JPS62286961A - Novel oxime ester compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R1 is H, 1-6C alkyl, 1-6C alkoxy or nitro; R2 is 1-6C alkyl or 6-10C aromatic hydrocarbon group; R3 is R2, 1-6C alkoxy or 6-10C aryloxy). EXAMPLE:1-Ethoxy-3-phenylpropanetrione 2-(O-ethoxycarbonyl)oxime. USE:A photo-polymerization initiator. It has high storage stability in dark place ad exhibits high rate of photo-setting even if the resistor ink has strong absorption in near-ultraviolet range. PREPARATION:The objective compound of formula I can be produced by reacting the compound of formula II with a nitrosation agent such as NaNO2 preferably at -10-+30 deg.C for 6-20hr and reacting the resultant compound of formula III with an acid halide of formula IV (X is halogen) preferably at -10-+30 deg.C for 30min-2hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator and a method for producing the same.

[Background of the invention]

Photochemical polymerization is becoming increasingly important in industry, especially for coatings that need to be cured within a short period of time, such as photoresist curing, printing, and ink drying. The curing method using light irradiation in the presence of a photopolymerization initiator has the great advantage of increasing the curing speed.

Since the curing speed largely depends on the photopolymerization initiator,
Attempts have been made to replace conventional photopolymerization initiators with superior compounds. Conventionally known effective photopolymerization initiators include, for example, the West German patent (DT-PS).
Benzoin-ethers such as those described in British Patent No. 1/37/2/(:
Examples include oxime ester compounds as described above.

These known photoinitiators have several disadvantages in use, the most significant being the storage in the dark of the photopolymerizable system mixed with such photoinitiators in some cases. It does not have both stability and high photocuring speed. (2) In order to increase the photocuring rate of these known photopolymerization initiators (2) Many attempts have been made to use them in combination with sensitizers, or the expected sensitizing effect cannot be obtained. In particular, when the dyest or ink has strong absorption in the near ultraviolet region (<300=<00 nm), for example, it may contain aromatic polyimide or polyamide, or contain organic or inorganic pigments, fine particles, or When filled with filler (2), the photocuring speed decreased significantly.

Therefore, the advent of photoinitiators that have good storage stability in the dark, initiate photopolymerization faster than known photoinitiators, and give higher yields of polymer per unit time. It was valued industrially.

Industrial productivity can be improved by using these improved photoinitiators.

[Problem that the invention seeks to solve]

In view of these circumstances, the present inventors developed a photopolymerization initiator that has good storage stability in the dark and has a high photocuring rate even in the near-ultraviolet region (2) where dyests and inks have strong absorption. We have conducted extensive research to provide the following.

[Means to solve the problem]

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

That is, the present invention provides general formula (1) [wherein R1 is a hydrogen atom, an alkyl group having 7 to 7 carbon atoms, an alkyl group having 7 to 7 carbon atoms, or a nitro group,
R2 is an alkyl group having 1 to 2 carbon atoms, or an aromatic hydrocarbon group having 1 to θ carbon atoms, R3 is an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 1 carbon atoms, and 1 to 10 carbon atoms. represents an aromatic hydrocarbon or an aryloxy group having 6 to 10 carbon atoms.

Preferred examples of R1 include a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an etkyne group, a nitro group, etc.
Preferred examples of 2 include methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so
-butyl group, tert-butyl group, phenyl group, tolyl group, etc., and preferred examples of R3 include ethyl group, n-proyl group, is.

-propyl group, n-butyl group, 1so-butyl group, te
rt-butyl group, methoxy group, ethquine group, n-propoquine group, 1so-propoxy group, n-butquine group, 1
Examples include so-butquine group, tert-butoxy group, phenyl group, tolyl group, phenoxy group, and triloxy group.

Examples of the oxime ester compound represented by the general formula (1) include, but are not limited to, the following.

The present invention also provides a method for producing the oxime ester compound (1). That is, (1) the following general formula (
11 ) Next (:, a compound represented by the following general formula (IT) (referred to as a chemical compound (ff)) R3-C-X ... (ff), which is characterized by being reacted with the compound represented by the formula (1) The invention relates to a method for producing the compound.

