CN105199018A

CN105199018A - Novel oxime ester photoinitiator as well as preparation and application thereof

Info

Publication number: CN105199018A
Application number: CN201510745356.2A
Authority: CN
Inventors: 吴吉; 蒋雷; 敖文亮; 张齐; 武瑞; 毛桂红; 罗想; 周海兵; 董月国; 韩时操; 赵建新
Original assignee: Changzhou Jiuri Chemical Co Ltd
Current assignee: Tianjin Jiuri Semiconductor Materials Co ltd
Priority date: 2015-11-06
Filing date: 2015-11-06
Publication date: 2015-12-30
Anticipated expiration: 2035-11-06
Also published as: CN105199018B

Abstract

The invention discloses a novel oxime ester photoinitiator shown as general formulae I and II as well as preparation and an application thereof. The photoinitiator has excellent storage stability, photographic sensitivity, developing performance, pattern integrity and the like.

Description

Oxime ester photoinitiator, its preparation and application

Technical Field

The invention relates to a new oxime ester photoinitiator, a preparation method thereof and a photopolymer initiator using the compound as an olefinic unsaturated compound system.

Background

The photochemical characteristics of oxime ester compounds were first reported by Awernerl in 1904, and oxime ester compounds were initially used as photoinitiators in 1970, wherein the oxyacyl oxime ester photoinitiator QuantacurePDO (formula I) was widely commercialized but gradually eliminated due to its poor thermal stability. Oxime ester compounds have been actively studied in recent years, and there are, for example: macromol. symp.2004, 217, 77; patents CN101014569A, CN101321727A, CN101679394A, CN101687794A, CN99108598, CN02811675, CN1800885A, CN1928716A, CN101158812A, CN101525393A, CN101634807A, and WO2008138733a1, WO0052530a1, WO2007071497a1, WO2009019173a1, WO2009147031a2, WO2009147033a1, etc. describe some oxime esters of carbazole structure and oxime ester side chain dimer type compounds of related structure. On the basis of the above, commercial oxime ester compound photoinitiators OXE01 and OXE02 appear, and a photosensitive system formed by the compounds has sensitive response to 405 or 365 nm light, and has important application in the BM and RGB manufacturing field of large-screen LCD displays, and products with similar properties also include oxime esters 305 and 304 disclosed in CN101565472B and CN 101508744B. The disclosed photoinitiators can meet the general application requirements of the photocuring fields such as current display panels, color filters and the like to different degrees.

However, the development of electronic technology is changing day by day, the existing products begin to show up insufficiently in some application fields, and the update of the products also puts higher requirements on the photoinitiator. For example, most photoresists currently used for gap control materials have poor heat resistance, and are prone to collapse during baking or packaging processes, so that the gap material shrinks, and the cost is increased by increasing the height of the gap control material during coating, exposure, development and other processes, and small molecules melted by heat will contaminate the liquid crystal during collapse. For another example, in the manufacture of high-end color filters, on one hand, the photoinitiator needs to meet the basic requirements of high solubility and good thermal stability, and on the other hand, the high color quality performance of the photoinitiator needs to be a highly colored resist, and as the pigment content increases, the curing of the color resist becomes more difficult, and the definition and integrity of the cured image also have higher requirements, so that a higher-sensitivity initiator is needed to solve the above problems.

In the field of photo-curing, a photoinitiator with high photosensitivity, high stability and easy preparation is still the first development choice in the field, and the research and development of photoinitiators with higher performance will be a core work in the field.

Disclosure of Invention

The invention aims to provide a novel oxime ester photoinitiator with excellent performance and preparation and application thereof. The photoinitiator not only has excellent performances in the aspects of storage stability, photosensitivity, recessiveness, pattern integrity and the like, but also shows obviously improved photosensitivity and thermal stability compared with similar photoinitiators.

