JPH0755925B2 - Novel oxime ester compound and synthetic method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator and a method for synthesizing the same.

[Background of the Invention]

The photochemical polymerization method is increasing in industrial importance in the case of a coating film which needs to be cured particularly in a short time such as curing and printing of photoresist and drying of ink. The curing method by irradiation with light in the presence of a photopolymerization initiator has a great advantage in that the curing speed is increased as compared with the usual curing method. Since the curing rate largely depends on the photopolymerization initiator, attempts have been made to replace the conventional photopolymerization initiator with a more excellent compound. Examples of conventionally known effective photopolymerization initiators include benzoin-ethers as described in West German Patent (DT-PS) 1694149 and British Patent 1537921. Oxime ester compounds and the like.

These known photoinitiators have several drawbacks in use, the greatest of which is the storage of the photopolymerizable system in the dark, in some cases mixed with such photoinitiators. It is a combination of stability and high photocuring speed. Further, in order to increase the photo-curing speed of these known photo-polymerization initiators, many attempts have been made to use them in combination with a sensitizer, or the expected sensitizing effect may not be obtained in some cases. . In particular, when the resist or ink has strong absorption in the near-ultraviolet region (300 to 400 nm), for example, an aromatic polyimide or polyamide is contained, or an organic or inorganic pigment, fine particles or filler is filled. At times, the decrease in photocuring rate was significant.

Therefore, the emergence of photoinitiators that have good storage stability in the dark, initiate photopolymerization faster than known photoinitiators, and give higher polymer yields per unit of time. It was industrially desired. Use of these improved photopolymerization initiators can improve industrial productivity.

[Problems to be solved by the invention]

In view of such circumstances, the inventors of the present invention selected a photopolymerization initiator having good storage stability in the dark and a high photocuring rate even when the resist or the ink has strong absorption in the near ultraviolet region. We have earnestly studied to provide it.

[Means for solving problems]

As a result, they have found that an oxime ester compound having a specific structure is suitable for the purpose, and completed the present invention.

That is, the present invention has the general formula (I) [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₃ represents an alkyl group having 1 to 6 carbon atoms]. The present invention relates to a novel oxime ester compound characterized by the following.

Preferred examples of R ₁ and R ₂ are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group and the like, and a preferred example of R ₃ is a methyl group, an ethyl group, a propyl group and the like.

Examples of the oxime ester compound represented by the general formula (I) include the following compounds.

1,3-Diphenyl-propanetrione-2- (0-methoxycarbonyl) oxime 1,3-diphenyl-propanetrione-2- (0-ethoxycarbonyl) oxime 1,3-bis (4-methylphenyl) -propanetrione- 2- (0-Ethoxycarbonyl) oxime 1,3-bis (4-methoxyphenyl) -propanetrione-2- (0-ethoxycarbonyl) oxime The present invention also provides a method for synthesizing the oxime ester compound (I). It is provided. That is, (i) a compound represented by the following general formula (II) (hereinafter referred to as compound (II)) Alternatively, a compound represented by the following general formula (III) (hereinafter referred to as compound (III)) Alternatively, a mixture of a compound represented by the formula (II) and a compound represented by the formula (III) is reacted with hydroxylamine or a salt thereof to give a compound represented by the following general formula (IV) (hereinafter referred to as compound (IV) Name) (Ii) Next, a compound represented by the following general formula (V) (hereinafter referred to as compound (V)) The present invention relates to a method for synthesizing a compound represented by the formula (I), which comprises reacting with

[Wherein, X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₃ represents an alkyl group having 1 to 6 carbon atoms. Show. The synthesis method will be described in detail below.

Compound (II) and compound (III), which are raw materials for the synthesis of oxime ester compound (I), are Org.Synth.coll.Vol.II.
It can be synthesized according to the method described on pages 244-245. For example, a compound represented by the formula (VI) [In the formula, R ₁ and R ₂ have the same meaning as described above] is dissolved in a halogenated hydrocarbon such as chloroform, methylene chloride, carbon tetrachloride and the like, and a halogenating reagent such as chlorine, bromine or iodine is reacted with this. To give a compound of formula (VII) [In the formula, X and X'represent chlorine, bromine and iodine, respectively. ]
Can lead to. Further, the compound (VII) is acetic acid,
The compound (II) can be obtained by treating with a corresponding alkali metal salt of sodium, potassium, lithium or the like in a carboxylic acid such as propionic acid or butyric acid. The compound (III) can be synthesized by distilling the compound (II) thus obtained under reduced pressure or using a dehydrating agent such as dicyclohexylcarbodiimide or anhydrous copper sulfate.

