Ionium salt compound with biphenyl structure and preparation method and application thereof

Abstract

The present invention provides an iodonium salt compound with a biphenyl structure, a preparation method and an application thereof. Such compounds are represented by the general formula M, wherein R1 is independently selected from one of a hydrogen atom, a C1-C 10 alkyl or one of a C1-C 10 alkoxy or a methoxy group, R2 is selected from one of a C1-C 10 linear or branched alkyl, R3 is independently selected from a hydrogen atom, a fluorine atom or a trifluoromethyl group, R4 and R5 are each independently selected from a hydrogen atom or an oxygen atom and one of a methyl group, an ester group, a cyano group, R6 represents a hydrogen atom, a C1-C 10 alkyl or one of a C1-C 10 alkoxy or a fluorine atom or one of a trifluoromethyl group, a cyano group, a nitro group, X ‑ is an anion. The iodonium salt compound provided by the present invention introduces different electron-donating and electron-withdrawing substituents, ensuring good sensitivity in the range of 300-425 nm light radiation, and thus having a wide applicable wavelength range and high photolysis efficiency.

Description

Technical Field

[0001] The present invention relates to the fields of chemical synthesis, photocuring and photoresist, and in particular to the structure of a diaryliodonium salt compound having a biphenyl structure and being sensitive to ultraviolet and visible light, a preparation method thereof, and applications in the fields of photocuring and photoresist, in particular, applications in cationic UV curing adhesive formulations. Background Art

[0002] As an important photopolymerization initiator and photoacid generator for photoresist, iodonium salt has always attracted attention and is one of the important cationic photoinitiators currently used. It has high photoacid generation efficiency, fast photoreaction speed and simple synthesis. Especially in the current situation where photosensitive polymers are increasingly used and various photoresist raw materials are stuck, the design and preparation of iodonium salts are very important. At present, the commercial iodonium salts on the market are mainly aromatic iodonium salts. According to different anions, they can be divided into two categories: one is iodonium salts with metal ions, and the other is iodonium salts with sulfonic acid groups without metal ions. The former cannot be used in the photoresist industry because it contains metal ions, but is mainly used in the photocuring industry, requiring a relatively long ultraviolet absorption spectrum and relatively low price requirements; the latter is more used in the photoresist industry because it has aromatic substituents and can be mainly used in the field of I-line or G-line lithography. At present, there are few reports on iodonium salt compounds with strong absorption ability in the near-ultraviolet-visible light region. Therefore, it is necessary to develop iodonium salts with independent intellectual property rights.

[0003] The most commonly used photoinitiators can be divided into two categories: one is free radical photoinitiators, such as the commercially available OXE01 and OXE02 oxime esters, benzophenone and its derivative photoinitiators, and the other is cationic photoinitiators, such as triphenylsulfonium salts, diaryliodonium salts and other ion-type initiators. UV-curing adhesives using free radical photoinitiators have problems such as high shrinkage, great influence of "oxygen inhibition", and inability to achieve dark area curing, which limits their application in the assembly of complex electronic devices.

[0004] Diaryliodonium salts and triarylsulfonium salts are the main commercial types of cationic photoinitiators due to their high photoinitiating activity. However, the cationic photoinitiators currently used in the commercial market generally have the problem of too short absorption wavelength (less than 300nm) and poor matching with the emission wavelength of commercially commonly used UV light sources (for example: 365nm, 395nm, etc.), which seriously affects the curing effect of cationic UV-curing adhesives. In order to solve this problem, one method is to add chemical photosensitizers to increase the absorption wavelength and quantum efficiency of the photoinitiator by sensitization, but the additional photosensitizer increases the system complexity of the adhesive; another method is to develop cationic photoinitiators with new structures to fundamentally solve the problem of wavelength mismatch. Therefore, how to design and synthesize cationic photoinitiators with better matching with the absorption wavelength of existing commercial UV-vis light sources and apply them to UV curing has also become an urgent problem to be solved. Summary of the invention

[0005] In view of the shortcomings of the prior art, the first object of the present invention is to provide a diaryl iodonium salt compound with a biphenyl structure, and to extend the wavelength of the cationic initiator by group modification, thereby solving the technical problem of the short wavelength (less than 300nm) of commercial iodonium salts in the prior art.