[In the formula, X is a halogen atom, R1 is a hydrogen atom, and the number of carbon atoms is l
an alkyl group having from 1 to 2 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a -tro group; R2 is an alkyl group having 1 to 1 carbon atoms;
is an alkyl group having 7 to 7 carbon atoms, an alkyl group having 7 to 7 carbon atoms, an aromatic hydrocarbon having 1 to 10 carbon atoms,
or an aryloxy tail having a carbon number of O to IO] The production method will be described in detail below.

Compound (1) can be obtained by reacting compound (Il) with a nitroning agent. As a nitroning agent, the following formula R4-No, M-NO, (in the formula, R4 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and M represents an alkali metal or an alkaline earth metal) is used. The nitrites shown in [shown] are listed, and preferred are nitrous acid, sodium nitrite, potassium nitrite, methyl nitrite, ethyl nitrite, and butyl nitrite.The reaction temperature and time are not limited, but Each is preferably 1/θ to 30°C and 6 to -0 hours.

Since the product precipitates from the reaction system, it can be obtained by filtering it, but it may also be purified by silica gel chromatography or subjected to treatments such as recrystallization. The compound thus obtained can be identified by thin layer chromatography or liquid chromatography.The compound can be identified in a synthesis solvent in the presence of a base.
By reacting with an acid halide (ff), it leads to an oxime ester compound (+).Synthesis solvents include halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride; acetone, methyl ethyl ketone, and methyl isobutyl. Ketone hydrocarbons such as ketones and methylisoamyl ketone; Aromatic hydrocarbons such as benzene, toluene, and quinolene; Ether hydrocarbons such as diethyl ether, tetrahydrofuran, dioxane, and diisopropyl ether; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone Sulfoxides and sulfones such as dimethylformoquinde and dimethylsulfone are listed.In addition, basic substances such as pyridine and triethylamine can also be used as synthesis solvents.As dehydrohalogenation agents, A conventionally used hydrogen halide scavenging base can be used.For example, a tertiary amine represented by (Rs)zRsN [wherein R, and R6 each represent an alkyl group having 1 to 2 carbon atoms. ], or the following formula [wherein R7, R,, R, each represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a cycloalkyl group, and RIG represents an alkyl group having 1 to 2 carbon atoms, or a cycloalkyl group; Indicates the group.

] Aromatic amines, pyridine, imidazole,
Examples include triazole, quinoline, pyrimidine, morpholine and derivatives thereof.

As acid halides, general (= following formula R3-C-XI [wherein R3 is an alkyl group of carbon number / to
It represents an alkoxy group having 6 to 6 carbon atoms, an aromatic hydrocarbon having 6 to 6 carbon atoms, or an aryloxy group having 6 to 6 carbon atoms, and X represents chlorine, bromine or iodine. ]. Examples of this include methyl chlorocarbonate,
Examples include, but are not limited to, ethyl chlorocarbonate, ethyl bromocarbonate, propionyl chloride, propionyl bromide, benzoyl chloride, benzoyl bromide, toluic acid chloride, and toluic acid bromide. Reaction temperature and time (although there are no restrictions on the second one, each is preferably -10 to 30°C, 30 minutes to
It is 2 hours. In the production of oxime ester compound (1), the compound (preferably) is dissolved in a ketone hydrocarbon such as acetone or a halogenated hydrocarbon such as chloroform as a solvent, and a third compound such as triethylamine is dissolved. The process involves treatment with ethyl chlorocarbonate or benzoyl chloride in the presence of a grade amine at θ to 0°C for 3 minutes to 1 hour. Compound (1) obtained in this manner can be obtained by removing the by-product salt of hydrogen halide and a base through a liquid separation operation or a filtration operation (second step), and then removing the solvent under reduced pressure. This crude product can be obtained as white needle-like crystals by recrystallization from a suitable solvent, preferably an alcohol-based, ketone-based aliphatic hydrocarbon, or aromatic hydrocarbon.

Compound (1) thus obtained is identified by thin layer chromatography, melting point, IR1/H-NMR, etc. Next(
: A more detailed explanation will be given in the following examples.

