Acrylate film-forming resin, preparation method thereof, photoresist and application

Abstract

The invention discloses acrylate film-forming resin and a preparation method thereof, photoresist and application, and belongs to the technical field of photoresist, the acrylate film-forming resin has a structure as shown in a chemical formula (1), # imgabs0 #. The acrylate film-forming resin is prepared by performing free radical polymerization reaction on an acrylic monomer containing a hydrophilic group and an acrylic monomer containing a sulfur atom and an aromatic ring group; through free radical polymerization reaction, an acrylic monomer containing a hydrophilic group and an acrylic monomer containing a sulfur atom and an aromatic ring group are copolymerized. In a designed chemical structure of acrylic resin, sulfur atoms, aromatic ring groups and hydrophilic groups, which are adjustable in number, are ingeniously introduced. According to the structural design, the refractive index and the adhesive force of the photoresist are remarkably improved, and a foundation is laid for optimizing the comprehensive performance of the resin.

Description

Technical Field

[0001] The invention belongs to the technical field of photoresists, and in particular relates to an acrylate film-forming resin and a preparation method thereof, photoresist and application thereof. Background Art

[0002] With the rapid development of science and technology, people's performance requirements for scientific and technological products are constantly increasing, driving optical products to have higher and higher performance requirements for optical components. For example, optical lenses, microlenses, anti-reflection films, optical fibers, light-emitting diodes and holographic projections can all be prepared with high-refractive-index optical materials to obtain better performance.

[0003] Acrylic resins, as traditional organic optical materials, offer advantages such as lightweight, photopolymerizability, excellent weather resistance, impact resistance, good transparency, easy processing and molding, and low cost. They are widely used in ophthalmic lenses, precision optical instruments, microelectronics, and optical devices. However, most current acrylic film-forming resins exhibit simple linear structures, resulting in poor plasma etching resistance. Furthermore, the resins exhibit poor adhesion to substrates, making them easily peelable.

[0004] The molecular backbone of acrylic film-forming resins is primarily composed of carbon-carbon and carbon-oxygen single bonds. These chemical bonds are relatively easy to break at high temperatures, resulting in poor heat resistance. For example, when the temperature exceeds a certain threshold, the carbon-oxygen single bonds may undergo thermal decomposition reactions, leading to degradation of the resin molecular chain. Prior art techniques can improve the resin's heat resistance by adding inorganic fillers such as silica and alumina to form a heat conduction network within the resin, rapidly dissipating heat. However, the addition of inorganic fillers may reduce the resin's transparency, affecting its application in optical applications.

[0005] While existing technologies improve heat resistance, they often find it difficult to balance the long-term stability and mechanical properties of resins at high temperatures, which leads to potential reliability issues in some application scenarios with long-term high-temperature operation. Summary of the Invention

[0006] The purpose of the present invention is to provide an acrylate film-forming resin and a preparation method thereof, a photoresist and an application thereof, so as to solve the problems of low refractive index, poor adhesion and heat resistance of the acrylate film-forming resin.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] In a first aspect, the present application provides an acrylic film-forming resin having a structure shown in formula (1):

[0009]

[0010] In formula (1), R1 is H or methyl, R2 is a hydrophilic group, the ratio of m:n:p is (10-60):(1-10):(10-30), and m, n and p respectively represent the molar content of the corresponding structural units, which is calculated based on the feed amount.

[0011] Furthermore, the hydrophilic group is one of the structures shown below:

[0012]

[0013] Furthermore, the weight average molecular weight of the high-refractive acrylic film-forming resin is preferably 10,000-25,000 g / mol.

[0014] The second aspect of the present application provides a method for preparing an acrylic film-forming resin, comprising the following steps:

[0015] The first monomer M1, the second monomer M2, and the third monomer M3 are added to a solvent and subjected to a free radical polymerization reaction in the presence of an initiator to obtain an acrylate film-forming resin;

[0016] The first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); the molar ratio m:n:p of the first monomer M1, the second monomer M2 and the third monomer M3 is (10-60): (1-10): (10-30);

[0017]

[0018] Furthermore, the free radical polymerization reaction is preferably carried out at 60-80°C.

