CN111324012A - Modified photoinitiator and preparation method and application thereof - Google Patents

Modified photoinitiator and preparation method and application thereof Download PDF

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CN111324012A
CN111324012A CN201811541558.5A CN201811541558A CN111324012A CN 111324012 A CN111324012 A CN 111324012A CN 201811541558 A CN201811541558 A CN 201811541558A CN 111324012 A CN111324012 A CN 111324012A
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photoinitiator
modified photoinitiator
hydrogen
modified
integer
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CN111324012B (en
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王石进
孙涛
刘永祥
桑伟
任雪艳
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Guan Eternal Material Technology Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/087—Compounds of unknown structure containing a Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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Abstract

The invention provides a modified photoinitiator and a preparation method and application thereof, wherein the modified photoinitiator is formed by connecting a benzophenone main group and a hydrogen-containing silicone oil substituent group, and the preparation method of the modified photoinitiator comprises the following steps: (1) performing halogenation reaction on hydrogen-containing silicone oil to obtain an intermediate product; (2) and carrying out substitution reaction on the intermediate product and the benzophenone compound to obtain the modified photoinitiator. The modified photoinitiator is used for photoresist. The modified photoinitiator provided by the invention has the characteristic of surface enrichment, can have higher concentration on the surface of liquid, can effectively solve the problem that an inverted trapezoidal triangular area formed by a photosensitive resin composition in a developing process is not high in curing degree and is broken by a developing solution, and finally obtains a slope angle with a smooth surface and a proper angle.

Description

Modified photoinitiator and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoresist, in particular to the technical field of color photoresist, and particularly relates to a modified photoinitiator and a preparation method and application thereof.
Background
The color filter is an important component of the liquid crystal display panel, and the liquid crystal display can realize visual colorization through the color filter. The preparation of the color filter mainly utilizes the light-initiated curing mechanism of a photoinitiator, and the photoinitiator is used as a key component of a light-cured material and plays a decisive role in the light-cured degree and speed of the material.
In the preparation process of the color filter, the photoinitiator is subjected to a curing reaction under the action of deep ultraviolet DUV or extreme ultraviolet EUV, but because ultraviolet light is irradiated from the upper part, the surface curing degree is higher than that of the lower part. Especially, at the edge part of the mask pattern, an inverted trapezoidal structure appears under the flushing of the developing process, and the inverted trapezoidal structure is softened and melted at high temperature in the post-baking process and is attached to the glass substrate to form a regular trapezoid, namely a slope angle with a certain angle. The formed slope angle has important influence on subsequent processes of the color filter, such as an ITO sputtering process and the like, and the adverse effect can be generated when the angle is too large or too small.
In the prior art, photoinitiators are uniformly distributed on the surface and inside of a color photoresist, in an exposure process, although the edge part of a pattern has a high upper polymerization degree and a low lower polymerization degree, an inverted trapezoidal structure is formed in a development process, the problems of insufficient polymerization degree and low curing degree still exist in the upper corner part of the inverted trapezoidal structure, and the pattern is broken in the development process to form an incomplete inverted trapezoidal structure. The incomplete inverted trapezoidal structure can form a slope angle with a larger angle after a postbaking process, and the slope angle exceeds the specification of the color filter.
CN106565864B discloses a fluorenyloxime ester-containing photoinitiator, which is simple in synthesis, low in cost and good in solubility, can be applied to aspects of color photoresists, black matrixes, photo spacers, rib grids, dry films, semiconductor photoresists, printing ink and the like, and has excellent storage stability and film-forming performance.
CN103703030A discloses a photoinitiator comprising an aromatic ring-containing photoinitiator group, CH, which initiates a free radical polymerization reaction upon exposure to actinic radiation2、CO、C(O)CH2O、C(O)CH2S、C(O)CH2CH2S, acrylate or polyol acrylate, and the like, and the invention also provides a photocuring composition containing the photoinitiator, which has the characteristic of extremely low mobility, but the photocuring composition forms an inverted trapezoidal triangular region after exposure, has low curing degree, is easy to break by developer and forms a large-angle slope angle.
CN107272336A discloses a photosensitive resin composition, which comprises an ultraviolet photosensitive prepolymer resin, a reactive diluent monomer, a photoinitiator, and optionally a colorant and an alkali-soluble resin, wherein the photoinitiator is at least one selected from oxime ester compounds and derivative compounds taking oxime ester compounds as main structures. The composition has high sensitivity and good developability, high resolution and excellent adhesion with a substrate, is very suitable for preparing a black matrix with high light shielding performance, a high-precision and high-quality color filter and a liquid crystal display device, and can also be applied to light spacers and ribs, photoresist, wet films, dry films and the like.