The technical scheme for realizing the purpose of the invention is as follows:

novel oxime ester photoinitiators having the general formula I, II:

wherein,

n =1 or 2;

R₁、R₂、R₃the alkyl groups can be the same or different and are independently selected from C1-C20 straight chain or branched chain alkyl, C3-C8 cycloalkyl, C7-C10 phenyl substituted alkyl;

R₄、R₅、R₆the alkyl groups can be the same or different and are independently selected from C1-C20 straight chain or branched chain alkyl groups, C3-C8 cycloalkyl groups and C6-C20 aryl groups, wherein the alkyl groups of C1-C20 are unsubstituted or substituted by one or more halogen, phenyl and alkoxy.

In a preferred embodiment of the present invention, the above oxime ester photoinitiators of the general formulae I and II are:

R₁、R₂、R₃independently selected from independently representIs a straight chain or branched chain alkyl of C1-C5, a C5-C6 cycloalkyl, a C7-C10 phenyl substituted alkyl;

R₄、R₅、R₆independently selected from C1-C5 straight chain or branched chain alkyl, C3-C8 cycloalkyl, C6-C10 aryl, wherein the C1-C20 alkyl is unsubstituted or substituted by one or more halogen, phenyl, alkoxy.

The invention also relates to a preparation method of the oxime ester photoinitiator with the general formula I and II, which comprises the following steps:

1) taking triphenylphosphine as a raw material, and acylating on phenyl under the catalysis of aluminum trichloride, ferric trichloride or zinc chloride;

2) oxidizing the obtained acylation product to obtain a phosphine oxide intermediate;

3) the phosphine oxide intermediate is reacted with a nitrite ester (e.g.: ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc.) or nitrites (such as sodium nitrite, potassium nitrite, etc.) to carry out oximation reaction;

4) reacting a product oxime obtained by the oximation reaction with acyl chloride to obtain oxime ester;

。

n and R₁、R₂、R₃、R₄、R₅、R₆Is as defined above.

In the above preparation methods, the starting materials used are all compounds known in the art, and are commercially available or prepared by known synthetic methods. The preparation method is simple, does not produce polluting wastes in the preparation process, has high product purity and good yield, and is suitable for industrial mass production.

The invention also relates to a novel oxime ester photoinitiator shown in the general formulas I and II, which comprises the following components in a photocuring composition:

a) at least one ethylenically unsaturated photopolymerizable compound and

b) at least one compound of general formula I or II as photoinitiator.

The compound containing an ethylenically unsaturated double bond may contain one or more double bonds. They may be of low molecular weight (monomeric) or relatively high molecular weight (oligomeric). Examples of monomers containing double bonds are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl-or 2-hydroxyethyl acrylate, isobornyl acrylate, or methyl or ethyl methacrylate; a silicone acrylate; acrylamide, methacrylamide, N-substituted (meth) acrylamides; vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl-and halostyrenes, N-vinylpyrrolidone, vinyl chloride or 1, 1-dichloroethylene.

Monomers containing two or more double bonds, such as ethylene glycol, propylene glycol, neopentyl glycol, the diacrylates of 1, 6-hexanediol and bisphenol A, 4, 4' -bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and tris (2-acryloylethyl) isocyanurate.

Examples of polyunsaturated compounds having a relatively high molecular weight (oligomeric) are acrylated epoxy resins and polyethers, polyurethanes; acrylated or vinyl ether or epoxy containing polyesters. The unsaturated oligomers may also be unsaturated polyester resins, mostly prepared with maleic acid, phthalic acid and one or more diols and having a molecular weight of about 500-3000. In addition, vinyl ether monomers and vinyl ether oligomers, as well as maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones, may also be used.

The ethylenically unsaturated compounds can also be esters of ethylenically unsaturated carboxylic acids and polyol epoxy compounds, and polymers containing ethylenically unsaturated groups in the main or side chain groups, such as unsaturated polyesters, polyamides or polyurethanes and copolymers thereof, polybutadiene or butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acrylic groups in the side chains, and mixtures of one or more of these polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

Suitable polyols are aromatic polyols and especially aliphatic and cycloaliphatic polyols. Aromatic polyols such as hydroquinone, 4' -dihydroxydiphenyl, 2-bis (4-hydroxyphenyl) propane, and also (novolak) and phenolic resins A. Aliphatic and cycloaliphatic polyols, such as alkylene glycols, preferably C2-12, for example ethylene glycol, 1, 2-or 1, 3-propanediol, 1,2-, 1, 3-or 1, 4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of preferably 200-1500, 1, 3-cyclopentanediol, 1,2-, 1, 3-or 1, 4-cyclohexanediol, 1, 4-dimethylolcyclohexane, glycerol, pentaerythritol, trimethylolpropane, dipentaerythritol or sorbitol, etc.

