Photosensitive resin and manufacturing method thereof, photosensitive resin composition and photoresist

Abstract

The alkali-soluble photosensitive resin composition containing the comb-shaped structure has the advantages of being rapid in development, good in adhesive force, stable in heat resistance, sensitive in light sensitivity, rapid in curing, flat in surface after pattern forming, uniform in chromaticity and the like. The invention also relates to application of the photosensitive resin composition in preparation of a color filter, and the prepared color filter has good adhesive force.

Description

Technical Field

[0001] The present invention relates to the field of liquid crystal display manufacturing, and in particular to a photosensitive resin and a manufacturing method thereof, a photosensitive resin composition, and a color photosensitive resin composition containing the photosensitive resin. Background Art

[0002] Photoresist, also known as photoresist, is a photosensitive resin composition composed of photosensitive resin, photoinitiator and solvent. It can undergo cross-linking curing or degradation reaction (called photolithography) under the irradiation of ultraviolet light beam. Adding colorants (red, green and blue) to the photoresist makes a color photoresist (or a color photosensitive / photosensitive resin composition). The color photoresist is applied to a glass substrate to form a film and then photolithographed by ultraviolet light to form a color pattern to form a color filter. Color filters used for color liquid crystal display devices or shooting elements are usually manufactured using a pigment dispersion method: a red, blue or green monochrome photoresist is evenly coated on a glass substrate with a black matrix pattern, and then heated and dried to form a film (called pre-baking), and the formed coating is exposed to ultraviolet light, developed, and heated to cure (called post-baking) to obtain a single color color filter. Repeating the above operation according to different colors as needed can form a color filter containing three-color pixels, which is used in the field of thin film transistor liquid crystal display (TFT-LCD).

[0003] Photosensitive resin (sometimes also called prepolymer, oligomer or oligomer) is an important component of photosensitive resin composition. It is a photosensitive resin with relatively low molecular weight, which has a group that can undergo photocuring reaction. It is also an important material for the photosensitive resin composition to maintain stability after curing under ultraviolet light. Although there are many types of photosensitive resins, they are subject to the production and application process requirements of color filters. They must have a faster photocuring rate, a certain hardness, flexibility, thermal stability, adhesion, a faster development speed, good resolution, suitable curing shrinkage, and a certain yellowing resistance and chemical resistance. In addition, non-toxic or low irritation and high compatibility with the photocuring system are also necessary properties. However, such a large number of performance requirements inevitably have contradictory properties that need to be balanced. While taking into account several properties, the existing photosensitive resin materials often make concessions on some of them.

[0004] As people's living standards continue to improve, high color gamut has become the key development direction of TFT-LCD in the future. High color gamut means ensuring high color saturation of the three primary colors. To ensure high color saturation, it is necessary to increase the amount of pigment in the color photoresist. The increase in the amount of pigment in the color photoresist means that the formula development becomes slower. At the same time, a larger amount of pigment will also lead to a decrease in the adhesion of the color photoresist on the glass.

[0005] In view of the current insufficient performance of photosensitive resins, it is a realistic problem that needs to be solved urgently to develop a photosensitive resin with multiple excellent properties and design a color photosensitive resin composition around this photosensitive resin. Summary of the Invention

[0006] The object of the present disclosure is to provide a color photosensitive resin composition containing a comb-shaped photosensitive resin, which is characterized by high adhesion and excellent photosensitivity. Specifically, the comb-shaped photosensitive resin for the color photosensitive resin composition provided by the present invention has a structural formula represented by formula (H):

[0007]

[0008] In formula (H),

[0009] R 1 is H, and the two Rs 1 are not both H at the same time; R 2 is H, and the two Rs 2 are not both H at the same time; R 3 is H, and, and the two Rs 3 are not both H at the same time; R 5 is an alkyl group with 1 to 6 carbon atoms, Ph represents a phenyl group,

[0010] p = 0 to 300, q = 0 to 300, r = 0 to 600, p, q, r are not all 0 at the same time; n = 0 to 300, m = 0 to 600, and the total molecular weight of the resin = 1000 to 30000.

[0011] The above-mentioned comb-shaped photosensitive resin has a poly(norbornene) main chain and has strong rigidity. The side chain contains hydroxyl, carboxyl, and methacrylate structures. Among them, the hydroxyl group can improve the adhesion to the black glue organic layer or the silicon nitride substrate, and the hydroxyl group, carboxyl group, and polymethacrylate structure can improve the compatibility and stability of the resin in the photosensitive resin composition; the carboxyl group can improve the solubility of the photosensitive resin in the alkaline developer and improve the resolution; the resin also contains acrylic groups that can participate in photopolymerization, further improving the connection between the resin and other components of the color glue and enhancing the adhesion.

[0012] In a preferred embodiment of the present invention, R 5 is methyl,

[0013] p = 2 to 30, q = 2 to 30, r = 2 to 30, p + q + r is 10 to 80; n = 2 to 150, m = 2 to 50, preferably p = 2 to 20, q = 2 to 10, r = 2 to 10, p + q + r is 20 to 50; n = 2 to 10, m = 2 to 10,

[0014] Total molecular weight of the resin = 5000 to 20000.

[0015] On the other hand, the present invention provides a method for preparing a comb-shaped photosensitive resin, which is characterized by including a step of subjecting the monomer represented by formula B, the monomer represented by formula D, and the monomer represented by formula G to ring-opening metathesis polymerization under the action of a metal catalyst:

[0016]

[0017] R 1 is H, and the two Rs 1 are not both H at the same time; R 2 is H, and the two Rs 2 are not both H at the same time; R 3 is H, and, and the two Rs 3 are not both H at the same time; R 5 is an alkyl group having 1 to 6 carbon atoms.

[0018] In a preferred embodiment of the preparation method of the present invention, it is characterized in that R 5 is methyl, and monomers B, D, and G are polymerized according to the feeding ratio of p:q:r, where p = 2 to 30, q = 2 to 30, r = 2 to 30, p + q + r is 10 to 80; n = 2 to 150, m = 2 to 50,

[0019] preferably p = 2 to 20, q = 2 to 10, r = 2 to 10, p + q + r is 20 to 50; n = 2 to 10, m = 2 to 10.

[0020] In a preferred embodiment of the preparation method of the present invention, the metal catalyst is a ruthenium metal catalyst, preferably a Grubbs catalyst or a Hoveyda-Grubbs catalyst, and a further preferred metal catalyst is the following catalyst

[0021]

[0022] On the other hand, the present invention provides a photosensitive resin composition, which is characterized in that the photosensitive resin composition contains the above-mentioned comb-shaped photosensitive resin, and optionally a polyfunctional monomer, an initiator, a co-initiator, a solvent, and optionally an additive.

[0023] On the other hand, a color photoresist of the present invention comprises the above photosensitive resin composition and a colorant; the amount of the colorant is 200 to 500 parts by weight relative to 100 parts by weight of the photosensitive resin, and the colorant is a pigment and / or a dye. Detailed Description of the Invention

[0024] The following provides a more detailed explanation of the elements of the present invention.

[0025] In order to pursue development sensitivity, the main carbon chain of the photosensitive resin of existing color photoresists is generally a saturated carbon chain, and its photosensitive developability depends on the developability of the unsaturated groups on the side chain. Through in-depth research, the inventors unexpectedly found that when unsaturated double bonds are also introduced into the main chain, the photosensitive performance is improved, and due to the improvement of the connectivity between the resin itself and other components of the color resist and the substrate, there are beneficial effects on heat resistance, adhesion, and the profile after etching. Therefore, the inventors designed and synthesized the following photosensitive resin (prepolymer) of the present invention:

[0026] Its structural formula is represented by formula (H):

[0027]

[0028] In formula (H),

[0029] R 1 is H, and the two Rs 1 are not both H at the same time; R 2 is H, and the two Rs 2 are not both H at the same time; R 3 is H, and, and the two Rs 3 are not both H at the same time; R 5 is an alkyl group having 1 to 6 carbon atoms, and Ph represents a phenyl group,

[0030] p = 0 to 300, q = 0 to 300, r = 0 to 600, and p, q, and r are not all 0 at the same time; n = 0 to 300, m = 0 to 600, and the total molecular weight of the resin = 1000 to 30000.