[0019] Furthermore, the initiator is any one of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisovaleronitrile, azobisisoheptanenitrile, benzoyl peroxide, and tert-butyl benzoyl peroxide.

[0020] The solvent is one or more of methanol, ethyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and cyclohexanone.

[0021] Furthermore, the second monomer M2 is prepared by the following steps:

[0022] Step 1), 4,4-dimercaptodiphenyl sulfide and isocyanatoethyl methacrylate are subjected to an addition reaction in acetone, which is recorded as D1; the molar ratio of 4,4-dimercaptodiphenyl sulfide to isocyanatoethyl methacrylate is 1:(1.5-2); the temperature of the addition reaction is preferably 0-20°C;

[0023] Step 2), removing acetone from D1 obtained in step 1), and purifying it by column chromatography to obtain white crystals (4,4-dimercaptodiphenyl sulfide diisocyanate dimethacrylate), which is the second monomer M2;

[0024] The reaction principle is as follows:

[0025]

[0026] Furthermore, the third monomer M3 is prepared by the following steps:

[0027] Step 1), 4,4-dihydroxydiphenyl sulfide, triethylamine, and acryloyl chloride are subjected to an addition reaction in anhydrous ethyl acetate to obtain E1; the molar ratio of 4,4-dihydroxydiphenyl sulfide to acryloyl chloride is 1:(1.5-2); the temperature of the addition reaction is 0-20°C;

[0028] Step 2) removing ethyl acetate from E1 obtained in step 1) and purifying to obtain white crystals (4,4-dihydroxydiphenyl sulfide diacrylate), which is the third monomer M3.

[0029] The reaction principle is as follows:

[0030]

[0031] In a third aspect, the present application provides a photoresist comprising a solvent, a photosensitizer and the above-mentioned acrylate film-forming resin.

[0032] The photosensitizer is one or more of naphthoquinone diazide sulfonate, p-o-naphthoquinone diazide, naphthoquinone diazide, naphthoquinone diazide, and naphthoquinone diazide;

[0033] The solid content of the photoresist is 10% to 38%.

[0034] The fourth aspect of the present application proposes an application of the above-mentioned photoresist in a photolithography process, wherein the photoresist is coated on glass and sequentially subjected to pre-baking, exposure and development, wherein a 0.4 wt % tetramethylammonium hydroxide aqueous solution is used as a developer.

[0035] Beneficial effects of the present invention:

[0036] The present invention copolymerizes an acrylic monomer containing a hydrophilic group with an acrylic monomer containing a sulfur atom and an aromatic ring group through a free radical polymerization reaction. The designed acrylate chemical structure cleverly incorporates a controllable number of sulfur atoms and aromatic ring groups. This structural design not only significantly improves the refractive index and adhesion of the photoresist but also lays the foundation for optimizing the overall performance of the resin.

[0037] In the present invention, the molar ratio of monomers containing hydrophilic groups and having sulfur atoms and aromatic ring groups: the first monomer M1, the second monomer M2 and the third monomer M3 is controlled to be (10-60): (1-10): (10-30), thereby achieving a significant improvement in the heat resistance of the resin. This optimization not only enhances the stability of the photoresist in high-temperature environments, but also further expands its application potential in the fields of high-precision microelectronics manufacturing and optical devices. Through this unique monomer combination and ratio control, the present invention successfully balances the multiple key properties of the acrylate film-forming resin, making it perform well in terms of optical properties, adhesion and heat resistance, and provides a new solution for the development of photoresist technology. Through the synergistic effect of the three monomers, the present invention effectively overcomes the problems of poor adhesion and insufficient heat resistance of traditional acrylate photoresists while maintaining the advantages of high resolution and high sensitivity of acrylate resins, thereby expanding its scope of application in advanced photolithography processes. DETAILED DESCRIPTION

[0038] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0039] Obviously, the following descriptions are merely some examples or embodiments of the present application. Those skilled in the art can apply the present application to other similar scenarios without inventive effort. Furthermore, it is also understood that, although the effort involved in such a development process may be complex and lengthy, for those skilled in the art related to the content disclosed in the present application, changes in design, manufacturing, or production based on the technical content disclosed in the present application are merely conventional technical means and should not be construed as an insufficiency of the content disclosed in the present application.

