A photosensitive resin composition, a varnish, and a cured film thereof

Abstract

The application discloses a photosensitive resin composition, a varnish and a cured film thereof, and comprises the following components in percentage by weight: a monomer compound 10-50%, a polymer 10-50%, an initiator 0.1-10%, a colorant 20-30%, a binder 0.1-5% and an interfacial active agent 0.01-1%. The monomer compound is a pentaerythritol acrylic acid modified compound. The composition does not produce gelation phenomenon, and the formed cured film can effectively solve the problem of poor solubility in an alkaline developing solution in a developing process, can reduce the filtration cost, and can improve the process yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive resin, more particularly, the present application relates to a photosensitive resin composition, varnish and cured film thereof. BACKGROUND

[0002] In the process of forming a pattern of a cured film of a photosensitive resin composition in a lithography process, the resin composition often appears gelation or the dispersion of a dyeing pigment, a dye or a fluorescent or phosphorescent material appears agglomeration after the key necessary processes of vacuum drying and pre-baking treatment, so that the solubility of the cured film of the composition in the commonly used alkaline developing solution is poor in the developing process, which directly leads to the following two problems:

[0003] 1. The alkaline developing solution used in the process directly leads to the decline of developing power because a large amount of incompletely salinized dissolved compound components appear in it, the phenomena include the decrease of the conductivity of the developing solution, the developing solution changes from clear to turbid state and contains a large amount of suspended substances, which directly leads to the large increase of the consumption rate of the filter cartridge consumables used in the tank body;

[0004] 2. The alkaline developing solution which is not highly completely filtered is reused through pipeline design, so that a large amount of suspended substances flow back through the nozzle of the developing equipment to cause blockage or be sprayed onto the glass substrate used in the color filter to form foreign matter pollution, which greatly reduces the process yield. SUMMARY

[0005] In view of this, the present application provides a photosensitive resin composition to solve the problem that the composition components of the prior art are prone to gelation, the solubility of the cured film formed in the alkaline developing solution in the developing process is poor, and the filtering efficiency is improved.

[0006] Based on this, the technical scheme of the present application is as follows:

[0007] The photosensitive resin composition includes, by weight ratio: monomer compound 10-50%, polymer 10-50%, initiator 0.1-10%, coloring agent 20-30%, adhesive 0.1-5%, and interfacial active agent 0.01-1%;

[0008] The monomer compound has the structural general formula of formula (1):

[0009]

[0010] wherein R represents two functional groups of R1 and R2; R1 and R2 respectively correspond to the structures of formula (2), formula (3)

[0011] Further, the molar ratio of R1 : R2 of the groups in the monomer compound is greater than 1.

[0012] Further, the polymer is selected from one or more of polysiloxane, cardo resin, methacrylic acid or acrylic acid resin polymerizable compound.

[0013] Preferably, the average molecular weight of the polymer is 15000 to 16000.

[0014] Further, the initiator is selected from halogenated hydrocarbon derivatives, compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having an imidazole skeleton, phosphine compounds, hexaarylbiimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aryl onium salts, α-hydroxy ketone compounds, α-amino ketone compounds.

[0015] Further, the adhesion agent is a silane compound containing a hydrolyzable group, which is a substituent that forms a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction, directly bonded to a silicon atom.

[0016] Further, the surfactant is selected from one or more of fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, polysiloxane surfactants.

[0017] Further, the colorant is an organic molecular color pigment or dye; the color pigment is selected from at least one of diimmonium compounds, squarylium inner onium salt compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, tetrakis- tea-embedded triphenyl compounds, ammonium compounds, immonium compounds, azo compounds, allium quinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexa-porphyrin compounds, metal dithiol compounds, copper compounds, tungsten compounds, and metal borides; the color dye is selected from at least one of pyrazole azo compounds, aniline azo compounds, triarylformazan compounds, allium quinone compounds, allium pyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenoxazone compounds, pyrrolopyrrole azomethine compounds, phthalocyanine compounds, benzofuran compounds, indigo compounds, pyrromethene compounds.

[0018] A photosensitive resin varnish including the photosensitive resin composition described above, and a solvent.