[0006] The second object of the present invention is to provide a method for preparing the diaryliodonium salt compound having a biphenyl structure.

[0007] The third object of the present invention is to provide the use of the above-mentioned diaryliodonium salt compound having a biphenyl structure in the fields related to photocuring and photolithography.

[0008] To achieve the above object, the solution of the present invention is:

[0009] A diaryl iodonium salt compound having a biphenyl structure, wherein one aromatic ring in the main structure is a benzene ring, and the other aromatic ring is a biphenyl conjugated system with various substituents, which is connected by cationic iodine to form an onium salt structure, and is connected with the corresponding anion X - Together they form a neutral salt, the molecular structure of which is shown in the general formula M:

[0010]

[0011] in,

[0012] R1 is independently selected from hydrogen atom, C1-C 10 One of the alkyl groups or C1-C 10 An alkoxy group or anisole group;

[0013] R2 is selected from C1-C 10 A straight chain or branched chain alkyl group;

[0014] R3 is independently selected from a hydrogen atom, a fluorine atom or a trifluoromethyl group;

[0015] R4 and R5 are independently selected from a hydrogen atom or an oxygen atom and one of a methyl group, an ester group, and a cyano group, wherein when it is an oxygen atom, R4 and R5 are combined to form an oxygen atom;

[0016] R6 represents a hydrogen atom, C1-C 10 One of the alkyl groups or C1-C 10 An alkoxy group or a fluorine atom or a trifluoromethyl group, a cyano group, or a nitro group.

[0017] Furthermore, the anion X - The structure includes but is not limited to:

[0018]

[0019] Among them, the anion X - Preferred is hydrogen X1 or X11.

[0020] The preferred structural formula of the diaryliodonium salt type compound having a biphenyl structure is as follows:

[0021]

[0022] A method for preparing the above-mentioned diaryliodonium salt compound having a biphenyl structure comprises the following steps:

[0023] (1) A phenylboronic acid containing R1 and R2 substitutions and a bromobenzaldehyde containing R3 substitutions are subjected to a coupling reaction at room temperature in an organic solvent under the protection of an inert gas using a metal catalyst and a base as an acid binding agent to obtain an intermediate 1;

[0024]

[0025] (2) Under the protection of inert gas, intermediate 1 and a compound containing R4 and R5 substitutions are reacted in an organic solvent using a weak base as a catalyst at room temperature to obtain intermediate 2;

[0026]

[0027] (3) Dissolving intermediate 1 or intermediate 2, p-toluenesulfonic acid and diacetyl iodobenzene substituted with R6 in an organic solvent and reacting at room temperature to obtain the target molecule Mn-In-X1;

[0028]

[0029] (4) The target molecule Mn-In-X1 and the anion X - The salt exchange can be completed by dissolving in an organic solvent in an equal molar ratio and reacting with stirring at room temperature in the dark to obtain M with different anions;

[0030]

[0031] The overall preparation process is as follows:

[0032]

[0033] Furthermore, in step (1), the metal catalyst may be selected from one or more of palladium / carbon, tetrakis(triphenylphosphine)palladium or palladium dichloride.

[0034] Furthermore, in step (1), the organic solvent can be selected from one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, dichloromethane or a 1:1 water / ethanol solution.

[0035] Furthermore, in step (1), the base can be selected from one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide or potassium tert-butoxide.

[0036] Furthermore, in step (2), the catalyst weak base can be selected from one or more of sodium carbonate, potassium carbonate, cesium carbonate, piperidine, pyridine or triethylamine.

[0037] Furthermore, in step (2), the organic solvent may be selected from one or more of N,N-dimethylformamide, dichloromethane, methanol or ethanol.

[0038] Furthermore, in step (3), the organic solvent may be selected from one or more of chloroform, dichloromethane, methanol or acetic acid.

