Trans, trans-diketone oxime ester isomer, manufacturing method thereof and application thereof

Abstract

Involved are a diketone oxime ester compound shown in formula I and a manufacturing method therefor, and a photo-curable composition using the compound of formula I as a photoinitiator. The composition has extremely high light sensitivity and relatively low yellowing resistance when applied to prepare a color filter for a light resistance device such as a display screen.

Claims

1. A compound of formula I, art isomer in which both oxime groups are trans form, ##STR00007##

2. A manufacturing method for the compound of formula I of claim 1, comprising the following steps: (1) Step 1: carrying out dipropionylation on a diphenyl sulfide to obtain a compound of formula II; ##STR00008## (2) Step 2: carrying out selective oximation, a method comprising subjecting the compound of the formula II and an alkyl nitrite to an oxime reaction of the carbonyl ortho carbon atoms in an acidic solution to obtain a corresponding diketone oxime intermediate compound of formula Ill, ##STR00009## and (3) Step 3: carrying out an esterification reaction on the intermediate compound of formula III and an acetic anhydride or an acetyl chloride to obtain a compound of formula I, ##STR00010##

3. A photo-curable composition comprising a compound of formula I of claim 1 as a photoinitiator and at least one free-radically polymerizable carbon-carbon double bond compound.

4. The photo-curable composition of claim 3, wherein the photoinitiator accounts for 0.05-15% by weight of the total composition, and the carbon-carbon double bond compound and other components account for the remaining percentages other than the above components.

5. The photo-curable composition of claim 3, wherein the carbon-carbon double bond compound is selected from acrylate compounds and methacrylate compounds.

6. The photo-curable composition of claim 3, wherein further comprising an additive.

7. The photo-curable composition of claim 6, wherein the additive comprises a developable resin, a pigment or a dye.

8. Use of a photo-curable composition, comprising: firstly using any one photo-curable composition of claim 3 for the manufacture of one of the following colored or transparent articles: coating, ink, adhesive, and photoresist; and the article is then used for printing, 3D printing, production of color filter in display device, electronic device packaging, and printed circuit board dielectric layer.

9. A method for curing a photo-curable composition, comprising diluting the photo-curable composition of claim 3 with a solvent, coating the photo-curable composition on a substrate, drying off the solvent, and curing the coated layer by irradiating with light having a wavelength of 190-600 nm.

10. The curing method of the photo-curable composition of claim 9, wherein the light is from a high-pressure mercury lamp or an LED lamp.

11. A process for producing a relief pattern, the relief pattern is obtained from the coating film after coated on the substrate and dried off the solvent of claim 9 by removing unexposed part by exposure and development methods.

12. A color filter comprising black, red, green and blue pixels obtained from the composition comprising the compound of formula I of claim 1, a photo-curable monomer, an alkali-soluble resin, a pigment and an additive by coating, drying, exposing, developing and heat treating sequentially.

13. Use of a photo-curable composition, comprising: firstly using any one photo-curable composition of claim 4 for the manufacture of one of the following colored or transparent articles: coating, ink, adhesive and photoresist; and the article is then used for printing, 3D printing, production of color filters in display devices, electronic device packaging, and printed circuit board dielectric layers.

14. Use of a photo-curable composition, comprising: firstly using any one photo-curable composition of claim 5 for the manufacture of one of the following colored or transparent articles: coating, ink, adhesive and photoresist; and the article is then used for printing, 3D printing, production of color filters in display devices, electronic device packaging, and printed circuit board dielectric layers.

15. Use of a photo-curable composition, comprising: firstly using any one photo-curable composition of claim 6 for the manufacture of one of the following colored or transparent articles: coating, ink, adhesive and photoresist; and the article is then used for printing, 3D printing, production of color filters in display devices, electronic device packaging, and printed circuit board dielectric layers.

16. Use of a photo-curable composition, comprising: firstly using any one photo-curable composition of claim 7 for the manufacture of one of the following colored or transparent articles: coating, ink, adhesive and photoresist; and the article is then used for printing, 3D printing, production of color filters in display devices, electronic device packaging, and printed circuit board dielectric layers.

17. A method for curing a photo-curable composition, comprising diluting the photo-curable composition of claim 4 with a solvent, coating the photo-curable composition on a substrate, drying off the solvent, and curing the coated layer by irradiating with light having a wavelength of 190-600 nm.

18. A method for curing a photo-curable composition, comprising diluting the photo-curable composition of claim 5 with a solvent, coating the photo-curable composition on a substrate, drying off the solvent, and curing the coated layer by irradiating with light having a wavelength of 190-600 nm.

19. A method for curing a photo-curable composition, comprising diluting the photo-curable composition of claim 6 with a solvent, coating the photo-curable composition on a substrate, drying off the solvent, and curing the coated layer by irradiating with light having a wavelength of 190-600 nm.

