesion to the resin base material. Further, since the hard coat composition has a polymer matrix in which the silsesquioxane compound is crosslinked by ring-opening and polymerization reaction of an epoxy group, surface hardness comparable to that of glass can be realized.
• the surface hardness (pencil hardness) of the hard coat layer forming surface of the hard coat film is preferably HB or more, more preferably H or more, further preferably 2H or more, and may be 3H or more or 4H or more.
• the hard coat film has high surface hardness as described above and is also excellent in bending resistance.
• the hard coat film preferably has a small diameter ⁇ of the mandrel at which cracks occur in the hard coat layer when the cylindrical mandrel test is performed with the hard coat layer forming surface on the outside. If the thickness of the hard coat layer is the same, the smaller the diameter of the mandrel, the better the bending resistance. For example, when the thickness of the hard coat layer is 10 ⁇ m, the diameter of the mandrel in which cracks occur in the hard coat layer is preferably 8 mm or less, more preferably 6 mm or less, and may be 4 mm or less, or 2 mm or less. When the hard coat layer is formed by using the same material, the thicker the hard coat layer, the larger the mandrel diameter ⁇ tends to be.
• the total light transmittance of the hard coat film is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more.
• the haze of the hard coat film is preferably 1.5% or less, more preferably 0.9% or less, further preferably 0.7% or less, and particularly preferably 0.5% or less.
• the amount of change in haze ⁇ Haze was preferably 0.3% or less, preferably 0.2% or less. More preferably, 0.1% or less is further preferable.
• the hard coat film may be provided with various functional layers on the hard coat layer or on the non-formed surface of the hard coat layer of the resin base material.
• the functional layer include an antireflection layer, an antiglare layer, an antistatic layer, a transparent electrode and the like.
• the hard coat film may be provided with a transparent adhesive layer.
• the hard coat film of the present invention Since the hard coat film of the present invention has high transparency and excellent mechanical strength, it is suitably used for a cover window provided on the surface of an image display panel, a transparent substrate for a display, a transparent substrate for a touch panel, a substrate for a solar cell, and the like. be able to. Since the hard coat film of the present invention is excellent in bending resistance in addition to transparency and mechanical strength, it can be particularly suitably used as a cover window or substrate film for curved displays and flexible displays.
• TBAB tetrabutylammonium bromide
• ⁇ Synthesis example 5 > 19.7 g (80.2 mmol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 23.8 g (120 mmol) of phenyltrimethoxysilane, in a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. And 174 g of dioxane was charged and stirred uniformly. After that, a polycondensation reaction and distillation of volatile components were carried out in the same manner as in Synthesis Example 4 to obtain silsesquioxane compound 5.
• T3 / T2 ratio The 29 Si-NMR spectrum was measured using an NMR (600 MHz) manufactured by Agilent, and the ratio T3 / T2 (molar ratio) between the SiO 3/2 body (T3 body) and the SiO 2/2 body (T2 body) was determined. I asked.
• Table 1 shows the molar ratio of the raw materials (silane compounds), the types of catalysts, and the evaluation results (T3 / T2 ratio and number average molecular weight Mn) of the silsesquioxane compounds in Synthesis Examples 1 to 5.
• the silsesquioxane compound of Synthesis Example 1 using magnesium chloride, which is a neutral salt catalyst, as the condensation catalyst had a T3 / T2 ratio of less than 5, whereas Synthesis Examples 2 to 2 using a basic catalyst. In 4, the T3 / T2 ratio of the silsesquioxane compound exceeded 5. In Synthesis Example 5, in which the ratio of phenyltrimethoxysilane, which is a silane compound containing no alicyclic epoxy group, was large, the T3 / T2 ratio of the silsesquioxane compound was less than 0.8. It can be seen that a silsesquioxane compound in which the ratio of T3 compounds is within a predetermined range can be obtained by carrying out a condensation reaction of a silane compound containing an alicyclic epoxy group using a neutral salt catalyst.
• the above hard coat composition was applied to one surface of the transparent polyimide film (thickness 50 ⁇ m) of Example 12 of WO2020 / 004236 using a bar coater so that the film thickness after heating was 10 ⁇ m, and the temperature was 120 ° C. Was heated for 10 minutes. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated so that the integrated light amount at a wavelength of 365 nm was 1000 mJ / cm 2. Then, the heat treatment was carried out at 80 ° C. for 2 hours to obtain a hard coat film having a hard coat layer having a thickness of 10 ⁇ m on one surface of the transparent polyimide film.