[0040] However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters or repeated descriptions of substantially identical structures may be omitted. This is to avoid unnecessary redundancy in the following description and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter recited in the claims.

[0041] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution, and all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0042] The following is a detailed description of an acrylic film-forming resin and its preparation method, photoresist and application in the embodiments of the present application.

[0043] In a first aspect of the present application, an acrylate film-forming resin is provided, having a structure shown in formula (1):

[0044]

[0045] In formula (1), R1 is H or a methyl group, R2 is a hydrophilic group, and the ratio of m:n:p is (10-60):(1-10):(10-30), where m, n, and p represent the molar content of the corresponding structural unit, respectively, and are calculated based on the feed amount. m:n is (10-60):(1-10), such as 10:1, 15:2, 20:3, 25:4, 30:5, 35:6, 40:7, 45:8, 50:9, 60:10, or any value therebetween. n:p is (1-10):(10-30), such as 1:10, 2:12, 3:14, 4:16, 5:18, 6:20, 7:22, 8:24, 9:26, 10:30, or any value therebetween. It should be noted that the acrylic ester film-forming resin represented by formula (1) is only used to indicate the structural units contained and the content of each structural unit, and is not used to indicate the connection relationship between the structural units. Such structural units may exist in the form of random copolymers, alternating copolymers or block copolymers, preferably in the form of random copolymers.

[0046] In the present invention, the hydrophilic group is one of the structures shown below:

[0047]

[0048] In the present invention, the weight-average molecular weight of the high-refractive acrylate film-forming resin is preferably 10,000-25,000 g / mol, such as 10,000 g / mol, 12,000 g / mol, 14,000 g / mol, 16,000 g / mol, 18,000 g / mol, 20,000 g / mol, 25,000 g / mol, or any value therebetween. The PDI is preferably 1.6-2.1, such as 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, or any value therebetween. PDI is a polymer dispersity index, which is used to describe the molecular weight distribution of a polymer. The acrylate film-forming resin provided by the present invention has a higher PDI value and a wider molecular weight distribution range, which is more conducive to adjusting its performance.

[0049] A second aspect of the present invention provides a method for preparing an acrylic film-forming resin, comprising the following steps:

[0050] The first monomer M1, the second monomer M2, and the third monomer M3 are added to a solvent and subjected to a free radical polymerization reaction in the presence of an initiator to obtain an acrylate film-forming resin;

[0051] The first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); the molar ratio m:n:p of the first monomer M1, the second monomer M2 and the third monomer M3 is (10-60): (1-10): (10-30);

[0052]

[0053]

[0054] In the present invention, the free radical polymerization reaction temperature is preferably 60-80° C., such as 60° C., 62° C., 64° C., 66° C., 68° C., 70° C., 72° C., 74° C., 76° C., 78° C., 80° C., or any value therebetween. The polymerization reaction time is preferably 6-12 h, such as 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, or any value therebetween.

[0055] In the present invention, the initiator is any one of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisovaleronitrile, azobisisoheptanenitrile, benzoyl peroxide, and tert-butyl benzoyl peroxide.

[0056] In the present invention, the solvent is one or more of methanol, ethyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and cyclohexanone.

