Preparation method of negative photosensitive resin composition and cured pattern

Abstract

The present invention belongs to the field of photocuring technology, and specifically discloses a negative photosensitive resin composition and a cured film, wherein the negative photosensitive resin composition comprises the following components in parts by weight: (A) an alkali-soluble resin polymer, (B) a crosslinking agent, (C) a reactive diluent, and (D) a photoinitiator, wherein the crosslinking agent comprises a first crosslinking agent and a second crosslinking agent, wherein the first crosslinking agent is a compound containing an alkyloxy group, and the second crosslinking agent is a compound containing an epoxy group; the reactive diluent comprises a first reactive diluent and a second reactive diluent, wherein the first reactive diluent is a monofunctional tertiary amine compound containing an acrylic functional group, and the second reactive diluent is a multifunctional compound containing two or more unsaturated double bonds; the preparation method of the cured pattern is that the negative photosensitive resin composition is baked, exposed, developed, and cured. The formed cured pattern of the present invention has good adhesion and tensile properties.

Description

Technical Field

[0001] The invention relates to the technical field of photocuring, and in particular to a negative photosensitive resin composition and a method for preparing a cured pattern. Background Art

[0002] In electronic parts such as integrated circuit elements, organic EL elements, and printed circuit boards, various resin films are needed according to the different requirements of the electronic parts, such as protective films for preventing deterioration and damage of the parts themselves; planarizing films for flattening the surface of the elements and wiring; electrical insulating films for maintaining electrical insulation; image separation films for separating the light-emitting parts; optical films for focusing and diffusing light, etc.

[0003] Photosensitive resin compositions that can form resin films for various purposes as described above can be divided into positive photosensitive resin compositions and negative photosensitive resin compositions according to the solubility of the photosensitive portion in the developer. For the positive type, the exposed portion dissolves in the developer; for the negative type, the exposed portion is insoluble in the developer, while the other portion that is not exposed dissolves in the developer. The difference in properties between the positive photosensitive resin composition and the negative photosensitive resin composition is mainly due to the difference in components such as the resin polymer and the crosslinking agent used in the process.

[0004] The existing synthesis and improvement of thermosetting resin polymers and the processing of functional patterns mainly rely on photosensitizers to form positive resin compositions, which cannot form thick films due to low sensitivity; the resin polymers lose their alkali solubility and pose environmental hazards when developed with organic solvents. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects of the above-mentioned prior art and provide a negative photosensitive resin composition with high development retention rate, good adhesion and tensile properties and a method for preparing a cured pattern.

[0006] To achieve the above objectives and other related objectives, the present invention provides the following technical solutions.

[0007] In a first aspect, the present invention provides a negative photosensitive resin composition, comprising the following components in parts by weight:

[0008]

[0009] The crosslinking agent includes a first crosslinking agent and a second crosslinking agent, wherein the first crosslinking agent is an alkyloxy-containing compound, and the second crosslinking agent is an epoxy-containing compound. In the present invention, the crosslinking agents are all small-molecule thermal crosslinking agents, which can reduce the thermal stress between the resins during temperature rise and curing, thereby improving the overall substrate adhesion after curing. The first crosslinking agent will promote the alkali dissolution rate of the resin, and the second crosslinking agent will inhibit the alkali dissolution rate of the resin. The simultaneous use of the two can balance the alkali dissolution rate of the overall composition.

[0010] The reactive diluent includes a first reactive diluent and a second reactive diluent, wherein the first reactive diluent is a monofunctional tertiary amine compound containing an acrylic functional group, and the second reactive diluent is a multifunctional compound containing two or more unsaturated double bonds. The reactive diluents in the present invention are all small molecule reactive diluents, which can increase the flexibility of the entire cross-linked network during the photo-cross-linking reaction, and fill the gaps between the resins to increase the cross-linking density. The first type of reactive diluent can increase the degree of bonding between the resin and the photo-cross-linked network, thereby reducing the total amount of reactive diluent used, and the second type of reactive diluent mainly provides the performance of the photo-cross-linked network.