Therefore, there is a need in the art to develop a photoinitiator with suitable surface enrichment characteristics, so that a photosensitive composition containing the photoinitiator forms an inverted trapezoid with a large curing degree after exposure, and is not easily broken by a developer, thereby forming a slope angle with a suitable angle.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a modified photoinitiator having the structure of formula (I);
Figure BDA0001908224850000031
in the formula (I), R1、R2、R3And R4Each independently selected from any one of C1-C12 alkyl, C1-C6 hydroxyalkyl, C1-C6 halogenated alkyl, C1-C6 hydroxylamino or hydroxyl;
in the formula (I), X is a residual group of hydrogen-containing silicone oil after losing one hydrogen.
The hydrogen-containing silicone oil has the characteristic of surface enrichment, namely the characteristic of surface enrichment in a system, the residual group of the hydrogen-containing silicone oil after losing one hydrogen is introduced to the meta position of carbonyl in a benzophenone compound, and the characteristic of surface enrichment of the modified photoinitiator is endowed, so that the modified photoinitiator can have higher concentration on the surface of liquid, the problem that an inverted trapezoidal triangular area formed in a developing process of a photosensitive resin composition is not high in curing degree and is broken by a developing solution can be effectively solved, and finally, a slope angle with a smooth surface and a proper angle (for example, 30-60 degrees) is obtained.
Preferably, X is selected from any one of the following structures:
Figure BDA0001908224850000032
n is an integer of 0-20;
n is10 is an integer of 0 to 20, etc., and n is2Is an integer of 0 to 20, n1+n2Is an integer of 0 to 20.
The structure of X is a high molecular structure, n is the number (polymerization degree) of a repeating unit, and molecules with different polymerization degrees can be obtained in the process of high molecular synthesis, so that the value of n is a range of values, namely an integer of 0-20, and n is an integer of1、n2、n1+n2The same is true.
X is selected from the methyl silicone oil substituent, and the hydrogen-containing methyl silicone oil has stronger surface enrichment performance, so that the surface enrichment performance of the modified photoinitiator can be further improved.
Preferably, n1Is 0.
Preferably, the structure of X is
Figure BDA0001908224850000041
And n is an integer of 0-20.
The terminal group hydrogen-containing methyl silicone oil is selected because the structure of the modified photoinitiator is more stable when hydrogen is at a terminal position, and the formed structure is easily influenced by a large group at the middle position and is unstable.
The second object of the present invention is to provide a method for preparing the modified photoinitiator according to the first object, comprising the steps of:
(1) performing halogenation reaction on hydrogen-containing silicone oil to obtain an intermediate product;
(2) carrying out substitution reaction on the intermediate product and a benzophenone compound shown in a formula (II) to obtain the modified photoinitiator;
Figure BDA0001908224850000042
in the formula (II), R1、R2、R3And R4Each independently selected from any one of C1-C12 alkyl, C1-C6 hydroxyalkyl, C1-C6 halogenated alkyl, C1-C6 hydroxylamino or hydroxyl.
The benzophenone compound is a photoinitiator, the hydrogen-containing silicone oil is a leveling agent, the benzophenone compound has the surface enrichment characteristic, the modified photoinitiator obtained through the reaction of the photoinitiator and the leveling agent has the effects of both the photoinitiator and the leveling agent, namely the surface enrichment characteristic of the modified photoinitiator is endowed, so that the modified photoinitiator can have higher concentration on the surface of liquid, the problem that an inverted trapezoidal triangular area formed in a developing process of the photosensitive resin composition is not high in curing degree and is broken by developing solution can be effectively solved, and finally, a slope angle with a smooth surface and a proper angle (for example, 30-60 degrees) is obtained.
Preferably, the hydrogen-containing silicone oil comprises any one of the following compounds:
Figure BDA0001908224850000051
n is an integer of 0-20;
n is1Is an integer of 0 to 20, n2Is an integer of 0 to 20, n1+n2Is an integer of 0 to 20.
The hydrogen-containing dimethyl silicone oil is selected from the hydrogen-containing dimethyl silicone oil to react with the benzophenone compound, and the hydrogen-containing dimethyl silicone oil has stronger surface enrichment performance, so the surface enrichment performance of the modified photoinitiator can be further improved.
Preferably, n1Is 0.
Preferably, the hydrogen-containing silicone oil is
Figure BDA0001908224850000052
Preferably, the halogenation reaction is a chlorination reaction, and the chlorination reaction is performed in a chlorine atmosphere.