Compound (II), compound (III) or a mixture of compound (II) and compound (III) can be converted to compound (IV) by treating with hydroxylamine or a salt thereof in an alcohol solvent. Here, as the alcohol solvent, an aliphatic alcohol having 1 to 10 carbon atoms,
Or the following formula [In the formula, R ₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₅ represents a methyl group or an ethyl group. ] Aromatic alcohols represented by Examples of the hydroxylamine salt include mineral acid salts such as hydrochloric acid and sulfuric acid, or the following formulas R ₆ -COOH, HOO
CR ₇ -COOH [wherein R ₆ is a hydrogen atom or has 1 to 3 carbon atoms]
Represents an alkyl group of R ₇ is R 0 or has 1 to 3 carbon atoms.
Is an alkylene group. ] The salt with the carboxylic acid shown by these is preferable, and a hydrochloride, a sulfate, and an oxalate are preferable. The reaction temperature and time are not limited, but are preferably 60 to 160 ° C. and 30 minutes to 2 hours, respectively. Of these, a particularly preferable example is to dissolve the compound (II) or the compound (III), or a mixture thereof in methanol or ethanol, add hydroxylamine hydrochloride or sulfate to the solution, and add 1- Compound (IV) is obtained by reacting for 2 hours. The product is obtained directly by removing the solvent,
Processing such as purification by silica gel chromatography or recrystallization may be performed here. The compound (IV) thus obtained is identified by thin layer chromatography or liquid chromatography.

Compound (IV) is converted to oxime ester compound (I) by reacting halogenated carbonic acid alkyl ester compound (V) in the presence of a base in a synthetic solvent. Synthetic solvents include halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride; ketone-based hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl isoamyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include ether hydrocarbons such as diethyl ether, tetrahydrofuran, dioxane, and diisopropyl ether; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxides and sulfones such as dimethyl sulfoxide and dimethyl sulfone. In addition to this, it is also possible to use a basic substance such as pyridine or triethylamine as a synthesis solvent. As the dehydrohalogenating agent, conventionally used hydrogen halide scavenging bases can be used. For example, a tertiary amine represented by (R ₈ ) ₂ R ₉ N [in the formula, R ₈ and R ₉ each represent an alkyl group having 1 to 4 carbon atoms]. ] Or [In the formula, Ra, Rb, and Rc each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, and Rd represents an alkyl group having 1 to 7 carbon atoms or a cycloalkyl group. ] Aromatic amines, pyridines, imidazoles, triazoles, quinolines, pyrimidines, morpholines and derivatives thereof represented by

The halogenated carbonic acid alkyl ester compound generally has the following formula [Wherein R ₃ represents an alkyl group having 1 to 6 carbon atoms, X 3
Represents chlorine, bromine and iodine. ] Is shown. Examples of this include methyl chlorocarbonate, ethyl chlorocarbonate, isopropyl chlorocarbonate, isobutyl chlorocarbonate, methyl bromocarbonate, ethyl bromocarbonate, ethyl iodocarbonate,
Examples include iodocarbonic acid isobutyl ester. Reaction temperature,
There is no limit to the time, but each is preferably -10 to 30.
C, 30 minutes to 2 hours. In the synthesis of the oxime ester compound (I), particularly preferably, a ketone-based hydrocarbon such as acetone or a halogenated hydrocarbon such as chloroform is used as a synthetic solvent, and the compound (IV) is dissolved therein to obtain a tertiary amine such as triethylamine. In the presence of amine, it is treated with chlorocarbonic acid ethyl ester at 0 to 20 ° C. for 30 minutes to 2 hours. The compound (I) thus obtained can be obtained by removing the salt of by-product hydrogen halide and a base by liquid separation operation or filtration operation, and then removing the solvent under reduced pressure. The crude product is obtained as white needle crystals by recrystallization from a suitable solvent, preferably an alcohol-based, ketone-based aliphatic hydrocarbon or aromatic hydrocarbon. The compound (I) thus obtained was analyzed by thin layer chromatography, melting point, IR, ¹³
It is identified by C, ¹ H-NMR and the like. Next, a more detailed description will be given in the following examples.