[0039] Furthermore, in step (4), X - The salts corresponding to the various anions selected from the above may be sodium salts or potassium salts. The organic solvent is a mixed solvent of a first solvent, a second solvent, a third solvent and a fourth solvent, wherein the first solvent is selected from at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and isopropanol; the second solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, tetrahydrofuran and dioxane; the third solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, tetrahydrofuran and dioxane; the fourth solvent is selected from at least one of acetonitrile, methanol, ethanol, isopropanol, acetone and water.

[0040] Furthermore, the method also includes washing intermediate 1, intermediate 2 and final product M; the solvent used when washing intermediate 1 product is petroleum ether and dichloromethane; the solvent used when washing intermediate 2 product is anhydrous ethanol; the solvent used when washing final product M is ether / dichloromethane / acetone.

[0041] An application of the above-mentioned diaryliodonium salt compound having a biphenyl structure as a photoinitiator in a photocuring formulation system or as an intermediate, raw material or reagent for chemical synthesis.

[0042] Furthermore, the emission wavelength of the light source of the photoinitiator is ultraviolet light or visible light.

[0043] Furthermore, the light-curing formulation system comprises:

[0044] (1) containing at least one compound of the general formula M as a photoinitiator or one of the photoinitiator components;

[0045] (2) Containing at least one polymerizable compound containing unsaturated double bonds (such as (meth)acrylate monomers, oligomers and resins) and / or epoxides (glycidyl ethers or cyclohexene oxide derivatives);

[0046] (3) The amount of the compound of the general formula M is 0.5-10 parts by weight per 100 parts by weight of the total amount of the polymerizable components in the system;

[0047] (4) A small amount of additives (such as acetone, dichloromethane and other low-boiling point solvents), as well as defoaming agents, leveling agents, dyes, inorganic fillers, etc., are added as required.

[0048] The (meth)acrylate monomer is selected from at least one of tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA).

[0049] The oligomer and the resin are both selected from at least one of epoxy acrylate, polyurethane acrylate or polyester acrylate.

[0050] The epoxycyclohexane derivative is selected from at least one of epoxycyclohexane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

[0051] An application of the above-mentioned diaryliodonium salt compound having a biphenyl structure as a photoacid generator in the field of photoresist preparation.

[0052] Due to the adoption of the above scheme, the beneficial effects of the present invention are:

[0053] (1) Advantages in structure and performance: The diaryl iodonium salt compound with a biphenyl structure provided by the present invention introduces different electron-pushing and electron-pulling substituents, especially one phenyl in the classic diphenyl iodonium salt is changed to biphenyl, and an electron-withdrawing aldehyde group or cyano group is introduced in the para position of the biphenyl iodonium salt, further expanding the conjugated structure, thereby effectively expanding the light absorption range of the iodonium salt, the maximum wavelength range of the iodonium salt compound is 301-352nm, and the absorption spectrum covers the wavelength range of 300-425nm. It has good sensitivity within the light radiation range, thus having the advantages of a wide applicable wavelength range, high photolysis efficiency, and good compatibility with monomers and resins.

[0054] (2) Advantages in application: The diaryl iodonium salt compound with a biphenyl structure provided by the present invention is an iodonium salt compound with a long absorption wavelength. It has been optimized and innovated according to the needs of existing scenarios and has made outstanding expansions in various industrial scenario applications. In addition, the raw materials in the preparation process are simple and easy to obtain, and the synthesis route is simple, which is convenient for preparation and large-scale production.

[0055] (3) Advantages in practical application effects: The preferred diaryliodonium salt compound having a biphenyl structure is a white powder, which has potential advantages such as anti-bleaching effect after being used in a photocuring formulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The figure is a general structural formula diagram of the diaryl iodonium salt compound having a biphenyl structure of the present invention.

[0057] Figure 2 is the M-I1-X2 in CD3CN in Example 2 of the present invention 1 H NMR spectrum.

[0058] Figure 3 is the M-I3-X1 in CD3CN in Example 4 of the present invention 1 H NMR spectrum.