The benzophenone compound is subjected to chlorination reaction in the chlorine atmosphere, so that the substitution reaction with hydrogen-containing silicone oil in the step (2) is facilitated, and the important effect on improving the yield of the target product is achieved.
Preferably, the catalyst of the chlorination reaction comprises chloroplatinic acid.
The chloroplatinic acid is selected as the catalyst of the chlorination reaction because the chloroplatinic acid has higher activity, is easy to release chloride ions and has more sufficient reaction with active hydrogen, thereby obtaining higher yield.
Preferably, the temperature of the chlorination reaction is 110-130 ℃, such as 112 ℃, 115 ℃, 118 ℃, 120 ℃, 122 ℃, 125 ℃ or 128 ℃, preferably 115-120 ℃, such as 116 ℃, 117 ℃, 118 ℃ or 119 ℃, etc.; the chlorination reaction time is 2-4 h, such as 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h, 3.8h or 3.9 h.
When the temperature of the chlorination reaction is 110-130 ℃, particularly 115-120 ℃, the yield of the modified photoinitiator is higher (more than 80%), the molecular weight distribution is narrower, the molecular weight distribution coefficient (PDI) is in the range of 1.1-1.4, a series of side reactions can be generated when the temperature is too high, the PDI is increased, the molecular weight distribution is not uniform, the chlorination reaction is incomplete when the temperature is too low, and the yield of the target product is low.
The chlorination reaction time is controlled within 2-4 h, the most ideal intermediate product can be obtained, the time is too short, chlorination is incomplete, the time is too long, and a series of side reactions can be possibly initiated.
Preferably, the catalyst for the chlorination reaction is added dropwise.
Preferably, the dropping rate is 0.02-0.05 mL/s, such as 0.025mL/s, 0.03mL/s, 0.035mL/s, 0.04mL/s, or 0.045 mL/s.
Preferably, the chlorination reaction is carried out in an acrylate-based solvent.
Preferably, the acrylate-based solvent includes any one or a combination of at least two of acrylate, methyl acrylate and ethyl acrylate.
The chlorination reaction is carried out in the acrylate solvent because the acrylate solvent and the benzophenone compound have good compatibility, which is more beneficial to the smooth reaction and the target product with higher yield is obtained.
Preferably, the temperature of the substitution reaction is 80 to 90 ℃, such as 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃ or 89 ℃, preferably 85 ℃;
the time of the substitution reaction is 1-2 h, such as 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h or 1.9 h.
When the temperature of the substitution reaction is 80-90 ℃, particularly 85 ℃, the yield of the modified photoinitiator is high, the molecular weight distribution is narrow (namely the PDI is small), a series of side reactions can be generated when the temperature is too high, the PDI is increased, the molecular weight distribution is uneven, the substitution reaction is incomplete when the temperature is too low, and the yield of a target product is low.
Preferably, the intermediate product is added dropwise.
Preferably, the dropping rate is 0.5-2.0 mL/s, such as 0.6mL/s, 0.8mL/s, 1.0mL/s, 1.2mL/s, 1.5mL/s, 1.6mL/s, or 1.8 mL/s.
Preferably, the preparation method specifically comprises the following steps:
(1) adding 100 parts by weight of the hydrogen-containing silicone oil and 700-900 parts by weight of an acrylate solvent, such as 710 parts by weight, 750 parts by weight, 780 parts by weight, 800 parts by weight, 820 parts by weight, 850 parts by weight, 880 parts by weight or 890 parts by weight, into a flask, heating to 110-130 ℃, adding 30-40 parts by weight of chloroplatinic acid, such as 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight or 39 parts by weight, and the like, reacting for 2-4 hours in a chlorine atmosphere, cooling to room temperature, extracting, and concentrating to obtain an intermediate product;
(2) adding 100 parts by weight of the benzophenone compound and 750-1000 parts by weight of a second solvent, such as 760 parts by weight, 780 parts by weight, 900 parts by weight, 920 parts by weight, 950 parts by weight, 980 parts by weight or 990 parts by weight, into a flask, heating to 80-90 ℃, adding 40-50 parts by weight of the intermediate product, reacting for 1-2 hours, and cooling to room temperature after the reaction is finished to obtain the modified photoinitiator.
Preferably, the second solvent comprises toluene and/or xylene.
The solvent used for the extraction is well known to those skilled in the art and is therefore not limiting and, by way of example, toluene and/or xylene may be chosen.
The third purpose of the invention is to provide the application of the modified photoinitiator, which is used for photoresist.