The invention also relates to the application of the novel oxime ester photoinitiator shown in the general formulas I and II in a photocuring composition (namely a photosensitive composition). Without limitation, the photoinitiator can be applied to color Resists (RGB), black resists (BM), steric barriers (Photo-spacers), dry films, semiconductor photoresists, inks, and the like.

Detailed Description

The following further describes particular embodiments of the present invention to facilitate further understanding of the present invention by those skilled in the art, and does not constitute a limitation to the right thereof.

Example 1: compound 1Preparation of

1) Preparation of 4,4 ', 4 ' ' -triacetyl triphenylphosphine: dissolving triphenylphosphine (52.5 g, 0.2 mol) in 300ml dichloromethane, controlling the reaction temperature at 20-30 ℃, adding aluminium trichloride (82.7 g, 0.62 mol) and dropwise adding acetyl chloride (48.7, 0.62 mol), stirring for 2h after dropwise adding, stopping the reaction, pouring the reaction solution into diluted hydrochloric acid prepared from 800g and 130ml concentrated hydrochloric acid, stirring for 0.5h, standing to separate out an organic phase, extracting a water phase with dichloromethane, combining the organic phases, washing with 200ml saturated sodium bicarbonate solution until the pH value of the organic phase becomes neutral, drying, desolventizing and recovering the solvent to obtain a light yellow oily substance with the purity of 97%, or directly carrying out the next oxidation reaction without recovering the solvent.

2) Adding 22.7g of 30% hydrogen peroxide into the neutral organic phase in the step 1), reacting for 3 hours at 60 ℃, respectively adding a sodium sulfite solution and a saturated sodium bicarbonate solution to wash after the reaction is finished, finally drying the organic phase with anhydrous magnesium sulfate, and recovering the solvent to obtain a yellow oily substance.

3) Dissolving hydrogen chloride in an organic solvent to obtain a solution of hydrogen chloride THF, taking 200g of the THF solution of hydrogen chloride, wherein the content of hydrogen chloride is selected from 30g, adding the 4,4 ', 4 ' ' -triacetyl triphenylphosphine oxide obtained in the step 2), stirring and dissolving, dropwise adding 15.5g of tert-butyl nitrite, carrying out heat preservation reaction until the raw materials are completely reacted, and recovering the solvent to obtain 72.0g of an orange oily liquid.

4) Dissolving the oily substance obtained in the step 3) in dichloroethane, cooling to 0 ℃, adding 47.0g of triethylamine, dropwise adding 35.3g of acetyl chloride, after the raw materials completely react, adding 3% dilute hydrochloric acid under the condition that the pH is = 2-3, stirring for 30min, standing for layering, washing an organic phase, drying, recovering a solvent, cooling to obtain a yellow oily substance, purifying by column chromatography (EtOAc/hexane = 40/1) to obtain a colorless oily substance, and confirming the structure of a final product by nuclear magnetic resonance hydrogen spectrum, wherein the specific characterization result is as follows:¹H-NMR（CDCl3，400MHz）：7.98(d，6H),7.67(dd，³J(H,H)=8.3Hz,³J(P,H)=11.1Hz，6H),2.48(s，9H),1.90(s，9H)；³¹P-NMR(CDCl3，400MHz)：27.7(s)。

example 2: compound 2Preparation of

1) Preparation of 4,4 ', 4 ' ' -triisobutyryl triphenylphosphine: dissolving triphenylphosphine (52.5 g, 0.2 mol) in 300ml dichloromethane, controlling the reaction temperature at 20-30 ℃, adding aluminium trichloride (82.7 g, 0.62 mol) into isobutyryl chloride (42.6 g, 0.40 mol) and butyryl chloride (16.5 g, 0.21 mol) dropwise respectively, stirring for 2h after dropwise adding, stopping reaction, pouring the reaction solution into diluted hydrochloric acid prepared from 800g and 130ml concentrated hydrochloric acid, stirring for 0.5h, standing to separate out an organic phase, extracting a water phase with dichloromethane, combining the organic phases, washing with 200ml saturated sodium bicarbonate solution until the pH value of the organic phase becomes neutral, drying, desolventizing and recovering a solvent to obtain a light yellow oily substance with the purity of 96.7%.

