WO2022145754A1 - Résine de silsesquioxane et composition anti-reflet comprenant celle-ci et ayant des propriétés de protection contre les empreintes digitales - Google Patents

Résine de silsesquioxane et composition anti-reflet comprenant celle-ci et ayant des propriétés de protection contre les empreintes digitales Download PDF

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WO2022145754A1
WO2022145754A1 PCT/KR2021/017975 KR2021017975W WO2022145754A1 WO 2022145754 A1 WO2022145754 A1 WO 2022145754A1 KR 2021017975 W KR2021017975 W KR 2021017975W WO 2022145754 A1 WO2022145754 A1 WO 2022145754A1
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group
formula
silsesquioxane resin
composition
fluorine
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PCT/KR2021/017975
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English (en)
Korean (ko)
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임해량
남동진
최승석
유현석
김영모
오성연
박한빈
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주식회사 동진쎄미켐
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Priority to CN202180083216.7A priority Critical patent/CN116601247A/zh
Priority to JP2023535807A priority patent/JP2024501200A/ja
Publication of WO2022145754A1 publication Critical patent/WO2022145754A1/fr

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    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the present invention relates to a silsesquioxane resin and a composition comprising the same, and more particularly, to a composition having excellent antireflection effect and water repellency at the same time, and a cured product obtained by curing the same.
  • window covers for display protection are being replaced with flexible plastics from non-bending tempered glass.
  • Anti-fingerprint, scratch-resistance and anti-reflection coatings are becoming important as a technology to protect the surface of large-area displays and to compensate for the disadvantages of plastics, which have relatively low transmittance compared to glass and poor image realization.
  • titanium dioxide (TiO 2 ) or niobium pentoxide (Nb 2 O 5 ), a high refractive material, and silicon dioxide (SiO 2 ), a low refractive material, are alternately deposited on a substrate to reflect it.
  • An anti-multilayer film was formed.
  • large-area coating is not possible and productivity is lowered due to the difficulty of the continuous process.
  • Korean Patent Registration KR 1395681 B1 a coating layer having a water repellency function is laminated on a substrate separately from an antireflection coating layer to realize an antireflection function and a water repellency function through an individual coating layer.
  • a process of laminating after curing each coating layer is required, which makes the wet coating process difficult, and thus processability and productivity are deteriorated.
  • an object of the present invention is to be applicable to a continuous process and a wet coating process advantageous for large-area coating, so that it is possible to form a cured product having excellent anti-reflection properties and water repellency while providing excellent productivity. To provide possible compositions.
  • Another object of the present invention is to provide a cured product having a low refractive index while having excellent antireflection effect and water repellency properties of visible light.
  • the silsesquioxane resin according to an embodiment of the present invention includes structural units represented by Chemical Formulas 1 to 3 below.
  • R 1 is each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 of an aryl group, a fluorinated organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R 1 is a fluorinated organic group having 1 to 30 carbon atoms;
  • R 2 is each independently hydrogen, or a substituted or unsubstituted C 1 to C 10 alkyl group.
  • composition according to another embodiment of the present invention includes the silsesquioxane resin, an initiator, and a solvent.
  • a cured product according to another embodiment of the present invention is obtained by curing the composition.
  • a display device includes the cured product.
  • composition containing the silsesquioxane resin according to the present invention can be applied to a wet process, eliminating the need for expensive vacuum dry deposition equipment, and not only can form a cured product with excellent processability and productivity, but is also included in the composition. It imparts physical properties such as excellent antireflection effect, water repellency, anti-fingerprint, stain resistance and scratch resistance, and has the effect of lowering the refractive index.
  • the cured product according to the present invention has excellent water repellency, anti-fingerprint properties, stain resistance and chemical resistance, and is located on the outermost layer of electronic products having a touch screen type as a coating layer to stably protect the display from fingerprints or scratches. can play a role
  • the silsesquioxane resin according to an embodiment of the present invention includes all of the structural units of Chemical Formulas 1 to 3, and when applied to a cured product, it can impart both an anti-reflection effect and a water-repellent property without a separate additional coating. It works.