• Examples 2 to 7 In the preparation of the hard coat composition, the amount of the photocationic polymerization initiator added was changed as shown in Table 2, and 0.5 weight of polyether-modified polydimethylsiloxane (“BYK-300” manufactured by BYK) was added as a leveling agent. Partially added. The thickness of the hard coat layer was changed as shown in Table 2. Except for these changes, a hard coat film was produced in the same manner as in Example 1.
• composition of the hard coat composition used for preparing the hard coat films of Examples 1 to 7 and Comparative Examples 1 to 5 type of silsesquioxane compound and its T3 / T2 ratio, and formulation of a polymerization initiator and a leveling agent.
• the amount), the thickness of the hard coat layer, and the evaluation results of the hard coat film are shown in Table 2.
• the blending amount (solid content amount) of the polymerization initiator and the leveling agent with respect to 100 parts by weight of the silsesquioxane compound is represented by parts by weight.
• the hard coat films of Comparative Examples 1 to 3 using the silses oxane compounds 2 to 4 having a T3 / T2 ratio of more than 5 had excellent surface hardness, but the thickness of the hard coat layer was 10 ⁇ m (or less).
• the mandrel diameter ⁇ was 10 mm or more, and the bending resistance was insufficient.
• Comparative Example 4 in which the thickness of the hard coat layer was increased the surface hardness was improved as compared with Comparative Example 3, but the mandrel diameter ⁇ was further increased.
• the hard coat film of Comparative Example 5 using the silses oxane compound 5 having a small T3 / T2 ratio had a mandrel diameter ⁇ of 6 mm and was excellent in bending resistance, but had a low pencil hardness of B and a surface as a hard coat layer. The hardness was insufficient.
• Example 1 using the silses oxane compound 1 having a T3 / T2 ratio of 2.3 had both excellent surface hardness and bending resistance.
• the pencil hardness tended to increase as the thickness of the hard coat layer increased.
• the thicker the hard coat layer the larger the mandrel diameter tended to be.
• Example 7 in which the thickness of the hard coat layer was 37 ⁇ m the mandrel diameter exceeded 10 mm, but in comparison with Comparative Example 4, Example 7 had a high surface hardness and a small mandrel diameter (that is, bending resistance). It can be seen that a hard coat layer having a higher hardness and excellent bending resistance can be formed when compared with a silses oxane compound having a T3 / T2 ratio of 5 or more.
• Examples 8 to 18 A hard coat film was prepared in the same manner as in Example 1 except that the composition of the hard coat composition and the thickness of the hard coat layer were changed as shown in Table 3 using silsesquioxane compound 1. The surface hardness and bending resistance of the obtained hard coat film were evaluated. For the hard coat films of Examples 13 to 18, the water contact angles before and after the steel wool test described below were also measured.
• the water contact angle (initial value) of the hard coat layer was measured by the sessile drop method with the hard coat layer of the hard coat film as the upper surface. Using a reciprocating wear tester (Type30 manufactured by Heidon), a load of 500 g was applied to steel wool # 0000, and the steel wool test was carried out by reciprocating 500 times on the hard coat layer with a friction area of 4.5 cm 2. The water contact angle was measured again.
• Table 3 shows the composition of the hard coat composition used for producing the hard coat films of Examples 8 to 18, the thickness of the hard coat layer, and the evaluation results of the hard coat film. Table 3 also shows the evaluation results of Example 1 and Example 5. In the composition in Table 3, the blending amount (solid content) with the total resin content as 100 parts by weight is shown in parts by weight.
• Examples 8 to 12 to which the cationically polymerizable reactive additive was added also had excellent surface hardness and bending resistance as in Examples 1 to 7.
• the water contact angle was larger and the antifouling property was excellent as compared with Example 1 in which the leveling agent was not contained.
• the initial water contact angle was large, the contact angle was maintained high even after the steel wool test, and the stain resistance was excellent and the scratch resistance was excellent. It can be seen that it has.

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