Preferably, the modified photoinitiator is used for a color photoresist.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a hydrogen-containing silicone oil group without one hydrogen is introduced to the meta position of the benzophenone compound, so that the modified photoinitiator has a surface enrichment characteristic, the modified photoinitiator can have a higher concentration on the surface of liquid, the problem that an inverted trapezoidal triangular area formed in a developing process of the photosensitive resin composition is not high in curing degree and is broken by a developing solution can be effectively solved, and a slope angle with a smooth surface and a proper angle (for example, 30-60 degrees) is finally obtained.
(2) In the preferable technical scheme, the modified photoinitiator obtained by selecting the hydrogen-containing methyl silicone oil group to replace the benzophenone compound has better surface enrichment performance, and when the modified photoinitiator is used for the photosensitive resin composition, the curing degree of an inverted trapezoidal triangular area can be further improved, a slope angle with a smaller angle is obtained, and the surface is smooth.
(3) According to the invention, the benzophenone compound is grafted with the hydrosilicon oil group to obtain the modified photoinitiator, the photoinitiator is endowed with the leveling property, the modified photoinitiator with the surface enrichment characteristic is obtained, the modified photoinitiator can have higher concentration on the surface of liquid, the problem that an inverted trapezoidal triangular area formed in the developing process of the photosensitive resin composition is not high in curing degree and is broken by developing solution can be effectively solved, and the slope angle with smooth surface and proper angle (such as 30-60 degrees) is finally obtained, and the method is simple to operate.
(4) In the preferred technical scheme, chloroplatinic acid is selected as a catalyst of the chlorination reaction, the temperature of the chlorination reaction is controlled to be 110-130 ℃ (especially 115-120 ℃), the temperature of the substitution reaction is controlled to be 80-90 ℃, the obtained modified photoinitiator has narrower molecular weight distribution, PDI can be controlled to be 1.1-1.4, and the yield (more than 80%) of the modified photoinitiator formed by grafting the benzophenone compound and the hydrogen-containing silicone oil can be further improved.
Drawings
FIG. 1 is an SEM image of a green photoresist PEMT-CG02 added with a modified photoinitiator provided in example 1 of the present invention before post-baking.
FIG. 2 is an SEM image of a green photoresist PEMT-CG02 post-bake with the addition of a modified photoinitiator provided in example 1 of the present invention.
FIG. 3 is an SEM image of a green resist PEMT-CG02 with the addition of a photoinitiator provided by comparative example 1 of the present invention before post-baking.
FIG. 4 is an SEM image of a green resist PEMT-CG02 post bake with the addition of a photoinitiator provided by comparative example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the photoinitiator comprises the following steps:
(1) adding hydrogen-containing silicone oil 1 into a four-mouth bottle provided with a stirrer, a thermometer, a chlorine gas protection device and a dropping funnel in a chlorine gas atmosphere
Figure BDA0001908224850000091
(n is less than or equal to 20) (PMX-200, Dow Corning) 100 weight parts, adding organic solvent acrylate 800 weight parts, heating to 116 ℃, adding chloroplatinic acid 30 weight parts through a dropping funnel, and reacting for 3 hours. After the reaction is completed, gradually cooling to room temperature under stirring, extracting by toluene, and removing the toluene by a distillation method to obtain an intermediate product.
(2) The photoinitiator 4, 4-bis (diethylamino) benzophenone was added in a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel
Figure BDA0001908224850000101
(Liyang Biotech Co., Ltd.) 100 parts by weight and toluene 1000 parts by weight, heating to dissolve the photoinitiator, heating to 85 ℃, adding 50 parts by weight of the intermediate product, placing the exhaust port of the condenser tube in water, and reacting for 1.5 h. After the reaction is finished, cooling to room temperature, gradually generating white crystalline particles, and performing suction filtration to obtain a solid with the yield of 95 percent, namelyModified photoinitiators
Figure BDA0001908224850000102
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3200，PDI＝1.012。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.14ppm (12H, s), 0.66ppm (6H, s), 1.20ppm (12H, t), 2.87ppm (2H, t), 7.40 to 7.70ppm (7H, t).
Example 2
The difference from example 1 is that hydrogen-containing silicone oil 1 is replaced with hydrogen-containing silicone oil 2
Figure BDA0001908224850000103
(n1+n2Less than or equal to 20) to obtain the modified photoinitiator with the yield of 85 percent
Figure BDA0001908224850000111
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝2600，PDI＝1.242。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.16ppm (12H, s), 0.64ppm (6H, s), 1.22ppm (12H, t), 2.89ppm (2H, t), 7.45 to 7.72ppm (7H, t).
Example 3
The difference from example 1 is that hydrogen-containing silicone oil 1 is replaced with hydrogen-containing silicone oil 3
Figure BDA0001908224850000112
(n1+n220 ℃ or less) to give a yield of 94% of modified photoinitiator:
Figure BDA0001908224850000113
Figure BDA0001908224850000121
a mixture of (a).