[Reference example/]

/-Production of nitoxy-3-phenylpropanetrionecooxime Benzoylacetic acid ethyl ester j00'? (2,/3 moles)! Add t to glacial acetic acid in a separate flask (take two parts, add !t to glacial acetic acid, add sodium nitrite, 2/O
An aqueous solution J″00td in which f (3,0 mol) was dissolved was 7
Drop slowly over time. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred and reacted for 7 nights.

After filtering the product, it is washed with water (7-ditoxy-3-phenylpropane trionecooxime is obtained. Yield: θOf, Rf (8i/hequinane:ethyl acetate=
,? : / )=0. /7.

〔Example/〕

/-Etquin-3-phenylpropanetrioneco(0
-Production of ethoxycarbonyl) oxime/-Ethoxy 3-phenylpropanetrione 2-oxime 200? (
/, 0 mol) in S with a dropping funnel, thermometer, and drying tube.
3 tons of acetone taken in a Separa flask and dried
Add and stir to dissolve. Add triethylamine/10f (1 mol) to this (= triethylamine/10f (1 mol) under water cooling and stirring, and then dropwise add (; ethyl chlorocarbonate/20? (/, 1 mol) over 9θ minutes. Stir and react at 20°C or below for 30 minutes. .

Filtration of by-product triethylamine hydrochloride (removed from the second stage)
After that, the solvent is removed under reduced pressure (2- to 2-ethoxycarbonyl-3-phenylpropanetrione 2-
(0-ethoxycarbonyl)oxime can be obtained. It can be further obtained as pure white needle crystals by recrystallization from ethanol≦00−.

Yield=2/Of Melting point=≦θ~63℃ Rf (8i/hexane:ethyl acetate=j:/)=
θ, 2-element analysis C14HISNO6 Theoretical value C=j7jl1%%H=j, 76%, N=&,
7♂chi analysis value C=57.29, H=5. Leave 1.
N=g, 70chi IR/4♂θα′″, C=N /H−NMRδ/,, 2~/j (4H, rn, −
0-CH, -C13X 2 ) (DM80d・)a'1
．． / ~4t,t(4tH17,-〇-CH,-〇)(
, X 2 ) δ7j~? , 0 (jH%m%arom) This compound is designated as A-/.

[Example]

Production was carried out in the same manner as in Example 2, except that benzoyl chloride was used instead of chlorocarbonate ethyl ester.

Product/-ethoxy 3-phenylpropanetrione,
2-(0-benzoyl)oxime yield = 230'l, white needle crystal melting point = evening ♂ ~ 60°C old (Si/hexane:ethyl acetate = j:/) = 0.3
Seven element analysis Cl5H1? NO8 Theoretical value C = 66.4, H = g, Otsu J'', N nige, 3X analysis value C = 46.3♂chi, H = ri, 7guchi, N = g,, 29chi IR/, g!01-1:;
C= N (K" / 720 cyr-' -〇-0-/
♂00α-1ゝC==0 /H-NMRδ/, 3(3H, t, -0-CH2-
OH,) (DM80da) 6g, g(,zH,q
, -0-CH2-CH3) δ7.3~/, /(/θH,
m%arom) This compound is designated as A-2.

[Example 3] Produced in the same manner as Reference Example and Example, except that P-toluylacetic acid ethyl ester was used instead of benzoylacetic acid ethyl ester.

Product /-ethoxy! -(4t-methylphenyl)propanetrioneco-(0-ethoxycarbonyl)oxime Yield = 24tOf White needle crystal elemental analysis Cl5H1? NO8 Theoretical value C= j? , ≦3, H=j, J'r, N, ! 3rd coefficient analysis value C=J-♂, ≦θ, H=! ,≦3
C=N (KBr) /720α-L-C-0- /♂00 cm-' -0-C-0-/H-NMR
δ/,,2~/,j (≦H1m, -0-OH,-C
H, X, 2) (DM80d・) 64. g(jH13
, -1, -8Hs) δ4t, / ~41. t (4tH
, m, -OCH2CH3X 2') δ7. j 〜♂
, 0 (4tH, m, arom) This compound A-
Set it to 3.

[Example G]

Except for using P-methoxypenzoylacetic acid ethyl ester instead of benzoylacetic acid ethyl ester,
Production was carried out in the same manner as Reference Example/and Example/.

