WO2020228191A1

WO2020228191A1 - Preparation method for dye and optical film

Info

Publication number: WO2020228191A1
Application number: PCT/CN2019/104468
Authority: WO
Inventors: 查宝
Original assignee: 深圳市华星光电技术有限公司
Priority date: 2019-05-14
Filing date: 2019-09-05
Publication date: 2020-11-19
Also published as: CN110194901A

Abstract

The present invention provides a preparation method for a dye and an optical film. The method comprises: adding a rhodamine dye to thionyl chloride for reaction, and removing the thionyl chloride in a reaction solution; then adding the reactant and propenoic acid 4-hydroxy R ester to anhydrous tetrahydrofuran for reaction to obtain a second reaction solution; removing the anhydrous tetrahydrofuran in the second reaction solution; and washing the reactant with dichloromethane and methanol, and performing separation by using a chromatography column to obtain a dye monomer.

Description

Preparation method of dye and optical film

Technical field

The present invention relates to the field of display technology, in particular to a dye preparation method and an optical film.

Background technique

With the development of display technology, the color gamut of the display is constantly improving. The high color gamut means that the display can display more colorful colors and has a stronger color display ability, thereby effectively avoiding distortion and color blocks in the display process. As the types of colors increase, the color switching of the screen in the display can be more natural, making the level of the screen more distinct, showing more details and closer to the real effect.

For liquid crystal displays, since the screen itself does not have self-luminous properties, the improvement of the color gamut is mainly achieved by color film filters of the three primary colors (red, green, and blue); in addition, the color gamut can also be adjusted by adjusting the backlight There are currently two main ways to improve the purity of the backlight: using blue LEDs and red and green fluorescent materials for backlighting; using quantum dot (QD) backlight technology.

However, since the red, green, and blue primary colors are not purified in the process of increasing the color gamut, that is, there are cyan light and yellow-orange light, the above two color gamut enhancement methods make the final red, green and blue light not Pure. As the color gamut increases, light penetration also decreases, making it difficult to achieve an increase in brightness while increasing the color gamut.

technical problem

Although the stray light other than RGB is currently absorbed by rhodamine-based materials, rhodamine-based dyes have a shoulder on the left side of the maximum absorption peak, which absorbs part of the blue and green light. Rhodamine-based dyes are easy to produce Agglomeration causes the absorption of the shoulder peak to increase, and the green part directly affects the transmittance, resulting in a decrease in the transmittance.

Therefore, it is necessary to provide a dye preparation method and optical film to solve the problems existing in the prior art.

Technical solutions

The purpose of the present invention is to provide a dye preparation method and an optical film, which can improve the brightness of the three primary colors while improving the purity of the three primary colors.

In order to solve the above technical problems, the present invention provides a dye preparation method, which includes:

Adding rhodamine dyes to thionyl chloride to react to obtain a first reaction solution;

Removing the thionyl chloride in the first reaction solution to obtain a first reactant;

Adding the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran for reaction to obtain a second reaction liquid;

Removing the anhydrous tetrahydrofuran in the second reaction solution to obtain a second reactant; and

The second reactant is washed with dichloromethane and methanol, and separated by a chromatographic column to obtain the dye monomer; the volume ratio of the dichloromethane to the methanol is 1:2;

Wherein, the rhodamine dye includes the following chemical structural formula:

as well as

At least one of

Wherein X ^- include, but are not limited to, ^{^{^{F -, Cl -, Br -}}} , CF 3 SO 3 -, CF 2 HSO 3 - and CFH ₂ SO ₃ ^-; wherein ₁ ~ R ₅ and the structure of R ₇ ~ R _11, R comprises Straight chain alkanes, branched alkanes, alkoxy straight and branched alkanes, chains containing ester groups, F substituted alkane derivatives, conjugated structures connected by alkoxy groups and ester groups, and At least one of the compounds containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group ranges from 1 to 30;

R ₇ can also include, but is not limited to, -F, -Cl, -Br, -I, and -CN substituent groups;

R ₈ to R ₁₁ also include at least one of -F, -Cl, -Br, and -I substituent groups, as well as amino -NH ₂ , carboxyl -COOH, hydroxyl -OH, sulfate -SH, and aldehyde -COH , -COO- ester, acyl -COCl, -COBr, nitrile -CN, a nitro group -NO _2, an amino group -NH _2, = NH, ≡N, benzene, and at least one phenolic ring.