3) Dissolving hydrogen chloride in an organic solvent to obtain a solution of hydrogen chloride THF, taking 200g of the THF solution of hydrogen chloride, wherein the content of hydrogen chloride is selected from 30g, adding the 4-acetyl-4 ', 4 ' ' -diisobutyl triphenyl phosphine oxide obtained in the step 2), stirring and dissolving, dropwise adding 15.5g of tert-butyl nitrite, keeping the temperature for reaction until the raw materials are completely reacted, and recovering the solvent to obtain 80.9g of an orange oily liquid.

4) Dissolving the oily substance obtained in the step 3) in dichloroethane, cooling to 0 ℃, adding 47.0g of triethylamine, dropwise adding 35.3g of acetyl chloride, adding 3% dilute hydrochloric acid after the raw materials completely react, keeping the pH value of the solution at = 2-3, stirring for 30min, standing for layering, washing an organic phase with water, drying, recovering a solvent, and purifying by column chromatography (EtOAc/hexane = 40/1) to obtain a colorless oily substance, wherein the structure of a final product is confirmed by nuclear magnetic resonance hydrogen spectroscopy, and the specific characterization result is as follows:

¹H-NMR（CDCl3，400MHz）：7.96(d，6H),7.68(dd，³J(H,H)=8.3Hz,³J(P,H)=11.1Hz，6H),2.08(s，9H),1.90(s，3H),1.79~1.82(m，2H),1.09(d，12H)；³¹P-NMR(CDCl3，400MHz)：27.8(s)。

example 3: compound 3Preparation of

1) Preparation of 4,4 ', 4 ' ' -triacetyl triphenylphosphine: dissolving triphenylphosphine (52.5 g, 0.2 mol) in 300ml dichloromethane, controlling the reaction temperature at 20-30 ℃, adding aluminium trichloride (82.7 g, 0.62 mol) dropwise acetyl chloride (48.7, 0.62 mol), stirring for 2h after dropwise addition, stopping the reaction, pouring the reaction solution into 800g diluted hydrochloric acid prepared by 130ml concentrated hydrochloric acid, stirring for 0.5h, standing to separate out an organic phase, extracting an aqueous phase by dichloromethane, combining the organic phases, washing by 200ml saturated sodium bicarbonate solution until the pH value of the organic phase becomes neutral, drying, desolventizing and recovering the solvent to obtain a light yellow oily substance with the purity of 97%.

3) Dissolving hydrogen chloride in an organic solvent to obtain a solution of hydrogen chloride THF, taking 200g of the THF solution of hydrogen chloride, wherein the content of hydrogen chloride is selected from 30g, adding the 4,4 ', 4 ' ' -triacetyl triphenylphosphine oxide obtained in the step 2), stirring and dissolving, dropwise adding 15.5g of tert-butyl nitrite, carrying out heat preservation reaction until the raw materials are completely reacted, and recovering the solvent to obtain 72.5g of an orange oily liquid.

4) Dissolving the oily substance obtained in the step 3) in dichloroethane, cooling to 0 ℃, adding 47.0g of triethylamine, dropwise adding 87.0g of benzoyl chloride, adding 3% dilute hydrochloric acid after the raw materials completely react, keeping the pH value of the solution at = 2-3, stirring for 30min, standing for layering, washing an organic phase with water, drying, recovering a solvent, purifying by column chromatography (EtOAc/hexane = 40/1) to obtain a colorless oily substance, and confirming the structure of a final product by nuclear magnetic resonance hydrogen spectroscopy, wherein the specific characterization result is as follows:

¹H-NMR（CDCl3，400MHz）：8.25(d，6H),7.33~7.89(m，21H),1.87(s，3H)；³¹P-NMR(CDCl3，400MHz)：27.8(s)。

structure of target product and its application¹The H-NMR data are shown in Table 1:

TABLE 1

Example 18: evaluation of Performance

By formulating the exemplary photocurable compositions, the photoinitiators of the present invention of formula I and II were evaluated for various applications, including storage stability, sensitivity, developability, pattern integrity, and the like.