[0057] Furthermore, the second monomer M2 is prepared by the following steps:

[0058] Step 1), 4,4-dimercaptodiphenyl sulfide and isocyanoethyl methacrylate are subjected to an addition reaction in acetone, which is recorded as D1;

[0059] Step 2), removing acetone from D1 obtained in step 1), and purifying it by column chromatography to obtain white crystals (4,4-dimercaptodiphenyl sulfide diisocyanate dimethacrylate), which is the second monomer M2;

[0060] The reaction principle is as follows:

[0061]

[0062] In the present invention, in step 1) of preparing M2, the molar ratio of 4,4-dimercaptodiphenyl sulfide to ethyl isocyanate methacrylate is 1:(1.5-2), such as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1 or any value therebetween; the molar ratio of 4,4-dihydroxydiphenyl sulfide to acryloyl chloride is 1:(1.5-2), such as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1 or any value therebetween;

[0063] The temperature of the addition reaction is preferably 0-20°C, such as 0°C, 2°C, 4°C, 6°C, 8°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C or any value therebetween.

[0064] Furthermore, the third monomer M3 is prepared by the following steps:

[0065] Step 1), 4,4-dihydroxydiphenyl sulfide, triethylamine, and acryloyl chloride are subjected to addition reaction in anhydrous ethyl acetate to obtain E1;

[0066] Step 2) removing ethyl acetate from E1 obtained in step 1) and purifying to obtain white crystals (4,4-dihydroxydiphenyl sulfide diacrylate), which is the third monomer M3.

[0067] The reaction principle is as follows:

[0068]

[0069] In the present invention, in step 1) of preparing M3, the molar ratio of 4,4-dihydroxydiphenyl sulfide to acryloyl chloride is 1:(1.5-2), such as 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1 or any value therebetween; the addition reaction temperature is preferably 0-20°C; such as 0°C, 2°C, 4°C, 6°C, 8°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C or any value therebetween.

[0070] A third aspect of the embodiments of the present application provides a photoresist comprising a solvent, a photosensitizer and the above-mentioned acrylate film-forming resin.

[0071] The photosensitizer is one or more of naphthoquinone diazide sulfonate, p-o-naphthoquinone diazide, naphthoquinone diazide, naphthoquinone diazide, and naphthoquinone diazide;

[0072] The solid content of the photoresist is 10% to 38%, such as 10%, 14%, 18%, 22%, 26%, 30%, 34%, 38% or any value therebetween.

[0073] The fourth aspect of the embodiment of the present application proposes an application of the above-mentioned photoresist in a photolithography process, wherein the photoresist is coated on glass and sequentially subjected to pre-baking, exposure and development, wherein a 0.4 wt % tetramethylammonium hydroxide aqueous solution is used as a developer.

[0074] The following is a detailed description with reference to the embodiments.

[0075] Example 1

[0076] This embodiment provides a preparation method of an acrylic acid ester film-forming resin:

[0077] At room temperature, 3.2 g of methacrylic acid, 2.1 g of 4,4-dimercaptodiphenyl sulfide diisocyanatoethyl dimethacrylate, 12.2 g of 4,4-dihydroxydiphenyl sulfide diacrylate, and 0.53 g of azobisisobutyronitrile were dissolved in 70 g of propylene glycol methyl ether acetate. The mixture was heated to 60° C. under a nitrogen atmosphere for 12 h and then cooled to room temperature to obtain an acrylic resin, designated P1, having a weight-average molecular weight of 20101 g / mol and a PDI of 2.08.

[0078] Wherein, the structure of P1 is shown in formula (5):

[0079]

[0080] Example 2

[0081] This embodiment provides a preparation method of an acrylic acid ester film-forming resin:

[0082] At room temperature, 4.7 g of oxirane methacrylate, 1.7 g of 4,4-dimercaptodiphenyl sulfide diisocyanatoethyl dimethacrylate, 9.9 g of 4,4-dihydroxydiphenyl sulfide diacrylate, and 1.78 g of azobisisobutyronitrile were dissolved in 70 g of methanol. The mixture was heated to 50° C. under a nitrogen atmosphere for 6 h, and then cooled to room temperature to obtain an acrylic resin, designated P2, having a weight-average molecular weight of 18101 g / mol and a PDI of 1.64.