[0011] Furthermore, the cross-linking agent is selected from at least one of the following technical features:

[0012] a1) The first cross-linking agent is selected from the following structural formula:

[0013]

[0014] Among them, in formula B-1, R b1 , R b2 , R b3 and R b4 Each independently selected from C 1 ~C 6 In formula B-2, R b5 , R b6 , R b7 , R b8 , R b9 and R b10 Each independently selected from C 1 ~C 6 The alkyl group;

[0015] a2) the second crosslinking agent is selected from at least one of the following structural formulas,

[0016]

[0017] Among them, in formula B-3, R b11 and R b12 Each independently selected from a hydrogen atom or C 1 ~C6 In formula B-4, M b C 5 ~C 7 In formula B-5, R b13 , R b14 and R b15 Each independently selected from an epoxy structure or C 1 ~C 6 The alkyl group of R b13 , R b14 and R b15 At least one of them is an epoxy structure.

[0018] Furthermore, the cross-linking agent is selected from at least one of the following technical features:

[0019] a11) The first cross-linking agent is specifically selected from at least one of the following structures:

[0020]

[0021] a21) The second cross-linking agent is specifically selected from at least one of the following structures:

[0022]

[0023] Furthermore, the active diluent is selected from at least one of the following technical features:

[0024] b1) The first reactive diluent is selected from the following general structural formula:

[0025] Among them, R c1 Selected from hydrogen atoms or C 1 ~C 6 The alkyl group, R c2 and R c3 Each independently selected from C 1 ~C 6 An alkyl group, X is an oxygen atom or an imino group, 1≦q≦6;

[0026] b2b2) The second reactive diluent is selected from at least one of the following structural formulas:

[0027]

[0028] Among them, in formula C-2, R c4 Selected from hydrogen atoms or C 1 ~C 6 The alkyl group, X c Select from the following structures

[0029] Rc5 is selected from a hydrogen atom or a hydroxyl group, 2≦m≦4, and the dotted line is a bonding bond;

[0030] In formula C-3, R c6 and R c7 Each independently selected from a hydrogen atom or C 1 ~C 6 The alkyl group, M c C 5 ~C 10 Cyclic hydrocarbon groups;

[0031] In formula C-4, R c8 , R c9 and R c10 Each independently selected from a hydrogen atom or C 1 ~C 6 The alkyl group, Y c Select from the following structures The dotted line is the connecting key. The dotted line is the bonding key.

[0032] Furthermore, the active diluent is selected from at least one of the following technical features:

[0033] b11) The first reactive diluent is selected from at least one of the following structures:

[0034]

[0035] b21) The second reactive diluent is selected from at least one of the following structures:

[0036]

[0037]

[0038] Further, the photoinitiator includes a free radical photoinitiator and a co-initiator;

[0039] The free radical photoinitiator is selected from at least one of photoinitiator 819, photoinitiator TPO, photoinitiator TPO-L, photoinitiator OXE-01, photoinitiator OXE-02, photoinitiator OXE-03, photoinitiator OXE-04, photoinitiator BP, photoinitiator MBP, photoinitiator MK, photoinitiator EMK, photoinitiator ITX, photoinitiator DETX, photoinitiator CTX, photoinitiator CPTX, and photoinitiator BCIM;

[0040] The auxiliary initiator is selected from at least one of triethanolamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethylaniline, N,N-dihydroxyethyl-p-toluidine, hydrogen donor NPG, benzoic acid (2-dimethylamino) ethyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4,4',4"-tris (dimethylamino) triphenylmethane and the like hydrogen donors

[0041] Furthermore, the alkali-soluble resin polymer includes at least one of the following technical features:

[0042] c1) the weight average molecular weight of the alkali-soluble resin polymer is 3000-50000;

[0043] The preferred weight average molecular weight is 5000-30000,

[0044] A further preferred weight average molecular weight is 19000-24000

[0045] c2) the dissolution rate of the alkali-soluble resin polymer is

[0046] Preferred is

[0047] It is further preferred that

[0048] c3) The alkali-soluble resin polymer is selected from the following structural formula:

[0049]

[0050] Among them, the X 1 At least one selected from a benzene ring-containing structure and a siloxane-containing structure, Y 1 is selected from at least one of a benzene ring structure and a polyether structure; 7 is a hydrogen atom or an acylated structure; 0≦p≦2.