[0059] Figure 4 This is a UV-visible absorption spectrum of the molecules synthesized by M-I1-X2, M-I3-X2, M-I8-X2, and M-I11-X2 in acetonitrile solution in the embodiments of the present invention.

[0060] Figure 5 This is a curve chart of the kinetic test of the film cationic polymerization rate induced by the molecules M-I1-X2, M-I3-X2, M-I8-X2, and M-I11-X2 in the embodiments of the present invention under 365nm light excitation.

[0061] Figure 6This is a kinetic curve of the thick film free radical polymerization rate initiated by the molecules of M-I1-X2, M-I3-X2, M-I8-X2, and M-I11-X2 in the embodiments of the present invention under the excitation of a 365nm LED light source.

[0062] Figure 7 This is the photolithography sensitivity diagram of the M-I11-X2 molecule in the embodiment of the present invention under the excitation of a 365nm LED light source. DETAILED DESCRIPTION

[0063] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented on the premise of the technical solution of the invention, and a detailed implementation method and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0064] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0065] The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0066] Example 1: Synthesis of M-I1-X1, the reaction route is as follows:

[0067]

[0068] Step 1: Dissolve 3.1 g of 2-methoxy-phenylboronic acid and 3.5 g of 4-bromobenzaldehyde in 40 mL of ethanol / water (1:1) mixture, stir at room temperature for 10 min, add 7.1 g of anhydrous sodium carbonate, add 0.06 g of palladium / carbon catalyst under nitrogen protection, react at room temperature for 0.5 h, monitor by thin layer chromatography, after the reaction of the raw materials is completed, filter to obtain a solid, remove the palladium / carbon catalyst and excess raw materials by column chromatography, and recrystallize from dichloromethane / petroleum ether to obtain intermediate 1 with a yield of 90%.

[0069] Step 2: Dissolve 3.8 g of p-toluenesulfonic acid and 3.38 g of diacetyl iodobenzene in 28 mL of dichloromethane, stir at room temperature for 15 min, add 2.12 g of intermediate 1, react overnight in the dark under nitrogen protection, and monitor by thin layer chromatography. After the reaction of the raw materials is completed, remove the solvent, wash with water, and recrystallize from dichloromethane / ether to obtain M-I1-X1 with a yield of 82%.

[0070] Example 2: The reaction route of M-I1-X2 is as follows:

[0071]

[0072] Specific steps: 2g of M-I1-X1 and 2g of sodium hexafluoroantimonate were dissolved in a 20mL dichloromethane / acetone mixed solution, stirred at room temperature for 4h under nitrogen protection and in the dark, the solvent was removed, washed with water, and recrystallized from dichloromethane / ether to obtain M-I1-X2 with a yield of 80%; 1 H NMR (400MHz, CD3CN) δ10.07 (s, 1H), 8.17–8.05 (m, 4H), 7.98 (d, J=8.3Hz, 2H), 7.77–7.68 (m, 3H), 7.57 (t, J=7.9Hz, 2H), 7.23 (s, 1H), 3.89 (s, 3H). The specific NMR spectrum is as follows Figure 2 shown.

[0073] Example 3: The reaction route of M-I1-X3 is as follows:

[0074]

[0075] Specific steps: dissolve 2g of M-I1-X1 and 2g of sodium ((4-adamantyl)-1-phenoxy)-1,1,2,2-tetrafluoroethane 1-sulfonate in 20mL of a mixed solution of dichloromethane / acetone, stir and react at room temperature for 4h under nitrogen protection and in the dark, remove the solvent, wash with water, and recrystallize from dichloromethane / ether to obtain M-I1-X3 with a yield of 86%.

[0076] Example 4: Synthesis of M-I3-X1, the specific reaction route is as follows:

[0077]

[0078] Step 1: Dissolve 3 g of intermediate 1 and 1 g of malononitrile prepared in Example 1 in 15 mL of methanol, stir at room temperature for 10 min, add 0.071 g of piperidine, react at room temperature for 0.5 h under nitrogen protection, monitor by thin layer chromatography, after the reaction of the raw materials is completed, filter to obtain a solid, and recrystallize from dichloromethane / petroleum ether to obtain intermediate 2 with a yield of 94%.