The present invention also provides a method for preparing the dye, which includes:

Removing the anhydrous tetrahydrofuran in the second reaction solution to obtain a second reactant;

The second reactant is washed with dichloromethane and methanol, and separated by a chromatographic column to obtain the dye monomer.

The present invention also provides an optical film, the optical film layer, the material of which includes dye monomers, resins, and photoinitiators; the dye monomers include:

Among them, the structure of R ₆ includes linear alkanes, branched alkanes, linear alkoxy, branched alkanes, chains containing ester groups, F substituted alkane derivatives, through alkoxy and ester groups. At least one of the connected conjugated structure and the compound containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group is in the range of 1-30.

Beneficial effect

In the dye preparation method and the optical film of the present invention, the rhodamine dye is added to thionyl chloride to react to obtain a first reaction solution, and the thionyl chloride in the first reaction solution is removed, To obtain a first reactant; add the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran to react to obtain a second reaction solution, and remove the anhydrous tetrahydrofuran in the second reaction solution, A second reactant is obtained; the second reactant is washed with dichloromethane and methanol, and separated by a chromatography column to obtain a dye monomer. Due to the monomerization of rhodamine dyes, the stability of the rhodamine dyes after monomerization is stronger, so as to avoid polymerization reaction, reduce the energy of blue absorption and filter light, and improve the purity of the three primary colors. , Improve the brightness.

Description of the drawings

Fig. 1 is a schematic diagram of the structure of the optical film of the present invention.

Embodiments of the invention

The description of the following embodiments refers to the attached drawings to illustrate specific embodiments that the present invention can be implemented. The directional terms mentioned in the present invention, such as "up", "down", "front", "rear", "left", "right", "in", "out", "side", etc., are for reference only The direction of the additional schema. Therefore, the directional terms used are used to describe and understand the present invention, rather than to limit the present invention. In the figure, units with similar structures are indicated by the same reference numerals.

The preparation method of the dye of the present invention includes:

S101, adding rhodamine dyes to thionyl chloride for reaction to obtain a first reaction liquid;

For example, in one embodiment, the rhodamine dye is added to the thionyl chloride SOCl ₂ solvent, and the two are allowed to react for a period of time at a preset temperature to obtain the first reaction solution.

S102. Remove the thionyl chloride in the first reaction solution to obtain a first reactant.

Then, the thionyl chloride solvent in the first reaction solution is removed by vacuum distillation to obtain the first reactant. It is understandable that the method of removing the thionyl chloride solvent may be other methods, and is not limited to the vacuum distillation method.

Wherein, the molar amount of the rhodamine dye ranges from 15 mmol to 30 mmol.

Wherein, the capacity range of the thionyl chloride is 20ml-60ml.

Wherein, the molar amount of the 4-hydroxy R acrylate is in the range of 10 mmol-40 mmol.

Wherein, the capacity range of the anhydrous tetrahydrofuran is 50ml-150ml.

The reaction temperature of the rhodamine dye and the thionyl chloride ranges from 80°C to 100°C, preferably 90°C.

For example, the rhodamine dye includes at least one of rhodamine B, rhodamine 6G, rhodamine 19, rhodamine 101, and rhodamine 110 derivatives, and the chemical structural formula of the rhodamine 6G derivatives is as follows:

The chemical structural formula of the derivatives of Rhodamine 19 is as follows:

The chemical structural formula of the derivatives of Rhodamine 101 is as follows:

The chemical structural formula of the derivatives of Rhodamine 110 is as follows:

Wherein X- includes but not limited to F-, Cl-, Br-, CF ₃ SO ₃ -, CF ₂ HSO ₃ -and CFH ₂ SO ₃ -; wherein the structures of R ₁ ～R ₅ and R ₇ ～R ₁₁ include Straight chain alkanes, branched alkanes, alkoxy straight and branched alkanes, chains containing ester groups, F substituted alkane derivatives, conjugated structures connected by alkoxy groups and ester groups, and At least one of the compounds containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group ranges from 1 to 30;

R ₇ may also include, but is not limited to, F, Cl, Br, I and CN substituent groups;