[0051] The alkali-soluble resin polymer also includes at least one of the following technical features:

[0052] d1) X 1 At least one selected from the following structures

[0053]

[0054] Among them, the dotted line represents the bonding bond;

[0055] d2) Y 1 At least one selected from the following structures,

[0056]

[0057]

[0058] Among them, the dotted line represents the bonding bond;

[0059] d3) The acylated structure is prepared by an acylating agent and a hydroxyl group, wherein the acylating agent is selected from at least one of norbornene anhydride, maleic anhydride, methacrylic anhydride, allyl succinic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride

[0060] Preferably, the acylating agent is selected from at least one of norbornene anhydride, maleic anhydride and methacrylic anhydride.

[0061] Furthermore, it also includes an organic solvent,

[0062] Preferably, the organic solvent is selected from at least one of anisole, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, γ-butyrolactone, N-methylpyrrolidone and ethyl lactate.

[0063] The second aspect of the present invention provides a method for preparing a cured pattern, comprising coating the negative photosensitive resin composition according to any one of claims 1 to 9 on a substrate, and performing baking, exposure, development and curing to obtain a cured pattern.

[0064] Furthermore, it also includes at least one of the following technical features:

[0065] e1) the baking temperature is 80-120° C.;

[0066] e2) The baking time is 1 to 10 minutes; for example, 3 minutes

[0067] e3) The exposure is performed using a 200W ultraviolet mercury lamp exposure machine;

[0068] e4) the developer is a 2.38% tetramethylammonium hydroxide aqueous solution;

[0069] e5) the curing temperature is 160-400° C.;

[0070] e6) The curing time is 1 to 3 hours, such as 1.5 hours.

[0071] e7) The thickness of the cured film is 5 to 20 μm, such as 7 μm.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] The present invention can provide a negative photosensitive resin composition that can be developed using alkali after exposure and can be cured at low temperature. When a crosslinking agent and a reactive diluent are used in combination, the negative photosensitive resin composition can obtain a higher development film retention rate at low energy during exposure, and the cured film has good adhesion and tensile properties. DETAILED DESCRIPTION

[0074] Unless otherwise indicated, implied from the context, or customary in the prior art, all parts and percentages in this application are based on weight, and the test and characterization methods used are all current as of the filing date of this application. Where applicable, the contents of any patent, patent application or publication referred to in this application are fully incorporated herein by reference, and their equivalent patent families are also incorporated by reference, especially the definitions of synthesis techniques, product and processing designs, polymers, comonomers, initiators or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

[0075] Numerical ranges in this application are approximate values, so unless otherwise specified, they may include values ​​outside the range. Numerical ranges include all values ​​from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the recorded component, physical or other properties (such as molecular weight, melt index, etc.) are 100 to 1000, it means that all single values ​​are clearly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a range comprising a value less than 1 or comprising a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately regarded as 0.0001, 0.001, 0.01 or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is generally considered to be 0.1. These are only specific examples of what is intended, and all possible combinations of numerical values ​​between the lowest and highest values ​​recited are considered to be expressly stated in this application. The numerical ranges within this application provide, among other things, calcium-containing filler content, stirring temperature, and various features and properties of these components.

[0076] When used with respect to chemical compounds, unless expressly specified otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly specified otherwise.

[0077] The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes, and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, unless explicitly stated, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, adjuvants or compounds. On the contrary, except for those necessary for operating performance, the term "essentially consisting of..." excludes any other components, steps or processes from the scope of any description of the term below. The term "consisting of..." does not include any components, steps or processes that are not specifically described or listed. Unless explicitly stated, the term "or" refers to the listed individual members or any combination thereof.

[0078] Example

[0079] The embodiments of the present invention will be described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.