[0079] Step 2: Dissolve 2.1 g of p-toluenesulfonic acid and 1.8 g of diacetyl iodobenzene in 15 mL of dichloromethane, stir at room temperature for 15 min, add 1.6 g of intermediate 2, react overnight in the dark under nitrogen protection, and monitor by thin layer chromatography. After the reaction of the raw materials is completed, remove the solvent, wash with water, and recrystallize from dichloromethane / ether to obtain M-I3-X1 with a yield of 82%; 1H NMR (400MHz, CD3CN) δ8.15 (s, 1H), 8.10–8.07 (m, 3H), 7.99 (d, J = 8.3 Hz, 2H), 7.69 (dd, J = 15.9, 7.5 Hz, 3H), 7.53 (dd, J = 8.0, 3.1 Hz, 3H), 7.16 (dd, J = 22.2, 8.6 Hz, 3H), 3.88 (s, 3H), 2.33 (s, 3H). For specific NMR spectra, see Figure 3 .

[0080] Example 5: Synthesis of M-I3-X2, please refer to Example 2 for details.

[0081]

[0082] Yield: 81% 1 H NMR(400MHz,CD3CN)δ8.15(s,1H),8.14–8.07(m,4H),8.01(d,J=8.3Hz,2H),7.73 (dd, J=8.0, 4.3Hz, 3H), 7.56 (t, J=7.9Hz, 2H), 7.25 (d, J=8.7Hz, 1H), 3.90 (s, 3H).

[0083] Example 6: Synthesis of M-I8-X1, specifically refer to Example 1, except that 2-methoxyphenylboronic acid in step 1 is replaced with 2,4-dimethoxyphenylboronic acid. Others are the same as Example 1, and the molecular structure is shown in the figure below. The yield of M-I8-X1 is 86%. 1 HNMR(400MHz,CD3CN)δ10.17(s,1H),8.10–8.07(m,3H),7.99(d,J=8.3Hz,2H),7.66(dd,J=15.9, 7.5Hz, 3H), 7.51 (dd, J=8.0, 3.1Hz, 3H), 7.26 (dd, J=22.2, 8.6Hz, 3H), 4.04 (s, 3H), 3.88 (s, 3H).

[0084]

[0085] Example 7: Synthesis of M-I8-X2, please refer to Example 2 for details, and the molecular structure is shown in the figure below. 1 H NMR(400MHz,CD3CN)δ10.16(s,1H),8.17–8.05(m,4H),7.98(d,J=8.3Hz,2H),7 .77–7.68(m,3H),7.57(t,J=7.9Hz,2H),7.23(s,1H),4.01(s,3H),3.89(s,3H).

[0086]

[0087] Example 8: Synthesis of M-I11-X1, specifically referring to Example 3, except that 2-methoxyphenylboronic acid in step 1 is replaced with 2,4-dimethoxyphenylboronic acid. Others are the same as Example 3, and the molecular structure is shown in the figure below. Yield 84%. 1 H NMR(400MHz,CD3CN)δ8.11(s,1H),8.10–8.07(m,3H),7.99(d,J=8.3Hz,2H),7.69(dd,J=15.9,7 .5Hz,3H),7.51(dd,J=8.0,3.1Hz,3H),7.14(dd,J=22.2,8.6Hz,3H),3.78(s,3H),2.31(s,3H).

[0088]

[0089] Example 9: Synthesis of M-I11-X2, refer to Example 1 for details, the molecular structure is shown in the figure below. Yield: 82%. 1 H NMR(400MHz,CD3CN)δ8.15(s,1H),8.14–8.07(m,4H),8.01(d,J=8.3Hz,2H),7.71(dd,J= 8.0, 4.3Hz, 3H), 7.53 (t, J = 7.9Hz, 2H), 7.22 (d, J = 8.7Hz, 1H), 4.06 (s, 3H), 3.90 (s, 3H).