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3100，PDI＝1.106。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.17ppm (12H, s), 0.63ppm (6H, s), 1.22ppm (12H, t), 2.82ppm (2H, t), 7.41 to 7.69ppm (7H, t).
Example 4
The difference from example 1 is that the heating temperature in step (1) was 115 ℃ and the yield was 94%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3230，PDI＝1.035。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.14ppm (12H, s), 0.68ppm (6H, s), 1.23ppm (12H, t), 2.85ppm (2H, t), 7.41 to 7.76ppm (7H, t).
Example 5
The difference from example 1 is that the heating temperature in step (1) was 120 ℃ and the yield was 90%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3400，PDI＝1.005。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.16ppm (12H, s), 0.67ppm (6H, s), 1.29ppm (12H, t), 2.81ppm (2H, t), 7.43 to 7.74ppm (7H, t).
Example 6
The difference from example 1 is that the heating temperature in step (1) was 110 ℃ and the yield was 87%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3150，PDI＝1.121。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.15ppm (12H, s), 0.67ppm (6H, s), 1.21ppm (12H, t), 2.88ppm (2H, t), 7.41 to 7.68ppm (7H, t).
Example 7
The difference from example 1 is that the heating temperature in step (1) was 130 ℃ and the yield was 89%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝2900，PDI＝1.142。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.16ppm (12H, s), 0.64ppm (6H, s), 1.21ppm (12H, t), 2.88ppm (2H, t), 7.41 to 7.68ppm (7H, t).
Example 8
The difference from example 1 is that the heating temperature in step (1) was 105 ℃ and the yield was 78%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝2800，PDI＝1.001。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.10ppm (12H, s), 0.61ppm (6H, s), 1.15ppm (12H, t), 2.75ppm (2H, t), 7.22 to 7.56ppm (7H, t).
Example 9
The difference from example 1 is that the heating temperature in step (1) was 135 ℃ and the yield was 75%.
Structural characterization:
(1) dissolving the modified photoinitiator in tetrahydrofuran, and using Waters-Breeze GPC gel permeationSpectral characterization to determine Mw＝2750，PDI＝1.261。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.11ppm (12H, s), 0.63ppm (6H, s), 1.22ppm (12H, t), 2.78ppm (2H, t), 7.42 to 7.59ppm (7H, t).
Example 10
The difference from example 1 is that chloroplatinic acid was replaced by antimony trichloride, giving a yield of 65%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝2200，PDI＝1.356。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.16ppm (12H, s), 0.59ppm (6H, s), 1.21ppm (12H, t), 2.83ppm (2H, t), 7.41 to 7.75ppm (7H, t).
Example 11
The difference from example 1 is that the heating temperature in step (2) was 80 ℃ and the yield was 94.6%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3160，PDI＝1.126。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.12ppm (12H, s), 0.67ppm (6H, s), 1.22ppm (12H, t), 2.89ppm (2H, t), 7.39-7.58 ppm (7H, t).
Example 12
The difference from example 1 is that the heating temperature in step (2) was 90 ℃ and the yield was 93.5%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3350，PDI＝1.125。
(2) CDCl at 400MHz3As a solvent1H NMR was conducted, and the results were as followsThe following: δ is 0.14ppm (12H, s), 0.66ppm (6H, s), 1.20ppm (12H, t), 2.87ppm (2H, t), 7.40 to 7.70ppm (7H, t).
Example 13
The difference from example 1 is that the heating temperature in step (2) was 75 ℃ and the yield was 75%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3100，PDI＝1.005。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.15ppm (12H, s), 0.67ppm (6H, s), 1.21ppm (12H, t), 2.89ppm (2H, t), 7.39-7.73 ppm (7H, t).
Example 14
The difference from example 1 is that the heating temperature in step (2) was 95 ℃ and the yield was 62%.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3400，PDI＝1.256。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.15ppm (12H, s), 0.61ppm (6H, s), 1.26ppm (12H, t), 2.81ppm (2H, t), 7.45 to 7.76ppm (7H, t).
Example 15
The preparation method of the photoinitiator comprises the following steps:
(1) adding hydrogen-containing silicone oil 1 into a four-mouth bottle provided with a stirrer, a thermometer, a chlorine gas protection device and a dropping funnel in a chlorine gas atmosphere
Figure BDA0001908224850000161
(n is less than or equal to 20)100 parts by weight, adding 700 parts by weight of organic solvent methyl acrylate, heating to 116 ℃, adding 30 parts by weight of chloroplatinic acid through a dropping funnel, and reacting for 2 hours. After the reaction is completed, gradually cooling to room temperature under stirring, extracting by toluene, removing the toluene by a distillation method,an intermediate product is obtained.
