WO2017043873A1 - Blue light absorption film - Google Patents

Abstract

The present invention relates to a blue light absorption film and, specifically, to a film and a compound contained in the film, wherein: the film has an excellent effect of absorbing the blue light that comes out from various display devices, thereby preventing deterioration of eyesight, eye damage, and sleep disorder; the film has excellent resistance to yellowing; the film increases effects of improving scratch resistance, water repellency, antifouling, anti-fingerprinting, thermal stability, gloss, and surface hardness; and especially, the film has a very high absorption power for a blue light of 400-470 nm wavelength band, which is harmful to the human body, but a relatively low absorption power for a blue light of 470-500 nm wavelength band, which is beneficial to the human body, and thus can give a beneficial effect to the human body.

Description

Blue light absorbing film

The present invention relates to a blue light absorbing film, and in particular, excellent blue light absorbing effect from various display devices can prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, Increases the antifouling, anti-fingerprint, thermal stability, glossiness and surface hardness improvement effects. In particular, the light absorption of blue light in the 400-470 nm wavelength, which is harmful to the human body, is very high, but the blue light in the 470-500 nm wavelength, which is beneficial to the human body, is highly effective. The light absorption for the relatively low relates to a film, a coating composition and a compound included therein which can bring a more beneficial effect on the human body.

In the display, light of various wavelengths is generated, and double UV and visible light may damage the human retina and pigment cell epithelium, but the human retina has a short wavelength (UV area) of less than 295 nm in the cornea, less than 400 nm. The short wavelength of is absorbed by the lens, and the human retina is exposed only to electromagnetic waves (visible light) in the 400-760 nm band and a few IR bands.

Blue light (blue light) is a strong energy of blue light from various display devices, but it is reported that it is invisible but can rapidly increase the free radicals of the eye and damage visual cells by up to 80%. , Dry eye, and sleep disorders, especially retinal and cellular damage in 400-450 nm (wavelength 1 region), and melatonin (sleep induction hormone) in 450-470 nm (wavelength 2 region). It adversely affects the human body such as suppression, arousal, and heart rate increase, but 470-500 nm (wavelength 3 region) has been reported to be useful for treating sleep disorders and depression.

To solve this, salicylic acid (

) Compound, benzophenone (

)

System compound, benzotriazole (

Attempts have been made to absorb blue light using a) -based compound or cyanoacrylate-based compound, but the yellowing phenomenon of the film is severe, and there is a problem that the blue light blocking effect is not large, and countermeasures are urgently needed.

In order to solve the above problems, the present invention is excellent in the blue light absorption effect can prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, antifouling properties, anti-fingerprint , Heat stability, glossiness and surface hardness improvement effect can be increased. Especially, the light absorption power of blue light in the wavelength range of 400-470 nm, which is harmful to the human body, is very high, but the light absorption power of blue light in the wavelength range of 470-500 nm, which is beneficial to the human body, is very high. Is a relatively low object to provide a blue light absorbing film that can bring a more beneficial effect on the human body.

In addition, the present invention is excellent in the blue light absorption effect can prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, antifouling properties, fingerprint resistance, thermal stability, gloss characteristics and It is possible to increase the surface hardness improvement effect, especially the light absorption of blue light in the wavelength range of 400-470 nm, which is harmful to the human body, is very high, while the light absorption power of the blue light in the wavelength range of 470-500 nm, which is beneficial to the human body, is relatively low. It provides a coating composition that can bring a beneficial effect.

It is also an object of the present invention to provide a compound useful for absorbing blue light.

The present invention to achieve the above object

In another aspect, the present invention provides a film containing a blue light absorbing compound represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; C ₁ -C ₄₀ alkyl groups which are unsubstituted or substituted with deuterium, halogen, amine groups, epoxy groups, (meth) acryl groups, siol groups, isocyanate groups, nitrile groups, nitro groups, and phenyl groups; C ₂ -C ₄₀ alkenyl group; C ₁ ~ C ₄₀ Alkoxy group; C ₃ -C ₄₀ cycloalkyl group; C ₃ ~ C ₄₀ Heterocycloalkyl group; C ₆ -C ₄₀ aryl group; C ₃ ~ C ₄₀ heteroaryl group; An aralkyl group of C ₃ ~ C _40; C ₃ -C ₄₀ aryloxy group; Or an C ₃ to C ₄₀ arylcyol group.

In another aspect, the present invention provides a coating composition comprising a blue light absorbing compound represented by the formula (1).

In another aspect, the present invention provides a blue light absorbing compound represented by the formula (1).

Film according to the present invention is excellent in the blue light absorption effect can prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, antifouling properties, anti-fingerprint, thermal stability, gloss Properties and surface hardness improving effect can be increased. In particular, the light absorption of the blue light of 400-470 nm wavelength harmful to the human body is very high, but the light absorption of the blue light of the wavelength 470-500 nm beneficial to the human body is relatively low can bring a more beneficial effect on the human body.

1 is a graph showing the results of measuring blue light absorption in a 400-500 nm region of a blue light absorbing film according to Examples and Comparative Examples of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Throughout the specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding other components unless specifically stated otherwise.

Hereinafter, the present invention will be described in detail.

The present invention provides a film comprising a blue light absorbing compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or a C ₃ ~ C ₄₀ aralkyl group or C ₃ ~ C ₄₀ aryloxy group or a C ₃ ~ C ₄₀ aryl olgi between the. Specifically, R ₃ is a C ₁ ~ C ₄₀ alkyl group which is unsubstituted or substituted with hydrogen, deuterium, halogen, amine group, epoxy group, (meth) acryl group, siol group, isocyanate group, nitrile group, nitro group, phenyl group or C ₂ ~ C ₄₀ alkenyl group or C ₁ ~ C ₄₀ alkoxy group or C ₃ ~ C ₄₀ cycloalkyl group or C ₃ ~ C ₄₀ heterocycloalkyl group or C ₆ ~ C ₄₀ aryl group or C ₃ ~ C ₄₀ may be a heteroaryl group or a C ₃ ~ C ₄₀ aralkyl group or C ₃ ~ aryloxy group or a C ₃ ~ C ₄₀ aryl group between all of the C _40.

More specifically, the compound is indole-3-acetamide, indole-3-carboxaldehyde, indole-3-carbinol And indole-3-thiocarboxamide, 2- (2-aminophenyl) indole and 2- (2-aminophenyl) indole. The compounds may be used by mixing two or more kinds.

The compound according to the present invention has a property of absorbing blue light in the 400 to 500 nm region. In particular, the compound has a very high light absorption of blue light of 400-450 nm (first wavelength region) and 450-470 nm (second wavelength region) harmful to the human body, while 470-500 nm (third wavelength region) beneficial to the human body. ), The light absorption of blue light is relatively low. Specifically, the ratio of the average light absorption of 400-470 nm of light and the average light absorption of 470-500 nm of light of the compound (light absorption of wavelength 1 + 2 / light absorption of wavelength 3) is 2- It may be 5, and for the same reason, the compound of the present invention may be more advantageous to the human body when applied to the blue light absorbing film.

Blue light absorbing film according to the present invention includes a compound represented by the formula (1), the compound may be included in the film substrate, or included as a separate coating layer, or may be included in the coating layer formed on one or both sides of the substrate In particular, the coating layer may be a hard coating layer.

The hard coating layer may be formed of a coating composition including the compound represented by Formula 1 and a silsesquioxane resin. When the silsesquioxane resin is included, hard coating of the film may be performed at the same time.

The silsesquioxane

,

,

And

It may be silsesquioxane including at least one of, or

And

It may be a silsesquioxane containing, or may be silsesquioxane represented by any one of the following Formulas 2 to 10.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

In the above, A is

And B is

ego,

D is

And E is

Is,

Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or A C ₃ to C ₄₀ aralkyl group or a C ₃ to C ₄₀ aryloxy group or a C ₃ to C ₄₀ arylthiol group, a and d are each independently an integer of 1 to 100,000, specifically a is 3 To 1000, d may be 1 to 500, more specifically a is 5 to 300, d may be 2 to 100, b is each independently an integer of 1 to 500, e is each independently 1 or 2, specifically may be 1, n is each independently an integer of 1 to 20, Specifically, it may be 3 to 10. Although not indicated above, a known chain unit applicable to the silsesquioxane composite polymer may be further included between each chain unit.

The silsesquioxane composite polymer represented by Formula 2 is

Mixing a basic catalyst and an organic solvent in a reactor and then adding an organic silane compound and condensing to prepare Chemical Formula 11; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid and then adding and stirring an organic silane compound to introduce a [D] d (OR ² ) ₂ structure into Chemical Formula 11 after the first step. step; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.

[Formula 11]

Wherein R ¹ , R ² , R ¹⁶ , D, a and d are the same as defined in Chemical Formulas 2 to 11.

Silsesquioxane composite polymer represented by Formula 3 of the present invention

A first step of preparing Chemical Formula 11 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [D] d (OR ³ ) ₂ and [D] d (OR ⁴ ) ₂ structures into the formula (11) after the first step as in the formula ( ³ ). A second step of adding and stirring an excess of the organic silane compound after the adjustment; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And through a third step of the reaction, it can be prepared by proceeding to the purification step to remove the cage structure as a by-product generated by recrystallization.

Silsesquioxane composite polymer represented by Formula 4 of the present invention

A first step of preparing Chemical Formula 11 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And a second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid and then adding and stirring an organic silane compound to introduce a [D] d (OR ⁵ ) ₂ structure into Chemical Formula 11 after the first step. step; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX ₂ structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.

Silsesquioxane composite polymer represented by the formula (5) of the present invention

A first step of preparing Chemical Formula 11 by mixing a basic catalyst and an organic solvent in a reactor, adding an organic silane compound, and adjusting the degree of condensation; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR ⁷ ) ₂ structure into the formula (11), and the reaction solution is acidified to adjust the organic silane compound. A second step of adding and stirring; And a third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the two steps.

