CN106749776B

CN106749776B - A kind of oxime ester lightlike initiating agent containing fluorenes

Info

Publication number: CN106749776B
Application number: CN201510645925.6A
Authority: CN
Inventors: 钱晓春; 胡春青; 于培培
Original assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Current assignee: Changzhou Tronly New Electronic Materials Co Ltd; Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date: 2015-10-08
Filing date: 2015-10-08
Publication date: 2019-07-12
Anticipated expiration: 2035-10-08
Also published as: CN106749776A

Abstract

The present invention discloses a kind of oxime ester lightlike initiating agent containing fluorenes as shown in following formula (I), the compound synthesis is simple, at low cost, and dissolubility is good when applied to curing field, has excellent storage stability and filming performance, it is low to expose demand, and developability and pattern integrity are excellent.

Description

Fluorenoxime ester photoinitiator

Technical Field

The invention belongs to the field of organic chemistry, and particularly relates to a fluorene-containing oxime ester photoinitiator, and synthesis and application thereof in the field of photocuring.

Background

Oxime ester compounds are well known to those skilled in the art as photoinitiators, and have outstanding activity and are widely used in high-end photoresists such as color filter films (RGB), Black Matrixes (BM), photo-spacers (photo-spacers), rib gratings (rib) and the like.

The common oxime ester photoinitiator takes carbazole or diphenyl sulfide group as a main group, so that the cost is high, and the solubility with matrix resin is often insufficient, so that the development of the photoinitiator with lower cost and good solubility is a pursued target on the premise that the sensitivity is not influenced.

Disclosure of Invention

The invention mainly aims to provide a fluorene-containing oxime ester photoinitiator which is simple to synthesize, low in cost, good in solubility and excellent in storage stability and film-forming property when applied to a photocuring composition.

The oxime ester photoinitiator containing fluorene has a structure shown as the following formula (I):

wherein,

R₁each independently represents hydrogen, halogen, C₁-C₂₀Straight or branched alkyl of (2), C₄-C₂₀Cycloalkylalkyl of (C)₂-C₂₀Alkenyl of (2), the-CH of these groups₂-is optionally substituted by-O-;

R₂represents C₃-C₂₀Cycloalkyl of, C₄-C₂₀Cycloalkylalkyl or alkylcycloalkyl of (a);

R₃represents C₁-C₂₀Straight or branched alkyl of (2), C₃-C₂₀Cycloalkyl radical, C₄-C₂₀Alkylcycloalkyl or cycloalkylalkyl, C₆-C₃₀Aryl or substituted aryl of, C₇-C₃₀Aralkyl of (2), C₂-C₂₀Alkenyl of (a);

a represents hydrogen, halogen, nitro, C₁-C₁₀Straight or branched alkyl of (2), C₄-C₁₀Alkylcycloalkyl or cycloalkylalkyl of (a);

x represents a null or a carbonyl group.

As a preferable technical scheme, in the fluorene oxime ester photoinitiator shown in the formula (I), R₁Each independently represents hydrogen, halogen, C₁-C₁₀Straight or branched alkyl of (2), C₄-C₁₀Cycloalkylalkyl of (a), of which-CH₂-is optionally substituted by-O-.

Further preferably, R₁Each independently represents hydrogen, C₁-C₆And one or two of the alkyl groups are not adjacent to-CH₂-is optionally substituted by-O-.

Preferably, R₂Represents C₃-C₁₀Cycloalkyl of, C₄-C₁₀Cycloalkylalkyl or alkylcycloalkyl of (a). Further preferably, R₂Represents C₃-C₆Cycloalkyl group of (a), terminal group by C₃-C₆Cycloalkyl-substituted C₁-C₄Straight or branched alkyl of (2), by C₁-C₄Alkyl substituted C₃-C₆A cycloalkyl group.

Preferably, R₃Represents C₁-C₁₀Straight or branched alkyl of (2), C₄-C₁₀Cycloalkylalkyl, phenyl, C₂-C₈Alkenyl groups of (a). Further preferably, R₃Represents C₁-C₆Straight or branched alkyl, end-capped by C₃-C₆Cycloalkyl-substituted C₁-C₄Straight or branched chain ofA chain alkyl group.

A is preferably nitro.