(2) The photoinitiator 4, 4-bis (diethylamino) benzophenone was added in a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel
Figure BDA0001908224850000171
100 parts by weight of xylene and 1000 parts by weight of xylene, heating to dissolve the photoinitiator, heating to 85 ℃, adding 40 parts by weight of the intermediate product, placing an exhaust port of a condenser tube in water, and reacting for 1 hour. After the reaction is finished, cooling to room temperature, gradually generating white crystalline particles, and performing suction filtration to obtain 94.5% of solid, namely the modified photoinitiator
Figure BDA0001908224850000172
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3500，PDI＝1.126。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.13ppm (12H, s), 0.65ppm (6H, s), 1.23ppm (12H, t), 2.89ppm (2H, t), 7.43 to 7.67ppm (7H, t).
Example 16
The preparation method of the photoinitiator comprises the following steps:
(1) adding hydrogen-containing silicone oil 1 into a four-mouth bottle provided with a stirrer, a thermometer, a chlorine gas protection device and a dropping funnel in a chlorine gas atmosphere
Figure BDA0001908224850000181
(n is less than or equal to 20)100 parts by weight, adding 900 parts by weight of organic solvent ethyl acrylate, heating to 116 ℃, adding 40 parts by weight of chloroplatinic acid through a dropping funnel, and reacting for 4 hours. After the reaction is completed, gradually cooling to room temperature under stirring, extracting by xylene, and removing the xylene by a distillation method to obtain an intermediate product.
(2) In a three-mouth bottle equipped with a stirrer, a thermometer and a dropping funnelIn the reaction solution, 4-bis (diethylamino) benzophenone serving as a photoinitiator is added
Figure BDA0001908224850000182
100 parts by weight of xylene and 1000 parts by weight of xylene, heating to dissolve the photoinitiator, heating to 85 ℃, adding 50 parts by weight of the intermediate product, placing an exhaust port of a condenser tube in water, and reacting for 2 hours. After the reaction is finished, cooling to room temperature, gradually generating white crystalline particles, and performing suction filtration to obtain a solid, namely the modified photoinitiator with the yield of 81.5 percent
Figure BDA0001908224850000183
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3150，PDI＝1.216。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.15ppm (12H, s), 0.64ppm (6H, s), 1.24ppm (12H, t), 2.89ppm (2H, t), 7.41-7.75 ppm (7H, t).
Example 17
The preparation method of the photoinitiator comprises the following steps:
(1) adding hydrogen-containing silicone oil 1 into a four-mouth bottle provided with a stirrer, a thermometer, a chlorine gas protection device and a dropping funnel in a chlorine gas atmosphere
Figure BDA0001908224850000191
(n is less than or equal to 20)100 parts by weight, adding 800 parts by weight of organic solvent ethyl acrylate, heating to 116 ℃, adding 40 parts by weight of chloroplatinic acid through a dropping funnel, and reacting for 4 hours. After the reaction is completed, gradually cooling to room temperature under stirring, extracting by xylene, and removing the xylene by a distillation method to obtain an intermediate product.
(2) The photoinitiator 4, 4-bis (diethylamino) benzophenone was added in a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel
Figure BDA0001908224850000192
100 parts by weight of xylene and 850 parts by weight of xylene, heating to dissolve the photoinitiator, heating to 85 ℃, adding 45 parts by weight of the intermediate product, placing an exhaust port of a condenser tube in water, and reacting for 2 hours. After the reaction is finished, cooling to room temperature, gradually generating white crystalline particles, and performing suction filtration to obtain a solid, namely the modified photoinitiator with the yield of 93.8 percent
Figure BDA0001908224850000193
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3260，PDI＝1.356。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.13ppm (12H, s), 0.65ppm (6H, s), 1.25ppm (12H, t), 2.93ppm (2H, t), 7.37 to 7.62ppm (7H, t).
Example 18
The preparation method of the photoinitiator comprises the following steps:
(1) adding hydrogen-containing silicone oil 1 into a four-mouth bottle provided with a stirrer, a thermometer, a chlorine gas protection device and a dropping funnel in a chlorine gas atmosphere
Figure BDA0001908224850000201
(n is less than or equal to 20)100 parts by weight, adding 850 parts by weight of organic solvent ethyl acrylate, heating to 116 ℃, adding 40 parts by weight of chloroplatinic acid through a dropping funnel, and reacting for 4 hours. After the reaction is completed, gradually cooling to room temperature under stirring, extracting by xylene, and removing the xylene by a distillation method to obtain an intermediate product.