[0080] The following are the various components used in the examples and comparative examples.

[0081] 1. Alkali soluble resin polymer A

[0082] Synthesis of Alkali-soluble Resin Polymer A1

[0083] 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.025 mol), 4,4'-diaminodiphenyl ether (0.020 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (0.005 mol), 4,4'-biphenyl ether dianhydride (0.49 mol) were dissolved in 190 g of N,N-dimethylformamide, stirred at room temperature for 12 hours, refluxed at 85°C for 4 hours, cooled to room temperature, and added with norbornene anhydride (0.04 mol) and methacrylic anhydride (0.01 mol). The mixture was stirred and reacted at -20 to 0°C for 24 hours. After filtration, precipitation and drying, a resin polymer A1 with a molecular weight of 24,000 was obtained.

[0084] Resin polymer A1 dissolution rate (ADR) measurement: Resin polymer A1 was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, and the ADR was measured to be

[0085] Synthesis of Alkali-soluble Resin Polymer A2

[0086] 2,2-Bis(4-hydroxy-3-aminophenyl)propane (0.015 mol), 4,4'-diaminodiphenyl ether (0.035 mol), 4,4'-biphenyl ether dianhydride (0.34 mol), 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride (0.14 mol) were dissolved in 220 g of N,N-dimethylformamide, stirred at room temperature for 12 hours, refluxed at 70°C for 6 hours, cooled to room temperature, maleic anhydride (0.025 mol) was added, stirred and reacted at 80-100°C for 6 hours, and resin polymer A2 with a molecular weight of 19000 was obtained after filtration, precipitation and drying.

[0087] Resin polymer A2 dissolution rate (ADR) measurement: Resin polymer A2 was immersed in a 2.38% TMAH aqueous solution, and the ADR was measured to be

[0088] Synthesis of Alkali-soluble Resin Polymer A3

[0089] 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.02 mol), 4,4'-diaminodiphenyl ether (0.03 mol), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (0.024 mol), 3,3',4,4'-biphenyltetracarboxylic dianhydride (0.025 mol), N,N-dimethylformamide diethyl acetal (0.2 mol) were dissolved in 230 g of N-methylpyrrolidone, stirred at room temperature for 12 hours, refluxed at 80°C for 5 hours, cooled to room temperature, maleic anhydride (0.025 mol) and methacrylic anhydride (0.015 mol) were added with stirring, reacted at 30-50°C for 12 hours, filtered, precipitated and dried to obtain resin polymer A3 with a molecular weight of 21000.

[0090] Resin polymer A3 dissolution rate (ADR) measurement: The resin polymer A3 was immersed in a 2.38% TMAH aqueous solution, and the ADR was measured to be

[0091] 2. Crosslinking agent B

[0092] B1: Tetramethoxymethyl glycoluril

[0093]

[0094] B2: Bisphenol A diglycidyl ether

[0095]

[0096] 3. Active diluent C

[0097] C1; Dimethylaminoethyl methacrylate

[0098]

[0099] C2: Triethylene glycol dimethacrylate

[0100]

[0101] C3: Trimethylallyl isocyanate

[0102]

[0103] 4. Photoinitiator combination D

[0104] D1, Photoinitiator: OXE-01, OXE-02, 819, EMK

[0105] Among them, the mass ratio of OXE-01, OXE-02, 819 and EMK is 2:1:5:1;

[0106] D2, photoinitiator: BP, ITX, EMK, hydrogen donor NPG,

[0107] Among them, the mass ratio of BP, ITX, EMK and NPG is 5:2:1:3;

[0108] D3, photoinitiator: 819, BP, ITX, hydrogen donor NPG

[0109] Among them, the mass ratio of 819, BP, ITX and NPG is 5:3:2:3;

[0110] 5. Organic solvents

[0111] 230 parts of gamma-butyrolactone.