[0083] Wherein, the structure of P2 is shown in formula (6):

[0084]

[0085] Example 3

[0086] This embodiment provides a preparation method of an acrylic acid ester film-forming resin:

[0087] At room temperature, 2.1 g of 3-hydroxy-1-adamantyl methacrylate, 0.5 g of 4,4-dimercaptodiphenyl sulfide diisocyanatoethyl dimethacrylate, 2.9 g of 4,4-dihydroxydiphenyl sulfide diacrylate, and 1.5 g of azobisisobutyronitrile were dissolved in 70 g of propylene glycol methyl ether. The mixture was heated to 80° C. under a nitrogen atmosphere for 12 h, and then cooled to room temperature to obtain an acrylic resin, designated P3, having a weight-average molecular weight of 20160 g / mol and a PDI of 1.92.

[0088] Among them, the structure of P3 is shown in formula (7):

[0089]

[0090] Example 4

[0091] This embodiment provides a preparation method of an acrylic acid ester film-forming resin:

[0092] At room temperature, 2.5 g of p-hydroxyphenol methacrylate, 0.79 g of 4,4-dimercaptodiphenyl sulfide diisocyanate ethyl dimethacrylate, 4.6 g of 4,4-dihydroxydiphenyl sulfide diacrylate, and 1.63 g of azobisisobutyronitrile were dissolved in 70 g of propylene glycol methyl ether. The mixture was heated to 80° C. under a nitrogen atmosphere for 12 h, and then cooled to room temperature to obtain an acrylic resin, designated P4, having a weight-average molecular weight of 18160 g / mol and a PDI of 1.73.

[0093] Among them, the structure of P4 is shown in formula (8):

[0094]

[0095] Example 5

[0096] This embodiment provides a preparation method of an acrylic acid ester film-forming resin:

[0097] At room temperature, 1.4 g of hydroxypropyl methacrylate, 0.54 g of 4,4-dimercaptodiphenyl sulfide diisocyanatoethyl dimethacrylate, 3.1 g of 4,4-dihydroxydiphenyl sulfide diacrylate, and 1.23 g of azobisisobutyronitrile were dissolved in 70 g of propylene glycol methyl ether. The mixture was heated to 80° C. under a nitrogen atmosphere for 12 h, and then cooled to room temperature to obtain an acrylic resin, designated P5, having a weight-average molecular weight of 15660 g / mol and a PDI of 1.84.

[0098] Among them, the structure of P5 is shown in formula (9):

[0099]

[0100] Example 6

[0101] This embodiment provides a preparation method of a photoresist:

[0102] 35 wt % of acrylic resin P1, 3.0 wt % of photosensitizer (2,1,4-diazonaphthoquinone sulfonate), and 62 wt % of solvent (propylene glycol methyl ether acetate) were added to a clean glass container, and the glass container was fixed under a mechanical stirrer and stirred at room temperature for 12 h to allow the components to be fully dissolved. Then, the mixture was filtered using a filter with a pore size of 50 nm to obtain acrylate photoresist F1.

[0103] Example 7

[0104] This embodiment provides a preparation method of a photoresist:

[0105] Acrylate photoresist was prepared according to the method of Example 6, except that acrylic resin P2 with the same mass fraction was used instead of acrylic resin P1. Other conditions were the same, to obtain acrylate photoresist F2.

[0106] Example 8

[0107] This embodiment provides a preparation method of a photoresist:

[0108] Acrylate photoresist was prepared according to the method of Example 6, except that acrylic resin P3 with the same mass fraction was used instead of acrylic resin P1. Other conditions were the same, to obtain acrylate photoresist F3.

[0109] Example 9

[0110] This embodiment provides a preparation method of a photoresist:

[0111] Acrylate photoresist was prepared according to the method of Example 6, except that acrylic resin P4 with the same mass fraction was used instead of acrylic resin P1. Other conditions were the same, to obtain acrylate photoresist F4.

[0112] Example 10

[0113] This embodiment provides a preparation method of a photoresist:

[0114] Acrylate photoresist was prepared according to the method of Example 6, except that acrylic resin P5 with the same mass fraction was used instead of acrylic resin P1. Other conditions were the same, to obtain acrylate photoresist F5.