Silsesquioxane composite polymer represented by the formula (6) of the present invention

A first step of preparing Chemical Formula 11 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And adding an acidic catalyst to the reactor to introduce the [B] b structure, the [D] d (OR ⁸ ) ₂ , and the [D] d (OR ⁹ ) ₂ structure into the chemical formula 11 after the first step. A second step of adding and stirring an excess of the organic silane compound after adjusting to acidity; And a third step of converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of removing the single cage generation structure through recrystallization and filtering after the third step.

Silsesquioxane composite polymer represented by the formula (7) of the present invention

A first step of preparing Chemical Formula 11 by mixing a basic catalyst and an organic solvent in a reactor and then adding and condensing an organic silane compound; And after the first step, an acidic catalyst is added to the reactor to introduce the [B] b structure and the [D] d (OR ¹⁰ ) ₂ structure into the formula (11), and the reaction solution is acidified to adjust the organic silane compound. A second step of adding and stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the second step; And a fourth step of introducing an [E] eX ₂ structure at the end of the composite polymer into the reactor after the third step, converting the reaction solution into an acidic atmosphere, and mixing and stirring the organosilane compound. Can be prepared.

Specifically, the pH of the reaction solution of the first step of the present invention in the method for preparing the formulas 2 to 7 is 9 to 11.5, the pH of the reaction solution of the second step is 2 to 4, the reaction solution of the third step The pH is 8 to 11.5, and the pH of the reaction solution in the fourth step of introducing Ee is 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.

Silsesquioxane composite polymer represented by the formula (8) of the present invention

Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organosilane compound and preparing two types of Chemical Formula 11 in which the degree of condensation is controlled; In order to introduce the structure [B] b and the structure [D] d (OR ¹² ) ₂ to the formula (11) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; And four steps of condensing and connecting two or more materials obtained through the three steps under basic conditions.

Silsesquioxane composite polymer represented by the formula (9) of the present invention

Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organosilane compound and preparing two types of Chemical Formula 11 in which the degree of condensation is controlled; In order to introduce the [B] b structure and the [D] d (OR ¹⁴ ) ₂ structure into the formula (11) obtained in step 1, the reaction solution was adjusted to acid by adding an acidic catalyst to the reactor, and then an organic silane compound was added. A second step of stirring; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two-step reaction; Condensing and connecting two or more substances obtained through the three steps under basic conditions; A fifth step of adding an acidic catalyst to the reactor for introducing [D] d (OR ¹³ ) ₂ after the fourth step to adjust the reaction solution to acid, followed by adding and stirring an organic silane compound; And a sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction.

Silsesquioxane composite polymer represented by Formula 10 of the present invention

Mixing a basic catalyst and an organic solvent in a reactor, followed by adding an organosilane compound and preparing two types of Chemical Formula 11 in which the degree of condensation is controlled; A second step of adding an acidic catalyst to the reactor to adjust the reaction solution to acidic acid in order to introduce the structure [B] b to the formula (11) obtained in step 1, and then adding and stirring an organic silane compound; A third step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after each two step reaction; Condensing and connecting two or more compounds obtained through the three steps in basic conditions; A fifth step of adding an acidic catalyst to a reactor for introducing [D] d (OR ⁵ ) ₂ to adjust the reaction solution to acidic acid after the fourth step, and then adding and stirring an organic silane compound; A sixth step of performing a condensation reaction by converting the reaction solution into basic by adding a basic catalyst to the reactor after the five step reaction; Including the seventh step of introducing the [E] eX ₂ structure to the end of the composite polymer after the sixth step to convert the reaction solution into an acidic atmosphere by mixing the organic silane compound by stirring the acidic catalyst into the reactor Can be prepared.

Specifically, the pH of the reaction solution of the first step is 9 to 11.5, the pH of the reaction solution of the second step is 2 to 4, the pH of the reaction solution of the third step in the method for preparing the polymer of Formula 8 to 10 Is 8 to 11.5, the pH of the reaction solution of the fourth step is 9 to 11.5, the pH of the reaction solution of the fifth step is 2 to 4, 8 to 11.5 of the reaction solution of the sixth step, and Ee is introduced. PH of the reaction solution of the seventh step is 1.5 to 4. Within the above range, not only the yield of the silsesquioxane composite polymer prepared is high, but also the mechanical properties of the manufactured silsesquioxane composite polymer can be improved.

If necessary, in order to further introduce the [B] b structure and the [D] d (OR) ₂ structure to each of the composite polymers, an acidic catalyst was added to the reactor to adjust the reaction solution to acidic acid, and then an organic silane compound was added. Stirring; And [B] b repeating units in the composite polymer through the step of performing a condensation reaction by adding a basic catalyst to the reactor and converting the reaction solution to basic after the above step.

In addition, by converting the reaction solution was added an acid catalyst to the reactor in order to introduce a [E] eX ₂ structure at the ends of each of the composite polymer, if necessary with an acidic atmosphere, and comprising the step of stirring a mixture of an organosilane compound of the composite polymer The terminal may further include a repeating unit of [E] e.

In the method for preparing the silsesquioxane composite polymer, a mixed catalyst of two or more basic catalysts is specifically used as a basic catalyst, and neutralized and acidified with an acidic catalyst to induce rehydrolysis, and again two or more basic catalysts. Acidity and basicity can be continuously controlled in one reactor by proceeding to basic condensation using a mixed catalyst of.

In this case, the basic catalyst may be prepared by appropriately combining two or more materials selected from a metal based catalyst and an amine based catalyst selected from the group consisting of Li, Na, K, Ca and Ba. Specifically, the amine basic catalyst may be tetramethylammonium hydroxide (TMAH), and the metallic basic catalyst may be potassium hydroxide (KOH) or sodium bicarbonate (NaHCO ₃ ). In the mixed catalyst, the content of each component may be arbitrarily adjusted at a ratio of 10 to 90:10 to 90 parts by weight of the amine based catalyst and the metal based catalyst. Within the above range, the reactivity between the functional group and the catalyst may be minimized during hydrolysis, and thus, the defects of organic functional groups such as Si-OH or Si-alkoxy may be significantly reduced, thereby freely controlling the degree of condensation. In addition, the acidic catalyst may be used without limitation so long as it is an acidic material commonly used in the art, for example, may be used a general acidic material such as HCl, H ₂ SO ₄ , HNO ₃ , CH ₃ COOH, Organic acids such as latic acid, tartaric acid, maleic acid and citric acid can also be applied.

In the method for preparing the silsesquioxane composite polymer of the present invention, the organic solvent may be used without limitation as long as it is an organic solvent commonly used in the art, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol , Alcohols such as cellosolves, ketones such as lactate, acetone, methyl (isobutyl) ethyl ketone, glycols such as ethylene glycol, furan systems such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N Polar solvents such as methyl-2-pyrrolidone, as well as hexane, cyclohexane, cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, Various solvents, such as acronitrile, methylene chloride, octadecylamine, aniline, dimethylsulfoxide, benzyl alcohol, can be used.

In addition, as the organosilane-based compound of the silsesquioxane composite polymer of the present invention R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , Organosilanes comprising R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² can be used Specifically, the organic silane compound containing a phenyl group or an amino group having an effect of improving the chemical resistance of the silsesquioxane composite polymer to improve the non-swelling property, or the curing density of the composite polymer to increase the mechanical strength and hardness of the cured layer An organic silane compound containing an epoxy group or a (meth) acryl group having an effect of improving can be used.

Specific examples of the organosilane compound include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3 -Glycidoxy propyl) dimethyl ethoxy silane, 3- (methacryloxy) propyl trimethoxy silane, 3, 4- epoxy butyl trimethoxy silane, 3, 4- epoxy butyl triethoxy silane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltri-t-butoxy Silane, vinyltriisobutoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimeth Methoxysilane, dimethyl tetramethoxysiloxane, diphenyltetramethoxysiloxane, etc. are mentioned, You may use individually by 1 type or in combination of 2 or more types. It is more advantageous to use two or more kinds in combination for physical properties of the final composition.

The silsesquioxane of the present invention can be adjusted to 1 to 99.9% or more of condensation in order to secure excellent storage stability to obtain a wide range of applications. That is, the content of the alkoxy group (OR) bonded to the terminal and central Si can be adjusted from 50% to 0.01% with respect to the entire bonding group.

In addition, by adjusting the content of the repeating unit [B] b or [E] e, the physical properties of the substrate including the surface hardness can be further improved.

The weight average molecular weight of the silsesquioxane may be 1,000 to 500,000, specifically 1,000 to 80,000, and more specifically 2,000 to 50,000. In this case, the processability and physical properties of the silsesquioxane can be improved simultaneously.

The coating composition of the present invention may be coated alone as a solvent-free type when the silsesquioxane composite polymer is a liquid, and may be configured to include an organic solvent in the case of a solid phase. In addition, the coating composition may further include an initiator or a curing agent.

Specifically, the coating composition is a compound represented by Formula 1; Silsesquioxane composite polymer represented by any one of Formulas 2 to 10; It may include an organic solvent, an initiator commonly used in the art that is compatible with the composite polymer, and optionally further include additives such as curing agents, plasticizers, sunscreens, and other functional additives, such as curability, heat resistance, UV protection, a plasticizing effect, etc. can be improved.

In the coating composition of the present invention, the blue light absorbing compound represented by Formula 1 is specifically included in 0.001 to 10% by weight, and more specifically 0.1 to 5% by weight. Within the above range, it has an excellent blue light absorption and satisfies the resistance to yellowing while maintaining transparency of the film, and also has excellent compatibility with silsesquioxane, thereby further improving the physical properties of the hard coating of the film. .

The silsesquioxane composite polymer may include 5 to 90 wt% of the coating composition. If within the above range can further improve the mechanical properties of the cured film of the coating composition.