[0090]

[0091] <Experiment 1>

[0092] The UV-visible absorption spectra and related photophysical parameters of the target products in different embodiments were tested.

[0093] Accurately weigh a certain amount of the sample in the embodiment, dissolve it in a volumetric flask, and then test the UV-visible absorption spectrum. The specific curve is as follows: Figure 4 The maximum absorption wavelength, the molar extinction coefficient at the maximum absorption wavelength and the molar extinction coefficient at 365 nm are shown in Table 1.

[0094] Table 1 Photophysical parameters of four iodonium salts in acetonitrile solution in the examples

[0095]

[0096] <Experiment 2>

[0097] M-I1-X2, M-I3-X2, M-I8-X2, M-I11-X2 in epoxy group-containing monomer formula, in LED light curing experiment and coating property test:

[0098] Prepared according to the following formula (by weight percentage):

[0099] Bifunctional resin (EPOX): 97%

[0100] Photoinitiator M-I1-X2 or M-I3-X2 or M-I8-X2 or M-I11-X2 (with hexafluoroantimonate): 2%

[0101] The mixture prepared in the above example was applied to cardboard to form a coating of about 25-30 μm, and a unit power of 1000 mW / cm was used. 2 An LED light source (3 cm wide and 80 cm long LED surface light source) with an emission wavelength of 365 nm is used as the excitation light source and is placed on a variable speed conveyor belt. The criterion for photopolymerization curing to be completed is that no marks are left by repeated pressure and scratching of fingernails.

[0102] The results show that the compounds of this example are all efficiently cured at a speed higher than 25 m / min.

[0103] The coating obtained by light curing was tested for hardness by a hand-cranked pencil hardness tester, and the hardness was measured to be 3H.

[0104] The photopolymer kinetic curve of the formulation system under the excitation of a 365nm LED light source was tested by FT-IR, and the conversion rate was calculated based on the change in the relevant epoxy functional groups. The specific curve is as follows: Figure 5 As shown. Therefore, it can be found that the polymerization initiation effects of the four initiators are relatively good.

[0105] <Experiment 3>

[0106] M-I1-X2, M-I3-X2, M-I8-X2, M-I11-X2 in acrylate monomer formula, LED light curing experiment and coating property test:

[0107] Prepared according to the following formula (by weight percentage):

[0108] Trifunctional acrylate monomer, trimethylolpropane triacrylate (TMPTA): 97%

[0109] Photoinitiator M-I1-X2 or M-I3-X2 or M-I8-X2 or M-I11-X2 (with hexafluoroantimonate): 2%

[0110] The mixture prepared in the above example was applied to a cardboard to form a coating of about 30-35 μm, and a unit power of 1000 mW / cm was used. 2 An LED light source (3 cm wide and 80 cm long LED surface light source) with an emission wavelength of 365 nm is used as the excitation light source and is placed on a variable speed conveyor belt. The criterion for photopolymerization curing to be completed is that no marks are left by repeated pressure and scratching of fingernails.

[0111] The results show that the compounds of this example are all efficiently cured at a speed higher than 30 m / min.

[0112] The coating obtained by light curing was tested for hardness by a hand-cranked pencil hardness tester, and the hardness was measured to be 2H.

[0113] The photopolymer kinetic curve of the formulation system under the excitation of a 365nm LED light source was tested by FT-IR, and the conversion rate was calculated based on the change in the relevant double bond functional groups. The specific curve is as follows: Figure 6 As shown. Therefore, it can be found that the polymerization initiation effects of the four initiators are relatively good.

[0114] <Experiment 4>

[0115] Yellowing Testing of Light-Curing Formulations

[0116] The photocured coating was slowly aged by mercury lamp for 15 times and then the Δb value was tested. It was found that the iodonium salt formulas of M-I1 and M-I3 had a Δb<3.

