BLUE LIGHT BLOCKING SYSTEM CONTAINING PYRAZOLINE OR/AND PHENYLACRYLIC COMPOUNDS

Abstract

A blue light blocking system including a pyrazoline compound of formula (I) or/and a phenylacrylic compound of formula (II) is provided. The compound of formula (I) or formula (II) can absorb most blue light of shorter wavelength that hurt eyes, but let that of the longer wavelength pass through, so that the transmitted light makes an excellent visual effect for human. The system can be applied to products such as optical films, optical lenses, goggles, skin care, lighting, coatings, adhesives, or panels. These products have a light-colored appearance and their transmitted light makes for an excellent visual effect.

##STR00001##

Claims

1. A blue light blocking system comprising at least one blue light blocking film layer, and/or a basal layer, and/or one or more release film layers, wherein the blue light blocking film layer is essential and includes at least a compound selected from formula (I) and/or formula (II), ##STR00016## R.sub.1 to R.sub.3 are each independently selected from H, straight or branched C.sub.1 to C.sub.6 alkyl, OR.sub.3, and N(R.sub.3).sub.2, R.sub.4 to R.sub.6 are each independently selected from H, and straight or branched C.sub.1 to C.sub.6 alkyl, R.sub.7 to R.sub.8 are each independently selected from COOR.sub.9, CONR.sub.10R.sub.11, COR.sub.12, and CN, R.sub.9 is selected from H, straight or branched C.sub.1 to C.sub.18 alkyl, and polyethylene glycol groups, R.sub.10 to R.sub.12 are each independently selected from H, straight or branched C.sub.1-C.sub.6 alkyl, and phenyl.

2. (canceled)

3. The blue light blocking system according to claim 1, wherein, the compound is selected from formula (I-1), (I-2), (I-3), (II-1) and (II-2): ##STR00017##

4. The blue light blocking system according to claim 1, wherein the compound of the formula (I) or formula (II) is used separately.

5. The blue light blocking system according to claim 1, wherein, the compound of formula (I) and the compound of formula (II) are used in combination, and a mass ratio of the compounds ranges from 1:5 to 5:1.

6. A blue light blocking composition for preparing the blue light blocking layer of claim 1, comprising at least a compound selected from formula (I) and/or formula (II), and polymerizable monomers or polymers.

7. The blue light blocking composition according to claim 6, comprising at least a compound selected from formula (I) and/or formula (II), an initiator or initiators, and polymerizable monomers and/or prepolymers.

8. The blue light blocking composition according to claim 6, wherein, the monomer includes one or more acrylic, acrylic ester, methacrylic, methacrylic ester, hydroxyacrylic, methacrylic, vinyl, styrene, diene, vinyl fluoride, chlorine ethylene, acrylonitrile, vinyl acetate, silicone acrylate, epoxy acrylate, polyurethane acrylate, ethylene oxide, isocyanate, polyol, polythiol, polyamine amine, alcohol amine, and thiol amine.

9. The blue light blocking composition according to claim 6, further comprising one or more auxiliaries selected from stabilizer, UV absorber, leveling agent, defoamer, dispersant, chain transfer agent, coupling agent, catalysts, toughener, tackifier, plasticizer, thickener, thinner, flame retardant, polymerization inhibitor, preservative, hardener, and acid-base blender.

10. The blue light blocking composition according to claim 6, wherein, a mass range of formula (I) or/and formula (II) is from 0.01% to 20%, a mass range of initiator content is from 0.01% to 10%, a mass range of monomer or prepolymer or polymer content is from 5 to 99.98%.

11. Use of a compound or a combination of compounds selected from the formula (I) and/or formula (II) according to claim 1, for blocking blue light.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0055] The present invention is further described below with reference to the drawings and the embodiments.

[0056] FIG. 1 shows UV-VIS absorption of the compounds (I-1) and (II-1) of the present invention

[0057] FIG. 2 is a schematic diagram of the side of the blue light blocking film: 1. the release layer, 2. the blue light blocking layer, 3. the basal layer

[0058] FIG. 3 is a schematic diagram of the side of the blue light blocking OCA optical adhesive (Optically Clear Adhesive): 1. a release layer, 2. a blue light blocking layer, and 3. a release layer.