[Example 1] Synthesis of 1,3-diphenylpropanetrione 2-oxime from diphenyltriketone hydrate Org.Synth.coll.Vol.II Diphenyltriketone synthesized by the method shown on pages 244-245. Hydrate 150g
(0.6 mol) is placed in a 2l eggplant flask and ethanol 1.2l
After heating and dissolving, hydroxylamine hydrochloride 4
Add 1.7 g (0.6 mol) and heat to reflux for 1 hour. By removing the reaction solvent under reduced pressure, 1,3-diphenylpropanetrione 2-oxime is obtained.

Yield 150g, Rf (Si / hexane: ethyl acetate = 5: 1) = 0.10.
Met.

Example 2 Synthesis of 1,3-diphenylpropanetrione 2-oxime from 1,3-diphenylpropanetrione Org.Synth.coll.Vol.II Synthesized by the method shown on page 244-245 1, 45 g of 3-diphenylpropanetrione (0.
(19 mol) in 1 eggplant flask and 400 ml of ethanol
After heating and dissolving, hydroxylamine hydrochloride 1
Add 3.2 g (0.19 mol) and heat to reflux for 1 hour. By removing the reaction solvent under reduced pressure, 1,3-diphenylpropanetrione 2-oxime is obtained. Yield 45g, Rf (S
It was i / hexane: ethyl acetate = 5: 1) = 0.10.

Example 3 Synthesis of 1,3 diphenylpropanetrione 2-oxime from a mixture of diphenyltriketone hydrate and 1,3-diphenylpropanetrione Org.Synth.coll.Vol.II, pages 244-245. By the method described, a mixture of diphenyltriketone hydrate and 1,3-diphenylpropanetrione is obtained. 120 g of this mixture is placed in a 2 l eggplant flask, ethanol 1 is added, and the mixture is heated and stirred to dissolve. After completely dissolving, 33.5 g (0.5 mol) of hydroxylamine hydrochloride was added and the mixture was heated under reflux for 1 hour. By removing the reaction solvent under reduced pressure,
1,3-diphenylpropanetrione 2-oxime is obtained. Yield 122g, Rf (Si / hexane: ethyl acetate = 5: 1)
= 0.10.

Example 4 Synthesis of 1,3-diphenylpropanetrione 2- (O-ethoxycarbonyl) oxime 1,3-diphenylpropanetrione 2-oxime 150 g
(0.6 mol) 3l with dropping funnel, thermometer and drying tube
Transfer to a separa flask and add 1.8 liters of dried acetone to dissolve with stirring. With stirring under ice-cooling, 66 g (0.65 mol) of triethylamine was added, and 70 g (0.65 mol) of ethyl chlorocarbonate was slowly added dropwise over 30 minutes. Stir for 30 minutes at 20 ℃ or below. After removing triethylamine hydrochloride as a by-product by filtration, the synthetic solvent is removed under reduced pressure to obtain crude 1,3-diphenylpropanetrione 2- (O-ethoxycarbonyl) oxime. Further, this can be obtained as a pure white needle crystal by recrystallization from 300 ml of a mixed solvent of ethanol / hexane = 5/1.

Yield 48g mp 99~101 ℃ Rf (Si / hexane: ethyl acetate = 5: 1) Elemental analysis C ₁₈ H ₁₅ NO ₅ theoretical C = 66.46%, H = 4.65 %, N = 4.31% analysis C = 66.28% , H = 4.68%, N = 4.38% 1 H-NMR (DMSOd6) δ1.20 (3H, t, -OCH 2 -C H 3) δ4.25 (2H, q, -O- C H 2 -CH 3 ) Δ 7.60-8.20 (10H, m, arom) ¹³ C-NMR (DMSOd6) δ 188, 189 (S, S, δ152, 160 (S, S, C = N, δ129~138 (m, arom) δ66~69 ( t, -O- C H 2 -CH 3) δ13~17 (q, -O-CH 2 - C H 3) IR 1660cm -1 C = N 1680,1700cm ^-1 C = O This compound is designated as A-1.