That is to say, the structures of R ₁ to R ₅ and R ₇ to R ₁₁ can be non-conjugated structures (straight-chain alkanes, or branched alkanes, alkoxy-based straight or branched alkanes, and ester-containing chains. F-substituted alkane derivatives, the carbon chain length can range from 1 to 30, etc.), R ₁ to R ₅ can also be conjugated structures connected by alkoxy and ester groups or contain hetero Ring compound. The heterocyclic compound may be five- and six-membered heterocyclic, benzoheterocyclic compounds and the like. Five-membered heterocyclic compounds include but are not limited to furan, thiophene, pyrrole, thiazole, imidazole, etc.; six-membered heterocyclic compounds include but are not limited to pyridine, pyrazine, pyrimidine, pyridazine, etc. and condensed ring heterocyclic compounds: indole, quine Phrin, pteridine, acridine, etc.

S103. Add the first reactant and 4-hydroxy R acrylate to dry tetrahydrofuran for reaction to obtain a second reaction liquid; for example, add the first reactant and 4-hydroxy R acrylate to dry tetrahydrofuran The reaction is allowed to react for a period of time at a set temperature to obtain a second reaction liquid.

S104. Remove the anhydrous tetrahydrofuran in the second reaction solution to obtain a second reactant;

For example, the second reaction liquid is washed with saturated brine, and the second reaction liquid is washed with saturated sodium bicarbonate solution to remove the anhydrous tetrahydrofuran to obtain the second reactant.

Wherein, the chemical structural formula of the 4-hydroxy R acrylate is as follows:

S105: Wash the second reactant with dichloromethane and methanol, and separate it with a chromatographic column to obtain a rhodamine dye monomer.

For example, the second reactant is washed with a detergent of dichloromethane DCM: methanol MeOH and separated by a chromatographic column to obtain a dye monomer, and the dye monomer is a rhodamine dye monomer.

The dye monomer includes:

Wherein, the volume ratio of the dichloromethane to the methanol is 1:2.

Taking rhodamine B as an example, the preparation method of the above dye specifically includes:

S201. Add Rhodamine B to the SOCl ₂ solvent of thionyl chloride, and allow the two to react at 90° C. for 6 hours to obtain a first reaction solution; then, the second reaction solution in the first reaction solution is distilled under reduced pressure. The thionyl chloride solvent is removed to obtain the first reactant. The chemical structure of Rhodamine B is as follows:

S202, adding the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran for reaction, and reacting at 20°C for 24 hours to obtain a second reaction liquid;

S203. Wash the second reaction liquid with saturated brine, and wash the second reaction liquid with saturated sodium bicarbonate solution to remove the anhydrous tetrahydrofuran to obtain a second reactant.

S204, the second reactant is washed with dichloromethane DCM: methanol MeOH detergent, and separated by a chromatographic column to obtain rhodamine B dye monomer.

The simplified chemical equations of S201 to S204 above are as follows:

The present invention also provides an optical film, which includes an optical film layer, the material of which includes the above-mentioned dye monomer, resin and photoinitiator; in addition, it also includes a solvent and additives. The manufacturing method of the optical film includes the following steps:

S301. Mix the above dye monomers, resins, photoinitiators, solvents, and additives to obtain materials for the optical film layer, as shown in Table 1:

Table 1. The main composition and content of the material of the optical film layer

The resin mainly uses transparent acrylic resin, which includes dimethylaminoethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, and isooctyl methacrylate. One or more.

The photoinitiator can be an acetophenone derivative: α,α-diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one And one or more of HMPP.

The solvent may be one or a mixture of PGMEA (propylene glycol methyl ether acetate), PGME propylene glycol monomethyl ether, and MEA ethanolamine.

The additives may be silane coupling agents and the like.

S302, coating the optical film material on the substrate, exposing it and thermally baking it to obtain an optical film layer containing rhodamine dye monomers.

For example, as shown in FIG. 1, the above-mentioned optical film material is coated on the substrate 21, and then exposed to it with an exposure mask (Mask) to cause the above-mentioned optical film material to undergo a crosslinking reaction, and then it is thermally baked After baking, the optical film layer 22 containing rhodamine dye monomers is obtained. The substrate 21 may be one of a polarizer, an overcoat (OC), an organic flat layer (the material is perfluoroalkoxy resin, PFA), and a color film resist.