[0112] Example 1

[0113] A negative photosensitive resin composition:

[0114]

[0115]

[0116] Method for preparing cured pattern

[0117] The above components were fully dissolved, and then a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked at 100°C for 4 minutes on a contact hot plate to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200 W was used for pattern exposure, and development was performed in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 190mJ, a development film retention rate of 94%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0118] Example 2

[0119] A negative photosensitive resin composition:

[0120]

[0121] Method for preparing cured pattern

[0122] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 195mJ, a development film retention rate of 85%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0123] Example 3

[0124] A negative photosensitive resin composition:

[0125]

[0126] Method for preparing cured pattern

[0127] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 210mJ, a development film retention rate of 87%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0128] Example 4

[0129] A negative photosensitive resin composition:

[0130]

[0131] Method for preparing cured pattern

[0132] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 205mJ, a development film retention rate of 91%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0133] Example 5

[0134] A negative photosensitive resin composition:

[0135]

[0136] Method for preparing cured pattern

[0137] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 235mJ, a development film retention rate of 86%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0138] Example 6

[0139] A negative photosensitive resin composition:

[0140]

[0141]

[0142] Method for preparing cured pattern

[0143] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 195mJ, a development film retention rate of 89%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0144] Example 7

[0145] A negative photosensitive resin composition:

[0146]

[0147] Method for preparing cured pattern

[0148] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 220mJ, a development film retention rate of 92%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0149] Example 8

[0150] A negative photosensitive resin composition:

[0151]

[0152] Method for preparing cured pattern

[0153] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 290mJ, a development film retention rate of 89%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0154] Example 9

[0155] A negative photosensitive resin composition:

[0156]

[0157] Method for preparing cured pattern

[0158] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 245mJ, a development film retention rate of 88%, an adhesion of 100 / 100, a tensile strength of>120MPa, and an elongation at break of>10%. The specific results are shown in Tables 1 and 2.

[0159] Comparative Example 1

[0160] A negative photosensitive resin composition:

[0161] Alkali soluble resin polymer A1 100 parts

[0162] Photoinitiator combination D1 12 parts

[0163] 230 parts of γ-butyrolactone

[0164] Method for preparing cured pattern

[0165] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 380mJ, a development film retention rate of 79%, an adhesion of 95 / 100, a tensile strength of 98MPa, and an elongation at break of 7.1%. The specific results are shown in Tables 1 and 2.

[0166] Comparative Example 2

[0167] A negative photosensitive resin composition:

[0168]

[0169] Method for preparing cured pattern

[0170] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 415mJ, a development film retention rate of 80%, an adhesion of 88 / 100, a tensile strength of 102MPa, and an elongation at break of 4.4%. The specific results are shown in Tables 1 and 2.

[0171] Comparative Example 3

[0172] A negative photosensitive resin composition:

[0173]

[0174] Method for preparing cured pattern

[0175] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 395mJ, a development film retention rate of 68%, an adhesion of 93 / 100, a tensile strength of 87MPa, and an elongation at break of 5.3%. The specific results are shown in Tables 1 and 2.

[0176] Comparative Example 4

[0177] A negative photosensitive resin composition:

[0178] Alkali soluble resin polymer A3 100 parts

[0179] Photoinitiator combination D3 13 parts

[0180] 230 parts of γ-butyrolactone

[0181] Method for preparing cured pattern

[0182] The above components were fully dissolved, and a spin coating method was used on a 4-inch silicon wafer. The rotation speed was adjusted and baked on a contact hot plate at 100°C for 4 minutes to form a photosensitive film of a specific film thickness. A UV mercury lamp exposure machine with a power of 200W was used for pattern exposure, and development was carried out in a TMAH 2.38% solution. After curing at 180°C for 0.5 hours and 250°C for 2 hours at a heating rate of 5 degrees Celsius per minute from room temperature, the temperature was lowered to 150°C at a rate of 2°C per minute, and then lowered to room temperature at a rate of 5°C per minute to obtain a 7um cured film with a photosensitivity of 340mJ, a development film retention rate of 73%, an adhesion of 95 / 100, a tensile strength of 99MPa, and an elongation at break of 6.5%. The specific results are shown in Tables 1 and 2.

[0183] The specific compositions and related properties of the above-mentioned Examples 1-9 and Comparative Examples 1-4 are shown in Table 1 below.