DETAILED DESCRIPTION

[0059] The following is a description of specific embodiments of the present invention. These are not limited to these embodiments.

Example 1

Synthesis of a Compound of Formula (I-1), 1-phenyl-3-(4-butylstyryl)-5-(4-tert-butylphenyl) pyrazoline

[0060] ##STR00009##

[0061] 16.2 g of 4-tert-butylbenzaldehyde and 3.0 g of acetone were added to a freshly prepared sodium methoxide solution and stirred at room temperature for 3 hours. It was washed with water and dried to obtain the product bis (2-(4-tert-butyl) phenylvinyl) ketone. 7 g of bis (2-(4-tert-butyl) phenylvinyl) ketone and 2.2 g of phenylhydrazine were reacted in acetic acid for 4 hours. After cooling, the product was purified to give 1-phenyl-3_(4-butylstyryl)-5-(4-tert-butylphenyl) pyrazoline, mp 192-197 C. UV-VIS (ETOH .max.) 387 nm.

Example 2

Synthesis of (I-2) Compound, 1-phenyl-3-(p-methoxystyryl)-5-(p-methoxyphenyl)pyrazol

[0062] ##STR00010##

[0063] The same method as in Example 1, but replacing 4-tert-butylbenzaldehyde with p-methoxybenzaldehyde to obtain 1-phenyl-3-(p-methoxystyryl)-5-(p-methoxyphenyl) Pyrazoline (I-2) compound, melting point 159 C. UV-VIS (ETOH .max.) 381 nm.

Example 3

Synthesis of a Compound of Formula (I-3), phenyl-3-(p-dimethylaminostyryl)-5-(p-dimethylaminophenyl) pyrazoline

[0064] ##STR00011##

[0065] The same method as in Example 1, but replacing 4-tert-butylbenzaldehyde with p-dimethylaminobenzaldehyde to obtain phenyl-3-(p-dimethylstyryl)-5-(p-dimethyl aminophenyl) pyrazoline, melting point 192 C., UV-VIS (ETOH.max.) 419 nm.

Example 4

Synthesis of Compound (II-1), dimethyl-2-(4-(dimethylamino) benzylidene) malonate

[0066] ##STR00012##

[0067] Dissolve 15 g of 4-(dimethylamino) benzaldehyde and 14.5 g of dimethyl malonate in dichloromethane and stir. Add molecular sieve to remove water and install a calcium chloride tube to prevent water. 1 ml of piperidine and 0.6 ml of acetic acid were added, and the reaction was heated at reflux temperature for 2 hours. Fresh molecular sieves were added during the reaction. After the reaction is completed, the solvent is removed, and the dimethyl 2-(4-(dimethylamino) benzylidene) malonate (I-1) compound is obtained after acid washing and drying. The melting point is 87-88 C. UV-VIS (CH.sub.3CN max.) 384 nm.

Example 5

Synthesis of a Compound (II-2), ethyl 2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylate

[0068] ##STR00013##

[0069] The same method as in Example 4 except that ethyl 2-cyanoacetate was used instead of dimethyl malonate to obtain ethyl 2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylate ester (II-2) compound, melting point: 125-126 C. UV-VIS (CH.sub.3CN max.) 420 nm.

Example 6

Synthesis of the Compound (I-3), stearyl alkyl 2-cyano-3-(4-(dimethylamino) phenyl) acrylate

[0070] ##STR00014##

[0071] 24 g of compound II-2 was dissolved in toluene and heated at reflux in a condensing trap at 110 C. To the toluene solution were added 27 g of stearyl alcohol and 1.5 g of p-toluenesulfonic acid. The reaction was monitored by HPLC. After the reaction was completed, it was dried by vacuum filtration to obtain compound (II-3). MS (M/Z: 468.4).

Example 7

Synthesis of a Compound of Formula (II-4), 2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylic acid polyether ester

[0072] ##STR00015##

[0073] The same method as in Example 6, Methoxypolyethylene glycol 350 was used instead of stearyl alcohol, and the product was purified by GPC to obtain 2-ethyl-2-cyano-3-(4-(dimethylamino) phenyl) acrylic acid polyether ester (II-4) Compounds.