In addition, the coating composition may further include an organic solvent, and as the organic solvent, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, cellosolve, lactate, acetone, methyl (isobutyl Ketones such as ethyl ketone, glycols such as ethylene glycol, furan compounds such as tetrahydrofuran, polar solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone, as well as hexane and cyclohexane Cyclohexanone, toluene, xylene, cresol, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, methylene chloride, octadecylamine, aniline, dimethyl sulfoxide, benzyl alcohol, etc. Various solvents may be used, but are not limited thereto. The amount of the organic solvent is included in the remaining amount excluding the composite polymer, the initiator, and optionally added additives. Specifically, it may be included in an amount of 95% by weight or less.

In the coating composition of the present invention, the initiator or the curing agent may be appropriately selected and used according to the organic functional group contained in the silsesquioxane composite polymer.

As a specific example, when an organic system capable of post-curing such as an unsaturated hydrocarbon, a siol system, an epoxy system, an amine system, or an isocyanate group is introduced into the organic functional group, various curing using heat or light is possible. At this time, the change due to heat or light can be achieved in the polymer itself, and the curing step can be achieved by diluting with the organic solvent as described above.

In addition, in the present invention, for curing and post-reaction of the composite polymer, various initiators may be used, and the initiator may be included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the total composition, and when included in an amount within the above range, Permeability and coating stability can be satisfied at the same time.

The hardener may be included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the total composition.

The present invention may further include additives such as UV absorbers, antioxidants, antifoaming agents, leveling agents, water repellents, flame retardants, and adhesion improving agents for the purpose of improving hardness, strength, durability, formability, etc. through a curing process or a post reaction. Can be. Such additives are not particularly limited in use, but may be appropriately added within a range that does not impair the properties of the film, that is, properties such as flexibility, light transmittance, heat resistance, hardness and strength. Each of the additives is preferably included in an amount of 0.01-10 parts by weight based on 100 parts by weight of the total weight of the composition.

In addition, in the present invention, the film base material may be a transparent film, and specific examples of the film include COC (Cyclic olefin copolymer), PAc (Polyacrylate), PC (Polycarbonate), PE (Polyethylene), PEEK (Polyetheretherketone), PEI (Polyetherimide) , Polyethylenenaphthalate (PEN), Polyethersulfone (PES), Polyethylene terephtalate (PET), Polyimide (PI), Polyolefin (PO), Polymethylmethacrylate (PMMA), Polysulfone (PSF), Polyvinylalcohol (PVA), Polyvinylcinnamate (acetyl) acetyl TAC , Polysilicon (Poly Silicone), polyurethane (Polyurethane) and epoxy resin (Epoxy Resin) film of the material selected from the group consisting of can be used. The material may be composed of a single layer or two or more layers having different characteristics of the same material, and may also be a transparent film in which two or more plastics are mixed through coextrusion.

In the present invention, a method for coating the coating composition on a transparent film is known as spin coating, bar coating, slit coating, dip coating, natural coating, reverse coating, roll coating, spin coating, curtain coating, spray coating, gravure coating, and the like. Those skilled in the art can arbitrarily select and apply among the methods. Also in the curing method, photocuring or thermosetting can be appropriately selected and applied according to the functional group of the composite polymer. Specifically, in the case of thermal curing, the curing temperature is 80 to 120 ℃, and the curing may be photocuring, the photocuring may be ultraviolet curing, specifically, it may be cured to 200mJ to 2000mJ using a UV lamp. .

In addition, the film of the present invention may further perform the step of aging. The aging step may be aged between 50 to 100 ℃, the time may be about 3 to 48 hours. Through the aging step, the coating layer is stably generated, and the adhesion between the film and the coating layer can be further improved, and the surface of the coating layer has excellent surface hardness, transparency, scratch resistance, water repellency, antifouling properties, fingerprint resistance, and thermal stability. And gloss characteristics.

In the present invention, the coating thickness of the coating composition may be arbitrarily adjusted, specifically 0.01 to 500 um, more specifically 0.1 to 300 um, even more specifically 1 to 100 um range. Within this range, the excellent blue light absorbency can satisfy the yellowing phenomenon of the film at the same time, the film surface can not only stably secure the surface hardness of 7H or more, but also exhibits excellent physical properties in the film surface properties.

The blue light absorbing film according to the present invention includes a blue light absorbing compound represented by the formula (1), so that the average light absorption of 400-470 nm (first wavelength range + second wavelength range) is 30 to 70% (transmittance is 30 to 70%). 70%), the average light absorption of 470-500 nm (third wavelength region) may be 40 to 20% (transmittance of 60 to 80%), more specifically, the light absorption of the first wavelength region is 50 To 85% (transmittance of 15 to 50%), the light absorption of the second wavelength region may be 65 to 35% (transmittance of 35 to 65%), the light absorption of the third wavelength region is 40 to 20 % (Transmittance of 60 to 80%). In the blue light absorbing film of the present invention, the ratio of the average light absorption rate between the wavelength ranges (the light absorption rate in the wavelength 1 + 2 region / the light absorption rate in the wavelength 3 region) has 2-5 to absorb as much of the blue light as harmful to the human body. The blue light, which is beneficial to the human body, is relatively absent and more advantageous to the human body.

The blue light absorbing film of the present invention may be applied to a display device. Specifically, the display device may be a smartphone, a tablet PC, a notebook PC, an AIO (All-In-One) PC, an LCD monitor, a TV, an advertisement board, or a touch panel. It may be a flexible smart device (wearable smart device) that requires the flexibility of the film.

The form of the film included in the display device is not particularly limited, and may be, for example, in the form of a window cover film or a protective film. The display device according to the present invention includes a blue light absorbing film to prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, antifouling properties, anti-fingerprint, thermal stability, It is possible to increase the glossiness and surface hardness enhancement effect. Especially, the light absorption power of blue light of 400-470 nm wavelength which is harmful to human body is very high while the light absorption power of blue light of 470-500 nm wavelength which is beneficial to human body is relatively low. It can have a more beneficial effect on the human body.

Hereinafter, specific examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

In the embodiment of the present invention, ECHETMS is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, GPTMS is Glycidoxypropytrimethoxysilane, MAPTMS is (methacryloyloxy) propyltrimethoxysilane, PTMS is Phenyltrimethoxysilane, MTMS is Methyltrimethoxysilane, and ECHETMDS is Di (epoxycyclohexyethyl) Di (glycidoxypropyl) tetramethoxy disiloxane, MAPTMDS stands for Di (methacryloyloxy) propy, PTMDS stands for Di (phenyl) tetramethoxy disiloxane, and MTMDS stands for Di (Methyl) tetramethoxy disiloxane.

Example 1 Synthesis of Silsesquioxane A-D Structured Polymer and Preparation of Coating Composition

In the synthesis step, continuous hydrolysis and condensation were carried out step by step as follows.

Example 1-a Preparation of Catalyst

In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).

Example 1-b Synthesis of Linear Silsesquioxane Structure

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 1-a was added dropwise, followed by stirring at room temperature for 1 hour, and then 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having the same linear structure as the formula (11) has a molecular weight of 8,000 styrene.

Example 1-c Generation of a continuous cage structure

To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at one time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, part of the sample was collected and analyzed by ²⁹ Si-NMR. As a result, analytical peaks of the structure introduced using the phenyl group appeared as two sharp forms. It was confirmed that the above was manufactured. In addition, the styrene reduced molecular weight was measured to 11,000, n value was 4-6. ²⁹ Si-NMR (CDCl ₃ ) δ

Example 1-d Preparation of Coating Composition

20 g of the silsesquioxane composite polymer obtained in Example 1-c, 3 g of indole-3-acetamide as a blue light absorbing compound, 77 g of ethanol, 0.5 g of photocurable irrure initiator, BYK 0.05 g of the siloxane additive was uniformly mixed to prepare a coating composition.

Example 1-e Coating

The coating composition prepared in 1-d was coated on a PC (i-components, Glastic 0.5T) film to a thickness of 30 um, and then cured to prepare a blue light absorbing film. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

In addition, the monomers described in Table 1 were applied to produce a silsesquioxane composite polymer and a coating composition. In this case, the method used in Examples 1-b, 1-c, 1-d, and 1-e was equally applied.

Table 1

Method of implementation	1-b Method Applicable Monomer	1-c method applied monomer		Molecular Weight (Mw)
		Precursor	Introduction of cage
One	ECHETMS	PTMDS	PTMS	11,000
1-1	PTMS	PTMDS	PTMS	8,000
1-2	MTMS	MTMDS	MTMS	48,000
1-3	GPTMS	GPTMDS	GPTMS	25,000
1-4	MAPTMS	MAPTMDS	MAPTMS	21,000
1-5	ECHETMS	ECHETMDS	ECHETMS	3,000
1-6	ECHETMS	MTMDS	MTMS	9,000
1-7	ECHETMS	GPTMDS	GPTMS	11,000
1-8	ECHETMS	MAPTMDS	MAPTMS	18,000
1-9	PTMS	ECHETMDS	ECHETMS	36,000
1-10	PTMS	MTMDS	MTMS	120,000
1-11	PTMS	GPTMDS	GPTMS	11,000
1-12	PTMS	MAPTMDS	MAPTMS	110,000
1-13	MTMS	ECHETMDS	ECHETMS	18,000
1-14	MTMS	PTMDS	PTMS	5,000
1-15	MTMS	GPTMDS	GPTMS	80,000
1-16	MTMS	MAPTMDS	MAPTMS	35,000
1-17	GPTMS	ECHETMDS	ECHETMS	7,000
1-18	GPTMS	PTMDS	PTMS	120,000
1-19	GPTMS	MTMDS	MTMS	100,000
1-20	GPTMS	MAPTMDS	MAPTMS	4,000
1-21	MAPTMS	ECHETMDS	ECHETMS	35,000
1-22	MAPTMS	PTMDS	PTMS	2,800
1-23	MAPTMS	MTMDS	MTMS	8,000
1-24	MAPTMS	GPTMDS	GPTMS	180,000

Example 2 Synthesis of Silsesquioxane D-A-D Structured Polymer

In order to prepare a composite polymer having a D-A-D structure, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1-a and 1-b, and then to produce a continuous D-A-D structure was carried out by the following method.