  • R 1 is each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 of an aryl group, a fluorinated organic group having 1 to 30 carbon atoms, an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group, and at least one of R 1 is a fluorinated organic group having 1 to 30 carbon atoms;
  • R 2 is each independently hydrogen, or a substituted or unsubstituted C 1 to C 10 alkyl group.
  • the fluorinated organic group may be, for example, a fluoroalkyl group.
  • Chemical Formula 1 has a form in which two Si are not connected to each other, and due to the structure, pores are formed in the silsesquioxane resin, and in the composition according to an embodiment of the present invention It contains anti-reflection properties.
  • the silsesquioxane resin is included in the composition according to an embodiment of the present invention to improve adhesion and contribute to forming a stable cured product.
  • OR 2 is capable of covalent bonding with Si-OH or Si-O on the glass surface, so that when the composition is used as a coating composition, bonding and adhesion to the substrate are increased during coating.
  • Chemical Formula 3 is included in the composition according to an embodiment of the present invention to provide resin properties, water repellency, and a function of enabling a low refractive index.
  • the silsesquioxane resin may include a fluorine-containing organic group, and specifically may be positioned at the R 1 site of Chemical Formulas 1 to 3 above.
  • the composition according to the present invention contains the fluorine-containing organic group, there is an effect that water-repellent properties are imparted. Therefore, when the silsesquioxane resin according to the present invention is included in the composition, it can impart antireflection effects, water repellency, anti-fingerprint properties and low refractive properties.
  • the fluorine-containing organic group may have 3 or more carbon atoms.
  • the fluorine-containing organic group may be included in all of Chemical Formulas 1 to 3, and when the number of carbon atoms is less than 3, the water repellency and anti-reflection effect of the composition may deteriorate, and when the carbon number is greater than 15, the fluorine-containing organic group Due to excessively large size and reduced compatibility, it is difficult to prepare a composition containing the silsesquioxane resin in the form of a cured product, and even after curing, a problem of bad haze may occur, specifically, if the composition containing the silsesquioxane resin is 12 or less, case is good
  • the silsesquioxane resin may be copolymerized by including 1 to 100,000 units of each structural unit represented by Chemical Formulas 1 to 3 independently. If at least one type of each structural unit is not included, there may be a problem in that the composition lacks the antireflection function, the adhesive strength improvement function, and the water repellency imparting function provided by the structure, and the structural unit is 100,000 in the resin. When more than dogs are included, the polymer chain of the resin becomes excessively long and does not dissolve in a solvent, so there may be a problem in that wet coating becomes impossible when applied as a coating composition. More specifically, the inclusion of 1,000 to 10,000 of each structural unit in the resin has an advantageous effect on wet coating while effectively maintaining the properties provided by each structural unit.
  • the resin may be a block copolymer, and may be a random copolymer in which the unit structures of Chemical Formulas 1 to 3 are randomly arranged, but the type of copolymer is not limited thereto.
  • the ratio of the structural unit of Formula 2 is higher than the ratio range ((n+k)/m ⁇ 1), the antireflection function and water repellency of the composition may be deteriorated, and the ratio of the structural unit of Formula 2 compared to the ratio When this is low ((n+k)/m>1), the adhesion of the composition is lowered, and when formed into a coating layer, a problem in which the coating layer is easily detached from the substrate under the coating layer may occur.
  • the structural units of Formula 1 may have superior antireflection function and water repellency of the composition as compared to the structural units of Formula 3 above.
  • the ratio (n:k) of the number of structural units of Formula 1 to the number of structural units of Formula 3 is preferably 20:1 to 1:20.
  • the silsesquioxane resin may include the structural units of Chemical Formulas 1 to 3, and may be a resin represented by Chemical Formula 4 below.
  • R 1 is each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 aryl group, carbon number 1 to 30 fluorine-containing organic group, amino group, (meth)acryl group, vinyl group, epoxy group or thiol group, and at least one of R 1 is a fluorine-containing organic group having 1 to 30 carbon atoms;
  • R 2 is each independently hydrogen, or a substituted or unsubstituted C 1 to C 10 alkyl group; Wherein n, m, and k are each independently an integer of 1 to 100,000.