[0184] Photosensitivity: The minimum exposure energy required to maintain a film thickness change of less than 1% within 10 seconds after the substrate is exposed during development.

[0185] Film retention rate: Based on the boundary that the exposed part is just exposed after development, the residual film thickness of the unexposed part after development is T1, so the development film retention rate is T1 / original film thickness T.

[0186] Adhesion: The substrate is copper, and the test is carried out according to ASTM D3359 using a grid knife.

[0187] Tensile strength and elongation at break: Tested using a universal tensile testing machine in accordance with ASTM D882

[0188] Table 1 Example and Comparative Example Proportions

[0189]

[0190] Table 2 Performance of Examples and Comparative Examples

[0191]

[0192] Compared with Comparative Example 1-3, the difference between Example 1-9 is that two different cross-linking agents and three different reactive diluents are used in the resin composition in Example 1-9, while the cross-linking agent and reactive diluent are not used simultaneously in Comparative Example 1-3. Compared with Comparative Example 4, the difference between Example 1-9 and Comparative Example 4 is that two different cross-linking agents and three different reactive diluents are used in the resin composition in Example 1-9, while Comparative Example 4 only uses three different reactive diluents.

[0193] In Examples 1-9, the photosensitivity is between 190-290 mJ, with a maximum value of 290 mJ and a minimum value of 190 mJ; the development film retention rate is between 88-94%, with a maximum value of 94% and a minimum value of 88%, the adhesion is 100 / 100, the tensile strength is greater than 120 MPa, and the elongation at break is greater than 10%.

[0194] In comparative examples 1-4, the photosensitivity is between 340-410mJ, with a maximum value of 410mJ and a minimum value of 340mJ; the development film retention rate is between 68-80%, with a maximum value of 80% and a minimum value of 68%, the adhesion is 88 / 100-95 / 100, the tensile strength is 87-102MPa, and the elongation at break is 4.4-7.1%.

[0195] Therefore, the negative photosensitive resin composition is used in combination with different crosslinking agents and different reactive diluents, and a higher development film retention rate can be obtained at low energy during exposure, and the cured film has good adhesion and tensile properties.

[0196] The above-mentioned cured film can be applied to the semiconductor, electronic products and other industries, and can be specifically applied to the metal insulation layer, surface protection layer, stress buffer layer, device support layer and the like of semiconductor elements, packaging substrates and printed circuit boards.

Claims

1. A negative photosensitive resin composition, characterized in that: The composition comprises the following components in parts by weight: The cross-linking agent includes a first cross-linking agent and a second cross-linking agent, wherein the first cross-linking agent is a compound containing an alkyloxy group, and the second cross-linking agent is a compound containing an epoxy group; The reactive diluent includes a first reactive diluent and a second reactive diluent, wherein the first reactive diluent is a monofunctional tertiary amine compound containing an acrylic functional group, and the second reactive diluent is a multifunctional compound containing two or more unsaturated double bonds; a1) the first cross-linking agent is selected from at least one of the following structural formulas, Among them, in formula B-1, R b1 , R b2 , R b3 and R b4 Each independently selected from C1 to C6 alkyl; in formula B-2, R b5 , R b6 , R b7 , R b8 , R b9 and R b10 Each independently selected from C1 to C6 alkyl; a2) the second crosslinking agent is selected from at least one of the following structural formulas, Among them, in formula B-3, R b11 and R b12 Each is independently selected from a hydrogen atom or a C1-C6 alkyl group; In formula B-4, M b is a C5-C7 cyclic hydrocarbon group; In formula B-5, R b13 , R b14 and R b15 Each is independently selected from an epoxy structure or a C1-C6 alkyl group, and R b13 , R b14 and R b15 At least one of them is an epoxy structure; b1) The first reactive diluent is selected from the following general structural formula: Among them, R c1 is selected from a hydrogen atom or a C1-C6 alkyl group, R c2 and R c3 Each is independently selected from C1-C6 alkyl, X is an oxygen atom or an imino group, 1≦q≦6; b2) The second reactive diluent is selected from at least one of the following structural formulas: Among them, in formula C-2, R c4 is selected from a hydrogen atom or a C1-C6 alkyl group, X c Select from the following structures R c5 Selected from hydrogen atom or hydroxyl group, 2≦m≦4, the dotted line is the bond; In formula C-3, R c6 and R c7 Each independently selected from a hydrogen atom or a C1-C6 alkyl group, M c C5~C 10 Cyclic hydrocarbon groups; In formula C-4, R c8 , R c9 and R c10 Each independently selected from a hydrogen atom or a C1-C6 alkyl group, Y c Select from the following structures The solid lines are connecting bonds and the dotted lines are bonding bonds.