Example 2-a Generation of Excess Continuous Cage Structure

To the mixed solution of Example 1-b 0.36% by weight of HCl aqueous solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 25 parts by weight, which is 5 times the amount of Diphenyltetramethoxydisiloxane used in Example 1-b, was added dropwise at one time to achieve stable hydrolysis, and after stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 20%, 10 parts by weight of 0.36 wt% HCl aqueous solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was taken and analyzed by ²⁹ Si-NMR, and the analysis peak of the structure introduced using the phenyl group appeared as two sharp forms, and it was confirmed that the DAD polymer was prepared without any remaining by-products. In addition, the styrene reduced molecular weight was measured as 14,000, n value was 4-6. In addition, unlike the AD structure in the Si-NMR analysis, the peak around -68ppm, which was seen at the end of the A structure, disappeared, and the end of the A structure was converted into the D structure, thereby confirming that the DAD structure was generated. ²⁹ Si-NMR (CDCl ₃ ) δ -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 2 below. At this time, the manufacturing method was equally applied to the method used in Example 2.

TABLE 2

Method of implementation	1-b Method Applicable Monomer	2-a method applied monomer		Molecular Weight (Mw)
		Precursor	Introduction of cage
2	ECHETMS	PTMDS	PTMS	14,000
2-1	PTMS	PTMDS	PTMS	9,000
2-2	MTMS	MTMDS	MTMS	52,000
2-3	GPTMS	GPTMDS	GPTMS	30,000
2-4	MAPTMS	MAPTMDS	MAPTMS	24,000
2-5	ECHETMS	ECHETMDS	ECHETMS	6,000
2-6	ECHETMS	MTMDS	MTMS	12,000
2-7	ECHETMS	GPTMDS	GPTMS	13,000
2-8	ECHETMS	MAPTMDS	MAPTMS	21,000
2-9	PTMS	ECHETMDS	ECHETMS	38,000
2-10	PTMS	MTMDS	MTMS	150,000
2-11	PTMS	GPTMDS	GPTMS	18,000
2-12	PTMS	MAPTMDS	MAPTMS	123,000
2-13	MTMS	ECHETMDS	ECHETMS	23,000
2-14	MTMS	PTMDS	PTMS	9,000
2-15	MTMS	GPTMDS	GPTMS	91,000
2-16	MTMS	MAPTMDS	MAPTMS	41,000
2-17	GPTMS	ECHETMDS	ECHETMS	12,000
2-18	GPTMS	PTMDS	PTMS	131,000
2-19	GPTMS	MTMDS	MTMS	110,000
2-20	GPTMS	MAPTMDS	MAPTMS	6,000
2-21	MAPTMS	ECHETMDS	ECHETMS	38,000
2-22	MAPTMS	PTMDS	PTMS	5,000
2-23	MAPTMS	MTMDS	MTMS	12,000
2-24	MAPTMS	GPTMDS	GPTMS	192,000

Except for using the silsesquioxane composite polymer prepared in Example 2, the coating composition was prepared by mutatis mutandis of Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 3 : Synthesis of Silsesquioxane E-A-D Structured Composite Polymer

In order to prepare an E-A-D composite polymer, the following examples were used, and a coating composition was prepared by a method similar to that described in Example 1 above. Preparation of the catalyst and the linear structure was used in the same manner as in Example 1, and then to produce the E-A-D structure was carried out by the following method.

Example 3-a Generation of Chain Terminal E Structure

To the AD mixture obtained in Example 1-c, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of 0.36% by weight aqueous HCl solution was added dropwise, and the pH was adjusted to have an acidity, and the temperature was adjusted to 30 at 4 ° C. Stirred for a minute. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

Example 3-b Introduction of a Cage to the Terminal E Structure

After preparing the organic layer of the resultant obtained in Example 3-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 3-a in progress, to achieve stable hydrolysis, and after stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (4). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 3-c] Removal of By-products by Precipitation and Recrystallization, Obtaining the Result

After the reaction mixture was obtained in Example 3-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 4 was obtained along with various byproducts by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was 17,000 in terms of styrene, n value was 4-6, in particular, the results of formula (4) are as follows.

²⁹ Si-NMR (CDCl ₃ ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 3 below. In this case, the method used in Example 3 was equally applied.

TABLE 3

Method of implementation	1-b Method Applicable Monomer	1-c method applied monomer		3-a method applied monomer	3-b method applied monomer	Mw
		Precursor	Introduction of cage
3	ECHETMS	PTMDS	PTMS	MTMDS	MAPTMS	17,000
3-1	ECHETMS	ECHETMDS	ECHETMS	ECHETMDS	ECHETMS	12,000
3-2	PTMS	PTMDS	PTMS	PTMDS	PTMS	18,000
3-3	MTMS	MTMDS	MTMS	MTMDS	MTMS	59,000
3-4	GPTMS	ECHETMDS	ECHETMS	GPTMDS	GPTMS	41,000
3-5	MAPTMS	MAPTMDS	MAPTMS	MAPTMDS	MAPTMS	31,000
3-6	ECHETMS	ECHETMDS	ECHETMS	PTMDS	PTMS	16,000
3-7	ECHETMS	ECHETMDS	ECHETMS	MTMDS	MTMS	12,000
3-8	ECHETMS	ECHETMDS	ECHETMS	GPTMDS	GPTMS	16,000
3-9	ECHETMS	ECHETMDS	ECHETMS	MAPTMDS	MAPTMS	92,000
3-10	ECHETMS	PTMDS	PTMS	ECHETMDS	ECHETMS	25,000
3-11	ECHETMS	MTMDS	MTMS	ECHETMDS	ECHETMS	38,000
3-12	ECHETMS	GPTMDS	GPTMS	ECHETMDS	ECHETMS	56,000
3-13	ECHETMS	MAPTMDS	MAPTMS	ECHETMDS	ECHETMS	97,000
3-14	PTMS	PTMDS	PTMS	ECHETMDS	ECHETMS	24,000
3-15	PTMS	PTMDS	PTMS	MTMDS	MTMS	31,000
3-16	PTMS	PTMDS	PTMS	ECHETMDS	ECHETMS	21,000
3-17	PTMS	PTMDS	PTMS	MAPTMDS	MAPTMS	64,000
3-18	PTMS	ECHETMDS	ECHETMS	PTMDS	PTMS	120,000
3-19	PTMS	MTMDS	MTMS	PTMDS	PTMS	210,000
3-20	PTMS	GPTMDS	GPTMS	PTMDS	PTMS	23,000
3-21	PTMS	MAPTMDS	MAPTMS	PTMDS	PTMS	160,000
3-22	MTMS	MTMDS	MTMS	ECHETMDS	ECHETMS	63,000
3-23	MTMS	MTMDS	MTMS	PTMDS	PTMS	52,000
3-24	MTMS	MTMDS	MTMS	GPTMDS	GPTMS	73,000
3-25	MTMS	MTMDS	MTMS	MAPTMDS	MAPTMS	98,000
3-26	MTMS	ECHETMDS	ECHETMS	MTMDS	MTMS	41,000
3-27	MTMS	PTMDS	PTMS	MTMDS	MTMS	15,000
3-28	MTMS	GPTMDS	GPTMS	MTMDS	MTMS	110,000
3-29	MTMS	MAPTMDS	MAPTMS	MTMDS	MTMS	45,000
3-30	GPTMS	GPTMDS	GPTMS	ECHETMDS	ECHETMS	35,000
3-31	GPTMS	GPTMDS	GPTMS	PTMDS	PTMS	33,000
3-32	GPTMS	GPTMDS	GPTMS	MTMDS	MTMS	48,000
3-33	GPTMS	GPTMDS	GPTMS	MAPTMDS	MAPTMS	29,000
3-34	GPTMS	ECHETMDS	ECHETMS	GPTMDS	GPTMS	19,000
3-35	GPTMS	PTMDS	PTMS	GPTMDS	GPTMS	156,000
3-36	GPTMS	MTMDS	MTMS	GPTMDS	GPTMS	116,000
3-37	GPTMS	MAPTMDS	MAPTMS	GPTMDS	GPTMS	12,000
3-38	MAPTMS	MAPTMDS	MAPTMS	ECHETMDS	ECHETMS	31,000
3-39	MAPTMS	MAPTMDS	MAPTMS	PTMDS	PTMS	28,000
3-40	MAPTMS	MAPTMDS	MAPTMS	MTMDS	MTMS	35,000
3-41	MAPTMS	MAPTMDS	MAPTMS	GPTMDS	GPTMS	31,000
3-42	MAPTMS	ECHETMDS	ECHETMS	MAPTMDS	MAPTMS	57,000
3-43	MAPTMS	PTMDS	PTMS	MAPTMDS	MAPTMS	9,000
3-44	MAPTMS	MTMDS	MTMS	MAPTMDS	MAPTMS	19,000
3-45	MAPTMS	GPTMDS	GPTMS	MAPTMDS	MAPTMS	213,000

Except for using the silsesquioxane composite polymer prepared in Example 3, the coating composition was prepared by mutatis mutandis of Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 4 : Synthesis of A-B-D Structured Composite Silsesquioxane Polymer

In the synthesis step, a continuous hydrolysis and condensation were carried out step by step to prepare a composite polymer having an A-B-D structure, and a coating composition was prepared by a method similar to that described in Example 1.

Example 4-a Preparation of Catalysts for Hydrolysis and Condensation Reactions

To adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).

Example 4-b Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B Precursor)

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 4-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through ¹ H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.

¹ H-NMR (CDCl ₃ ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.