  • the fluorinated organic group included in the silsesquioxane resin may be specifically positioned at the R 1 site of Chemical Formula 4 above. However, in addition to the fluorine-containing organic group at the R 1 position, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 30 aryl group, One of an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, or a thiol group may be positioned, and it is sufficient that the silsesquioxane resin has at least one fluorinated organic group.
  • the high specific gravity of the fluorinated organic group at the R 1 position compared to the other functional groups is effective in providing the composition with an antireflection function and water repellency.
  • the fluorinated organic group when included in the composition, it is possible to more effectively impart an antireflection function and water repellency.
  • the fluorinated organic group is included in less than 50 mol% of R 1 , the antireflection and water repellent effect of the composition including the silsesquioxane resin may be deteriorated, and when it is included in more than 90 mol%, the composition A problem that hardening does not proceed easily may occur.
  • 10 to 30 mol% of R 1 in Formula 4 is composed of one of an amino group, a (meth)acrylic group, a vinyl group, an epoxy group, and a thiol group, which helps to effectively cure the cured product.
  • the functional group consisting of one of the amino group, (meth)acryl group, vinyl group, epoxy group and thiol group consists of less than 10 mol% of R 1 , the cured product is not cured well, so that the durability of the cured product is deteriorated. If it is included in more than 30 mol%, the specific gravity of the fluorine-containing organic group is relatively reduced, so that properties such as anti-reflection function and water repellency may not be effectively imparted to the composition.
  • R 1 in Formula 4 may be composed of one functional group among an alkyl group, a cycloalkyl group, and a phenyl group in an amount of 0 to 20 mol%, that is, 20 mol% or less.
  • the alkyl group, the cycloalkyl group and the phenyl group are located in R 1 where the amino group, (meth)acrylic group, vinyl group, epoxy group, thiol group and fluorinated organic group are not located, and are contained in an amount of 20 mol% or less, so that the function of other functional groups is reduced It plays a role in making it work well enough. However, since it is not a main functional group in the silsesquioxane resin, it may not be included.
  • the composition according to an embodiment of the present invention includes an initiator and a solvent to form a cured product by curing the silsesquioxane resin, which is a binder resin.
  • Various initiators may be used as the initiator depending on the type of R 1 in Formulas 1 to 3 included in the silsesquioxane.
  • a radical initiator may be used, and as the radical initiator, trichloro acetophenone, diethoxy acetophenone, 1-phenyl-2- Hydroxy-2-methylpropane-1-one (1-phenyl-2-hydroxyl-2-methylpropane-1-one), 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl thiophenyl) )-2-morpholinopropane-1-one (2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one), 2,4,6-trimethyl benzoyl diphenylphosphine oxide (trimethyl benzoyl diphenylphosphine oxide), camphor quinine, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobis (2-methyl butyrate), 3,3-dimethyl radical photoinitiators such as -4-methoxy
  • R 1 when an epoxy is included in R 1 , as a specific example, as a photopolymerization cationic initiator, a sulfonium-based, such as triphenylsulfonium, diphenyl-4-(phenylthio)phenylsulfonium, diphenyliodonium, or bis(dode) iodonium such as silphenyl) iodonium, diazonium such as phenyldiazonium, ammonium such as 1-benzyl-2-cyanopyrininium and 1-(naphthylmethyl)-2-cyanopridinium, (4- Methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate iodonium, bis(4-t-butylphenyl)hexafluorophosphate iodonium, diphenylhexafluorophosphate iodonium, diphenyltri
  • a cationic initiator acting by heat a cationic or protonic acid catalyst such as triflate, boron trifluoride ether complex, boron trifluoride, etc.
  • various onium salts such as ammonium salt, phosphonium salt and sulfonium salt, and methyltriphenylphosphonium Bromide, ethyltriphenylphosphonium bromide, phenyltriphenylphosphonium bromide, etc. can be used without limitation, but are not limited to the above examples, and these initiators may also be added in various mixed forms, and the various radicals specified above Mixtures with initiators are also possible.