Product /-ethoxy3-(4t-methoxyphenyl)
Furopantrione 2-(0-z-4-dicarbonyl)oxime yield = 230? Elemental analysis of white needle crystal Cl581? NO? Theoretical value C = j j, 7 j %, H = jJO'4,
N=4tJ3% analysis value C=J''!, 6 riwa, H=6.
3j Sorry, N=gu, 3/壬IR/a I Ocm-'
C=N/♂00-1-0-C-0- /H-NMRδ/, 2~/, 4t (Is Hlm,
OCH2C) (3X-2) (DMSOds) J
3. , (3H,S,-ph-QC)]3) δ9. θ
~41J (4tH, m, 0CH2CH3x 2
) δ7.4t~! ,,2(4tH,m,arom)This compound is designated as A-g.

[Example evening]

Produced in the same manner as Reference Example/and Example/, except that methyl benzoylacetate was used instead of ethyl benzoylacetate.

Product /-Methoquin 3-phenylpropane trio 72
-(0-ethoxycarbonyl)oxime yield = 2/jf White needle crystal elemental analysis Cl5H13NO11 Theoretical value C=SS, Octopus LH=arc≦9%, N=5.0.
2 coefficient analysis value C=tt, ri0 coefficient, H=g, 73%, N=
J-, o/II R/ 410 cm-'';C=
N (KBr), 7 Yu. −・ −6−0−／♂00
Bei-'-o-c-o- /H-NMRδ/, 3 (J' H%t, -0-CH
2-CH3) (DMSOd6) Illusion, 2 (Yo□, 3,
-8-6H3) δ arc j (2H,Q, -0-CH2
-C) (3) δ7j ~/, θ(jH, m, arom)
This compound is designated as A-J-.

[Reference Example 2~//] Example of JP-A-72022! To 700 parts by weight of the polymer synthesized according to Table 7, the oxime compounds and sensitizers shown in Table 7 were added, and 720 parts by weight of N-methylpyrrolidone (dissolved).

On this m liquid ft silicone quaver: Nisbin coat (7
00 rpm x 7 sec) L and 70°C in air for 6 hours to obtain a uniform coating film. The film thickness was 70 μm.

Next, under a nitrogen atmosphere, gray scale (KodacPho)
tographic 5tep Tablet, A!
) through an ultra-high pressure mercury lamp (♂mW//111).
Exposure was made for a minute. After the wafer was left at 23° C. for 30 minutes, it was developed with an equal mixture of r-butyrolactone and xylene using a spray developing device, rinsed with xylene, and dried. Sensitivity was calculated as the number of stages from the curing state of each step of the gray scale. (The higher the number of steps, the higher the sensitivity. When the number of steps increases by 7 steps, it means that the exposure amount is lower by the amount of gray.) The obtained results are shown in Table 2.

(The following is a blank space) [Comparative Example/~6] An experiment was conducted on the composition shown in Table 2 in the same manner as Reference Examples 2~// using another photopolymerization initiator instead of the oxime compound of the present invention. The results shown in the same table were obtained.

Table 2 A-6; Benzophenone A-7: Benzyl^-♂: Benzoin methyl ether A-9 = Benzyl dimethyl ketal A-10: /-phenyl-/, 2-propanedione-co-(〇-ethoxycarbonyl)oxime A-//:/,,2-diphenyl-/,-monoethanedione-λ-(O-benzoyl)oxime

Claims (1)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [R_1 in the formula is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. group, or a nitro group, R_2 is an alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, R_3 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Aromatic hydrocarbon having 6 to 10 carbon atoms, or 6 carbon atoms
to 10 aryloxy groups] Novel oxime ester compound (2) (i
) Compound represented by the following general formula (II) ▲ Numerical formula, chemical formula,
There are tables, etc. ▼... (II) is reacted with a nitrosating agent to form a compound represented by the following general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (III) After making (ii ) Next, the compound represented by the following general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (IV) Formula (I) characterized by reacting with ▲ Numerical formulas, chemical formulas, tables, etc. ▼...(I) Process for producing a compound represented by (I) [In the above formula, group, R_2 is an alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, R_3 is an alkyl group having 1 to 6 carbon atoms, and 1 carbon number
represents an alkoxy group having 6 to 6 carbon atoms, an aromatic hydrocarbon having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms]