CN104098720B - Oxime ester photoinitiator containing heterocyclic thioether group as well as preparation method and application thereof - Google Patents
Oxime ester photoinitiator containing heterocyclic thioether group as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an oxime ester photoinitiator containing a heterocyclic thioether group as well as a preparation method and an application thereof. The oxime ester photoinitiator has a structure represented as a general formula (I). The heterocyclic thioether group is introduced in an oxime ester functional group for structural modification, so that the photoinitiator has the outstanding advantages of good solubility and stability and low probability of yellowing while maintaining high photosensitive activity.
Description
Technical field
The invention belongs to technical field of photoinitiator, particularly to a kind of oxime ester lightlike initiating agent containing heterocycle sulfide group
And its preparation method and application.
Background technology
The compound with oxime ester structure is extensively known in light trigger field.Such as, CN1241562A,
The patent documentations such as CN1514845A, CN101508744A disclose multiple oxime ester lightlike initiating agent, and this photoinitiator has excellent
Different photosensitive property, the curing field such as making that can be used in colored filter, light-emitting diode display.But this photoinitiator
The shortcomings such as existence storage stability the most more or less is the best, poor solubility, yellowing resistance are not enough.Design is closed
Become not only sensitivity high, and storage stability is good in actual use, dissolubility is good, the light of the excellent combination property of color inhibition draws
Send out agent and the development of photocuring technology is had important economy and social value.
Summary of the invention
For the deficiency of existing light trigger, it is an object of the invention to provide a kind of oxime esters containing heterocycle sulfide group
Light trigger, carries out structural modification by introducing heterocycle sulfide group in Wo Zhi functional group, and the light trigger of gained is keeping
While high photoreceptor activity, there is dissolubility and good stability and be difficult to the outstanding advantages of xanthochromia.
In order to reach above-mentioned technique effect, the technical solution used in the present invention is as follows:
A kind of oxime ester lightlike initiating agent containing heterocycle sulfide group, it has a structure as shown in logical formula (I):
(I)
Wherein,
Y is expressed as carbonyl (-CO-) or singly-bound；
R1、R1' independently represent heterocyclic group, optionally (optionally), in these heterocyclic groups one or
Multiple hydrogen atoms can be selected from halogen, nitro, hydroxyl, alkoxyl, C independently of one another1-C20Straight or branched alkyl, C3-C20
Cycloalkyl, C4-C20Cycloalkyl-alkyl, C4-C20Alkyl-cycloalkyl, benzyl, the group of phenyloxycarbonyl replaced；Or
R1、R1' one can be had to be expressed as phenyl ring；
R2Represent C1-C20Straight or branched alkyl, C4-C20Alkyl-cycloalkyl, C2-C10Alkenyl or phenyl, appoint
Selection of land, the one or more hydrogen atoms in these groups can be selected from halogen, nitro, carboxyl, aldehyde radical, alcoxyl independently of one another
Base, the group of phenyl are replaced；
R3For hydrogen, halogen, nitro, hydroxyl, alkoxyl, C1-C20Straight or branched alkyl, C3-C20Cycloalkyl, C4-
C20Cycloalkyl-alkyl, C4-C20Alkyl-cycloalkyl, C2-C10Alkenyl, phenyl, optionally, above-mentioned C1-C20Straight chain or
Branched alkyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C4-C20Alkyl-cycloalkyl, C2-C10Alkenyl, phenyl
In one or more hydrogen atoms can be selected from halogen independently of one another, nitro, hydroxyl, alkoxyl, the group of phenyl are replaced.
As preferred technical scheme, in structure shown in above-mentioned logical formula (I):
R1、R1' it is independently selected from the heterocyclic group containing O, N, S, optionally, or many in these heterocyclic groups
Individual hydrogen atom can be selected from halogen, nitro, hydroxyl, alkoxyl, C independently of one another1-C15Straight or branched alkyl, C3-C15's
Cycloalkyl, C4-C15Cycloalkyl-alkyl, C4-C15Alkyl-cycloalkyl, benzyl, the group of phenyloxycarbonyl replaced；
R2Selected from C1-C15Straight or branched alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl or phenyl, appoint
Selection of land, the one or more hydrogen atoms in these groups can be selected from halogen, nitro, carboxyl, aldehyde radical, alcoxyl independently of one another
Base, the group of phenyl are replaced；
R3For hydrogen, halogen, nitro, hydroxyl, alkoxyl, C1-C15Straight or branched alkyl, C3-C15Cycloalkyl, C4-
C15Cycloalkyl-alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl, phenyl, optionally, above-mentioned C1-C15Straight chain or
Branched alkyl, C3-C15Cycloalkyl, C4-C15Cycloalkyl-alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl, phenyl
In one or more hydrogen atoms can be selected from halogen independently of one another, nitro, hydroxyl, alkoxyl, the group of phenyl are replaced.
It is further preferred that in structure shown in above-mentioned logical formula (I):
R1、R1' be independently selected from following group: furyl, thienyl, 2H-pyranose, 4H-pyranose, pyridine radicals,
Pyrazinyl, pyrimidine radicals, pyridazinyl, triazine radical, 2,3-benzofuranyl, benzothienyl, diazosulfide base, indyl, different
Indyl, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, pteridine radicals, connection furyl, bithiophene base, connection pyrrole radicals, connection pyrrole
Oxazolyl, connection oxazolyl, connection isoxazolyl, connection thiazolyl, connection isothiazolyl, bisglyoxaline base, optionally, in above group
Or multiple hydrogen atom can be selected from halogen, nitro, hydroxyl, alkoxyl, C independently of one another1-C10Straight or branched alkyl, C3-
C10Cycloalkyl, C4-C10Cycloalkyl-alkyl, C4-C10Alkyl-cycloalkyl, benzyl, the group of phenyloxycarbonyl replaced；
R2Selected from C1-C10Straight or branched alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl or phenyl, appoint
Selection of land, the one or more hydrogen atoms in these groups can be selected from halogen, nitro, carboxyl, aldehyde radical, alcoxyl independently of one another
Base, the group of phenyl are replaced；
R3For hydrogen, halogen, nitro, hydroxyl, alkoxyl, C1-C10Straight or branched alkyl, C3-C10Cycloalkyl, C4-
C10Cycloalkyl-alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl, phenyl, optionally, above-mentioned C1-C10Straight chain or
Branched alkyl, C3-C10Cycloalkyl, C4-C10Cycloalkyl-alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl, phenyl
In one or more hydrogen atoms can be selected from halogen independently of one another, nitro, hydroxyl, alkoxyl, the group of phenyl are replaced.
It is particularly preferred that the oxime ester lightlike initiating agent containing heterocycle sulfide group shown in above-mentioned logical formula (I) is selected from following knot
Structure:
；；
；；
；；
；；
；；
；；
；；
；；
；；
；；
；
；；
；；
；；
；；
；。
The invention still further relates to contain shown in above-mentioned logical formula (I) the preparation method of the oxime ester lightlike initiating agent of heterocycle sulfide group,
This preparation method is with homemade heterocycle thioether R1SR1' it is initiation material, successively through Friedel-Crafts reaction, oximation reaction and esterification,
Obtain end product.
Reaction process (wherein X represents F, Cl, Br or I independently of one another) as follows:
As concrete a kind of embodiment, shown in above-mentioned logical formula (I), contain the oxime ester lightlike initiating agent of heterocycle sulfide group
Preparation method, comprise the following steps:
(1) synthesis of starting compound a
With RX(X as F, Cl, Br or I) and R ' SH as raw material, with highly basic such as KOH or NaOH as catalyst, at red copper oxid
Under effect, add quaternary ammonium salt or the phase transfer catalyst of quaternary phosphonium salt, be heated to reflux, synthesis material compound a.
(2) synthesis of midbody compound b
With R1SR1' it is raw material, and containing R2The acetyl halide compound of group, under aluminum chloride or zinc chloride effect, passes through
Friedel-Crafts reaction, synthetic intermediate compound b.
(3) synthesis of midbody compound c
By midbody compound b under the effect of hydrogen chloride, sodium alkoxide or potassium alcoholate with nitrites (such as: nitrous ether (ethyl nitrite), Asia
Isoamyl nitrate, the different monooctyl ester of nitrous acid etc.) or nitrite (such as sodium nitrite, potassium nitrite etc.) carry out oximation reaction, generate
Intermediate c
(4) synthesis of midbody compound d
Midbody compound b is carried out oximation reaction with oxammonium hydrochloride. or oxammonium sulfate., generates intermediate d.
(5) synthesis of end product compound I or II
By midbody compound c or d and containing R3The acetyl halide compound of group or anhydride carry out esterification, the double oxime of synthesis
Ester lightlike initiating agent product I or II.
Moreover, it relates to the oxime ester lightlike initiating agent containing heterocycle sulfide group is photosensitive shown in above-mentioned logical formula (I)
Application in property (photocuring) compositions, particularly at chromatic photoresist (RGB), black photoresistance (BM), spatial obstacle thing (Photo-
Spacer), the aspect such as dry film, semiconductor light photoresist and ink.This product not only has wide range of applications, and applies effective.
Accompanying drawing explanation
Fig. 1 is the space charge force the performance test results of different light trigger.
Fig. 2 is the anti-yellowing property test result of different light trigger.
Detailed description of the invention
Below with reference to specific embodiment, the invention will be further described, but should not be construed as protecting the present invention
The restriction of scope.
Preparation embodiment
Embodiment 1:
The preparation of compound 1
(compound 1)
Step (1): the preparation of two thiophene thioethers
48.9g2-bromothiophene, 39.7g2-thienyl mercaptan, 0.8KOH, 0.4gCu is put in the four-hole boiling flask of 500mL2O、
1.0g tetrabutyl ammonium bromide, 60mLDMF, mix and blend, 130 DEG C are heated to reflux 12h, react complete, dichloromethane extractive reaction
Liquid, separates organic layer, washes organic layer, and faint yellow product 41.6g, yield 70.0%, purity 98.9% are steamed to obtain in rotation.
Step (2): the preparation of intermediate 1-1
39.7g bis-thiophene thioether, 28.0g AlCl is put in the four-hole boiling flask of 500mL3(finely ground), 100mL dichloromethane
Alkane, stirring, ice bath cools down, and when temperature is down to 0 DEG C, starts to drip 34.1g o-methyl-benzene chloroacetic chloride and 50mL dichloromethane
Mixed liquor, temperature controls below 10 DEG C, and about 1.5h adds, and continues stirring 0.5h, and temperature rises to 15 DEG C, continues to stir 2h, stops
Reaction.Reactant liquor is poured in the dilute hydrochloric acid that 400g ice and 65mL concentrated hydrochloric acid are made into, separate lower floor's feed liquid, upper strata with separatory funnel
Extracting with 50mL dichloromethane, extract merges with lower floor feed liquid, uses 10g NaHCO3The NaHCO being made into 200mL water3Solution
Washing, then wash 3 times with 200mL water, it is neutrality to pH value, with the anhydrous MgSO of 30g4Being dried except water, rotation steams dichloromethane, steams
After complete, it is weak yellow liquid that thick product in bottle is steamed in rotation, pours in the petroleum ether that 200mL normal pressure is steamed, and stirring, sucking filtration obtain white
Pulverulent solids, dries 5h, obtains product 56.26g, yield 85%, purity 96.6% in 80 DEG C of baking ovens.
Product structure is confirmed by proton nmr spectra, and embodiments result is as follows:
1H-NMR(CDCl3, 500MHz): 2.3392 (3H, s), 4.1714 (2H, s), 6.6573-6.7543(1H, m),
6.9022-7.0232(6H, m), 7.2468-7.4029(2H, d).
Step (3): the preparation of intermediate 1-2
Intermediate 1-1 16.5g, oxolane 100ml, concentrated hydrochloric acid 13.2g, nitrous acid is put in 250ml four-hole boiling flask
Isopentyl ester 11.8g, stirring at normal temperature 5h, stopped reaction, then material is poured in 2000ml large beaker, add 1000ml water and stir
Mix, use the extraction of 200g dichloromethane, extract adds the anhydrous MgSO of 50g4It is dried, sucking filtration, filtrate decompression rotation is evaporated off
Go, revolving bottle obtains oily dope, dope is poured into stirring in 150ml petroleum ether and separates out, sucking filtration, obtain white powder
Solid, 60 DEG C are dried 5h, obtain product 14.4g, yield 80%, relative purity 95.1%.
Product structure is confirmed by proton nmr spectra, and embodiments result is as follows:
1H-NMR(CDCl3, 500MHz): 2.01129(1H, s), 2.3501 (3H, s), 6.7563-6.7714(1H, m),
7.0334-7.0532(8H, m).
Step (4): the preparation of target product compound
In 250ml four-hole boiling flask, put into intermediate 1-2 18.0g, 100g dichloromethane, 4.1g triethylamine, stir under room temperature
Mixing 5min, then dropping 11.2g butyl chloride, about 30min dropping is complete, continues stirring 2h, is subsequently adding 5%NaHCO3Aqueous solution
Adjusting pH value to neutral, separatory funnel is layered, and takes lower organic layer, then washes 2 times with 200ml, the anhydrous MgSO of 50g4It is dried, rotates
Steaming solvent, obtain viscous liquid, recrystallizing methanol obtains white solid powder, filters, obtains product 17.6g, purity 99%.
Product structure is confirmed by proton nmr spectra, and embodiments result is as follows:
1H-NMR(CDCl3, 500MHz): 0.9351-1.1213 (3H, t), 1.5351-1.5913 (2H, m), 2.2737-
2.3923(5H, m), 6.7981-7.5821 (9H, m).
Embodiment 2-8:
With reference to the method for embodiment 1, corresponding reagent prepare the compound 2-8 shown in embodiment 2-8.The knot of target product
Structure and1H-NMR data are listed in table 1:
Table 1
Embodiment 16:
The preparation of compound 16
(compound 16)
Step (1): the preparation of intermediate 16-1
The same 1-1 of preparation method of intermediate 16-1.
Step (2): the preparation of intermediate 16-2
In 250ml four-hole boiling flask put into 16.1g intermediate 16-1,5.3g oxammonium hydrochloride., 7.8g sodium acetate, 80g ethanol,
25g water, heated and stirred back flow reaction 5h.Reaction mass is poured in large beaker, add the stirring of 1000ml water, left undisturbed overnight, take out
Filter, obtains white powdery solids, pours in 150ml THF, adds the anhydrous MgSO4 of 20g and is dried, and filtrate is rotated and boils off by sucking filtration,
Revolving bottle obtains oily dope, dope is poured into stirring in 100ml absolute methanol and separates out, sucking filtration, obtain white powder
Solid, 70 DEG C are dried 5h, obtain product 13.5g, yield 80%, purity 98.5%.
Step (3): the preparation of target product compound 16
16.9g intermediate 16-2,100ml dichloromethane, 7.7g acetic anhydride is put into, under room temperature in the four-hole boiling flask of 250ml
Stirring 2h, then uses 5%NaHCO3Aqueous solution adjusts pH value to neutral, and separatory funnel is layered, then washes one time with 100ml, 30g without
Water MgSO4Being dried, rotate and steam solvent, obtain viscous liquid, recrystallization i.e. can get white solid product, filters, and is dried,
Product 17g, yield 90%, purity 99%.
Product structure is confirmed by proton nmr spectra, and embodiments result is as follows:
1H-NMR(CDCl3, 500MHz): 1.4532 ~ 1.9011(11H, m), 2.3201 (3H, s), 2.9875 (2H, d),
6.6782-7.0126 (2H, m), 7.1553-7.56553 (3H, d).
With reference to the method for embodiment 16, corresponding reagent prepare the compound 17-20 shown in embodiment 17-20.Target is produced
The structure of thing and1H-NMR data are listed in table 2:
Table 2
Performance test
1. space charge force performance test
Utilizing REAL TIME INFRARED THERMAL IMAGE means of testing, the space charge force that the present invention is led to light trigger shown in formula (I) is evaluated.
With compound 1, compound 4, compound 7, compound 8, compound 16 and compound 20 as representative, by itself and conventional free radical
Light trigger isopropyl thioxanthone (ITX) and 1-hydroxycyclohexyl phenyl ketone (184), the most under equal conditions cause methyl
The double bond conversion rate of 2-(Acryloyloxy)ethanol polymerization is contrasted.
Double bond conversion rate is the highest, double bond conversion rate is the fastest, shows that the initiating activity of initiator is the highest.
Concrete operation step is as follows:
(1) photosensitive composite (component is mass parts) of composition it is formulated as follows:
Hydroxyethyl methylacrylate 100
Light trigger 3
Butanone (solvent) 25
(2) REAL TIME INFRARED THERMAL IMAGE detection
The above-mentioned compositions containing different light triggers is applied on KBr salt sheet respectively, is then placed in Nicolet5700 using
Ultraviolet light point source irradiates sample, and the ultraviolet light intensity of regulation sample surfaces is 35mW/cm2, the double bond conversion rate of monomer is with the reddest
Outer Real-time Collection, sets acquisition time as 300s, utilizes the change of the characteristic absorption peak of hydroxyethyl methylacrylate carbon-carbon double bond
Observe the intensity of variation of polyreaction.Double bond conversion rate (DC) is processed by OMNIC7.1 infrared software and Origin7.5 data
Software combines following formula and is calculated:
DC(%)=[1-(At/Ao)]*100%
In formula Ao and At be respectively sample before curing with illumination after t at 1630cm-1Place's hydroxyethyl methylacrylate
The area of double bond characteristic absorption peak.
Test result is as shown in Figure 1.It can be seen that compound 1, compound 4, compound 7, compound 8, chemical combination
Thing 16 and compound 20 all can cause hydroxyethyl methylacrylate to be polymerized, and final double bond conversion rate is close to 100%.Either cause
The final degree of polymerization or rate of polymerization, the light trigger of the present invention is obviously higher than traditional photoinitiator ITX and 184, table
Reveal the Photoinitiation Property of excellence.
Dissolubility in organic solvent and storage stability test
Under the conditions of 25 DEG C, test photoinitiator compound 1, compound 4, compound 7, compound 8, compound 16, change
Oxime ester photoinitiator 1-(6-o-methyl-benzene formoxyl-9-ethyl carbazole-3-base disclosed in compound 20 and CN101508744A)-
3-cyclopenta-propane-1-ketone-acetic acid oxime ester (PBG304) is in conventional organic solvent Ketohexamethylene, ethylene glycol monoethyl ether, propylene glycol first
Dissolubility in ether, propylene glycol methyl ether acetate, test result such as table 1；And the sample after dissolving stands 1 month, then make
It is right that content after placing in a solvent 1 month with high performance liquid chromatography detection sample solvent and the content dissolving front sample are carried out
Ratio, is tested light trigger storage stability by changes of contents, and it the results are shown in Table 2.