  • the initiator may be included in an amount of 0.1 to 5 parts by weight.
  • the initiator is included in an amount of less than 0.1 parts by weight, curing initiation is not performed well, and thus the formation of a cured product may be difficult. It may remain, and a problem of reducing the physical properties of the cured product may occur.
  • composition according to the present invention may further include an amine curing agent depending on the type of R 1 , for example, ethylenediamine, triethylenetetramine, tetraethylene pentamine, 1,3-diaminopropane, dipropylenetriamine , 3-(2-Aminoethyl)amino-propylamine, N,N'-bis(3-aminopropyl)-ethylenediamine, 4,9-dioxadothecan-1,12-diamine, 4,7,10 -trioxatridecane-1,13-diamine, hexamethylenediamine, 2-methylpentamethylenediamine, 1,3-bisaminomethylcyclohexane, bis(4-animocyclohexyl)methane, norbornenediamine and 1 ,2-diaminocyclohexane.
  • an amine curing agent depending on the type of R 1 , for example, ethylenediamine, triethylene
  • composition according to the present invention may further include a curing accelerator to promote the curing action, for example, acetoguanamine, benzoguanamine, and 2,4-diamino-6-vinyl-s-triazine.
  • a curing accelerator to promote the curing action
  • Triazine compounds imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, vinylimidazole and 1- Imidazole compounds such as methylimidazole, 1,5-diazabicyclo[4.3.0]nonene-5,1,8-diazabicyclo[5.4.0]undecene-7, triphenylphosphine, di Phenyl (p-triyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, ethyltriphenylphospho
  • phthalic anhydride trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetra Acid anhydride curing agents such as hydrophthalic anhydride, dodecenyl succinic anhydride and 2,4-diethyl glutaric anhydride can also be widely used.
  • the solvent included in the composition may be used regardless of the type as long as it can dissolve the silsesquioxane resin and the initiator.
  • a fluorine-based solvent is included in the solvent, fluorine in the fluorine-based solvent together with the fluorine-containing organic group of the silsesquioxane resin dissolved in the solvent may help to effectively impart anti-reflection properties and water-repellent properties of the composition.
  • the content of the fluorine-based solvent accounts for 80% by weight or more of the solvent, the significant effect increase due to the use of the fluorine-based solvent can be seen, and the composition is advantageous in forming a uniform cured product.
  • the composition when used as a coating composition, it can be uniformly coated on a substrate and a flat and even coating layer can be formed.
  • the solvent may be included in an amount of 80 to 99% by weight
  • the silsesquioxane resin may be included in an amount of 0.1 to 15% by weight.
  • the solvent is, for example, a solvent capable of dissolving the silsesquioxane resin, including ethyl nonafluoro isobutyl ether, ethyl nonafluorobutyl ether, perfluorobutyl ethyl ether, perfluorohexyl methyl ether, methyl alcohol, Alcohols such as ethyl alcohol, isopropyl alcohol, butyl alcohol and cellosolve; ketones such as lactate, acetone, and methyl (isobutyl) ethyl ketone; glycols such as ethylene glycol; furan such as tetrahydrofuran; In addition to polar solvents such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone, hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, di
  • the composition according to the present invention may further include a fluorine-based silane.
  • the fluorine-based silane has an effect of further improving the anti-fingerprint effect by increasing the slip property of the surface of the cured product when it is further included in the composition and cured, but there is no problem even if it is not included.
  • the fluorine-based silane is, for example, a silane containing a perfluoro (poly) ether group, chlorosilane, dichlorosilane, trichlorosilane, alkylsilane, dialkylsilane, trialkylsilane, alkoxysilane, dialkoxysilane, trialkoxysilane , benzylsilane, dibenzylsilane, tribenzylsilane, cycloalkylsilane, dicycloalkylsilane, tricycloalkylsilane, chloro-dialkylsilane, dichloro-alkylsilane, chloro-dialkoxysilane, dichloro-alkoxysilane, alkyl- Dialkoxysilanes, derivatives and polymers of dialkyl-alkoxysilanes or fluorinated monomers and compounds partially or fully fluorinated in aliphatic chains having 1 to 20 carbons, si
  • the composition according to an embodiment of the present invention is a composition comprising the silsesquioxane resin of the present invention, and may be used as a coating composition, a film forming composition, an injection molding composition, a membrane forming composition, etc., but is not limited thereto. does not
  • the cured product according to an embodiment of the present invention is a cured product formed by curing the composition, and may be a coating layer, a functional film, an injection molded product, a membrane, and the like, but is not limited thereto.
  • the cured product may have a refractive index of 1.20 to 1.45, and the refractive index of the composition before curing as the cured product may also have a low refractive index of 1.20 to 1.45 similar to the refractive index of the cured product.
  • the cured product may be a coating layer, and the composition may be cured while forming a coating layer on a substrate. Since the coating layer has water repellency and antireflection functions at the same time, it is not necessary to form two layers each having water repellency and antireflection functions as in the prior art, and accordingly, the fairness and productivity of coating layer formation are greatly improved.
  • the cured product When the cured product is a coating layer, it may be coated on a glass or plastic material and a substrate or a hard coating layer. When coated on the hard coating layer, the cured product has excellent adhesive properties, and by coating the composition according to the present invention on the hard coating layer, a cured product having a thickness of 30 to 250 nm can be formed.
  • the thickness range can be adjusted according to the wavelength of the irradiated light, and as a specific example, by forming a coating layer at a level of 1/4 of the wavelength of visible light, destructive interference occurs in the coating layer to prevent reflection of visible light in the coating layer according to the present invention
  • the effect can be imparted, it is not limited to the anti-reflection effect in the visible ray region, and it can be applied to light such as ultraviolet rays and infrared rays.
  • the coating layer according to the present invention exhibits excellent water-repellent properties, anti-fingerprint, stain-resistance and scratch-resistance properties.
  • the composition according to the present invention can be applied by a wet coating method in the process of forming the coating layer.
  • a wet coating method in the process of forming the coating layer.
  • the composition according to the present invention has the effect of increasing the productivity as well as the excellent physical properties of the coating layer because large-area coating and continuous processing are possible through wet coating.
  • the display device is a display device including the cured product, and specifically, the cured product may be applied to a coating layer of the display device.
  • the cured product according to an embodiment of the present invention is not limited to a display device, and for example, it can be applied to devices or products such as spectacle lenses, camera lenses, architectural windows, display panels, automobile glass, and solar cells. Of course, it can be applied to the device or product to reduce the light reflected on the surface and exhibit the effect of increasing the light transmittance.
  • a 20 wt% aqueous solution of Na 2 CO 3 was separately prepared, and 20 g of the aqueous solution was added dropwise to the flask containing the reactant at one time. Thereafter, the temperature was raised to 100° C. and the condensation reaction was carried out for 1 day.
  • the mixture in which the condensation reaction has proceeded was subjected to layer separation and purification of water and toluene twice, and after confirming that the pH was neutral, the toluene layer was separated and all toluene was removed by vacuum to obtain a silsesquioxane resin.
  • a silsesquioxane resin was obtained in the same manner as in Preparation Example 1, except that 100 g of methanol of Preparation Example 1 was changed to 800 g of methanol and mixed.
  • a silsesquioxane resin was obtained in the same manner as in Preparation Example 1, except that 100 g of methanol of Preparation Example 1 was changed to 30 g of methanol and mixed.
  • a silsesquioxane resin was obtained in the same manner as in Preparation Example 1, except that 100 g of methanol of Preparation Example 1 was changed to 500 g of methanol and mixed.
  • a silsesquioxane resin was obtained in the same manner as in Preparation Example 1, except that 100 g of methanol of Preparation Example 1 was mixed with 50 g of methanol.
  • a 20 wt% aqueous solution of Na 2 CO 3 was prepared separately, and 20 g of the aqueous solution was added dropwise to the flask containing the reactant at one time. Thereafter, the temperature was raised to 100° C. and the condensation reaction was carried out for 1 day.