Example 8

Blue Light Blocking Composition and Film

[0074] 150 g of butyl acrylate, 95 g of methyl methacrylate, 15 g of acrylic acid, 5.8 g of blue light blocking agent, and 6 g of benzoyl peroxide were mixed in an ethyl acetate/toluene solvent, added to a reaction vessel, and heated to 75 C. After 2 hours, an additional of 6 g benzoyl peroxide (in solvent) was slowly added dropwise, and the reaction continued for about 6 hours. The viscosity was monitored. After the reaction was completed, the temperature was lowered to room temperature. After coating on a PET film and removing the solvent by drying, a blue light blocking film (100 gun) containing blue light blocking agent was obtained. Measure the transmittance of blue light band at 400 nm. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Blue light transmittance of Example 8 Light transmittance % Blue light (400 nm) blue light blocking agent transmittance % Ex. 8 blank, II-5 >80% Compound I-1, I-2, I-3, II-1, II-2 <20%

Example 9

Combination of Blue Light Blocking Agents

[0075] Table 2 shows the application of the compound of formula (I) alone, or a combination (I-1), (I-2), and (I-3), against blue light. Table 3 shows the application of the compound of formula (II) alone, or a combination of (II-1), (II-2), (II-5) against blue light. Table 4 shows the application of the combinations of (I-1), (II-1) and (II-5).

[0076] The 380-400 nm absorption in Tables 2 to 4 indicates the absorption of shorter wavelength blue light (higher energy). Basically, the greater the absorption, the better the protection against shorter wavelengths of blue light will be. The UVA1 & 380 nm-450 nm absorption in Table 2 indicates that it absorbs both long-wavelength UVA1 (about 340-400 nm) and blue light of 380 nm-450 nm, basically, the greater the absorption, the better the protection effect against long-wavelength ultraviolet light (UVA1) and full-band blue light. The UVAB & 380 nm-450 nm absorption in Tables 3 and 4 indicates that it absorbs both UVAB (about 290-400 nm) ultraviolet light and blue light in the full-band of 380 nm-450 nm, the greater the absorption, the better the protection against ultraviolet (UVAB) and full-band blue light. In Tables 2 to 4, 410 nm-450 nm absorption decreases indicates that the absorption from 410 nm to 450 nm decreases gradually and the transmitted blue light has better color visual effects. means poor effect, + means good effect, ++ means very good effect, and +++ means excellent effect.

TABLE-US-00002 TABLE 2 Combinations of compounds of formula (I) 410-450 UVA1 & 380-400 nm I-1 I-2 I-3 380-450 nm nm absorption (%) (%) (%) absorption absorption decrease 1 100 0 0 ++ +++ +++ 2 0 100 0 ++ +++ ++ 3 0 0 100 ++ +++ ++ 4 0 40-60 40-60 +++ +++ ++ 5 40-60 40-60 0 ++ +++ +++ 6 40-60 0 40-60 +++ +++ ++ 7 30-40 30-40 30-40 +++ +++ ++

TABLE-US-00003 TABLE 3 Combinations of compounds of formula (II) 410-450 UVAB(290-400 380-400 nm II-1 II-2 II-5 nm)& 380-450 nm absorption (%) (%) (%) nm absorption absorption decrease 1 100 0 0 + +++ +++ 2 0 100 0 + +++ ++ 3 0 0 100 4 0 40-60 40-60 ++ +++ ++ 5 40-60 40-60 0 + +++ ++ 6 40-60 0 40-60 ++ +++ +++ 7 30-40 30-40 30-40 +++ +++ ++

TABLE-US-00004 TABLE 4 Combinations of formula (I) and formula (II) compounds 410-450 UVAB & 380-400 nm I-1 II-1 II-5 380-450 nm nm absorption (%) (%) (%) absorption absorption decrease 1 40-60 40-60 0 + +++ +++ 2 30-40 30-40 30-40 +++ +++ +++

[0077] The above embodiments are not to limit the scope of protection of the present invention. The various types of the present invention, as well as technical solutions obtained by equivalent or equivalent substitutions, all fall within the protection scope of the present invention.