(2) The photoinitiator 4, 4-bis (diethylamino) benzophenone was added in a three-necked flask equipped with a stirrer, a thermometer and a dropping funnel
Figure BDA0001908224850000202
100 parts by weight of xylene and 750 parts by weight of xylene, heating to cause photoinitiationDissolving the reagents, heating to 85 ℃, adding 45 parts by weight of the intermediate product, placing an exhaust port of a condensing tube into water, and reacting for 2 hours. After the reaction is finished, cooling to room temperature, gradually generating white crystalline particles, and performing suction filtration to obtain a solid, namely the modified photoinitiator with the yield of 93.9 percent
Figure BDA0001908224850000211
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3200，PDI＝1.116。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.13ppm (12H, s), 0.67ppm (6H, s), 1.22ppm (12H, t), 2.91ppm (2H, t), 7.41 to 7.66ppm (7H, t).
Example 19
The difference from example 1 is that hydrogen-containing silicone oil 1 is replaced by phenyl silicone oil
Figure BDA0001908224850000212
(n is less than or equal to 20) and the yield is 50.6 percent.
Structural characterization:
(1) the modified photoinitiator was dissolved in tetrahydrofuran and characterized using Waters-Breeze GPC gel permeation chromatography to determine Mw＝3800，PDI＝1.458。
(2) CDCl at 400MHz3As a solvent1H NMR characterization, results are as follows: δ is 0.19ppm (12H, s), 0.78ppm (6H, s), 0.55ppm (5H, s), 1.26ppm (12H, t), 2.98ppm (2H, t), 7.62 to 7.89ppm (7H, t).
Comparative example 1
A photoinitiator: 4, 4-bis (diethylamino) benzophenone
Figure BDA0001908224850000221
Comparative example 2
The difference from example 1 is that 4, 4-bis (diethylamino) benzophenone is replaced by 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.
And (3) performance testing:
(1) the modified photoinitiators in the above examples and the photoinitiators in the comparative examples were added to green resists (PEMT-CG 02, ancient cooking vessel science) in equal amounts, the obtained resists were subjected to development processes under the same conditions, respectively, and HITACHI SU8010SEM tests were performed on the post-baked resists to obtain SEM images (20K magnification), the slope angles were measured and the average values were calculated, respectively, and the slope angle values shown in table 1 were the average values.
(2) The surface roughness Ra of the photoresist after baking was measured by a surface roughness tester (precision of tokyo, EB-35B).
The results of the performance tests are shown in table 1.
TABLE 1
Figure BDA0001908224850000222
Figure BDA0001908224850000231
The comparison example and the comparison example show that the slope angles of the photoresists in the examples are all in the range of 30-60 degrees, and are optimal angles, the surface roughness Ra of the photoresists is only 4.5nm at most, and the photoresists are in a smooth state, while the slope angles of the photoresists in the comparison examples are 75 degrees, Ra is 7.3nm, and the photoresists are in a rough state, which shows that the problem that an inverted trapezoidal triangular area formed in a developing process by a photosensitive resin composition is not high in curing degree and is broken by a developing solution can be effectively solved by adding the modified photoinitiator, and the phenomenon that the surface of a color glue is uneven in curing degree and is rough after development is improved. The hydrogen-containing silicone oil group without one hydrogen is introduced into the benzophenone photoinitiator structure, so that the modified photoinitiator has the characteristic of surface enrichment, the modified photoinitiator can have higher concentration on the surface of liquid, the curing degree of an inverted trapezoidal triangular area is higher, the original form of the inverted trapezoidal triangular area is retained, and a slope angle with a proper angle and a smooth surface is formed after postbaking.
In addition, as can be seen from comparing fig. 1 to 4, the green photoresist added with the modified photoinitiator provided in example 1 has a complete inverted trapezoidal triangular form before post-baking (fig. 1), is not broken by the developer, and forms a slope angle with a good slope after post-baking (fig. 2); the incomplete inverted trapezoidal triangular shape before post-baking (fig. 3) of the green resist to which the photoinitiator provided in comparative example 1 was added was due to the low degree of curing, and was broken by the developer during development, and a large slope angle was formed after post-baking (fig. 4).
Comparing example 1 with example 19, it can be seen that when the substituent on the benzophenone-based photoinitiator is a methylsilicone oil substituent (example 1), the yield is higher, when the obtained modified photoinitiator is used for a photoresist, the inverse trapezoidal triangle shape of the photoresist in the developing process is more complete, a better slope angle is formed after post-baking, when the substituent on the benzophenone-based photoinitiator is a non-methylsilicone oil substituent, the yield is lower, and the corresponding effect is worse, because the structural stability formed by the non-methylsilicone oil substituted modified photoinitiator is relatively worse, the yield is lower, and the structure surface enrichment and migration functions of the structural photoinitiator are not obvious enough.