The dissolubility test in different solvents of table 1 light trigger
Changes of contents before and after table 2 light trigger standing in different solvents
As can be seen from the above table, obtained photoinitiator compound 1, compound 4, compound 7, compound 8, compound
16 and compound 20 in conventional organic solvent Ketohexamethylene, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate all
Having certain dissolubility, dissolubility is both with respect to existing PBG304(1-(6-o-methyl-benzene formoxyl-9-ethyl carbazole-3-
Base)-(3-cyclopenta acetone)-1-oxime-acetas) effective, and the stability that this photoinitiator is in organic solvent compares
Good, all can keep more than 1 month not decomposing in common solvent under the conditions of Liquid Detection display lucifuge.
Anti-yellowing property is tested
The light trigger (after butanone dissolves) of 2% mass is dissolved in hydroxyethyl methylacrylate, uses 20 μm bars to be coated with
Prepared solution is evenly coated on microscope slide by cloth device, is 150mW/cm in uv power density2Ultraviolet light under radiation solid
Change, often irradiate 5min and measure the yellow value degree of photocuring film, total irradiation time 120min.
With the light trigger of the present invention with compound 1, compound 4, compound 7, compound 8, compound 16 and compound
20 is representative, it is contrasted with PBG304.
The yellow value degree (YI) of coating thickness is measured by FDAC UV3600 ultraviolet-uisible spectrophotometer, test wavelength model
Enclose for 380-780nm, be analyzed with UV-Soultion software.
Test result is as shown in Figure 2.It can be seen that compound 1, compound 4, compound 7, compound 8, compound 16 and
The xanthochromia tendentiousness of compound 20 is much smaller for PBG304, after 10min, this gap the most clearly, and
And along with the prolongation of irradiation time, gap is increasing.The light trigger of the present invention shows low-yellowing and low-yellowing tendency
The advantage of property.
In sum, the oxime ester lightlike initiating agent not only light of heterocycle sulfide group is contained shown in logical formula I disclosed by the invention
Initiating activity is high, and dissolubility and good stability, color inhibition.
Claims (7)
1., containing the oxime ester lightlike initiating agent of heterocycle sulfide group, it has a structure as shown in logical formula (I):
Wherein,
Y is expressed as carbonyl (-CO-) or singly-bound；
R1、R1' it is independently selected from the heterocyclic group containing O, N, S, optionally, the one or more hydrogen in these heterocyclic groups
Atom can be selected from halogen, nitro, hydroxyl, alkoxyl, C independently of one another1-C15Straight or branched alkyl, C3-C15Cycloalkanes
Base, C4-C15Cycloalkyl-alkyl, C4-C15Alkyl-cycloalkyl, benzyl, the group of phenyloxycarbonyl replaced；
R2Selected from C1-C15Straight or branched alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl or phenyl, optionally,
One or more hydrogen atoms in these groups can be selected from halogen, nitro, carboxyl, aldehyde radical, alkoxyl, phenyl independently of one another
Group replaced；
R3For hydrogen, halogen, nitro, hydroxyl, alkoxyl, C1-C15Straight or branched alkyl, C3-C15Cycloalkyl, C4-C15Ring
Alkyl-alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl, phenyl, optionally, above-mentioned C1-C15Straight or branched alkane
Base, C3-C15Cycloalkyl, C4-C15Cycloalkyl-alkyl, C4-C15Alkyl-cycloalkyl, C2-C8Alkenyl, in phenyl one
Individual or multiple hydrogen atoms can be selected from halogen independently of one another, nitro, hydroxyl, alkoxyl, the group of phenyl are replaced.
2. the oxime ester lightlike initiating agent described in claim 1, it is characterised in that:
R1、R1' it is independently selected from following group: furyl, thienyl, 2H-pyranose, 4H-pyranose, pyridine radicals, pyrazine
Base, pyrimidine radicals, pyridazinyl, triazine radical, 2,3-benzofuranyl, benzothienyl, diazosulfide base, indyl, iso-indoles
Base, quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, pteridine radicals, connection furyl, bithiophene base, connection pyrrole radicals, connection pyrazoles
Base, connection oxazolyl, connection isoxazolyl, connection thiazolyl, connection isothiazolyl, bisglyoxaline base, optionally, in above group one or
Multiple hydrogen atoms can be selected from halogen, nitro, hydroxyl, alkoxyl, C independently of one another1-C10Straight or branched alkyl, C3-C10
Cycloalkyl, C4-C10Cycloalkyl-alkyl, C4-C10Alkyl-cycloalkyl, benzyl, the group of phenyloxycarbonyl replaced；
R2Selected from C1-C10Straight or branched alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl or phenyl, optionally,
One or more hydrogen atoms in these groups can be selected from halogen, nitro, carboxyl, aldehyde radical, alkoxyl, phenyl independently of one another
Group replaced；
R3For hydrogen, halogen, nitro, hydroxyl, alkoxyl, C1-C10Straight or branched alkyl, C3-C10Cycloalkyl, C4-C10Ring
Alkyl-alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl, phenyl, optionally, above-mentioned C1-C10Straight or branched alkane
Base, C3-C10Cycloalkyl, C4-C10Cycloalkyl-alkyl, C4-C10Alkyl-cycloalkyl, C2-C5Alkenyl, in phenyl one
Individual or multiple hydrogen atoms can be selected from halogen independently of one another, nitro, hydroxyl, alkoxyl, the group of phenyl are replaced.
3. the oxime ester lightlike initiating agent described in claim 1, it is characterised in that selected from having structure:
4. the preparation method of oxime ester lightlike initiating agent described in claim 1, it is characterised in that: with homemade heterocycle thioether R1SR1’
For initiation material, successively through Friedel-Crafts reaction, oximation reaction and esterification, obtain end product；
Reaction process is as follows:
Wherein, X represents F, Cl, Br or I independently of one another；
And heterocycle thioether R1SR1' i.e. the synthetic method of starting compound a is as follows:
With R1X and R1' SH is raw material, with KOH or NaOH as catalyst, under Red copper oxide effect, adds quaternary ammonium salt or quaternary alkylphosphonium salt
The phase transfer catalyst of class, is heated to reflux, synthesis material compound a.
5. the preparation method described in claim 4, it is characterised in that comprise the following steps:
(1) synthesis of starting compound a
With R1X and R1' SH is raw material, with KOH or NaOH as catalyst, under Red copper oxide effect, adds quaternary ammonium salt or quaternary alkylphosphonium salt
The phase transfer catalyst of class, is heated to reflux, synthesis material compound a；
(2) synthesis of midbody compound b
With R1SR1' it is raw material, and containing R2The acetyl halide compound of group, under aluminum chloride or zinc chloride effect, passes through Fu Ke
Reaction, synthetic intermediate compound b；
(3) synthesis of midbody compound c
Midbody compound b is carried out oximate with nitrites or nitrite under the effect of hydrogen chloride, sodium alkoxide or potassium alcoholate anti-
Should, generate intermediate c；
(4) synthesis of midbody compound d
Midbody compound b is carried out oximation reaction with oxammonium hydrochloride. or oxammonium sulfate., generates intermediate d；
(5) synthesis of end product compound I or II
By midbody compound c or d and containing R3The acetyl halide compound of group or anhydride carry out esterification, synthesize oxime esters light
Initiator product I or II.
6. the application in Photocurable composition of the oxime ester lightlike initiating agent according to any one of claim 1-3.
7. the oxime ester lightlike initiating agent according to any one of claim 1-3 chromatic photoresist, black photoresistance, spatial obstacle thing,
Application in dry film, semiconductor light photoresist and ink preparation.
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| CN106565864B (en) * | 2015-10-08 | 2018-10-02 | 常州强力电子新材料股份有限公司 | One kind oxime ester lightlike initiating agent containing fluorenes and its synthesis and application |
| CN110156728A (en) * | 2019-04-30 | 2019-08-23 | 同济大学 | 2- thiophenyl furans or thienyl ketoxime ester compound and its preparation method and application |
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