[0031] The main chain of the compound of the present invention has double bonds, so as a photosensitive resin, it has the characteristics of high sensitivity, good adhesion, and good heat resistance. Through molecular design, the number of hydroxyl and carboxyl groups in the constituent monomers of the present invention is high, and the side chain also contains (meth)acrylate groups that can participate in photopolymerization. Overall, it can further improve characteristics such as sensitivity, adhesion, and heat resistance. The norbornene five-membered ring in this application cooperates well with the double bonds in the main chain, making the molecular chain have appropriate rigidity and further improving heat resistance and adhesion.

[0032] The -C=O(OR) substituent as the side chain, where R is substituted with a hydroxyl group, a carboxyl group, or a (meth)acrylate group, is the key to maintaining moderate reactivity and stability in the present invention.

[0033] As a preferred embodiment of the present invention, R 5 is methyl, p = 2 - 30, q = 2 - 30, r = 2 - 30, and p + q + r is 10 - 80; n = 2 - 150, m = 2 - 50. Preferably, p = 2 - 20, q = 2 - 10, r = 2 - 10, and p + q + r is 20 - 50; n = 2 - 10, m = 2 - 10, and the total molecular weight of the resin is 5000 - 20000. The applicant has found that the viscosity, fluidity, synthesis difficulty, and storage stability of such a photosensitive resin are more suitable for industrial production.

[0034] The photosensitive resin of the present invention can be synthesized by known methods. Through in-depth research, the inventor has found that ring-opening metathesis polymerization occurs through a metal-catalyzed ring-opening reaction to form the photosensitive resin of the present invention, which can make the synthesis process of the photosensitive resin of the present invention highly versatile. This is the recommended synthesis method of the present invention. For example:

[0035] Under the action of a metal catalyst, the monomers represented by Formula B, the monomers represented by Formula D, and the monomers represented by Formula G are brought into contact with each other to undergo a ring-opening metathesis polymerization step. Preferably, monomers B, D, and G are polymerized according to the feeding ratio of p:q:r, where p = 2 - 30, q = 2 - 30, r = 2 - 30, and p + q + r is 10 - 80; n = 2 - 150, m = 2 - 50. More preferably, p = 2 - 20, q = 2 - 10, r = 2 - 10, and p + q + r is 20 - 50; n = 2 - 10, m = 2 - 10.

[0036] The above-mentioned metal catalyst of the present invention is preferably a ruthenium metal catalyst, and more preferably a Grubbs catalyst or a Hoveyda-Grubbs catalyst. The so-called Grubbs catalyst is the ruthenium carbene complex catalyst commonly referred to, which is a catalyst in olefin metathesis reactions. It has been developed in three generations. The first-generation Grubbs catalyst: It is a purple solid that is stable to air, water, acids, or alcohols and was discovered by Grubbs in 1995. Its IUPAC name is benzylidene-bis(tricyclohexyl phosphine)dichlororuthenium (benzylidene·dichloro·bis(tricyclohexylphosphine)ruthenium). It is currently mainly used in several types of olefin metathesis reactions such as olefin cross-metathesis reactions, ring-opening metathesis polymerization reactions, acyclic diene metathesis polymerization reactions, and ring-closing metathesis reactions. The second-generation Grubbs catalyst was an improvement of the first-generation catalyst in 1999. By systematically studying the structure-performance relationship of the catalyst, it was found that the activity of the catalyst is related to the dissociation of one of the phosphorus ligands. It is believed that during the catalytic cycle, it passes through a highly active monophosphorus intermediate and then undergoes oxidative addition with the olefin. An N-heterocyclic carbene ligand with stronger electron-donating ability and higher stability than the phosphorus ligand replaces one of the phosphorus ligands, thus obtaining the second-generation Grubbs catalyst. It has higher activity and selectivity than the original catalyst and similar stability. Its catalytic activity is two orders of magnitude higher than that of the first-generation catalyst. The dosage in ring-opening metathesis polymerization reactions can be reduced to one part per million, and the dosage in some ring-closing metathesis reactions is only five parts per ten thousand. It is particularly suitable for the synthesis of low-strain cyclic olefins and highly substituted olefins with large steric hindrance. Its IUPAC name is benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium (benzylidene·[1,3-bis(trimethylphenyl)-2-imidazolinylidene]·dichloro·(tricyclohexylphosphine)ruthenium). The third-generation Grubbs catalyst was reported in 2002 as an improvement of the second-generation Grubbs catalyst. Although the second-generation Grubbs catalyst has extremely excellent reactivity towards cross-metathesis and ring-opening metathesis, the molecular weight of the polymer synthesized using the Grubbs II catalyst is not easily controlled, and there will be a relatively wide PDI distribution (due to the slow polymerization initiation rate and fast chain growth rate of the G II catalyst).If an improved third-generation Grubbs catalyst is used, due to its fast initiation and relatively high ki / kp value, monodisperse homopolymers and block copolymers can be synthesized. As the preferred catalyst of the present invention, the third-generation Grubbs catalyst is preferred, and its chemical structure is generally as follows.

[0037]

[0038] In addition, as an improved Grubbs catalyst with better thermal stability, the Hoveyda-Grubbs catalyst is also a preferred catalyst in the present invention.

[0039] The color photoresist containing the photosensitive resin of the present invention can still have various excellent properties even when containing more colorants, and is suitable for use in high-end display devices.

[0040] The technical solution of the present invention will be further described below through specific examples. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0041] Examples

[0042] Synthesis Example 1 Synthesis of Hydroxypropylmethacrylate Norbornene [B]

[0043]

[0044] Wherein R 1 is H, R 5 is methyl,

[0045] Weigh 1 eq of norbornene dianhydride and add it to a flask, and add a sufficient amount of anhydrous acetonitrile as a solvent. After stirring and dissolving, add 1.5 eq of deionized water, and stir well at 50 °C overnight. Subsequently, add 0.4 eq of tetrabutylammonium bromide and 1.6 eq of glycidyl methacrylate. After fully dissolving, reflux the reaction mixture for 12 h, and remove the solvent under reduced pressure. After dissolving with ethyl acetate, remove impurities through a neutral Al2O3 chromatography column. Precipitate with n-hexane, collect the precipitate, and remove the solvent until the mass no longer changes to obtain [B].

[0046] Synthesis Example 2 Synthesis of Poly(methyl methacrylate) Norbornene [D]

[0047]

[0048] Wherein R 2 is H, R 5 is methyl,

[0049] Purification: Methyl methacrylate (MMA) was distilled under reduced pressure, successively passed through a drying column composed of 5A molecular sieves and an oxygen removal column composed of silver molecular sieves, condensed and sealed in a Schlenk flask, and weighed.

[0050] Under nitrogen protection, 50 mL of anhydrous THF was added to a 100 mL Schlenk flask, cooled to -78 °C, and 1 eq of sec-butyllithium was added and stirred well. According to the initiator dosage and the designed molecular weight, MMA monomer was added and stirred well until the monomer reaction was completed. 3 eq of ethylene oxide was added to the flask and stirred well. After the reaction was completed, the temperature was gradually raised to 5 °C. 5 mL of deionized water was added to the flask to terminate the reaction. After evaporating the solvent, the polymer was dissolved in methanol, precipitated with petroleum ether and washed repeatedly, and then dried in a vacuum oven at 40 °C to constant weight to obtain polymethyl methacrylate [C] with isobutyl and vinyl alcohol units at both ends. By 1 Monitoring the ratio of the methoxy characteristic peak of methyl methacrylate at δ = 3.68 μm and the hydroxyl characteristic peak at the end of the [C] chain at δ = 2.69 μm by 1H-NMR (Bruker Avance II 400M, CDCl3), the number of repeating units n of polymethyl methacrylate can be calculated. In this example, the molecular weight of [C] was 600 and the number of repeating units n = 4.99.

[0051] 1 eq of norbornene dianhydride was weighed and added to the flask, and a sufficient amount of anhydrous acetonitrile was added as a solvent. After stirring and dissolving, 1.5 eq of deionized water was added, and the mixture was stirred well at 50 °C overnight. Subsequently, 0.4 eq of tetrabutylammonium bromide and 1.6 eq of [C] with hydroxyl equivalent were added and dissolved well. The reaction mixture was refluxed for 12 h, and the solvent was removed under reduced pressure. After dissolving with ethyl acetate, impurities were removed through a neutral Al2O3 chromatography column. Precipitated with n-hexane, the precipitate was collected and the solvent was removed until the mass no longer changed to obtain [D].

[0052] Synthesis of Poly(2,3-dihydroxy)butadienyl Norbornene [F] in Synthesis Example 3

[0053] Purification: 1,3-Butadiene (BD) was distilled, successively passed through a drying column composed of 5A molecular sieves and an oxygen removal column composed of silver molecular sieves, condensed and sealed in a Schlenk flask, and weighed.

[0054]

[0055] R’ is H or R” is H or R 3 is H, R 5 is methyl

[0056] Under nitrogen protection, 50 mL of anhydrous THF was added to a 100 mL Schlenk flask, and the temperature was lowered to -78 °C. 1 eq of sec-butyllithium was added and stirred well. According to the amount of initiator used and the designed molecular weight, m eq of BD monomer was added and stirred well until the monomer reaction was completed. 3 eq of ethylene oxide was added to the flask and stirred well. After the reaction was completed, the temperature was gradually raised to 5 °C, and methanol was added to terminate the reaction. After evaporating the solvent, the polymer was dissolved in petroleum ether, precipitated with methanol and washed repeatedly, and then dried in a vacuum oven at 40 °C to constant weight to obtain a colorless viscous jelly - polybutadiene with isobutyl and vinyl alcohol units at both ends [E]. By 1 Monitoring the ratio of the double bond characteristic peak of 1,4-polybutadiene at δ = 5.33 - 5.61 μm and the characteristic peak of the hydroxyl group at the chain end of [E] at δ = 2.69 μm by 1H-NMR (Bruker Avance II 400M, CDCl3), the number of repeating units m of 1,4-polybutadiene can be calculated. In this example, the molecular weight of [E] is 600, and the number of repeating units m = 9.33.

[0057] 1 eq of norbornene dianhydride was weighed and added to the flask, and a sufficient amount of anhydrous acetonitrile was added as a solvent. After stirring and dissolving, 1.5 eq of deionized water was added, and the mixture was stirred well at 50 °C overnight. Subsequently, 0.4 eq of tetrabutylammonium bromide and 1.6 eq of [E] in terms of hydroxyl equivalent were added and dissolved well. The reaction mixture was refluxed for 12 h, and the solvent was removed under reduced pressure. It was dissolved well with ethyl acetate, and the impurities were removed by passing through a neutral Al2O3 chromatography column. After evaporating the solvent until the mass no longer changed, norbornenyl-polybutadiene [F] was obtained.

[0058] 1 eq of [F] and an amount of acetonitrile as the solvent were added to the flask and dissolved well. Subsequently, 0.2 m eq of formic acid and 1.1 m eq of H2O2 (25%) were added, and the mixture was stirred at room temperature (about 25 °C) for 6 hours. The solvent and unreacted small molecules were removed under reduced pressure. Then, an amount of acetonitrile as the solvent was added again and dissolved well. Subsequently, 0.1 m eq of zirconium chloride and a sufficient amount of water were added, and the mixture was stirred at room temperature (about 25 °C) overnight. The solvent was dried under reduced pressure. It was dissolved well with ethyl acetate, and the impurities were removed by passing through a neutral Al2O3 chromatography column. After evaporating the solvent until the mass no longer changed, a colorless viscous jelly, norbornenyl-poly(2,3-dihydroxy)butadiene [G], was obtained.

[0059] Synthesis of photosensitive resin poly(hydroxypropyl methacrylate norbornene)-co-(poly(methyl methacrylate norbornene))-co-(poly(2,3-dihydroxy)butadiene norbornene) [H] in Synthesis Example 4

[0060]

[0061] R 1 、R2 , R 3 has the same meaning as the above statement.