[Example 4-c] pH conversion reaction for generation of cage structure in chain (introduction of B, D structure)

To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, 5 parts by weight of DiPhenyltetramethoxydisiloxane was added dropwise, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, it could be confirmed that the cage-type structure was formed and introduced into the polymer chain separately from the linear structure. It was made. After 4 hours of mixing, some of the alkoxy groups in the B structure were changed to 0.025 mmol / g as a result of partial extraction and analysis by ²⁹ Si-NMR and ¹ H-NMR. It was confirmed that the ratio was introduced at 5: 5. In addition, the styrene reduced molecular weight was measured to 10,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

[Example 4-d] X introduction into B structure (introduction of B and D structure)

After preparing the organic layer of the resultant obtained in Example 4-c without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 4-c was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (5). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 4-e] Removal of By-products by Precipitation and Recrystallization, Obtained Result

200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 4-d, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 5 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 12,000, the n value of X was 4-6, the n value of Y was 4-6, in particular in the formula 5 results are as follows.

²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 4 below. In this case, the method used in Example 4 was equally applied.

Table 4

Method of implementation	4-b method applied monomer	4-c method applied monomer	4-d method applied monomer	Molecular Weight (Mw)
4	ECHETMS	PTMDS	MTMS	12,000
4-1	PTMS	PTMDS	PTMS	15,000
4-2	MTMS	MTMDS	MTMS	16,000
4-3	GPTMS	GPTMDS	GPTMS	56,000
4-4	MAPTMS	MAPTMDS	MAPTMS	9,500
4-5	ECHETMS	ECHETMDS	ECHETMS	7,500
4-6	ECHETMS	MTMDS	MTMS	16,000
4-7	ECHETMS	GPTMDS	GPTMS	23,000
4-8	ECHETMS	MAPTMDS	MAPTMS	9,500
4-9	PTMS	ECHETMDS	ECHETMS	72,000
4-10	PTMS	MTMDS	MTMS	68,000
4-11	PTMS	GPTMDS	GPTMS	11,000
4-12	PTMS	MAPTMDS	MAPTMS	110,000
4-13	MTMS	ECHETMDS	ECHETMS	23,000
4-14	MTMS	PTMDS	PTMS	9,500
4-15	MTMS	GPTMDS	GPTMS	64,000
4-16	MTMS	MAPTMDS	MAPTMS	12,000
4-17	GPTMS	ECHETMDS	ECHETMS	8,000
4-18	GPTMS	PTMDS	PTMS	451,000
4-19	GPTMS	MTMDS	MTMS	320,000
4-20	GPTMS	MAPTMDS	MAPTMS	15,000
4-21	MAPTMS	ECHETMDS	ECHETMS	45,000
4-22	MAPTMS	PTMDS	PTMS	351,000
4-23	MAPTMS	MTMDS	MTMS	14,000
4-24	MAPTMS	GPTMDS	GPTMS	160,000

Except for using the silsesquioxane composite polymer prepared in Example 4 to prepare a coating composition mutatis mutandis Example 1-d and then coated and cured on a PC substrate as in Example 1-e to absorb blue light A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 5 : Synthesis of D-A-B-D Structured Composite Silsesquioxane Polymer

The following method was used to prepare a composite polymer having a D-A-B-D structure, and a coating composition was prepared by the same method as in Example 1.

Example 5-a pH Conversion Reaction for Excess Production of D Structure (Introduction of B, D Structure)

To the mixture of Example 4-b in progress, 0.36 wt% HCl aqueous solution was added dropwise very slowly to 5 parts by weight, the pH was adjusted to have acidity, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 5 parts by weight to 25 parts by weight, which is 5 times the amount of Example 4-b, and after stirring for 1 hour, 5 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic pH of the mixed solution. Was adjusted. After completion of the reaction, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by ²⁹ Si-NMR and ¹ H-NMR. The amount of alkoxy groups in the B structure was changed to 0.012 mmol / g and the repeating units of B and D were about It was confirmed that the 1: 9 ratio was introduced. In addition, styrene conversion molecular weight was measured as 24,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

[Example 5-b] X Introduction in B Structure (Introduction of B, D Structure)

After the organic layer of the resultant obtained in Example 5-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 5-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 4-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (6). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 5-c] Removal of By-products by Precipitation and Recrystallization

200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 5-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum pressure. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 6 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 16,000, the n value of X was 4-6, the n value of Y was 4-6.

²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 5 below. At this time, the manufacturing method was equally applied to the method used in Example 5.

Table 5

Method of implementation	4-b method applied monomer	4-a method applied monomer	5-b method applied monomer	Molecular Weight (Mw)
2	ECHETMS	PTMDS	MTMS	16,000
5-1	PTMS	PTMDS	PTMS	19,000
5-2	MTMS	MTMDS	MTMS	20,000
5-3	GPTMS	GPTMDS	GPTMS	63,000
5-4	MAPTMS	MAPTMDS	MAPTMS	12,000
5-5	ECHETMS	ECHETMDS	ECHETMS	14,500
5-6	ECHETMS	MTMDS	MTMS	19,000
5-7	ECHETMS	GPTMDS	GPTMS	25,000
5-8	ECHETMS	MAPTMDS	MAPTMS	11,500
5-9	PTMS	ECHETMDS	ECHETMS	78,000
5-10	PTMS	MTMDS	MTMS	79,000
5-11	PTMS	GPTMDS	GPTMS	15,000
5-12	PTMS	MAPTMDS	MAPTMS	124,000
5-13	MTMS	ECHETMDS	ECHETMS	30,000
5-14	MTMS	PTMDS	PTMS	12,000
5-15	MTMS	GPTMDS	GPTMS	64,000
5-16	MTMS	MAPTMDS	MAPTMS	13,000
5-17	GPTMS	ECHETMDS	ECHETMS	12,000
5-18	GPTMS	PTMDS	PTMS	631,000
5-19	GPTMS	MTMDS	MTMS	421,000
5-20	GPTMS	MAPTMDS	MAPTMS	18,000
5-21	MAPTMS	ECHETMDS	ECHETMS	65,000
2-22	MAPTMS	PTMDS	PTMS	425,000
5-23	MAPTMS	MTMDS	MTMS	25,000
5-24	MAPTMS	GPTMDS	GPTMS	213,000

Except for using the silsesquioxane composite polymer prepared in Example 5, the coating composition was prepared in accordance with Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 6 : Synthesis of Silsesquioxane E-A-B-D Structured Composite Polymer

To prepare a composite polymer having an E-A-B-D structure, the following method was used, and a coating composition was prepared by the same method as in Example 1.

Example 6-a Generation of Chain Terminal E Structure

20 parts by weight of methylene chloride was added dropwise to the mixture obtained in Example 4-c, 5 parts by weight of a 0.36% by weight aqueous HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

[Example 6-b] Cage introduction into X of B structure and terminal E structure

After the organic layer of the resultant obtained in Example 6-a was prepared without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 6-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 1-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer as shown in the formula (7). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 6-c] Removal of By-products by Precipitation and Recrystallization

In Example 6-b, the reaction mixture was obtained, washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Chemical Formula 7 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 21,000, n value of X was 4-6, n value of Y was 4-6.

²⁹ Si-NMR (CDCl ₃ ) δ −68.2, −71.8 (sharp). -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 6 below. At this time, the manufacturing method was equally applied to the method used in Example 6.

Table 6

Method of implementation	4-b method applied monomer	4-c method applied monomer	6-a method applied monomer	6-b method applied monomer	Mw
6	ECHETMS	PTMDS	MTMDS	MAPTMS	21,000
6-1	ECHETMS	ECHETMDS	ECHETMDS	ECHETMS	18,000
6-2	PTMS	PTMDS	PTMDS	PTMS	19,000
6-3	MTMS	MTMDS	MTMDS	MTMS	31,000
6-4	GPTMS	ECHETMDS	GPTMDS	GPTMS	63,000
6-5	MAPTMS	MAPTMDS	MAPTMDS	MAPTMS	125,000
6-6	ECHETMS	ECHETMDS	PTMDS	PTMS	18,000
6-7	ECHETMS	ECHETMDS	MTMDS	MTMS	14,000
6-8	ECHETMS	ECHETMDS	GPTMDS	GPTMS	20,000
6-9	ECHETMS	ECHETMDS	MAPTMDS	MAPTMS	91,000
6-10	ECHETMS	PTMDS	ECHETMDS	ECHETMS	18,000
6-11	ECHETMS	MTMDS	ECHETMDS	ECHETMS	121,000
6-12	ECHETMS	GPTMDS	ECHETMDS	ECHETMS	80,000
6-13	ECHETMS	MAPTMDS	ECHETMDS	ECHETMS	112,000
6-14	PTMS	PTMDS	ECHETMDS	ECHETMS	35,000
6-15	PTMS	PTMDS	MTMDS	MTMS	91,000
6-16	PTMS	PTMDS	ECHETMDS	ECHETMS	45,000
6-17	PTMS	PTMDS	MAPTMDS	MAPTMS	75,000
6-18	PTMS	ECHETMDS	PTMDS	PTMS	140,000
6-19	PTMS	MTMDS	PTMDS	PTMS	220,000
6-20	PTMS	GPTMDS	PTMDS	PTMS	51,000
6-21	PTMS	MAPTMDS	PTMDS	PTMS	73,000
6-22	MTMS	MTMDS	ECHETMDS	ECHETMS	69,000
6-23	MTMS	MTMDS	PTMDS	PTMS	51,000
6-24	MTMS	MTMDS	GPTMDS	GPTMS	91,000
6-25	MTMS	MTMDS	MAPTMDS	MAPTMS	128,000
6-26	MTMS	ECHETMDS	MTMDS	MTMS	68,000
6-27	MTMS	PTMDS	MTMDS	MTMS	45,000
6-28	MTMS	GPTMDS	MTMDS	MTMS	265,000
6-29	MTMS	MAPTMDS	MTMDS	MTMS	105,000
6-30	GPTMS	GPTMDS	ECHETMDS	ECHETMS	101,000
6-31	GPTMS	GPTMDS	PTMDS	PTMS	95,000
6-32	GPTMS	GPTMDS	MTMDS	MTMS	73,000
6-33	GPTMS	GPTMDS	MAPTMDS	MAPTMS	51,000
6-34	GPTMS	ECHETMDS	GPTMDS	GPTMS	31,000
6-35	GPTMS	PTMDS	GPTMDS	GPTMS	315,000
6-36	GPTMS	MTMDS	GPTMDS	GPTMS	125,000
6-37	GPTMS	MAPTMDS	GPTMDS	GPTMS	45,000
6-38	MAPTMS	MAPTMDS	ECHETMDS	ECHETMS	94,000
6-39	MAPTMS	MAPTMDS	PTMDS	PTMS	35,000
6-40	MAPTMS	MAPTMDS	MTMDS	MTMS	80,000
6-41	MAPTMS	MAPTMDS	GPTMDS	GPTMS	83,000
6-42	MAPTMS	ECHETMDS	MAPTMDS	MAPTMS	74,000
6-43	MAPTMS	PTMDS	MAPTMDS	MAPTMS	10,000
6-44	MAPTMS	MTMDS	MAPTMDS	MAPTMS	65,000
6-45	MAPTMS	GPTMDS	MAPTMDS	MAPTMS	418,000

Except for using the silsesquioxane composite polymer prepared in Example 6, the coating composition was prepared in accordance with Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 7 Synthesis of Silsesquioxane A-B-A-D Structured Polymer

Synthesis step was carried out step by step, hydrolysis and condensation step by step, to prepare a coating composition in the same manner as in Example 1.