The invention also aims to provide a preparation method of the fluorene-containing oxime ester photoinitiator with the structure of the formula (I), which comprises the following steps:

(1) synthesis of intermediate a

The raw material a and the raw material b generate Friedel-crafts acylation reaction in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride to obtain an intermediate a,

the starting material b is R₂' -CO-Cl wherein R₂' represents R₂Or R₂-CH₂-, in particular, when X in formula (I) is null, then R₂' represents R₂When X is carbonyl, then R₂' represents R₂-CH₂-；

(2) Synthesis of intermediate b

When X is empty, the intermediate a is subjected to oximation reaction under the action of hydroxylamine hydrochloride and sodium acetate to generate an intermediate b;

when X is carbonyl, under the existence of organic solvent and concentrated hydrochloric acid, the intermediate a and nitrite are subjected to oximation reaction at normal temperature to generate an intermediate b;

(3) synthesis of Compounds of formula (I)

Intermediate b with acid anhydride (R)₃-CO)₂O or acyl chloride compounds R₃Carrying out esterification reaction on-CO-Cl to obtain a target product;

in the above-mentioned preparation methods, the starting materials used are all known compounds in the prior art, and can be commercially obtained or can be easily prepared by known synthetic methods.

The reactions involved in steps (1) - (3) are all conventional in the art for the synthesis of analogous compounds. Specific reaction conditions are readily determined by those skilled in the art, given the synthetic concepts disclosed herein.

In the Friedel-crafts reaction of step (1), the reaction temperature is usually-10 to 30 ℃. The organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and examples thereof include methylene chloride, dichloroethane, benzene, toluene, xylene, and the like.

The oximation reaction in step (2) is carried out in a solvent system, and the solvent used is not particularly limited as long as it can dissolve the starting materials and does not adversely affect the reaction.

When X is empty, the solvent used may be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water. The reaction was carried out under heating under reflux.

When X is carbonyl, the organic solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran, etc., the nitrite used may be selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc., and the nitrite used may be selected from sodium nitrite, potassium nitrite, etc.

The esterification reaction in the step (3) is carried out in an organic solvent, and the kind of the solvent is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected, and examples thereof include dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.

In the present invention, the fluorene-containing oxime ester compound represented by the above formula (I) may be further processedFrom R₁(one or two), R₂Or R₃Are polymerized in conjunction with each other to form a dimer. These dimerization products are considered to exhibit application properties similar to those of the fluorene-containing oxime ester photoinitiator represented by formula (I).

The invention also aims to provide application of the fluorene oxime ester containing photoinitiator shown in the formula (I) in a photocuring composition (namely a photosensitive composition). Without limitation, the photoinitiator may be applied to color Resists (RGB), Black Matrixes (BM), photo-spacers (photo-spacers), rib grids (rib), dry films, semiconductor photoresists, inks, and the like. The photoinitiator has excellent solubility in application, good storage stability, low exposure requirement (namely high sensitivity), and good developability and pattern integrity.

Detailed Description

The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.

Preparation examples

Example 1

(1) Preparation of intermediate 1a

Adding 120g of raw material 1a, 67g of aluminum trichloride and 100mL of dichloromethane into a 500mL four-neck flask, cooling to 0 ℃ in an ice water bath, dropwise adding a mixed solution of 80g of raw material 1b and 50mL of dichloromethane, controlling the temperature to be below 10 ℃, completing dropwise addition within about 2 hours, continuing stirring for 2 hours after completing dropwise addition, tracking and reacting a liquid phase to be complete, slowly pouring the material into diluted hydrochloric acid prepared from 800g of ice water and 100mL of concentrated hydrochloric acid (37%), stirring while adding, and then pouring into a liquid separation drainIn the bucket, the lower dichloromethane layer was separated and the aqueous layer was further washed with 50mL dichloromethane, the dichloromethane layers were combined, the dichloromethane layer was washed with 5% aqueous sodium bicarbonate (300 mL each for 3 times), then washed with water until the pH was neutral, dried over 150g anhydrous magnesium sulfate, filtered, the dichloromethane product solution was rotary evaporated, recrystallized from methanol, and oven dried at 70 ℃ for 2h to give 141g of intermediate 1a in 78% yield and 98% purity MS (m/z): 364(M +1)⁺。

(2) Preparation of intermediate 1b

Adding 73g of intermediate 1a, 14g of hydroxylamine hydrochloride, 16g of sodium acetate, 150mL of ethanol and 50mL of water into a 500mL four-neck flask, heating at 85 ℃, refluxing and stirring for 5h, stopping the reaction, pouring the material into a 2000mL big beaker, adding 1000mL of water, stirring, extracting with 200mL of dichloromethane, adding 50g of anhydrous MgSO (MgSO) into the extract liquor, and stirring₄Drying, performing suction filtration, performing rotary evaporation on the filtrate under reduced pressure to remove the solvent, rotating the bottle to obtain oily sticky matter, pouring the sticky matter into 150mL petroleum ether, stirring and separating out, performing suction filtration to obtain white powdery solid, drying at 60 ℃ for 5h to obtain an intermediate 1b57g, wherein the yield is 75%, the purity is 98%, and the mass ratio of MS (m/z): 379(M +1)⁺。

(3) Synthesis of Compound 1

Adding 38g of intermediate 1b and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 11g of acetic anhydride, continuing to stir for 2h after about 30min of dropwise addition is finished, and then adding 5% NaHCO₃Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO₄Drying, filtering, evaporating the solvent to obtain a viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain 36g of product with yield of 85% and purity of 99%.