In comparison with examples 1 and 4 to 9, when the temperature of the chlorination reaction is 110 to 130 ℃, particularly 115 to 120 ℃, the yield of the modified photoinitiator is higher, the molecular weight distribution is narrower (i.e. PDI is smaller), a series of side reactions can be generated due to too high temperature, the PDI is increased, the molecular weight distribution is not uniform, incomplete chlorination reaction can be caused due to too low temperature, and the yield of the target product is low.
It can be seen from comparison between example 1 and example 10 that chloroplatinic acid is selected as the catalyst for the chlorination reaction, and higher yield can be obtained compared with antimony trichloride, because chloroplatinic acid has higher activity, is easier to release chloride ions, and reacts with active hydrogen more sufficiently, thereby obtaining higher yield.
In comparative examples 1 and 11 to 14, when the temperature of the substitution reaction is 80 to 90 ℃, the yield of the modified photoinitiator is high, the molecular weight distribution is narrow (PDI is small), a series of side reactions can be generated when the temperature is too high, the PDI is increased, the molecular weight distribution is not uniform, the substitution reaction is incomplete when the temperature is too low, and the yield of the target product is low.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (12)

1. A modified photoinitiator, characterised in that the modified photoinitiator has the structure of formula (I);
Figure FDA0001908224840000011
in the formula (I), R1、R2、R3And R4Each independently selected from any one of C1-C12 alkyl, C1-C6 hydroxyalkyl, C1-C6 halogenated alkyl, C1-C6 hydroxylamino or hydroxyl;
in the formula (I), X is a residual group of hydrogen-containing silicone oil after losing one hydrogen.
2. The modified photoinitiator as defined in claim 1, wherein X is selected from any one of the following structures:
Figure FDA0001908224840000012
n is an integer of 0-20;
n is1Is an integer of 0 to 20, n2Is an integer of 0 to 20, and n1+n2Is 0 &20 is an integer of 20;
preferably, n1Is 0.
3. The modified photoinitiator as defined in claim 1 wherein X has the structure
Figure FDA0001908224840000013
And n is an integer of 0-20.
4. A method for preparing a modified photoinitiator according to any one of claims 1 to 3, comprising the steps of:
(1) performing halogenation reaction on hydrogen-containing silicone oil to obtain an intermediate product;
(2) carrying out substitution reaction on the intermediate product and a benzophenone compound shown in a formula (II) to obtain the modified photoinitiator;
Figure FDA0001908224840000021
in the formula (II), R1、R2、R3And R4Each independently selected from any one of C1-C12 alkyl, C1-C6 hydroxyalkyl, C1-C6 halogenated alkyl, C1-C6 hydroxylamino or hydroxyl.
5. The method according to claim 4, wherein the hydrogen-containing silicone oil comprises any one of the following compounds:
Figure FDA0001908224840000022
n is an integer of 0-20;
n is1Is an integer of 0 to 20, n2Is an integer of 0 to 20, n1+n2Is an integer of 0 to 20;
preferably, n1Is 0;
preference is given toThe hydrogen-containing silicone oil is
Figure FDA0001908224840000023
6. The method according to claim 4, wherein the halogenation reaction is a chlorination reaction, and the chlorination reaction is carried out in a chlorine atmosphere;
preferably, the catalyst of the chlorination reaction comprises chloroplatinic acid.
7. The method according to claim 4, wherein the chlorination reaction is carried out at a temperature of 110 to 130 ℃, preferably 115 to 120 ℃;
the chlorination reaction time is 2-4 h.
8. The preparation method according to claim 4, wherein the catalyst for the chlorination reaction is added dropwise;
preferably, the dropping rate is 0.02-0.05 mL/s.
9. The production method according to claim 4, wherein the chlorination reaction is carried out in an acrylate-based solvent;
preferably, the acrylate-based solvent includes any one or a combination of at least two of acrylate, methyl acrylate and ethyl acrylate.
10. The method according to claim 4, wherein the temperature of the substitution reaction is 80 to 90 ℃, preferably 85 ℃; the time of the substitution reaction is 1-2 h.
11. The method according to claim 4, wherein the intermediate product is added dropwise;
preferably, the dropping rate is 0.5-2.0 mL/s.
12. Use of a modified photoinitiator according to any one of claims 1 to 3 for a photoresist;
preferably, the modified photoinitiator is used for a color photoresist.
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