Example 7-a Preparation of Catalyst

In order to adjust the basicity, a catalyst 1a was prepared by mixing 10 wt% aqueous Potassium hydroxide (KOH) solution with 25 wt% aqueous tetramethylammonium hydroxide (TMAH).

Example 7-b Linear Silsesquioxane Synthesis (A Precursor)

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 15 parts by weight of tetrahydrofuran, 1 part by weight of the catalyst prepared in Example 7-a was added dropwise, and stirred at room temperature for 1 hour, followed by 2 20 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 15 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 5 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 6,000 styrene.

Example 7-c Synthesis of Linear Silsesquioxane Structures (Synthesis of A-B Precursors)

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 40 parts by weight of tetrahydrofuran, 0.5 parts by weight of the catalyst prepared in Example 7-a were added dropwise, followed by stirring at room temperature for 1 hour, and then 2 10 parts by weight of-(3,4-epoxycyclohexyl) ethyltrimethoxysilane was added dropwise, and 20 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 2 hours. The mixed solution was stirred and washed twice to remove the catalyst and impurities, and then filtered, and then linear silsesquioxane containing 0.1 mmol / g or less of the alkoxy group remaining through ¹ H-NMR analysis. This was then used to introduce the cage into the continuous reaction. XRD analysis confirmed that the overall structure is a linear structure through the XRD analysis. As a result of measuring the molecular weight, it was confirmed that the silsesquioxane having a linear structure had a molecular weight in terms of 8,000 styrene.

Example 7-d Synthesis of Linear Silsesquioxane Structure (Synthesis of A-B-A Precursor)

To a dried flask equipped with a cooling tube and a stirrer, 5 parts by weight of distilled water, 5 parts by weight of tetrahydrofuran, and 10 parts by weight of the prepared Example 7-a catalyst were added dropwise, followed by stirring at room temperature for 1 hour. 20 parts by weight of the 7-b precursor and the 7-c precursor were added dropwise, and 10 parts by weight of tetrahydroleuran was added dropwise thereto, followed by further stirring for 24 hours. The mixed solution during stirring was collected and washed twice to remove the catalyst and impurities, and after filtering, the SI-OH functional group formed at the terminal group was confirmed by IR analysis (3200 cm ^-1 ), and the molecular weight was measured. As a result, it was confirmed that the silsesquioxane having a linear structure had a molecular weight of 15,000 styrene.

¹ H-NMR (CDCl ₃ ) δ 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6.

Example 7-e Generation of Continuous Cage Structure (Introduction of D Structure)

To the mixed solution of Example 7-d 0.36% by weight of HCl solution was added very slowly 5 parts by weight, the pH was adjusted to have an acid, and stirred at a temperature of 4 ℃ 30 minutes. Thereafter, 5 parts by weight of diphenyltetramethoxydisiloxane was added dropwise at a time to achieve stable hydrolysis. After stirring for 1 hour, 7 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, a precursor of the D structure in which alkoxy is opened is formed separately from the linear polymer. A small amount of sample was taken and analyzed by H-NMR and IR to confirm the residual ratio of methoxy. When the residual ratio was 10%, 10 parts by weight of 0.36 wt% aqueous HCl solution was slowly added dropwise to adjust the pH to acidic. gave. Thereafter, 1 part by weight of Phenyltrimethoxysilane was added dropwise at a time, stirred for 15 minutes, and then 20 parts by weight of the catalyst prepared in 1-a was added. After 4 hours of mixing and stirring, it was confirmed that cage type polymer was formed in the polymer. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing and agitation, a portion was taken and analyzed by ²⁹ Si-NMR, and the analysis peak of the structure introduced using the phenyl group appeared as two sharp forms, and it was confirmed that the polymer was prepared without any remaining by-products. In addition, styrene conversion molecular weight was measured as 18,000.

²⁹ Si-NMR (CDCl ₃ ) δ -68.2, -72.3 (broad), -81.1 (sharp), -80.8 (sharp), -82.5 (broad)

[Example 7-f] X introduction in B structure (completion of A-B-A-D structure)

After preparing the organic layer of the resultant obtained in Example 7-e without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 7-e was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-shaped polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer. However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 7-g] Removal of by-products by precipitation and recrystallization, yield of the result

200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 7-f, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was a styrene conversion value of 24,000, the n value of X was 4-6, the n value of Y was 4-6.

In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 7 below. At this time, the manufacturing method was equally applied to the method used in Example 7.

TABLE 7

Method of implementation	7-b, c method applied monomer	7-e method applied monomer	7-f method applied monomer	Molecular Weight (Mw)
7	ECHETMS	PTMDS	MTMS	24,000
7-1	PTMS	PTMDS	PTMS	11,000
7-2	MTMS	MTMDS	MTMS	13,000
7-3	GPTMS	GPTMDS	GPTMS	23,000
7-4	MAPTMS	MAPTMDS	MAPTMS	14,500
7-5	ECHETMS	ECHETMDS	ECHETMS	12,500
7-6	ECHETMS	MTMDS	MTMS	53,000
7-7	ECHETMS	GPTMDS	GPTMS	11,000
7-8	ECHETMS	MAPTMDS	MAPTMS	9,000
7-9	PTMS	ECHETMDS	ECHETMS	48,000
7-10	PTMS	MTMDS	MTMS	90,000
7-11	PTMS	GPTMDS	GPTMS	32,000
7-12	PTMS	MAPTMDS	MAPTMS	150,000
7-13	MTMS	ECHETMDS	ECHETMS	17,000
7-14	MTMS	PTMDS	PTMS	38,500
7-15	MTMS	GPTMDS	GPTMS	15,000
7-16	MTMS	MAPTMDS	MAPTMS	17,000
7-17	GPTMS	ECHETMDS	ECHETMS	6,000
7-18	GPTMS	PTMDS	PTMS	18,000
7-19	GPTMS	MTMDS	MTMS	457,000
7-20	GPTMS	MAPTMDS	MAPTMS	16,000
7-21	MAPTMS	ECHETMDS	ECHETMS	97,000
7-22	MAPTMS	PTMDS	PTMS	951,000
7-23	MAPTMS	MTMDS	MTMS	15,000
7-24	MAPTMS	GPTMDS	GPTMS	12,000

Except for using the silsesquioxane composite polymer prepared in Example 7, the coating composition was prepared by mutatis mutandis of Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 8 : Synthesis of D-A-B-A-D Structured Composite Silsesquioxane Polymers

In order to prepare a composite polymer having a D-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.

Example 8-a pH Conversion Reaction for Excess Production of D Structure

15 parts by weight of 0.36 wt% HCl aqueous solution was added dropwise very slowly to the mixed solution of Example 7-d, which was adjusted to have an acidic pH, and stirred at a temperature of 4 ° C. for 30 minutes. Thereafter, the amount of diphenyltetramethoxydisiloxane was prepared by adding 25 parts by weight, which is 5 times the amount of Example 7-e, and added dropwise at once, and after stirring for 1 hour, 20 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic pH of the mixed solution. Was adjusted. After completion of the reaction, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed in vacuo so that the entire reactant was converted into an aqueous solution mixture. After 4 hours of mixing, some of them were collected and analyzed by ²⁹ Si-NMR and ¹ H-NMR. The amount of alkoxy groups in the B structure was changed to 0.006 mmol / g and the repeating units of B and D were about It was confirmed that the ratio was introduced at 5: 5. In addition, styrene conversion molecular weight was measured as 32,000. In addition, although the cage type structure was introduced, the molecular weight distribution of the single cage type material was not found in the GPC form of the polymer, and thus the cage structure was well introduced into the polymer chain through the continuous reaction.

¹ H-NMR (CDCl ₃ ) δ 7.5, 7.2, 3.7, 3.4, 3.3 (broad), 3.1, 2.8, 2.6, 1.5 (broad), 0.6. ²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -82.5 (broad)

Example 8-b Introducing X in B Structure

After preparing the organic layer of the resultant obtained in Example 8-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 100 parts by weight of the material obtained in Example 8-a was dissolved in 50 parts by weight of tetrahydrofuran, and then 5 parts by weight of distilled water was added to prepare a mixed solution. Thereafter, 10 parts by weight of 0.36 wt% HCl was added to the prepared solution, followed by stirring for 10 minutes, and then 3 parts by weight of Methyltrimethoxysilane were added dropwise at once to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to adjust the pH of the mixed solution in a basic state. At this time, the cage-type polymer is introduced to the X portion of the B structure, the reaction proceeds continuously in the reactor to form a polymer as shown in formula (9). However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 8-c] Removal of By-products by Precipitation and Recrystallization

200 parts by weight of methylene chloride was added to the mixture in which the reaction was completed in Example 8-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum reduction. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 9 was obtained without various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 36,000, the n value of X was 4-6, the n value of Y was 4-6.