[0062] Quantitative amounts of [B], [D], and [G] were added to a Schlenk flask, dissolved in anhydrous THF, and then a quantitative amount of the third-generation Grubbs catalyst was added. After reacting at room temperature for 3 hours, 3 - 5 drops of ethyl vinyl ether were added to terminate the reaction. The solvent was removed under reduced pressure. It was fully dissolved in ethyl acetate, and impurities were removed by passing through a neutral Al2O3 chromatography column. Petroleum ether was added to the collected solution to precipitate, and the supernatant was decanted. The remaining solvent was evaporated to dryness until the mass no longer changed, obtaining white powdery poly(hydroxypropyl norbornene methacrylate)-co-(polymethyl methacrylate norbornene)-co-(poly(2,3-dihydroxy)butadiene norbornene) [G].

[0063] By 1 1H-NMR (Bruker Avance II 400M, CDCl3), monitoring the characteristic double bond peaks of acrylate in the [B] unit at δ = 5.7 - 6.0 μm (the hydroxyl amount in the [B] unit can be calculated simultaneously), the characteristic double bond peaks of methoxy in the [D] unit at δ = 3.68 μm (the degree of polymerization of [C] needs to be combined), and the characteristic hydroxyl peaks of the [G] chain at δ = 3.2 - 3.3 μm (the hydroxyl amount of the [B] unit needs to be deducted, and the degree of polymerization of [E] needs to be combined), the proportion of each unit in [H] can be calculated. Using size exclusion chromatography (SEC), the molecular weight and molecular weight distribution of [H] can be measured. Among them, the third-generation Grubbs catalyst Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)bis(3-bromopyridine)

[0064] ruthenium(II) and ethyl vinyl ether were purchased from Macklin Reagents.

[0065] The structure of [H] measured in this experiment is as follows in the table:

[0066] Table 1 Structure and structural units of [H]

[0067]

[0068] Note:

[0069] The theoretical calculated value of the hydroxyl concentration [OH] = total molecular weight of the chain / number of hydroxyl groups on the chain. The smaller the [OH] value, the more hydroxyl groups on the corresponding chain;

[0070] The solid acid value Av was determined by the double titration method of NaOH / HCl.

[0071] Example 1

[0072] This embodiment provides a photosensitive resin composition, which is as follows:

[0073] 3 parts by weight of photoinitiator J, 1 part by weight of auxiliary initiator K, 200 parts by weight of colorant L, 100 parts by weight of multifunctional monomer M, 100 parts by weight of photosensitive resin [H-1], 0.2 parts by weight of additive O1, 0.3 parts by weight of O2, 100 parts by weight of solvent P1 and 50 parts by weight of solvent P2 were added and fully dissolved and mixed, and the solid content was controlled to be 20% to obtain a green photosensitive resin composition.

[0074] Photoinitiator J: tetraethyl Michler's ketone, purchased from Anaiji Chemical;

[0075] Co-initiator K: trade name Photomer 4771 (analytical grade), purchased from Corning Chemicals;

[0076] Colorant L1: green pigment dispersion, trade name G58, purchased from DIC Corporation;

[0077] Colorant L2: yellow pigment dispersion, trade name Y150, purchased from Toyo Ink;

[0078] L1 and L2 are mixed in proportion to form a mixed colorant L of a specified hue.

[0079] Multifunctional monomer M: dipentaerythritol hexaacrylate (analytical grade), purchased from Sartomer;

[0080] Additive N1: BYK-373 (trade name, purchased from BYK);

[0081] Additive N2: BYK-UV3570 (trade name, purchased from BYK);

[0082] Solvent P1: PGMEA (propylene glycol methyl ether acetate), purchased from Dow Chemical;

[0083] Solvent P2: PM (propylene glycol methyl ether), purchased from Dow Chemical.

[0084] Embodiments 2 to 4

[0085] The difference from Example 1 is that [H-1] is replaced by equal amounts of [H-2], [H-3], and [H-4].

[0086] Comparative Example 1

[0087] The difference from Example 1 is that [H-1] is replaced by an equal amount of [H-5].

[0088] Comparative Example 2

[0089] The difference from Example 1 is that [H-1] is replaced with an equal amount of [H-6].