  • the mixture in which the condensation reaction has proceeded was subjected to layer separation and purification of water and toluene twice, and after confirming that the pH was neutral, the toluene layer was separated and all toluene was removed by vacuum to obtain a silsesquioxane resin.
  • Table 1 shows the number of carbon atoms of F-alkyl (fluorinated organic group) of the resin obtained according to Preparation Examples and Comparative Preparation Examples, (n+k)/m ratio according to Formula 4, R 1 according to Formula 4 It shows the ratio of F-alkyl in the middle (mol%).
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Examples 2 to 5 was used.
  • a water repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 6 was used and 0.2 parts by weight of a radical thermal initiator (Wako V65) was used.
  • a radical thermal initiator Wako V65
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 7 was used and 0.02 parts by weight of a radical thermal initiator (Wako V65) was used.
  • a water repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 8 was used and 0.15 parts by weight of a radical thermal initiator (Wako V65) was used.
  • a radical thermal initiator Wako V65
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Preparation Example 9 was used and 0.05 parts by weight of a radical thermal initiator (Wako V65) was used.
  • a radical thermal initiator Wako V65
  • Water-repellent coating composition in the same manner as in Example 1, except that a mixed solvent in which a fluorine-based solvent (3M's FC-3283) and methyl ethyl ketone were mixed in a ratio of 7: 3 by weight was used as the solvent. was prepared.
  • a water-repellent coating composition was prepared in the same manner as in Example 6, except that methyl ethyl ketone was used as a solvent.
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Comparative Preparation Example 1 was used.
  • a water repellent coating composition was prepared in the same manner as in Example 1, except that the silsesquioxane resin obtained in Comparative Preparation Example 2 was used and 0.4 parts by weight of a radical thermal initiator (Wako V65) was used.
  • a radical thermal initiator Wako V65
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that a commercial silsesquioxane compound represented by the following formula [Hybrid plastics FL0578 (Trifluoropropyl POSS Cage Mixture)] was used instead of the silsesquioxane resin of the present invention did
  • a water-repellent coating composition was prepared in the same manner as in Example 1, except that a siloxane-based compound (Trifluoropropylmethylsiloxane) represented by the following formula was used instead of the silsesquioxane resin of the present invention.
  • a siloxane-based compound Trifluoropropylmethylsiloxane represented by the following formula was used instead of the silsesquioxane resin of the present invention.
  • ⁇ Refractive index It was measured using a prism coupler, and the average value was recorded by measuring 5 times per sample.
  • ⁇ Eraser abrasion resistance test conducted in accordance with KS B ISO 9211-4. In this case, an eraser dedicated to the abrasion resistance test was used, and 5,000 reciprocations were performed under a load of 1 kgf, and the contact angle value of the substrate surface was measured before and after the test.
  • the transmittance was 94.00 or more
  • the Haze was 0.5 or less
  • the refractive index was 1.40 or less.
  • no scratches occurred in the scratch test, and after the eraser abrasion resistance and chemical resistance test the contact angle was 95° or more, and the change in contact angle was small compared to before the test, indicating excellent abrasion resistance and chemical resistance.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 (n+k)/m 10-30 less than 1 over 50 1 to 10 30-50
  • Example 1 the transmittance and abrasion resistance of Example 1 are higher than those of Examples 2 and 4, and the higher the (n+k)/m value, the higher the transmittance and wear resistance. become more excellent
  • the contact angle shows a lower value than that of Example 1, and the (n+k)/m value exceeds 30 and the chemical resistance deteriorates. Therefore, in consideration of transmittance, eraser abrasion resistance, and chemical resistance, Example 1, in which the (n+k)/m value is 10 to 30, exhibits the most excellent effect.
  • Examples 1 and 6 to 9 are shown in Table 4 below based on the molar ratio of fluorinated organic groups of all R 1 in the structure of Formula 4 above.
  • Example 1 Example 6 Example 7 Example 8 Example 9 R 1 , fluorine-containing Molar ratio of organic groups (mol%) 65-85 less than 50 over 90 50 ⁇ 65 85-90
  • Example 1 the transmittance of Example 1 is higher than that of Examples 6 and 8, and as the molar ratio of the fluorinated organic groups increases, the transmittance becomes excellent.