²⁹ Si-NMR (CDCl ₃ ) δ -72.5 (broad), -81.1 (sharp), -80.8 (sharp), -79.9 (sharp), -81.5 (sharp), -82.5 (broad)

In addition, the silsesquioxane composite polymer and the coating composition were prepared by applying the monomers described in Table 8 below. At this time, the manufacturing method was equally applied to the method used in Example 8.

Table 8

Method of implementation	7-b, c method applied monomer	8-a Method Applicable Monomer	8-b Method Applicable Monomer	Molecular Weight (Mw)
8	ECHETMS	PTMDS	MTMS	36,000
8-1	PTMS	PTMDS	PTMS	14,000
8-2	MTMS	MTMDS	MTMS	18,000
8-3	GPTMS	GPTMDS	GPTMS	27,000
8-4	MAPTMS	MAPTMDS	MAPTMS	19,500
8-5	ECHETMS	ECHETMDS	ECHETMS	19,500
8-6	ECHETMS	MTMDS	MTMS	58,000
8-7	ECHETMS	GPTMDS	GPTMS	19,000
8-8	ECHETMS	MAPTMDS	MAPTMS	12,000
8-9	PTMS	ECHETMDS	ECHETMS	53,000
8-10	PTMS	MTMDS	MTMS	113,000
8-11	PTMS	GPTMDS	GPTMS	42,000
8-12	PTMS	MAPTMDS	MAPTMS	173,000
8-13	MTMS	ECHETMDS	ECHETMS	19,000
8-14	MTMS	PTMDS	PTMS	45,000
8-15	MTMS	GPTMDS	GPTMS	32,000
8-16	MTMS	MAPTMDS	MAPTMS	34,000
8-17	GPTMS	ECHETMDS	ECHETMS	12,000
8-18	GPTMS	PTMDS	PTMS	24,000
8-19	GPTMS	MTMDS	MTMS	486,000
8-20	GPTMS	MAPTMDS	MAPTMS	32,000
8-21	MAPTMS	ECHETMDS	ECHETMS	181,000
8-22	MAPTMS	PTMDS	PTMS	981,000
8-23	MAPTMS	MTMDS	MTMS	21,000
8-24	MAPTMS	GPTMDS	GPTMS	20,000

Except for using the silsesquioxane composite polymer prepared in Example 8, the coating composition was prepared by mutatis mutandis of Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Example 9 : Synthesis of Silsesquioxane E-A-B-A-D Structured Polymer

In order to prepare a composite polymer having an E-A-B-A-D structure, the following examples were used, and a coating composition was prepared by the same method as in Example 1.

Example 9-a Generation of Chain Terminal E Structure

To the mixture obtained in Example 7-g, 20 parts by weight of methylene chloride were added dropwise without further purification, 5 parts by weight of an aqueous 0.36% by weight HCl solution was added dropwise, the pH was adjusted to have an acidity, and 30 minutes at a temperature of 4 ° C. Stirred. Then, 1 part by weight of dimethyltetramethoxysilane was added dropwise. At this time, the portion that was not yet hydrolyzed in the molecular structure is easily converted into a hydrolyzate in the acidic aqueous solution layer separated from the solvent, and condensed in the resulting separate reactant and organic solvent layer to introduce E into the end unit. After stirring for 5 hours, stirring of the reaction was stopped and the temperature of the reactor was adjusted to room temperature.

Example 9-b Introducing cage to X of B structure and terminal E structure

After preparing the organic layer of the resultant obtained in Example 9-a without further purification, the terminal was converted into a cage structure using a trifunctional monomer. 3 parts by weight of Methyltrimethoxysilane was added dropwise to the mixed solution of Example 9-a in progress at a time to achieve stable hydrolysis. After stirring for 24 hours, 3 parts by weight of the catalyst prepared in Example 7-a was added again to give a basic state. PH of the mixed solution was adjusted. At this time, the cage-type polymer is introduced to the end of the E structure, the reaction proceeds continuously in the reactor to form a polymer. However, since it is obtained with other byproducts, a separate purification was required. Thereafter, the temperature was changed to room temperature, and tetrahydrofuran in the mixed solution was removed by vacuum to prepare a tablet.

[Example 9-c] Removal of By-products by Precipitation and Recrystallization

After the reaction mixture was obtained in Example 9-b, the mixture was washed with distilled water, and when the pH of the distilled water layer was neutral, the solvent was completely removed by vacuum. Thereafter, the precipitate was precipitated twice in methanol, and the unreacted monomer was removed, and the tetrahydrofuran and the aqueous solution were dissolved in 30 parts by weight in a solvent mixed at a weight ratio of 9.5: 0.5, and stored at a temperature of -20 ° C for 2 days. This is to facilitate the recrystallization of the material that is not introduced into the polymer, and closed by the cage structure, so that purification can be easily performed.

After the recrystallization process, the obtained solid material was filtered, and it was confirmed that the polymer of Formula 10 was obtained along with various by-products by vacuum reduction. In addition, when comparing the GPC results with the NMR results, it can be seen that the composite polymers can be obtained without any problem in view of the fact that the sharp form of the cage forms without the low molecular weight obtained in each stage of polymer growth. there was. At this time, the molecular weight was obtained in the styrene conversion value of 28,000, the n value of X was 4-6, the n value of Y was 4-6.

In addition, the silsesquioxane composite polymer was prepared by applying the monomers described in Table 9 below. In this case, the method used in Example 9 was equally applied.

Table 9

Method of implementation	7-b, c method applied monomer	7-e method applied monomer	9-a method applied monomer	9-b method applied monomer	Mw
9	ECHETMS	PTMDS	MTMDS	MAPTMS	28,000
9-1	ECHETMS	ECHETMDS	ECHETMDS	ECHETMS	24,000
9-2	PTMS	PTMDS	PTMDS	PTMS	21,000
9-3	MTMS	MTMDS	MTMDS	MTMS	36,000
9-4	GPTMS	ECHETMDS	GPTMDS	GPTMS	62,000
9-5	MAPTMS	MAPTMDS	MAPTMDS	MAPTMS	153,000
9-6	ECHETMS	ECHETMDS	PTMDS	PTMS	24,000
9-7	ECHETMS	ECHETMDS	MTMDS	MTMS	19,000
9-8	ECHETMS	ECHETMDS	GPTMDS	GPTMS	26,000
9-9	ECHETMS	ECHETMDS	MAPTMDS	MAPTMS	99,000
9-10	ECHETMS	PTMDS	ECHETMDS	ECHETMS	21,000
9-11	ECHETMS	MTMDS	ECHETMDS	ECHETMS	142,000
9-12	ECHETMS	GPTMDS	ECHETMDS	ECHETMS	70,000
9-13	ECHETMS	MAPTMDS	ECHETMDS	ECHETMS	72,000
9-14	PTMS	PTMDS	ECHETMDS	ECHETMS	15,000
9-15	PTMS	PTMDS	MTMDS	MTMS	51,000
9-16	PTMS	PTMDS	ECHETMDS	ECHETMS	85,000
9-17	PTMS	PTMDS	MAPTMDS	MAPTMS	95,000
9-18	PTMS	ECHETMDS	PTMDS	PTMS	160,000
9-19	PTMS	MTMDS	PTMDS	PTMS	240,000
9-20	PTMS	GPTMDS	PTMDS	PTMS	56,000
9-21	PTMS	MAPTMDS	PTMDS	PTMS	71,000
9-22	MTMS	MTMDS	ECHETMDS	ECHETMS	81,000
9-23	MTMS	MTMDS	PTMDS	PTMS	63,000
9-24	MTMS	MTMDS	GPTMDS	GPTMS	121,000
9-25	MTMS	MTMDS	MAPTMDS	MAPTMS	153,000
9-26	MTMS	ECHETMDS	MTMDS	MTMS	82,000
9-27	MTMS	PTMDS	MTMDS	MTMS	63,000
9-28	MTMS	GPTMDS	MTMDS	MTMS	310,000
9-29	MTMS	MAPTMDS	MTMDS	MTMS	125,000
9-30	GPTMS	GPTMDS	ECHETMDS	ECHETMS	97,000
9-31	GPTMS	GPTMDS	PTMDS	PTMS	45,000
9-32	GPTMS	GPTMDS	MTMDS	MTMS	61,000
9-33	GPTMS	GPTMDS	MAPTMDS	MAPTMS	52,000
9-34	GPTMS	ECHETMDS	GPTMDS	GPTMS	37,000
9-35	GPTMS	PTMDS	GPTMDS	GPTMS	365,000
9-36	GPTMS	MTMDS	GPTMDS	GPTMS	85,000
9-37	GPTMS	MAPTMDS	GPTMDS	GPTMS	75,000
9-38	MAPTMS	MAPTMDS	ECHETMDS	ECHETMS	144,000
9-39	MAPTMS	MAPTMDS	PTMDS	PTMS	85,000
9-40	MAPTMS	MAPTMDS	MTMDS	MTMS	60,000
9-41	MAPTMS	MAPTMDS	GPTMDS	GPTMS	53,000
9-42	MAPTMS	ECHETMDS	MAPTMDS	MAPTMS	12,000
9-43	MAPTMS	PTMDS	MAPTMDS	MAPTMS	10,000
9-44	MAPTMS	MTMDS	MAPTMDS	MAPTMS	32,000
9-45	MAPTMS	GPTMDS	MAPTMDS	MAPTMS	231,000

Except for using the silsesquioxane composite polymer prepared in Example 9, the coating composition was prepared in accordance with Example 1-d, and then coated and cured on a PC substrate as in Example 1-e to absorb blue light. A film was prepared. The blue light absorbing film has excellent resistance to yellowing and blue light absorption. In addition, the blue light absorbing compound may be selected from indole-3-carboxaldehyde, indole-3-carbinol, indole-3-thiocarboxamide, And 2- (2-aminophenyl) indole showed excellent blue light absorption and yellowing resistance comparable to when indole-3-acetamide was used. It was.