Since the stray light (yellow-orange light and cyan light) can be absorbed according to the selection of rhodamine dyes, the color gamut is improved, that is, the purity of the three primary colors is improved, and the transmittance is improved.

Since the dye of the present invention is obtained by monomerizing the structure of rhodamine dye, the stability of the rhodamine dye after monomerization is relatively strong, so as to avoid the agglomeration of rhodamine molecules to increase the shoulder peak. Reduce the absorption intensity of blue and green light due to shoulder peaks. While improving the purity of the three primary colors, it can avoid the excessive loss of brightness of the display. Reduce the energy of blue and filter absorption, that is, while improving the purity of the three primary colors. , Improve the brightness.

In addition, because the dye of the present invention is obtained by monomerizing the rhodamine dye structure, it is then mixed with a transparent resin and a photoinitiator, and exposed to crosslinking reaction, thereby making the rhodamine dye monomer Polymerization, this can make the rhodamine dye monomers form a monodisperse structure, avoid the agglomeration of rhodamine molecules to increase the shoulder peak, reduce the absorption intensity of blue and green light due to the shoulder peak, and improve the purity of the three primary colors at the same time, Can avoid excessive loss of brightness of the display. In addition, the use of rhodamine dye monomer polymerization can improve the thermal stability of the dye.

In the dye preparation method and the optical film of the present invention, the rhodamine dye is added to thionyl chloride to react to obtain a first reaction solution, and the thionyl chloride in the first reaction solution is removed, To obtain a first reactant; add the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran to react to obtain a second reaction solution, and remove the anhydrous tetrahydrofuran in the second reaction solution, A second reactant is obtained; the second reactant is washed with dichloromethane and methanol, and separated by a chromatography column to obtain a dye monomer. Due to the monomerization of rhodamine dyes, the stability of rhodamine dyes after monomerization is relatively strong, thereby avoiding polymerization reaction, reducing the energy of blue absorption and filtering, and improving the purity of the three primary colors. Improved brightness.

In summary, although the present invention has been disclosed as above in preferred embodiments, the above-mentioned preferred embodiments are not intended to limit the present invention. Those of ordinary skill in the art can make various modifications without departing from the spirit and scope of the present invention. Such changes and modifications, therefore, the protection scope of the present invention is subject to the scope defined by the claims.

Claims

A preparation method of dye, which includes:

Adding rhodamine dyes to thionyl chloride to react to obtain a first reaction solution;

Removing the thionyl chloride in the first reaction solution to obtain a first reactant;

Adding the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran for reaction to obtain a second reaction liquid;

Removing the anhydrous tetrahydrofuran in the second reaction solution to obtain a second reactant; and

The second reactant is washed with dichloromethane and methanol, and separated by a chromatographic column to obtain the dye monomer; the volume ratio of the dichloromethane to the methanol is 1:2;

Wherein, the rhodamine dye includes the following chemical structural formula:

as well as

At least one of

Wherein X - include, but are not limited to, F -, Cl -, Br - , CF 3 SO 3 -, CF 2 HSO 3 - and CFH 2 SO 3 -; wherein 1 ~ R 5 and the structure of R 7 ~ R 11, R comprises Straight chain alkanes, branched alkanes, alkoxy straight and branched alkanes, chains containing ester groups, F substituted alkane derivatives, conjugated structures connected by alkoxy groups and ester groups, and At least one of the compounds containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group ranges from 1 to 30;

R 7 can also include, but is not limited to, -F, -Cl, -Br, -I, and -CN substituent groups;

R 8 to R 11 also include at least one of -F, -Cl, -Br, and -I substituent groups, as well as amino -NH 2 , carboxyl -COOH, hydroxyl -OH, sulfate -SH, and aldehyde -COH , -COO- ester, acyl -COCl, -COBr, nitrile -CN, a nitro group -NO 2, an amino group -NH 2, = NH, ≡N, benzene, and at least one phenolic ring.
The method for preparing the dye according to claim 1, wherein the molar amount of the rhodamine-based dye ranges from 15 mmol to 30 mmol.
The dye preparation method according to claim 1, wherein the capacity of the thionyl chloride ranges from 20ml to 60ml.
The dye preparation method according to claim 1, wherein the molar amount of the 4-hydroxy R acrylate ranges from 10 mmol to 40 mmol.
The dye preparation method according to claim 1, wherein the capacity of the anhydrous tetrahydrofuran ranges from 50ml to 150ml.
The method for preparing the dye according to claim 1, wherein the reaction temperature of the rhodamine-based dye and the thionyl chloride ranges from 80°C to 100°C.
The method for preparing a dye according to claim 1, wherein