[0115] Comparative Example 1

[0116] Preparation of reference acrylate photoresist

[0117] A reference acrylate film-forming resin was prepared according to the method of Example 1, except that methacrylic acid with the same mass fraction was used instead of the second monomer M2. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP1.

[0118] A reference acrylate photoresist was prepared according to the method of Example 6, except that the reference acrylate film-forming resin DP1 was used instead of the acrylate film-forming resin P1 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF1.

[0119] Comparative Example 2

[0120] Preparation of reference acrylate photoresist

[0121] A reference acrylate film-forming resin was prepared according to the method of Example 2, except that the same mass fraction of methacrylate epoxypentane was used instead of the second monomer M2. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP2.

[0122] A reference acrylate photoresist was prepared according to the method of Example 7, except that the reference acrylate film-forming resin DP2 with the same mass fraction was used instead of the acrylate film-forming resin P2. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF2.

[0123] Comparative Example 3

[0124] Preparation of reference acrylate photoresist

[0125] A reference acrylate film-forming resin was prepared according to the method of Example 3, except that the same mass fraction of 3-hydroxy-1-adamantyl methacrylate was used instead of the second monomer M2. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP3.

[0126] A reference acrylate photoresist was prepared according to the method of Example 8, except that the reference acrylate film-forming resin DP3 with the same mass fraction was used instead of the acrylate film-forming resin P3. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF3.

[0127] Comparative Example 4

[0128] Preparation of reference acrylate photoresist

[0129] A reference acrylate film-forming resin was prepared according to the method of Example 4, except that the same mass fraction of p-hydroxyphenol methacrylate was used instead of the second monomer M2. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP4.

[0130] A reference acrylate photoresist was prepared according to the method of Example 9, except that the reference acrylate film-forming resin DP4 was used instead of the acrylate film-forming resin P4 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF4.

[0131] Comparative Example 5

[0132] Preparation of reference acrylate photoresist

[0133] A reference acrylate film-forming resin was prepared according to the method of Example 5, except that the same mass fraction of hydroxypropyl methacrylate was used instead of the second monomer M2. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP5.

[0134] A reference acrylate photoresist was prepared according to the method of Example 10, except that the reference acrylate film-forming resin DP5 was used instead of the acrylate film-forming resin P5 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF5.

[0135] Comparative Example 6

[0136] Preparation of reference acrylate photoresist

[0137] A reference acrylate film-forming resin was prepared according to the method of Example 1, except that methacrylic acid with the same mass fraction was used instead of the third monomer M3. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP6.

[0138] A reference acrylate photoresist was prepared according to the method of Example 6, except that the reference acrylate film-forming resin DP6 was used instead of the acrylate film-forming resin P1 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF6.

[0139] Comparative Example 7

[0140] Preparation of reference acrylate photoresist

[0141] A reference acrylic ester film-forming resin was prepared according to the method of Example 2, except that the third monomer M3 was replaced by methacrylate epoxypentane at the same mass fraction. Other conditions were the same to obtain a reference acrylic ester film-forming resin, which was recorded as DP7.

[0142] A reference acrylate photoresist was prepared according to the method of Example 7, except that the reference acrylate film-forming resin DP7 with the same mass fraction was used instead of the acrylate film-forming resin P2. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF7.

[0143] Comparative Example 8

[0144] Preparation of reference acrylate photoresist

[0145] A reference acrylate film-forming resin was prepared according to the method of Example 3, except that the third monomer M3 was replaced by 3-hydroxy-1-adamantyl methacrylate at the same mass fraction. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP8.

[0146] A reference acrylate photoresist was prepared according to the method of Example 8, except that the reference acrylate film-forming resin DP8 was used instead of the acrylate film-forming resin P3 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF8.

[0147] Comparative Example 9

[0148] Preparation of reference acrylate photoresist

[0149] A reference acrylate film-forming resin was prepared according to the method of Example 4, except that the third monomer M3 was replaced by p-hydroxyphenol methacrylate at the same mass fraction. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP9.