Comparative Example 1

The coating film was prepared in the same manner as in Example 9 except that the blue light absorbing compound was not included and coated in Example 9.

Comparative Example 2

A film was prepared in the same manner as in Example 9, except that the blue light absorbing compound was used as the benzophenol in Example 9.

Comparative Example 3

A film was prepared in the same manner as in Example 9, except that the blue light absorbing compound was used as the benzotriazole in Example 9.

Evaluation of Properties of Film According to Blue Light Absorption Compound Content

The coating composition prepared in Example 9 was coated on PET 188 um (Toray Industries, Inc.) to prepare a blue light absorbing film. In addition, the blue light absorbing film was prepared by varying the content of the blue light absorbing compound to measure the degree of yellowing phenomenon (Yellowish b *) and blue light transmittance, and are shown in Table 10 below.

In the following, the degree of yellowing (Yellowish b *) was measured by U-4100 (spectrophotometer), and the blue light transmittance was measured by NDH5000 (turbidimeter). The lower the transmittance, the better the blue light absorption.

Table 10

	Indole Compound Content
weight%
	0	0.001	0.1	0.5	One	3	5	7	10	15
Transmittance (%)	89	51	47	46	43	38	35	32	30	22
Yellowish b *	0.40	0.40	0.41	0.42	0.49	0.54	0.64	0.75	0.82	1.89

As shown in Table 10, when the blue light absorbing film of the present invention contained 0.001 to 10% by weight of the blue light absorbing compound, it was confirmed that the blue light absorbance and the yellowing phenomenon were excellent at the same time.

Evaluation of physical properties of film according to blue light absorbing compound

The degree of yellowing phenomenon (Yellowish b *) and the blue light transmittance of the blue light absorbing films prepared in Example 9 and Comparative Examples 1 to 3 were measured and shown in FIG. 1 and Table 11 below.

Table 11

coating	Yellowish b *
Comparative Example 1	0.52
Comparative Example 2	5.98
Comparative Example 3	3.87
Example 9	0.98

As shown in FIG. 1 and Table 11, when the blue light absorbing compound of the present invention was used, it was confirmed that the blue light absorption rate and the yellowing phenomenon were significantly superior to benzophenol or benzotriazole.

In addition, as shown in FIG. 1, the blue light absorbing film according to the present invention has an average light absorption of 30 to 70% (transmittance of 30 to 70%) of 400 to 470 nm (first wavelength range + second wavelength range). , The average light absorption of 470-500 nm (third wavelength region) is 40 to 20% (transmittance of 60 to 80%), more specifically, the light absorption of the first wavelength region is 50 to 85% (transmittance of 15 to 50%), the light absorption of the second wavelength region is 65 to 35% (35-65% transmittance), and the light absorption of the third wavelength region is 40 to 20% (60-80% transmittance). In addition, the ratio of average light absorption between wavelength ranges (light absorption rate in wavelength 1 + 2 area / light absorption area in wavelength 3 area) has 2-5 so that blue light harmful to human body is absorbed as much as possible, and blue light which is beneficial to human body is relatively absorbed. It was confirmed that it is very advantageous to the human body when applied as a protective film of the display device.

Film according to the present invention is excellent in the blue light absorption effect can prevent vision loss, eye damage, sleep disorders, excellent resistance to yellowing phenomenon, scratch resistance, water repellent properties, antifouling properties, anti-fingerprint, thermal stability, gloss Properties and surface hardness improving effect can be increased. In particular, the light absorption of the blue light of 400-470 nm wavelength harmful to the human body is very high, but the light absorption of the blue light of the wavelength 470-500 nm beneficial to the human body is relatively low can bring a more beneficial effect on the human body.

Claims (17)

1. A film comprising a blue light absorbing compound represented by Formula 1 below:

   [Formula 1]

   

   In Chemical Formula 1,

   R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or a C ₃ ~ C ₄₀ aralkyl group or C ₃ ~ C ₄₀ aryloxy group or a C ₃ ~ C ₄₀ aryl olgi between the.
2. The method of claim 1,

   A film comprising the blue light absorbing compound in a hard coating layer.
3. The method of claim 2,

   The hard coating layer is a film containing a silsesquioxane resin.
4. The method of claim 3,

   The silsesquioxane

   

   ,

   

   ,

   

   And

   

   A film comprising at least one of: wherein A is

   

   And B is

   

   ego,

   D is

   

   And E is

   

   Is,

   Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

   Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

   ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

   a and d are each independently an integer of 1 to 100,000,

   b are each independently an integer of 1 to 500,

   e are each independently 1 or 2,

   n is independently an integer of 1-20.
5. The method of claim 3,

   The silsesquioxane

   

   And

   

   Film containing:

   B is

   

   And D is

   

   Is,

   Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

   Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

   R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

   b is each independently an integer of 1 to 500, d is each independently an integer of 1 to 100,000, n is each independently an integer of 1 to 20.
6. The method of claim 3,

   The silsesquioxane is a film represented by any one of the following Chemical Formulas 2 to 10:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   [Formula 8]

   

   [Formula 9]

   

   [Formula 10]

   

   In Formulas 2 to 10, A is

   

   And B is

   

   ego,

   D is

   

   And E is

   

   Is,

   Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

   Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

   ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

   a and d are each independently an integer of 1 to 100,000,

   b are each independently an integer of 1 to 500,

   e are each independently 1 or 2,

   n are each independently an integer of 1 to 20,

   Between each chain unit may further include a known chain unit applicable to the silsesquioxane.
7. The method of claim 1,

   The film has an average light absorption of 30 to 70% for light of 400-470 nm.
8. The method of claim 1,

   The film has a ratio of average light absorption for light of 400-470 nm and average light absorption for light of 470-500 nm (light absorption in wavelength 1 + 2 / light absorption in wavelength 3). film.
9. The method of claim 1,

   The film is a film for display protection.
10. A coating composition comprising a blue light absorbing compound represented by Formula 1 and a silsesquioxane resin:

    [Formula 1]

    

    In Chemical Formula 1,

    R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or a C ₃ ~ C ₄₀ aralkyl group or C ₃ ~ C ₄₀ aryloxy group or a C ₃ ~ C ₄₀ aryl olgi between the.
11. The method of claim 10,

    Coating composition comprising 0.001 to 10% by weight of the compound of Formula 1, 5 to 90% by weight of the silsesquioxane resin and the remaining amount of the solvent.
12. The method of claim 10,

    The silsesquioxane

    

    ,

    

    ,

    

    And

    

    Coating composition comprising at least one of:

    A is

    

    And B is

    

    ego,

    D is

    

    And E is

    

    Is,

    Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

    Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

    ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

    a and d are each independently an integer of 1 to 100,000,

    b are each independently an integer of 1 to 500,

    e are each independently 1 or 2,

    n is independently an integer of 1-20.
13. The silsesquioxane

    

    And

    

    Film containing:

    B is

    

    And D is

    

    Is,

    Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

    Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

    R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²¹ and R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

    b is each independently an integer of 1 to 500, d is each independently an integer of 1 to 100,000, n is each independently an integer of 1 to 20.
14. The method of claim 10,

    The silsesquioxane is a coating composition represented by any one of the following Chemical Formulas 2 to 10:

    [Formula 2]

    

    [Formula 3]

    

    [Formula 4]

    

    [Formula 5]

    

    [Formula 6]

    

    [Formula 7]

    

    [Formula 8]

    

    [Formula 9]

    

    [Formula 10]

    

    In Chemical Formulas 2 to 10,

    A is

    

    And B is

    

    ego,

    D is

    

    And E is

    

    Is,

    Each Y is independently O, NR ²¹ or [(SiO _3/2 R) _{4 + 2n} O], at least one is [(SiO _3/2 R) _{4 + 2n} O],

    Each X is independently R ²² or [(SiO _3/2 R) _{4 + 2n} R], at least one is [(SiO _3/2 R) _{4 + 2n} R],

    ^{R, R 1, R 2,} R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or C ₃ ~ C ₄₀ Aralkyl group or C ₃ ~ C ₄₀ An aryloxy group or C ₃ ~ C ₄₀ An arylsilol group,

    a and d are each independently an integer of 1 to 100,000,

    b are each independently an integer of 1 to 500,

    e are each independently 1 or 2,

    n are each independently an integer of 1 to 20,

    Between each chain unit may further include a known chain unit applicable to the silsesquioxane.
15. A compound absorbing blue light in the 400-500 nm region represented by Formula 1 below:

    [Formula 1]

    

    In Chemical Formula 1,

    R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ are each independently hydrogen; heavy hydrogen; halogen; Amine groups; Epoxy groups; Cyclohexyl epoxy group; (Meth) acryl group; Siol group; Isocyanate group; Nitrile group; Nitro group; Phenyl group; Hydrogen, deuterium, a halogen, an amine group, an epoxy group, (meth) acrylic group, between olgi, isocyanate group, nitrile group, nitro group, C ₁ ~ is optionally substituted by a phenyl C ₄₀ alkyl group or a C ₂ ~ C ₄₀ of Alkenyl group or C ₁ to C ₄₀ alkoxy group or C ₃ to C ₄₀ cycloalkyl group or C ₃ to C ₄₀ heterocycloalkyl group or C ₆ to C ₄₀ aryl group or C ₃ to C ₄₀ heteroaryl group or a C ₃ ~ C ₄₀ aralkyl group or C ₃ ~ C ₄₀ aryloxy group or a C ₃ ~ C ₄₀ aryl olgi between the.
16. The method of claim 15,

    The compound is indole-3-acetamide, indole-3-carboxaldehyde, indole-3-carbinol, indole-3- Compound that is ciocarboxamide (indole-3-thiocarboxamide), 2- (2-aminophenyl) indole.
17. The method of claim 15,

    Compounds having a ratio of average light absorption for 400-470 nm light and average light absorption for light 470-500 nm (light absorption in wavelength 1 + 2 / light absorption in wavelength 3) are 2-5 .

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