[Example 5] Synthesis was performed in the same manner as in Example 1 and Example 4 except that bis (4-methylphenyl) triketone hydrate was used instead of diphenyltriketone hydrate.

Product 1,3-bis (4-methylphenyl) propanetrione 2- (O-ethoxycarbonyl) oxime Yield 45 g White needle crystals ¹ H-NMR δ1.20 (3H, t, -O-CH ₂ -CH ₃ ) δ2.30 (6H, s, ph- Me × 2) δ4.25 (2H, q, -OC H 2 -CH 3) δ7.20~8.00 (8H, m, arom) IR 1660cm -1 C = N 1680, 1700cm ^-1 C = O Elemental analysis C ₂₀ H ₁₉ NO ₅ theoretical value C = 67.98%, H = 5.42%, N = 3.96% Analytical value C = 68.16%, H = 5.40%, N = 3.91% This compound is designated as A-2.

[Example 6] Synthesis was performed in the same manner as in Example 2 and Example 4 except that 1,3-bis (4-methoxyphenyl) propanetrione was used instead of 1,3-diphenylpropanetrione. went.

Product 1,3-bis (4-methoxyphenyl) propanetrione 2- (O-ethoxycarbonyl) oxime Yield 40 g White needle crystals ¹ H-NMR δ1.20 (3H, t, -O-CH ₂ -C _{H 3) δ3.80 (6H, s} , ph-O Me × 2) δ4.25 (2H, q, -OC H 2 -CH 3) δ6.90~8.00 (8H, m, arom) IR 1665cm -1 C = N 1680, 1720cm ^-1 C = O Elemental analysis C ₂₀ H ₁₉ NO ₇ theoretical value C = 62.33%, H = 4.97%, N = 3.63% Analytical value C = 62.47%, H = 4.92%, N = 3.62% This compound is designated as A-3.

[Reference Example 1-6] To 100 parts by weight of the polymer synthesized according to Example 5 of Japanese Patent Application No. 59-193737, the additives shown in Table 1 were added and dissolved in 120 parts by weight of N-methylpyrrolidone. Spin coat (700 rpm x 7 sec) this solution on a silicon wafer,
A uniform coating film was obtained by drying in air at 70 ° C for 6 hours. The film thickness is
It was 70 μm.

Next, in a nitrogen atmosphere, grayscale (Kodac Photograph
ic Step Tablet.No.2) through the ultra high pressure mercury lamp (8mW / c
m ² ) and exposed for 5 minutes. After leaving this wafer at 23 ° C. for 30 minutes, it was developed with an equal amount mixture of r-butyrolactone and xylene using a spray type developing machine, rinsed with xylene and dried. The sensitivity was determined as the number of steps from the cured state of each gray scale step. (The higher the number of steps is, the higher the sensitivity is. When the number of steps is increased by 1, the exposure amount is
√ ▼ means low. ) The obtained results are shown in the same table.

[Comparative Examples 1 to 6] Other photopolymerization initiators were used instead of the oxime compound, and experiments were performed on the compositions of Table 2 in the same manner as in Reference Examples 1 to 6, and the results shown in the same table were obtained. Obtained.

Reference Example 7 The solutions prepared in Reference Examples 1 to 6 were stored in the dark at 22 ° C. for 30 days, and then evaluated in the same manner as in Reference Examples 1 to 6. There was no change in step sensitivity. Further, when the solutions prepared in Comparative Examples 5 and 6 were stored in the dark at 22 ° C. for 30 days and evaluated in the same manner as Comparative Examples 5 and 6, the step sensitivities were 2 and the sensitivity was lowered. It was observed.

Claims (2)

[Claims] 1. The following general formula (I): [Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms,
R ₃ represents an alkyl group having 1 to 6 carbon atoms], which is a novel oxime ester compound 2. A compound represented by the following general formula (II): Alternatively, a compound represented by the following general formula (III) Alternatively, a compound represented by the following general formula (IV) is obtained by reacting a mixture of the compound represented by the formula (II) and the compound represented by the formula (III) with hydroxylamine or a salt thereof. (Ii) Next, a compound represented by the following general formula (V) Formula (I) characterized by reacting with [Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₃ represents carbon] Represents an alkyl group of the numbers 1 to 6]