[0150] A reference acrylate photoresist was prepared according to the method of Example 9, except that the reference acrylate film-forming resin DP9 was used instead of the acrylate film-forming resin P4 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF9.

[0151] Comparative Example 10

[0152] Preparation of reference acrylate photoresist

[0153] A reference acrylate film-forming resin was prepared according to the method of Example 5, except that the third monomer M3 was replaced by hydroxypropyl methacrylate at the same mass fraction. Other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP10.

[0154] A reference acrylate photoresist was prepared according to the method of Example 10, except that the reference acrylate film-forming resin DP10 was used instead of the acrylate film-forming resin P5 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF10.

[0155] Comparative Example 11

[0156] Preparation of reference acrylate photoresist

[0157] A reference acrylate film-forming resin was prepared according to the method of Example 1, except that the molar ratio of the first monomer M1, the second monomer M2 and the third monomer M3, m:n:p, was 10:10:1, the total monomer input mass remained unchanged, and other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP11.

[0158] A reference acrylate photoresist was prepared according to the method of Example 6, except that the reference acrylate film-forming resin DP11 was used instead of the acrylate film-forming resin P1 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF11.

[0159] Comparative Example 12

[0160] Preparation of reference acrylate photoresist

[0161] A reference acrylate film-forming resin was prepared according to the method of Example 1, except that the molar ratio of the first monomer M1, the second monomer M2 and the third monomer M3, m:n:p, was 10:10:5, the total monomer input mass remained unchanged, and other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP12.

[0162] A reference acrylate photoresist was prepared according to the method of Example 6, except that the reference acrylate film-forming resin DP12 was used instead of the acrylate film-forming resin P1 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF12.

[0163] Comparative Example 13

[0164] Preparation of reference acrylate photoresist

[0165] A reference acrylate film-forming resin was prepared according to the method of Example 1, except that the molar ratio of the first monomer M1, the second monomer M2 and the third monomer M3, m:n:p, was 10:10:9, the total monomer input mass remained unchanged, and other conditions were the same to obtain a reference acrylate film-forming resin, which was recorded as DP13.

[0166] A reference acrylate photoresist was prepared according to the method of Example 6, except that the reference acrylate film-forming resin DP13 was used instead of the acrylate film-forming resin P1 at the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist, which was recorded as DF13.

[0167] Test Example 1

[0168] The acrylate photoresist obtained in Examples 6 to 10 and Comparative Examples 1 to 13 was used in a photoresist process. The specific steps were as follows: the acrylate photoresist solution obtained was injected into 2*1*0.5cm 2In a square acrylic mold, at room temperature and a light intensity of 80W / cm 2 The optical resin was cured under UV conditions for 2 minutes to obtain the optical resin. The refractive index of the optical resin is shown in Table 1.

[0169] Test Example 2

[0170] The acrylate photoresists obtained in Examples 6 to 10 and Comparative Examples 1 to 13 were used in a photoresist process. The specific operating steps were as follows: the acrylate photoresist solution obtained above was spin-coated onto glass at a spin coating speed of 300 rpm. After coating the photoresist solution, the glass sheet was pre-baked at 90° C. for 120 seconds. The glass sheet with the photoresist film was irradiated under an exposure machine to form a pattern, and the exposure amount was gradually changed. The exposed glass sheet was developed using a 0.4 wt % tetramethylammonium hydroxide aqueous solution for 65 seconds to obtain a photoresist pattern.

[0171] Interfacial Adhesion Performance Evaluation: Photoresist patterns formed on glass sheets were observed using an optical microscope. A value of √ indicates good resistance to peeling during development (even at high exposure doses, fine patterns showed little peeling); ○ indicates no peeling of large patterns, although some peeling of fine patterns was observed at high exposure doses; and × indicates complete peeling of the photoresist pattern, including the large pattern. The results are shown in Table 1.