1. Preparation of Photocurable compositions

Acrylate copolymer 100

(benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio of 70/10/20)) copolymer

（Mw：10,000））

Trimethylolpropane triacrylate (TMPTA) 100

2-3 parts of photoinitiator to be detected

PMA solvent 25

In the composition, the photoinitiator is oxime ester compound shown in general formulas I and II disclosed by the invention

The components are in parts by mass, or as comparative photoinitiators known in the art.

2. Exposure development

The photocurable composition was stirred away from the light, taken out of the PET template and coated with a wire bar, and dried at 165 ℃ for 150min to remove the solvent, thereby forming a coating film having a thickness of about 2 μm. Cooling the substrate with the coating film to room temperature, attaching a mask plate, exposing the coating film by using a high-pressure mercury lamp or an LED light source under the ultraviolet ray with the wavelength of 365-420 nm, 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 to fix the pattern, and evaluating the obtained pattern.

3. Evaluation of Properties of photo-curing composition

(1) Storage stability

After the liquid photocurable composition was naturally stored at room temperature for 3 months, 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.

(2) Sensitivity of light

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, and a smaller exposure demand indicates a higher sensitivity.

(3) 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:

o: no residue was observed in the unexposed parts;

very good: 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:

o: no pattern defects were observed;

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

solid content: many pattern defects were clearly observed.

The evaluation results are shown in table 2:

TABLE 2

Photoinitiator	Storage stability	Surface light energy mJ/cm²	Developability	Image integrity
					Example 1	A	40	○	◇
Example 2	A	38	○	◇
					Example 3	A	42	○	◇
Example 4	A	43	○	◇
					Example 5	A	37	○	◇
Example 6	A	71	◎	□
					Example 12	A	50	○	◇
Example 13	A	75	◎	□
					Example 14	A	52	◎	□
Example 16	A	55	○	◇
					Example 17	A	39	○	◇
OXE-01	B	205	◎	◆
					OXE-02	B	185	◎	□

As can be seen from the results shown in Table 2, the photocurable compositions containing the novel oxime ester photoinitiators of the general formulae I and II of the present invention have very good storage stability, and all show excellent sensitivity, developability and pattern integrity.

In conclusion, the novel oxime ester photoinitiator shown in the general formulas I and II disclosed by the invention has excellent application performance, and can greatly improve the performance of photocuring products when being applied to photocuring compositions.

Claims

1. Novel oxime ester photoinitiators having the general formula I, II:

wherein,

n =1 or 2;

2. The oxime ester photoinitiator according to claim 1, wherein:

R₁、R₂、R₃independently selected from straight or branched chain alkyl independently represented by C1-C5, C5-C6 cycloalkyl, C7-C10 phenyl substituted alkyl;

3. The oxime ester photoinitiator according to claim 1, which is prepared by a process comprising the steps of:

2) the phosphine oxide intermediate reacts with nitrite or nitrite under the action of hydrogen chloride, sodium alkoxide or potassium alkoxide

Carrying out oximation reaction;

3) reacting a product oxime obtained by the oximation reaction with acyl chloride to obtain oxime ester;

4) oxidizing the obtained acylation product to obtain a phosphine oxide intermediate;

wherein:

n =1 or 2;

4. The method according to claim 3, wherein the nitrite in step 2) is selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite; the nitrite is selected from sodium nitrite, potassium nitrite, etc.

5. A photocurable composition comprising:

a) at least one ethylenically unsaturated photopolymerizable compound and

b) at least one compound according to claim 1 as photoinitiator.