[0090] Comparative Example 3

[0091] The difference from Example 1 is that [H-1] is replaced with an equal amount of [H-7].

[0092] Performance Test

[0093] The photosensitive resin compositions obtained in the examples and comparative examples were subjected to performance tests. The lithography imaging method using the photosensitive resin composition includes the following steps:

[0094] The glass slide was washed and dried, and spin-coated to obtain a uniform film layer of 1.5 μm. Pre-baked at 90 °C for 120 s, exposed to 365 nm ultraviolet light, the exposure dose was 40 mJ / cm 2 , the distance between the mask and the coated film was 180 μm, the developer was 0.4% KOH solution, developed at 23 °C for 50 s, post-baked at 230 °C for 20 min, and the subsequent related properties were tested. The results are shown in Table 4.

[0095] Specific test methods and evaluation methods:

[0096] 1) System compatibility: The photosensitive resin composition was stored in the dark at 0 °C, and the change in its viscosity was tested (for 6 months), and lithographed according to the process conditions. The surface of the color film was observed under an OM at x500 magnification to check for the presence of particles.

[0097] The evaluation criteria are as follows:

[0098] O: The viscosity change value < ±5% mPa·s and there are no particles on the x500 surface;

[0099] Δ: The viscosity change value < ±10% mPa·s and there are no particles on the x500 surface;

[0100] ×: The viscosity change value > ±10% mPa·s or there are particles on the x500 surface;

[0101] 2) Chromaticity test: After post-baking, the pixel film thickness is 2.0 μm, and different samples of photosensitive resin compositions are coated. After post-baking, the film thickness at the fixed pixel positions on each substrate is measured with a step profiler, and the hue and brightness at this position are measured with a Konica Minolta CM-5 chroma meter. According to this value, the same hue value (x = 0.2800, y = 0.6100) is regressed by chromaticity fitting method to measure the film thickness and brightness. Since the amount of pigment dispersion is the same between different examples and comparative examples, at the same hue value, the greater the film thickness, the worse the color intensity of the photosensitive resin composition using this resin; at the same hue value, the higher the brightness Y, the better the light transmittance of the photosensitive resin composition using this resin.

[0102] 3) Development performance test: After post-baking, the slices are cut, and the lap joint between the pixel and the glass substrate is measured under a 5000-fold SEM.

[0103] The evaluation criteria are as follows:

[0104] O: The edge line is straight and there is no residual film;

[0105] Δ: The edge line is straight and there is a little residual film;

[0106] ×: The edge line is distorted or there is a lot of residual film, and the edge line is not clear;

[0107] 4) Adhesion measurement: Refer to the national standard GB / T 9286-1998 Cross-cut test method for paints and varnishes films for testing and rating. The adhesion is divided into 6 grades in total. The coating adhesion decreases in turn from grade 0 to grade 5. Grade 0 is the best, and the paint film is intact; grade 5 is the worst.

[0108] 5) Heat resistance test: The heat resistance of the resin is verified by the film reduction rate and color difference. After post-baking at 230 °C for 20 min and repeating the post-baking twice, the film thickness is measured with an XP-2 step profiler;

[0109] The film reduction rate S = (the film thickness after the first post-baking - the film thickness after the second post-baking) / the film thickness after the first post-baking. If S < 3%, it indicates better heat resistance;

[0110] The color difference is the color difference value between the sample after the second post-baking and the sample after the first post-baking, which is measured by a Konica Minolta CM-5 chroma meter. If ΔEab < 3%, it indicates better heat resistance;

[0111] Table 2 Test results of photosensitive resin compositions

[0112]

[0113]

[0114] As can be seen from Table 2:

[0115] 1. There are a large number of [D] units in the chain of [H] series resins, and PMMA materials can effectively improve the compatibility with other materials in the formulation.

[0116] 2. The [H] series resins have little effect on chromaticity and luminance.

[0117] 3. There is a positive correlation between the development property and the acid value of [H]. The higher the acid value, the faster the development and the less residual film. In Examples 1, 3, 4 and Comparative Example 3 (corresponding to the use of [H-1], [H-3], [H-4], [H-7]), the acid values are higher, so the development property is better.