20. A method for curing a photo-curable composition, comprising diluting the photo-curable composition of claim 7 with a solvent, coating the photo-curable composition on a substrate, drying off the solvent, and curing the coated layer by irradiating with light having a wavelength of 190-600 nm.

Description

DETAILED DESCRIPTION

[0042] The present disclosure can be illustrated in more detail from the examples, and all consumptions are based on weight, unless otherwise specified.

Embodiment 1 Synthesis

[0043] Synthesis of 4,4′-Dipropionyldiphenyl Sulfide (Compound of Formula II)

[0044] 79.0 G (0.424 mol) of diphenyl sulfide was weighed, dissolved in 600 g of 1,2-dichloroethane, and added with 124.4 g (0.933 mol) of anhydrous aluminum trichloride, followed by stirring and cooling to 0° C.; the temperature was kept below 5° C., 82.4 g (0.891 mol) of propionyl chloride was added dropwise, the addition was completed after 2h, and stirring was continued at 0° C. for 2h; the reaction solution was added dropwise into 450 ml of 10% diluted hydrochloric acid of which the temperature was controlled to be not higher than 30° C., stirring was continued for 1 h after adding, and the lower organic phase was separated; the organic phase was washed with 300 ml of water for three times in sequence, and subjected to reduced pressure distillation to recover the solvent to give 126 g of a residue; 240 ml of n-hexane was added while hot, and the temperature was kept to clarify the solution; natural cooling was carried out to enable it to crystallize, and when the solution temperature was lower than 30° C., the crystal bottle was put into an ice-water bath to continuously cool to 0° C.; suction filtration was carried out gave a white filter cake, which was dried under reduced pressure at 50° C. to give 117.6 g of white crystals with a yield of 93%, purity of 98.5% by HPLC analysis, and melting range of 123.1-130.3° C. .sup.1H-NMR data indicated that the product was 4,4′-dipropionyldiphenyl sulfide.

[0045] Synthesis of trans, trans-isomeric diketone oxime (compounds of formula III)

[0046] 30 G (0.1 mol) of 4,4′-dipropionyl diphenyl sulfide obtained from 1-1 was weighted, dissolved by 100 g of dimethyl sulfoxide, and added with 3.0 g of 36% concentrated hydrochloric acid; the temperature was kept on a water bath of 20-25° C. and the mixture was stirred, added dropwise with 25 g (0.24 mol) of n-butyl nitrite within 30 min, and stirred for 10 h; the reaction liquid was added dropwise into 1 L of ice water to separate a light yellow solid, followed by suction filtration, and drying under reduced pressure, 27 g of a product was obtained with a purity of 97.80% by an HPLC analysis, yield of 75%, and melting range of 162.8-169.5° C. .sup.1H-NMR data indicated that the product was a trans, trans-isomeric diketone oxime compound of formula III. .sup.1H-NMR (CDCl.sub.3), δ(ppm) value data: 2.022 (s, 6H, 2CH.sub.3), 7.425/7.452 (d, 4H, 4ArH), 7.823/7.851 (d, 4H, 4ArH), 12.450 (s, 2H, 2NOH).

[0047] Synthesis of Trans, Trans-Isomeric Diketone Oxime Ester (Compounds of Formula I)

[0048] In a reaction bottle, 24.5 g (0.068 mol) of a 1-2 product trans, trans-isomeric diketoximide (the compound of formula III) and 150 ml of toluene was added; the reaction bottle was put into a water bath of 20-25° C.; 19.6 g (0.19 mol) of acetic anhydride was added dropwise into the reaction bottle through a constant pressure dropping funnel, and stirred for 6 h; 100 ml of water was added into the reaction solution, and stirred for 30 min; the toluene phase was washed with 100 ml of 1% sodium bicarbonate solution, 50 ml of water and 50 ml of water sequentially, and toluene solution was filtered, distilled under reduced pressure to recover toluene to obtain 28.5 g of a crude yellow solid; 55 ml of hot ethyl acetate was added to dissolve the solid, and supplemented with 85 ml of hot n-hexane, naturally cooled to precipitate crystals; followed by suction filtration, and the filter cake was dried under vacuum to obtain 27.2 g of a light yellow solid crystal product with a content of 99.2% by the HPLC analysis, yield of 90.8%; and melting range of 108.0-111.5° C.; .sup.1H-NMR (CDCl.sub.3), δ (ppm) value data: 2.274 (s, 6H, 2CH.sub.3), 2.293 (s, 6H, 2COCH.sub.3), 7.417/7.445 (d, 4H, 4ArH), 8.050/8.078 (d, 4H, 4ArH).