[0172] Test Example 3

[0173] The acrylate photoresists obtained in Examples 6 to 10 and Comparative Examples 1 to 13 were used in a photoresist process. The specific steps are as follows:

[0174] Thermal stability evaluation: The relationship between sample mass and temperature was measured using a thermogravimetric analyzer (TGA-Q500) in a nitrogen atmosphere. Accurately weigh 10.0 mg of sample was heated from room temperature to 600°C in a nitrogen atmosphere at a heating rate of 10°C / min. Thermogravimetric analysis was performed on each polymer sample, and the temperature at which the sample lost 5% of its weight during heating was recorded.

[0175] Test Example 4

[0176] The acrylate photoresists obtained in Examples 6 to 10 and Comparative Examples 1 to 13 were used in a photoresist process. The specific steps are as follows:

[0177] Light transmittance evaluation: The test was performed using a UV-visible spectrophotometer Hitachi U-3010. The test wavelength range was 300 to 800 nm, the sampling interval was 1 nm, the test sample was attached to a clean glass sheet, and the surface of the test sample was smooth and flat. The sample film thickness was approximately 30 μm.

[0178] Table 1

[0179]

[0180]

[0181] The acrylate polymer with a high sulfur content in the acrylate photoresist prepared by the present invention exhibits high refractive index. The high molecular packing density of the molecular chain induced by the rigid unit and the high molar refractive index of the thioether bond synergistically impart high refractive index, and the flexible thioether bond in the molecular chain increases the chain mobility and reduces chain stacking. The test results of Examples 6 to 10 and Comparative Examples 1 to 13 show that the resin molecular chains of F1 to F5 contain urethane bonds and thiourethane bonds with low bond energy connected to the benzene ring (poor thermal stability), but F3 contains a rigid molecular monomer with excellent thermal stability. Therefore, the resin corresponding to F3 in Examples 6 to 10 has good thermal stability; the flexible thioether bond and methylene group are conducive to separating chromophores and disrupting intramolecular conjugated interactions; the bulky side groups perpendicular to the polymer main chain in the resin molecular chain corresponding to F3 restrict the movement of the polymer molecular chain, thereby exhibiting high light transmittance.

[0182] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0183] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. An acrylic film-forming resin, characterized in that It has the structure shown in formula (1): In formula (1), R1 is H or methyl, R2 is a hydrophilic group, the ratio of m:n:p is (10-60):(1-10):(10-30), and m, n and p respectively represent the molar content of the corresponding structural units, which is calculated based on the feed amount.

2. An acrylate film-forming resin according to claim 1, characterized in that, The hydrophilic group is one of the structures shown below:

3. An acrylate film-forming resin according to claim 1, characterized in that, The weight average molecular weight of the acrylic ester film-forming resin is 10,000-25,000 g / mol.

4. A method for preparing an acrylic film-forming resin according to any one of claims 1 to 3, characterized in that: The steps include: The first monomer M1, the second monomer M2, and the third monomer M3 are added to a solvent and subjected to a free radical polymerization reaction in the presence of an initiator to obtain an acrylate film-forming resin; The first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); 5. The method for preparing an acrylic acid ester film-forming resin according to claim 4, wherein: The free radical polymerization reaction is at 60-80°C.

6. The method for preparing an acrylic film-forming resin according to claim 4, wherein: The initiator is any one of azobisisobutyronitrile, dimethyl azobisisobutyrate, azobisisovaleronitrile, azobisisoheptanenitrile, benzoyl peroxide, and tert-butyl benzoyl peroxide.

7. The method for preparing an acrylic film-forming resin according to claim 4, wherein: The solvent is one or more of methanol, ethyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and cyclohexanone.

8. Use of the acrylate film-forming resin according to claim 1 in a photolithography process.

9. A photoresist, characterized in that The photoresist comprises a solvent, a photosensitizer and the acrylate film-forming resin according to claim 1.

10. The photoresist according to claim 9, characterized in that: The solid content of the photoresist is 10% to 38%; the photosensitizer is one or more of naphthoquinone diazide sulfonate, p-o-naphthoquinone diazide, o-quinone diazide, naphthoquinone diazide, and naphthoquinone diazide.

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