[0118] 4. Increasing the contents of hydroxyl and carboxyl groups in [H] can effectively improve the adhesion of the color film to the glass substrate. The main reason is that the hydroxyl and carboxyl groups on the photosensitive resin molecules can form hydrogen bonds with the exposed silicon oxygen atoms on the dry glass surface, and the hydrogen bonds fix the color film on the glass substrate, improving the ability of the pixel to resist the washing of the developer. [H-5] in Comparative Example 1 has fewer hydroxyl groups in the chain and poor adhesion; while [H-7] in Comparative Example 3 hardly contains hydroxyl groups in the chain, so the adhesion is the worst.

[0119] 5. In terms of heat resistance, the heat resistance of the norbornene structure is slightly better than that of the linear acrylate. Therefore, increasing the number of main chain norbornene units can improve the heat resistance of the formulation.

[0120] 6. Among the 4 examples and 3 comparative examples, [H-4] used in Comparative Example 4 has the best development property due to the highest acid value; due to containing more hydroxyl groups, it also has good adhesion; at the same time, the number of norbornene units in the chain is relatively large, having the best heat resistance among several examples.

[0121] The photoresist containing the photosensitive resin of the present invention has high adhesion, excellent photosensitivity, and other properties are also suitable for industrial production.

Claims

1. A comb-shaped photosensitive resin, characterized in that, Its structure is represented by the following formula (H): In formula (H), R 1 is H, and the two Rs 1 are not both H at the same time; R 2 is H, and the two Rs 2 are not both H at the same time; R 3 is H, and, and the two Rs 3 are not both H at the same time; R 5 is an alkyl group with 1 to 6 carbon atoms, and Ph represents a phenyl group, p = 0 to 300, q = 0 to 300, r = 0 to 600, p, q, and r are not simultaneously 0; n = 0 to 300, m = 0 to 600, and the total molecular weight of the resin = 1000 to 30000.

2. The comb-shaped photosensitive resin according to claim 1, wherein R 5 is methyl, p = 2 to 30, q = 2 to 30, r = 2 to 30, and p + q + r is 10 to 80; n = 2 to 150, m = 2 to 50. Preferably, p = 2 to 20, q = 2 to 10, r = 2 to 10, and p + q + r is 20 to 50; n = 2 to 10, m = 2 to 10. The total molecular weight of the resin = 5000 to 20000.

3. The preparation method of the comb-shaped photosensitive resin according to claim 1, characterized in that, It includes a step of subjecting the monomer represented by formula B, the monomer represented by formula D, and the monomer represented by formula G to ring-opening metathesis polymerization under the action of a metal catalyst: R 1 is H, and two Rs 1 are not both H at the same time; R 2 is H, and two Rs 2 are not both H at the same time; R 3 is H, and, and two Rs 3 are not both H at the same time; R 5 is an alkyl group with 1 to 6 carbon atoms.

4. The preparation method according to claim 3, wherein R 5 is methyl, and monomers B, D, and G are polymerized according to the feeding ratio of p:q:r, where p = 2 to 30, q = 2 to 30, r = 2 to 30, and p + q + r is 10 to 80; n = 2 to 150, m = 2 to 50, Preferably, p = 2 to 20, q = 2 to 10, r = 2 to 10, and p + q + r is 20 to 50; n = 2 to 10, m = 2 to 10.

5. The preparation method according to claim 3, characterized in that, The metal catalyst is a ruthenium metal catalyst, preferably Grubbs catalyst or Hoveyda-Grubbs catalyst.

6. The preparation method according to claim 5, characterized in that, The metal catalyst is 7. A photosensitive resin composition, characterized in that, The photosensitive resin composition contains the comb-shaped photosensitive resin according to claim 1, and optionally a polyfunctional monomer, an initiator, a co-initiator, a solvent, and optionally an additive.

8. A color photoresist, characterized in that, The color photoresist contains the photosensitive resin composition according to claim 7 and a colorant; Relative to 100 parts by weight of the photosensitive resin, the amount of the colorant used is 200 parts by weight to 500 parts by weight, and the colorant is a pigment and / or a dye.

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