Embodiment 2 Preparation of Alkali Soluble Resin

[0049] 180 G of benzyl methacrylate, 60 g of methacrylic acid, 60 g of hydroxyethyl methacrylate, 15 g of azobisisobutyronitrile, 6 g of dodecyl mercaptan and 1000 ml of toluene were uniformly mixed, and put into a constant-pressure dropping funnel; 1000 ml of toluene was put into a three-neck flask which was then installed with a stirring device, the constant-pressure dropping funnel and a thermometer, and after starting stirring, gas in the flask was replaced with nitrogen; the flask was heat to enable the temperature of the solvent to reach 80-85° C. and keep warm, the monomer mixed solution was started to add dropwise for about 1h; the reaction was continued for 6 h; followed by cooling naturally, stirring was stopped to allow the resin to settle, the upper clear solution was sucked, and the lower resin containing the solvent was filtered; the resin filter cake was eluted with 500 ml of toluene, and dried under reduced pressure to obtain 250 g of white powdery solid resin, which was dissolved in 1000 g of PMA (propylene glycol methyl ether acetate) as a 20% solution for later use.

Embodiment 3 Preparation and Development of Photoresists

[0050] All the components were prepared into the photo-curable composition according to the ink preparation method based on the weight ratio of the formulations 3A, 3B, 3C and 3D in Table 1, and the photo-curable composition was in a fluid liquid state.

[0051] Each of the above liquid compositions was coated on a glass surface using a line bar method, and baked for 3 minutes at 80° C. to evaporate off the solvent PMA, and the residual film thickness was measured to be 2 microns for later use.

[0052] First Group Exposure Tests

[0053] A 21-step gray gradient scale was placed on the film, 2000 W high-pressure mercury lamp light was filtered through a 365 nm grating filter, and the distance between the film and the grating was 10 cm to make the exposure amount reach 200 mJ/cm.sup.2.

[0054] Followed by immersion in a 1% sodium carbonate solution bath of 30° C. for 1 minute, the maximum step of film retention that could be displayed was recorded, the greater the number, the greater the photosensitivity of the composition measured, the higher the photo-cure rate and film-forming property of the photoresist, and the results are shown in Table 2.

[0055] Second Group Yellowness Test

[0056] Another standby coating film was taken, 2000 W high-pressure mercury lamp light was filtered through a 365 nm grating filter, and the distance between the film and the grating was 10 cm to make the exposure amount reach 200 mJ/cm.sup.2.

[0057] The exposed films were heated in a 230° C. oven for 30 min and the films were tested for yellowness indexes on a yellowness apparatus and the results are shown in Table 2.

TABLE-US-00001 TABLE 1 Composition raw material proportioning 3A 3B 3C 3D Sources Compound of 5 Embodiment 1 Embodiment 1 Comparative 5 Commercial product Compound 1 OXE01 Comparative 5 Prepared according to Compound 2 Embodiment 39 of patent CN 1514845A Comparative 5 Prepared according to Compound 3 Embodiment 1 of patent CN 103833872A Alkali soluble 500 500 500 500 Embodiment 2 resin solution Dipentaerythritol 100 100 100 100 Allnex Co., Ltd hexaacrylate

TABLE-US-00002 TABLE 2 Test Results 3A 3B 3C 3D Maximum film retention step 13 10 11 11 yellowness index (Yi D) 1.05 1.15 1.35 1.34

[0058] The results in Table 2 show that the exposure sensitivity of the 3A photoresist prepared using the compound of Embodiment 1 is significantly better than that of the photo-curable composition prepared using the control compound, increasing the sensitivity of the photoresist; the 3A photoresist formulated with the compound of Embodiment 1 has the lowest yellowness index.

Embodiment 4

[0059] Filter Film Preparation from Photoresist and Exposure Development

[0060] The formula included the following components: 500 parts of an alkali-soluble resin solution (Embodiment 2), 100 parts of dipentaerythritol hexaacrylate (Cytec), 8 parts of a photoinitiator and 50 parts of a red pigment L3920 (BASF). The ink was uniformly ground according to an ink preparation method, and four kinds of 4A-4D inks were obtained due to different initiators.

[0061] For the coating step, each of the above liquid compositions was coated on a glass surface using a line bar method, and baked for 3 minutes at 80° C. to evaporate off the solvent PMA, and the residual film thickness was measured to be 2 microns; a pattern mask with a transparent line width of 100 microns was covered; and 2000 W high-pressure mercury lamp light was filtered through a 365 nm grating filter, and the distance between the film and the grating was 10 cm to make the exposure amount reach 80 mJ/cm.sup.2.

[0062] The development was carried out for BP+10S with 1% aqueous sodium hydroxide solution, followed by rinsing with deionized water, and drying at 100° C., and the line width value CD after development was measured, and the experimental results are shown in Table 3. BP refers to the film breaking point during development.

TABLE-US-00003 TABLE 3 Red photoresist exposure evaluation Ink number Photoini- 4A 4B 4C 4D tiator Compound of Control Control Control sample formula I Compound 1 Compound 2 Compound 3 BP(s) 34 35 38 37 CD(μm) 105 96 99 100

[0063] As can be seen from Table 3, the ink 4A containing the compound of the present disclosure exhibits the best exposure sensitivity as judged by the Critical Dimension CD, i.e., the compound of the present disclosure is significantly more sensitive than all of the control compounds 1, 2, 3.