The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.

¹H-NMR(CDCl₃，500MHz)：1.0023-1.1128(3H，d)，1.409-1.4511(7H，m)，1.6157-1.6832(10H，m)，2.0824(3H，s)，8.0121-8.4465(6H，m)。

MS(m/z)：421(M+1)⁺。

Example 2

(1) Preparation of intermediate 2a

Adding 105g of raw material 2a, 67g of aluminum trichloride and 100mL of dichloromethane into a 500mL four-neck flask, cooling to 0 ℃ in an ice-water bath, dropwise adding a mixed solution of 74g of raw material 2b and 50mL of dichloromethane, controlling the temperature to be below 10 ℃, completing dropwise addition for about 2 hours, continuing to stir for 2 hours after dropwise addition, tracking the liquid phase until the reaction is completed, then slowly pouring the materials into diluted hydrochloric acid prepared from 800g of ice water and 100mL of concentrated hydrochloric acid (37%), stirring while adding, then pouring into a separating funnel, separating a dichloromethane layer at the lower layer, continuing to clean an aqueous layer with 50mL of dichloromethane, combining the dichloromethane layers, cleaning the dichloromethane layer with 5% sodium bicarbonate aqueous solution (300 mL each time and 3 times in total), then washing the dichloromethane layer with water until the pH value is neutral, drying the dichloromethane layer with 150g of anhydrous magnesium sulfate, filtering, then performing recrystallization on the dichloromethane solution, drying at 70 ℃ for 2 hours, 127g of intermediate 2a were obtained in 79% yield and 98% purity, MS (m/z): 322(M +1)⁺。

(2) Preparation of intermediate 2b

Adding 64g of intermediate 2a, 20g of 37% hydrochloric acid, 23g of isoamylnitrite and 100mL of tetrahydrofuran into a 250mL four-neck flask, stirring at normal temperature for 5 hours, and stopping reaction; the material was poured into a 2000mL beaker, 1000mL of water was added, stirring was carried out, 200mL of methylene chloride was used for extraction, and 50g of anhydrous MgSO was added to the extract₄Drying, vacuum filtering, rotary evaporating the filtrate under reduced pressure to remove solvent, rotating the bottle to obtain oily viscous substance, pouring the viscous substance into 150mL petroleum ether, stirring for precipitation, vacuum filtering to obtain white powdery solid, oven drying at 60 deg.C for 5 hr to obtain intermediate 1b57g with yield of 78% and purity of 98%％，MS(m/z)：351(M+1)⁺。

(3) Synthesis of Compound 2

Adding 35g of intermediate 2b and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 10g of propionyl chloride, continuing stirring for 2h after about 30min of dropwise addition is finished, and then adding 5% NaHCO₃Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO₄Drying, filtering, evaporating the solvent to obtain a viscous liquid, recrystallizing with methanol to obtain white solid powder, and filtering to obtain 35g of product with yield of 86% and purity of 99%.

¹H-NMR(CDCl₃，500MHz)：1.0162-1.1057(3H，t)，1.5069-1.5161(5H，m)，1.6755-1.6992(4H，m)，2.2624-2.3004(2H，m)，3.8774(2H，s)7.9151-8.3325(6H，m)。

MS(m/z)：407(M+1)⁺。

Example 3

Referring to the methods of examples 1 and 2, compounds 3 to 12 shown in the following table 1 were synthesized using the corresponding starting materials.

TABLE 1

Evaluation of Performance

1. Dissolution Performance test

The solubility of the photoinitiator in PGMEA is one of the parameters that represent its solubility and measure the performance of the photoinitiator. The solubility of the compound of formula (I) of the present invention in PGMEA at 25 ℃ was tested using the compound of formula (I) of the present invention and the conventional nitrocarbazole-containing oxime ester photoinitiators for comparison, and the results are shown in Table 2.

TABLE 2

Examples/comparative examples	Photoinitiator	Solubility in PGMEA (% by weight)
			Example 4	Compound 1	16％
Example 5	Compound 2	15％
			Example 6	Compound 6	16％
Example 7	Compound 7	15％
			Example 8	Compound 10	17％
Example 9	Compound 12	17％
			Comparative example 1	Compound A	Not dissolving
Comparative example 2	Compound B	Not dissolving

As can be seen from the above table, the two existing nitro carbazole containing oxime ester photoinitiators used as comparative compounds A and B are basically insoluble in PGMEA, while the compound of the present invention has good solubility in PGMEA, and both meet the requirement that the solubility in industrial application needs to be more than 8% by weight.