  • the contact angle of the eraser abrasion resistance and chemical resistance test of the eraser of Example 1 was low, and when the molar ratio of the fluorinated organic group was greater than or equal to a specific molar ratio, abrasion resistance and chemical resistance were deteriorated. Therefore, in consideration of permeability, abrasion resistance, and chemical resistance, Example 1 in which the molar ratio (mol%) of the fluorine-containing organic group of R 1 is 65 to 85 mol% shows the most excellent effect.
  • Examples 1 and 10 to 11 are shown in Table 5 below based on the weight% of the fluorine-based solvent in the solvent.
  • Example 1 Example 10
  • Example 11 Ratio of fluorine-based solvent in solvent (wt%) 100 10-80 not included
  • Example 1 is excellent in all performance compared to Example 10 containing less than 80% by weight of the fluorine-based solvent in the solvent, and Example 11 without the fluorine-based solvent (of Synthesis Example 6)
  • Example 6 using only a fluorine-based solvent compared to silsesquioxane resin is excellent in all performance. This indicates that the higher the content of the fluorine-based solvent, the better the overall performance.

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Abstract

La présente invention concerne une composition comprenant une résine de silsesquioxane contenant une unité structurale chimique particulière et un groupe fluoroalkyle, et un matériau durci obtenu par durcissement de la composition. Plus spécifiquement, la présente invention concerne une composition qui peut produire un matériau durci ayant d'excellentes propriétés antireflet et hydrofuges, et un matériau durci obtenu par durcissement de la composition.
PCT/KR2021/017975 2020-12-31 2021-12-01 Résine de silsesquioxane et composition anti-reflet comprenant celle-ci et ayant des propriétés de protection contre les empreintes digitales WO2022145754A1 (fr)

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CN202180083216.7A CN116601247A (zh) 2020-12-31 2021-12-01 倍半硅氧烷树脂以及包含倍半硅氧烷树脂且具有耐指纹特性的防反射组合物
JP2023535807A JP2024501200A (ja) 2020-12-31 2021-12-01 シルセスキオキサン樹脂、及びこれを含む耐指紋特性の反射防止組成物

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KR10-2020-0189890 2020-12-31
KR1020200189890A KR20220096987A (ko) 2020-12-31 2020-12-31 실세스퀴옥산 수지 및 이를 포함하고 내지문 특성을 가지는 반사방지 조성물

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120252920A1 (en) * 2009-12-04 2012-10-04 Macmillan Andrew Stabilization Of Silsesquioxane Resins
KR20150105603A (ko) * 2014-03-07 2015-09-17 주식회사 동진쎄미켐 실세스퀴옥산 복합 고분자를 포함하는 열가소성 수지 조성물
JP2019069586A (ja) * 2017-10-11 2019-05-09 凸版印刷株式会社 フィルム及び画像表示装置
KR20190056307A (ko) * 2017-11-16 2019-05-24 주식회사 동진쎄미켐 실세스퀴옥산 고분자 및 그를 포함하는 코팅 조성물
KR101996262B1 (ko) * 2017-09-01 2019-10-01 (주)휴넷플러스 차단성 수지 조성물, 광경화 차단막의 제조방법 및 전자소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120252920A1 (en) * 2009-12-04 2012-10-04 Macmillan Andrew Stabilization Of Silsesquioxane Resins
KR20150105603A (ko) * 2014-03-07 2015-09-17 주식회사 동진쎄미켐 실세스퀴옥산 복합 고분자를 포함하는 열가소성 수지 조성물
KR101996262B1 (ko) * 2017-09-01 2019-10-01 (주)휴넷플러스 차단성 수지 조성물, 광경화 차단막의 제조방법 및 전자소자
JP2019069586A (ja) * 2017-10-11 2019-05-09 凸版印刷株式会社 フィルム及び画像表示装置
KR20190056307A (ko) * 2017-11-16 2019-05-24 주식회사 동진쎄미켐 실세스퀴옥산 고분자 및 그를 포함하는 코팅 조성물

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