The chemical structural formula of the 4-hydroxy R acrylate is as follows:

Among them, the structure of R 6 includes linear alkanes, branched alkanes, linear alkoxy, branched alkanes, chains containing ester groups, F substituted alkane derivatives, through alkoxy and ester groups. At least one of the connected conjugated structure and the compound containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group is in the range of 1-30.
A preparation method of dye, which includes:

Adding rhodamine dyes to thionyl chloride to react to obtain a first reaction solution;

Removing the thionyl chloride in the first reaction solution to obtain a first reactant;

Adding the first reactant and 4-hydroxy R acrylate to anhydrous tetrahydrofuran for reaction to obtain a second reaction liquid;

Removing the anhydrous tetrahydrofuran in the second reaction solution to obtain a second reactant; and

The second reactant is washed with dichloromethane and methanol, and separated by a chromatographic column to obtain the dye monomer.
The method for preparing a dye according to claim 8, wherein the rhodamine dye comprises the following chemical structural formula:

as well as

At least one of

Wherein X - include, but are not limited to, F -, Cl -, Br - , CF 3 SO 3 -, CF 2 HSO 3 - and CFH 2 SO 3 -; wherein 1 ~ R 5 and the structure of R 7 ~ R 11, R comprises Straight chain alkanes, branched alkanes, alkoxy straight and branched alkanes, chains containing ester groups, F substituted alkane derivatives, conjugated structures connected by alkoxy groups and ester groups, and At least one of the compounds containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group ranges from 1 to 30;

R 7 can also include, but is not limited to, -F, -Cl, -Br, -I, and -CN substituent groups;

R 8 to R 11 also include at least one of -F, -Cl, -Br, and -I substituent groups, as well as amino -NH 2 , carboxyl -COOH, hydroxyl -OH, sulfate -SH, and aldehyde -COH , -COO- ester, acyl -COCl, -COBr, nitrile -CN, a nitro group -NO 2, an amino group -NH 2, = NH, ≡N, benzene, and at least one phenolic ring.
The method for preparing the dye according to claim 8, wherein the molar amount of the rhodamine dye ranges from 15 mmol to 30 mmol.
The dye preparation method according to claim 8, wherein the capacity of the thionyl chloride ranges from 20ml to 60ml.
The method for preparing the dye according to claim 8, wherein the molar amount of the 4-hydroxy R acrylate ranges from 10 mmol to 40 mmol.
The dye preparation method according to claim 8, wherein the capacity of the anhydrous tetrahydrofuran ranges from 50ml to 150ml.
The method for preparing the dye according to claim 8, wherein the volume ratio of the dichloromethane to the methanol is 1:2.
The method for preparing the dye according to claim 8, wherein the reaction temperature of the rhodamine dye and the thionyl chloride ranges from 80°C to 100°C.
The method for preparing a dye according to claim 1, wherein

The chemical structural formula of the 4-hydroxy R acrylate is as follows:

Among them, the structure of R 6 includes linear alkanes, branched alkanes, linear alkoxy, branched alkanes, chains containing ester groups, F substituted alkane derivatives, through alkoxy and ester groups. At least one of the connected conjugated structure and the compound containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group is in the range of 1-30.
An optical film, which includes:

The material of the optical film layer includes dye monomers, resins, and photoinitiators; the dye monomers include:

Among them, the structure of R 6 includes linear alkanes, branched alkanes, linear alkoxy, branched alkanes, chains containing ester groups, F substituted alkane derivatives, through alkoxy and ester groups. At least one of the connected conjugated structure and the compound containing a heterocyclic ring; the carbon chain length in the F-substituted alkane derivative group is in the range of 1-30.
The optical film according to claim 17, wherein

The resin includes one or more of dimethylaminoethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, cyclohexyl methacrylate, and isooctyl methacrylate.
The optical film according to claim 17, wherein

The photoinitiator can be an acetophenone derivative: α,α-diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one And one or more of HMPP.