[0019] A photosensitive resin cured film is obtained by applying the photosensitive resin varnish described above to a substrate, exposing the substrate, and the like.

[0020] The present application has the following advantages:

[0021] The photosensitive resin composition provided by the present application can effectively solve the problem of poor solubility in an alkaline developing solution in the developing process, reduce filtration costs, and improve process yield by modifying the free radical polymerizable monomer, changing the problem of easy gelation when combined with a polymer resin and a colorant, and forming a cured film. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0023] The present application provides a photosensitive resin composition to solve the problem of a large amount of filter loss and subsequent adhesion of insoluble substances to a glass substrate, which reduces yield, caused by incomplete dissolution of components in an alkaline developing solution in the developing process. The main reason for the above characteristics is that the polymerizable monomer compound component of the general photosensitive composition mentioned in the background art is replaced by a monomer compound having the structure of formula (1):

[0024]

[0025] wherein R represents two functional groups R1 and R2; R1 and R2 correspond to the structures of formula (2) and formula (3), respectively

[0026] Specifically, in the embodiments of the present application, the photosensitive resin composition includes: monomer compound A 10-50%, polymer B 10-50%, initiator C 0.1-10%, colorant D 20-30%, adhesive E 0.1-5%, and surfactant F 0.01-1%, based on 100% of the total weight.

[0027] In the photosensitive resin composition described above, the monomer compound A contains functional groups of formula (2) and (3), which are used to improve solubility and reaction cross-linking, respectively, to reduce the free amount and impart an acrylic structure by cross-linking with the polymer B, to improve the solubility of the cured film in the alkaline developing solution in the developing process, to reduce the filtration operation intensity, and to improve the yield.

[0028] As a preferred embodiment, in the structural formula (1) of the monomer compound A, the number of moles of the group R1:R2 is greater than 1, that is, the number of groups of formula (2) is greater than the number of groups of formula (3), which can take into account the solubility and the degree of cross-linking.

[0029] As a preferred embodiment, each component in the photosensitive composition is preferably:

[0030] Polymer B: one or more selected from polysiloxane, cardo resin, methacrylic acid or acrylic acid resin polymerizable compound; the average molecular weight of the polymer is 15000 to 16000 to improve the pattern development property.

[0031] Initiator C: a compound having photosensitivity to light from ultraviolet light to the visible region, a common photoradical polymerization initiator is selected. Examples include, but are not limited to, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having an imidazole skeleton, etc.), phosphine compounds and hexaarylbiimidazole, oxime compounds, organic peroxide, sulfur compounds, ketone compounds, aryl onium salt, α-hydroxy ketone compounds, α-amino ketone compounds, etc.

[0032] Coloring agent D: is an organic molecular color pigment or dye, pigments refer to Japanese Patent Application Publication No. 2013-077009, Japanese Patent Application Publication No. 2014-130338, International Publication No. 2015 / 166779, etc. At least one of diimmonium compound, squarylium compound, cyanine compound, phthalocyanine compound, naphthalocyanine compound, tetraphenoxytriphenyl compound, ammonium compound, immonium compound, azo compound, quinonoid compound, porphyrin compound, pyrrolopyrrole compound, oxonol compound, croconium compound, hexaphyrin compound, metal dithiol compound, copper compound, tungsten compound and metal boride. Color dye, pyrazole azo compound, aniline azo compound, triarylformazan compound, quinonoid compound, pyridone compound, benzylidene compound, oxonol compound, pyrazolotriazole azo compound, pyridone azo compound, cyanine compound, phenoxazone compound, pyrrolopyrrole azomethine compound, phthalocyanine compound, benzopyran compound, indigo compound, pyrromethene compound.

[0033] Binder E: a component for improving the adhesion of a substrate or the like to the infrared ray shielding film. The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the infrared ray shielding film. As the adhesion aid, a functional silane coupling agent is generally selected. The silane coupling agent refers to a silane compound having a hydrolyzable group and another functional group. In addition, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and forms a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. As the hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, or the like can be cited, and an alkoxy group is preferred. Further, examples of the functional group other than the hydrolyzable group include a vinyl group, a (methyl)allyl group, a (methyl)acryl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, and a ureido group. Among them, an amino group, a (methyl)acryl group, and an epoxy group are preferred, and one or more of the above components can be selected.