2. Storage stability and film formation Property test

Storage stability and film-forming properties of the photoinitiators of formula (I) of the invention were evaluated by formulating exemplary photocurable compositions.

(1) A photocurable composition was prepared as follows

200 parts by mass of an acrylic ester copolymer

[ benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv: 10000) ]

100 parts by mass of dipentaerythritol hexaacrylate

5 parts by mass of photoinitiator

Butanone (solvent) 900 parts by mass

In the composition, the photoinitiator is a fluorene-containing oxime ester compound shown in formula (I) disclosed by the invention or a photoinitiator known in the prior art (for comparison).

(2) Storage stability

After the liquid photocurable composition was naturally stored at room temperature for 1 month, the degree of precipitation of the substance was visually evaluated according to the following criteria:

a: no precipitation was observed;

b: precipitation was slightly observed;

c: significant precipitation was observed.

(3) Film forming property

The exemplary photocurable composition having the above composition was stirred under a yellow light, taken out of a PET stencil and applied to a film by roll coating, and dried at 90 ℃ for 2min to give a coating film having a dry film thickness of 2 μm. The substrate on which the coating film was formed was cooled to room temperature, a mask plate was attached, and long-wavelength radiation was realized with a FWHM filter using a high-pressure mercury lamp 1PCS light source. Exposing the coating film by ultraviolet rays with the wavelength of 370-420nm through the gaps of the mask plate, then soaking in 2.5% sodium carbonate solution at 25 ℃ for 20s for development, washing with ultrapure water, air-drying, hard-baking at 220 ℃ for 30min for fixing the pattern, and evaluating the obtained pattern.

① sensitivity

At the time of exposure, the minimum exposure amount at which the residual film ratio after development of the light-irradiated region in the exposure step is 90% or more is evaluated as the exposure demand. A smaller exposure requirement indicates a higher sensitivity.

② developability and Pattern integrity

The substrate pattern was observed with a Scanning Electron Microscope (SEM) to evaluate developability and pattern integrity.

The developability was evaluated according to the following criteria:

○ No residue was observed in the unexposed parts;

◎ A small amount of residue was observed in the unexposed parts, but the residue was acceptable;

●: a clear residue was observed in the unexposed parts.

Pattern integrity was evaluated according to the following criteria:

◇ No pattern defects were observed;

□: a small part of the pattern was observed to have some defects;

◆ A number of pattern defects were clearly observed.

The evaluation results are shown in table 3.

TABLE 3

As can be seen from Table 3, compared with the existing nitro carbazole-containing oxime ester photoinitiator, the photocuring composition containing the fluorene-containing oxime ester photoinitiator has good storage stability and low exposure demand which are all lower than 60mJ/cm²And the developing effect and the pattern integrity are better, and the film-forming property is very excellent.

On the whole, the fluorene-containing oxime ester photoinitiator shown in the formula (I) disclosed by the invention has excellent application performance, low cost of raw materials and preparation and good application prospect.

Claims

1. A fluorene-containing oxime ester photoinitiator has a structure shown as the following formula (I):

wherein,

R₁each independently represents hydrogen, C₁-C₆And one or two of the alkyl groups are not adjacent to-CH₂-is optionally substituted by-O-;

R₂represents C₃-C₆Cycloalkyl group of (a), terminal group by C₃-C₆Cycloalkyl-substituted C₁-C₄Straight or branched alkyl of (2), by C₁-C₄Alkyl substituted C₃-C₆A cycloalkyl group;

R₃represents end quilt C₃-C₆Cycloalkyl-substituted C₁-C₄Linear or branched alkyl of (a);

a represents nitro;

x represents a null or a carbonyl group.

2. The method for preparing the fluorenyloxime ester photoinitiator according to claim 1, comprising the following steps:

(1) synthesis of intermediate a

(2) Synthesis of intermediate b

(3) synthesis of Compounds of formula (I)

3. the production method according to claim 2, characterized in that: in the step (2), when X is empty, the solvent used is a mixed solvent of alcohol and water, and the reaction is carried out under a heating reflux state.

4. The production method according to claim 2, characterized in that: in the step (2), when X is carbonyl, the nitrite is selected from ethyl nitrite, isoamyl nitrite and isooctyl nitrite, and the nitrite is selected from sodium nitrite and potassium nitrite.

5. The use of the fluorooxime ester photoinitiator according to claim 1 in the field of photocuring.

6. Use according to claim 5, characterized in that: the field of photocuring comprises preparation of color light resistors, black matrixes, light spacers, rib grids, dry films, semiconductor photoresist and printing ink.