[0117] <Experiment 5>

[0118] The photoresist of the present invention is prepared by mixing the following components, the amount of each component being expressed as a percentage of the photoresist component by weight based on the total weight of the photoresist composition:

[0119] Photoresist component dosage (wt%)

[0120] Resin adhesive 99%

[0121] Photoacid generator M-I11-X2 (1%)

[0122] The resin adhesive was SU-8 2005 negative photoresist without adding a photoacid generator purchased from Nanjing BestU Co., Ltd.

[0123] The minimum light energy or minimum charge per unit area that can cause all photosensitive inks to react is called the sensitivity of the photosensitive ink, also known as the sensitivity. Use a 21-level exposure ruler to measure the sensitivity of the photosensitive ink. Figure 7 The actual picture of the exposure scale is shown. It is divided into 21 grids, of which the first grid allows all incident light to pass through, and the light intensity of each grid thereafter is the intensity of the previous grid. When testing the sensitivity, the process is basically the same as the development test. You only need to replace the mask with an exposure scale before exposure. After development and drying, confirm the exposure scale level, that is, read the resin curing condition on the exposure scale pattern after development. The sensitivity of the material can be determined accurately and quickly through the level.

[0124] Specific steps: After the prepared photoresist is coated with a coating machine, it is heated on a hot plate with the temperature controlled at about 100°C. After covering with a mask, a wavelength of 365nm (light intensity of about 100mW.cm -2 ) light source for 25 seconds, then heated on a hot plate at 100°C, and then developed in isopropyl alcohol to obtain a photolithographic pattern. The photolithographic effect is evaluated by the exposure level of the exposure ruler. Figure 7 As shown, the sensitivity of the prepared photoacid generator under specific conditions is 12-14 grids, which shows that it has a high sensitivity in the application of photoresist formulation. It also proves that the photoacid generator has great potential in the application of negative photoresist.

[0125] The above description of the embodiments is to facilitate the understanding and use of the present invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments. Improvements and modifications made by those skilled in the art based on the principles of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. A diaryl iodonium salt compound having a biphenyl structure, characterized in that: It consists of a benzene ring, a biphenyl conjugated system with several substituents, a cation iodine and an anion X - Composition, its molecular structure is shown in the general formula M: in, R1 is selected from a hydrogen atom or a C1-C 10 A type of alkoxy group; R2 is selected from C1-C 10 Straight chain alkyl; R3 is selected from a hydrogen atom; R4 / R5 is selected from cyano or R4 / R5 is combined to form an oxygen atom; R6 is selected from a hydrogen atom; The anion X - The structure is selected from: SbF6 - X2。 2. Use of the diaryliodonium salt compound having a biphenyl structure as claimed in claim 1 as a photoinitiator in a photocuring formulation system.

3. The use according to claim 2, characterized in that: The emission wavelength of the light source of the photoinitiator is ultraviolet light or visible light.

4. The use according to claim 2, characterized in that: The photocurable formulation system comprises: (1) containing at least one compound of the general formula M as a photoinitiator or one of the photoinitiator components; (2) a polymerizable compound containing at least one unsaturated double bond or epoxy monomer; (3) The amount of the compound of the general formula M is 0.5-10 parts by weight per 100 parts by weight of the total amount of the polymerizable components in the system; (4) Additives.

5. The use according to claim 4, characterized in that: The unsaturated double bonds are selected from commonly used acrylic ester monomers and resins in photocurable formulations.

6. The use according to claim 5, characterized in that: The acrylic ester monomer is selected from at least one of tripropylene glycol diacrylate, 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

7. The use according to claim 5, characterized in that: The resins are selected from at least one of epoxy acrylate, polyurethane acrylate or polyester acrylate.

8. The use according to claim 4, characterized in that: The epoxy monomer is selected from one or more of the commonly used glycidyl ether or cyclohexene oxide derivatives in the photocuring formula.

9. The use according to claim 8, characterized in that: The epoxycyclohexane derivative is selected from at least one of epoxycyclohexane and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.

10. The use according to claim 4, characterized in that: The auxiliary agent is selected from at least one of acetone and dichloromethane.

11. Use of the diaryliodonium salt compound having a biphenyl structure as claimed in claim 1 as a photoacid generator in the field of photoresist preparation.

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