[0034] Surfactant F: The surfactant can be selected from fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, polysiloxane surfactants, and the like, or the descriptions in International Publication No. 2015 / 166779, paragraphs 0238-0245, and International Publication No. 2016 / 158818, paragraphs 0166-0167, can be incorporated. The fluorine content in the fluorine-based surfactant is preferably 7-25 parts by mass. The fluorine-based surfactant having a fluorine content ratio within this range is effective in the thickness uniformity and liquid saving of the coating film, and also has good solubility in the composition.

[0035] As a preferred embodiment, in the above-described photosensitive resin composition, the polymer B includes repeating units of structures of formulae (4) to (8):

[0036]

[0037] wherein, as a matter of common knowledge in the art, p, q, r, s, and t each represent the degree of polymerization of a single repeating unit.

[0038] In another embodiment of the present application, a photosensitive resin varnish is provided, including the above resin composition, and an organic solvent G as necessary.

[0039] The organic solvent G can be selected from the compounds listed in Japanese Laid-Open Patent Publication No. 2011-232632 or at least one compound in the following group. It is preferable to have an amount of 500 parts by weight or less of the organic solvent G in 100 parts by weight of the photosensitive resin composition, because an appropriate ratio of the solvent can reduce the viscosity of the photosensitive resin composition, but if the ratio is too high, the thickness of the coated film can not be easily controlled.

[0040] In still another embodiment of the present application, a cured film comprising the above-mentioned photosensitive resin composition and a method for forming a filter are provided.

[0041] The photosensitive resin varnish formed using the above-mentioned material is coated on a substrate, exposed using a photomask and a radiation light source, heated or baked again before development to obtain a cured film, and then developed and baked after development to promote the curing reaction of the polymer, thereby obtaining a filter.

[0042] As an embodiment of the present application, the method for preparing a cured film or a filter is specifically as follows:

[0043] The photosensitive resin composition of the present application can be coated on the following substrates (Si, SiO2, SiN, SiN, TiN, WSi, BPSG, SOG, organic antireflection film, etc.) or treatment layers on the substrates (Cr, CrO, CrON, MoSi, SiO2, etc.) to obtain a coating layer having a thickness of 0.1 to 10.0 μm using a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating and doctor blade coating. Next, pre-baking is performed, and the conditions for pre-baking depend on the type and mixing ratio of each component, but generally, pre-baking is performed at a hot plate of 60 to 150°C for 10 seconds to 30 minutes, or preferably, pre-baking is performed at a temperature of 80 to 120°C for 30 seconds to 20 minutes to remove the solvent still contained in the photosensitive resin composition. Next, exposure is performed using a photomask having a predetermined pattern and a high-energy ray such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, an electron beam (e.g., electron beam and alpha ray), electromagnetic wave (X-ray, gamma ray and soft X-ray), excimer laser, synchrotron radiation, or one of the above light sources to obtain a target pattern. The exposure device can be an exposure machine using various methods such as mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens scanner, laser exposure, etc. In addition, exposure using a super resolution technique such as multiple exposure by performing multiple exposure or a method using a phase shift mask, annular illumination method, etc. can be performed. By using the super resolution technique, a pattern having higher resolution can be formed. The wavelength and energy of the light source are as follows: the wavelength is preferably selected from the range of 190 nm to 450 nm, and the exposure amount is about 10 to 300 mJ / cm 2 , preferably 100 to 200 mJ / cm 2 .

[0044] Next, the exposed portion is developed using a 0.1 to 5% by mass, preferably 2 to 3% by mass, of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH), choline hydroxide, tetraethylammonium hydroxide (TEAH), and tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or other aqueous alkali developer such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate; alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate. The method is rinsed for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, using a conventional method such as liquid immersion, immersion, shaking immersion, and spraying, to dissolve the exposed portion of the layer in the developer solution, leaving the unexposed portion undissolved, and without dissolving the substrate. After the development process, the desired pattern can be formed by air drying, for example, using compressed air or compressed nitrogen, after washing for 30 seconds or more and 90 seconds or less using ultrapure water. This process forms a negative pattern.

[0045] An organic solvent can also be used as a developer, including 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, and methylcyclohexanone, phenylacetone, methylphenylacetone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isopropyl formate, butyl formate, amyl formate, isoamyl formate, methyl pentanoate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, benzyl acetate, benzyl formate, phenethyl formate, methyl 3-phenylpropionate, benzyl propionate, phenethyl acetate, 2-phenylethyl acetate, and the like. These solvents can be used alone or in combination with two or more.

[0046] The rinsing after the development is performed using a solvent that is miscible with the developer but does not dissolve the cured film. Such a solvent is preferably an alcohol having 3 to 10 carbons, an ether compound having 8 to 12 carbons, an alkane, alkene, alkyne, or aromatic solvent having 6 to 12 carbons.

[0047] Finally, the cured film after the development is heated, and the polymerization reaction of the polymer is promoted by heating the patterned film using a heating device such as a hot plate or an oven. The heating temperature is, for example, higher than 200°C or lower than 250°C, and the heating time depends on the type of the heating device, for example, 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven.

[0048] The following examples and comparative examples are the compositions of each photosensitive resin, and the physical properties of each example and comparative example are detected after curing and film formation by experimental examples, which are used to verify the effect of the present application.

[0049] Table 1: Composition of photosensitive resin of examples and comparative examples

[0050]

[0051]

[0052] In the above Table 1: the structures of radical polymerization type monomer compounds A1, A2, A3, A4, A5 and A6 are respectively 0:8, 1:7, 5:3, 6:2, 7:1, 8:0 in the number ratio of groups R1 and R2 in formula (1). The synthesis method of monomer compounds A1 to A6 refers to the steps described in patent document CN103435516A, but for the compounds of structures A2 to A6, the original material of the described modified amino functional group needs to be replaced with maleic anhydride, and the addition ratio is adjusted to 0.15, 2.0, 3.2, 7.0 and 8.0 times the number of moles of the described trishydroxymethyl isopropylol, and the reaction is carried out according to the steps described therein to obtain the products of structures A2-A6. Polymer B is a combination of repeating units of structures of formula (4) to formula (8), which is composed in the order of 2:1:2:2:3 in molar ratio, and the molecular weight (Mw) is between 15000 and 16000 g / mol. Red and Blue colorants D represent red pigment 254 (C.I. Pigment Red 254) and blue pigment 15:6 (C.I. Pigment Blue 15:6), respectively.

[0053] The numbers in the brackets in each of the above examples 1-6 and comparative examples 1-7 represent the total composition ratio of the non-solvent in the overall formulation, and the solvent used is five times the non-volatile component mass.

[0054] Experimental example

[0055] The photosensitive resin composition mentioned by the curing film preparation method is coated on a glass substrate, and after vacuum drying and preheating treatment, the test piece is directly developed by the KOH 0.045wt% alkaline developing solution mentioned in the text of the present patent, the flowing developing solution is collected, and first visually judged for clarity after standing for 10 minutes, the judgment method is to measure the turbidity of the developing solution; in addition, a 5.0 μm needle cylinder type disc filter is used with a fixed pressure of 1 kg / cm 2Pushing was performed for the filtration test, and the evaluation method was to calculate the flow rate per minute (ml / min) and to classify it accordingly. The chemical resistance test was exemplified by the N-methylpyrrolidone (NMP) immersion test, which is a test in which a cured film is immersed in unheated NMP solvent for 30 minutes, and the variation in optical colorimetric value (CIE. 1976 Wxy) before and after the test is measured to calculate the deltaEab parameter, and then evaluated according to the following standards.

[0056] 1) The evaluation criteria for transparency were as follows:

[0057] D: turbidity of 15 or more;

[0058] C: 10 or more to less than 15;

[0059] B: 5 or more to less than 10;

[0060] A: less than 5.

[0061] 2) The flow rate (ml / min) evaluation criteria were as follows:

[0062] A: 10 to 15 ml / min;

[0063] B: 5 to 10 ml / min;

[0064] C: 1 to 5 ml / min;

[0065] D: less than 1 ml / min.

[0066] 3) The evaluation criteria for chemical resistance were as follows:

[0067] A: deltaEab < 3.0;

[0068] B: 3.0 < deltaEab < 5.0;

[0069] C: 5.0 < deltaEab < 10.0.