2. The negative photosensitive resin composition according to claim 1, characterized in that: The cross-linking agent is selected from at least one of the following technical features: a11) The first cross-linking agent is specifically selected from at least one of the following structures: a21) The second cross-linking agent is specifically selected from at least one of the following structures:

3. The negative photosensitive resin composition according to claim 1, characterized in that: The active diluent is selected from at least one of the following technical features: b11) The first reactive diluent is selected from at least one of the following structures: b21) The second reactive diluent is selected from at least one of the following structures:

4. The negative photosensitive resin composition according to claim 1, characterized in that: The photoinitiator includes a free radical photoinitiator and a co-initiator; The free radical photoinitiator is selected from at least one of photoinitiator 819, photoinitiator TPO, photoinitiator TPO-L, photoinitiator OXE-01, photoinitiator OXE-02, photoinitiator OXE-03, photoinitiator OXE-04, photoinitiator BP, photoinitiator MBP, photoinitiator MK, photoinitiator EMK, photoinitiator ITX, photoinitiator DETX, photoinitiator CTX, photoinitiator CPTX, and photoinitiator BCIM; The co-initiator is selected from at least one of triethanolamine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dihydroxyethylaniline, N,N-dihydroxyethyl-p-toluidine, NPG, (2-dimethylamino)ethyl benzoate, ethyl 4-dimethylaminobenzoate, 4,4',4"-tris(dimethylamino)triphenylmethane and the like hydrogen-containing donors.

5. The negative photosensitive resin composition according to claim 1, characterized in that: The alkali-soluble resin polymer includes at least one of the following technical features: c1) the weight average molecular weight of the alkali-soluble resin polymer is 3000-50000; c2) the dissolution rate of the alkali-soluble resin polymer is c3) The alkali-soluble resin polymer is selected from the following structural formula: Wherein, X1 is selected from at least one of a benzene ring-containing structure and a siloxane-containing structure, Y1 is selected from at least one of a benzene ring-containing structure and a polyether-containing structure; R7 is a hydrogen atom or an acylated structure; and 0≦p≦2.

6. The negative photosensitive resin composition according to claim 5, characterized in that: The alkali-soluble resin polymer also includes at least one of the following technical features: d1) X1 is selected from at least one of the following structures: Among them, the dotted line represents the bonding bond; d2) Y1 is selected from at least one of the following structures, Among them, the dotted line represents the bonding bond; d3) The acylated structure is prepared by reacting an acylating agent with a hydroxyl group, and the acylating agent is selected from at least one of norbornene anhydride, maleic anhydride, methacrylic anhydride, allyl succinic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

7. The negative photosensitive resin composition according to any one of claims 1 to 6, characterized in that: Organic solvents are also included.

8. A method for preparing a cured pattern, characterized in that: The negative photosensitive resin composition according to any one of claims 1 to 7 is coated on a substrate, and subjected to baking, exposure, development and curing to obtain a cured pattern.

9. The method for preparing a cured pattern according to claim 8, characterized in that: It also includes at least one of the following technical features: e1) the baking temperature is 80-120° C.; e2) the baking time is 1 to 10 minutes; e3) The exposure is performed using a 200W ultraviolet mercury lamp exposure machine; e4) the developer is a 2.38% tetramethylammonium hydroxide aqueous solution; e5) The curing temperature is 160-400°C.

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