[0070] Table 2: Performance test results

[0071]

[0072]

[0073] From the results of the performance tests in Table 2, it can be seen that the photosensitive resin compositions of Examples 1-6 have good transparency (rated as A) and filtration efficiency (rated as B or above). If the number of R2groups is reduced or the R2groups are not present, the degree of crosslinking will decrease, which will result in a loss of other necessary properties of the cured film (Comparative Examples 1 and 2). Therefore, when the number of R1groups is reduced and the number of R2groups is increased, the transparency and filtration efficiency of Comparative Examples 3 and 4 decrease significantly. When the R1groups are not present (Comparative Example 3), the transparency and filtration efficiency are comparable to those of the prior art (Comparative Example 7), but there is a large amount of insoluble material, which severely affects the filtration efficiency. When the amount of the free-radical polymerizable monomer compound A3 (R1:R2=5:3) is 70% (Comparative Example 5) and 30% (Comparative Example 6), the transparency and filtration efficiency are improved to varying degrees compared to those of Comparative Example 7, and the resistance to chemical agents is maintained at the same level.

[0074] Finally, it should be noted that, although the present application has been described in detail above with reference to the general description and specific embodiments, the above examples are only used to illustrate the technical solutions of the present application and are not intended to limit the present application; although the present application has been described in detail above with reference to the above examples, those skilled in the art should understand that the technical solutions described in the above examples can be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A photosensitive resin composition, characterized in that, By weight percentage: monomeric compounds 10-50%, polymers 10-50%, initiators 0.1-10%, colorants 20-30%, adhesives 0.1-5%, and surfactants 0.01-1%; Monomer compounds have the general structural formula of formula (1): ， Where R represents the two functional groups R1 and R2; R 1、 R2 corresponds to the structures of equations (2) and (3) respectively. 、 。 2. The photosensitive resin composition according to claim 1, characterized in that, The molar ratio of functional groups R1:R2 in the monomer compound is greater than 1.

3. The photosensitive resin composition according to claim 1, characterized in that, The polymer is selected from one or more polymeric compounds of polysiloxane, cardo type resin, methacrylic acid, or acrylic resin.

4. The photosensitive resin composition according to claim 2, characterized in that, The polymer has an average molecular weight of 15,000 to 16,000.

5. The photosensitive resin composition according to claim 1, characterized in that, The initiator is selected from one or more of the following: halogenated hydrocarbon derivatives, phosphine compounds, hexaaryl diimidazole, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, and α-amino ketone compounds.

6. The photosensitive resin composition according to claim 1, characterized in that, The adhesive is a silane compound containing hydrolyzable groups, which are substituents that are directly bonded to silicon atoms and form siloxane bonds through at least one of hydrolysis and condensation reactions.

7. The photosensitive resin composition according to claim 1, characterized in that, The surfactant is selected from one or more of fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants.

8. The photosensitive resin composition according to claim 1, characterized in that, The colorant is an organic molecular color pigment or dye; the color pigment is selected from at least one of diimide compounds, squaric acid monazine salt compounds, anthocyanin compounds, phthalocyanine compounds, naphthyl phthalocyanine compounds, tetrachlorotriazole triazine compounds, ammonium compounds, imide compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxacyanine compounds, ketone compounds, hexaporin compounds, metal dithiols, copper compounds, tungsten compounds, and metal borides; the color dye is selected from at least one of pyrazolium azo compounds, aniline azo compounds, triarylmethyl alkyl compounds, anthraquinone compounds, anthraquinone compounds, benzyl compounds, oxacyanine compounds, pyrazolium triazole azo compounds, pyridone azo compounds, anthocyanin compounds, phenanthrene compounds, pyrrolopyrazolium azomethine compounds, phthalocyanine compounds, benzo[a]piperanone compounds, indigo compounds, and pyrrolemethylene compounds.

9. A photosensitive resin varnish, characterized in that, It includes the photosensitive resin composition according to any one of claims 1-8, and a solvent.

10. A photosensitive resin-cured film, characterized in that, The photosensitive resin varnish of claim 9 is applied to a substrate and then exposed to the substrate.

Images