Initiator composition, negative photosensitive resin composition, preparation method for patterned cured film, and insulating film

Abstract

The present invention belongs to the technical field of photocurable photosensitive materials, and particularly relates to an initiator composition, a negative photosensitive resin composition, a preparation method for a patterned cured film, and an insulating film. The initiator composition comprises: 0.1-10 parts of a photoinitiator, 0.5-5 parts of an auxiliary photoinitiator, and 0.5-10 parts of a thermal initiator, wherein the photoinitiator is a hydrogen-abstracting photoinitiator; the auxiliary photoinitiator is a cationic photoinitiator; and the thermal initiator is a peroxide initiator. The negative photosensitive resin composition comprises: 100 parts of a polyimide precursor, 1.1-25 parts of the initiator, 0.1-10 parts of a polymerization inhibitor, and 5-50 parts of a cross-linking agent. The preparation method for a patterned cured film comprises: dissolving the negative photosensitive resin composition in an organic solvent, and performing exposing, developing and curing. The insulating film is formed by curing the negative photosensitive resin composition. The formed negative photosensitive resin composition has good storage stability, and has significantly improved exposure sensitivity during a pattern curing process; and the formed cured film has good elongation at break.

Description

Initiator composition, negative photosensitive resin composition, method for preparing patterned cured film, and insulating film TECHNICAL FIELD

[0001] The present application relates to the technical field of photocuring photosensitive materials, and particularly relates to an initiator composition, a negative photosensitive resin composition, a method for preparing a patterned cured film, and an insulating film. BACKGROUND

[0002] The photosensitive resin composition can undergo a photocuring reaction when irradiated with light to form a photosensitive resin film. The photosensitive resin film is subjected to a photolithography process to form a photosensitive resin film pattern. In the manufacturing process of electronic components and semiconductor devices, these patterns can be used as insulating film patterns or protective film patterns.

[0003] In order to make the photosensitive resin composition more convenient for patterning, a thermosetting resin is usually processed in the form of a precursor solution. In order to achieve excellent physical properties after curing of the photosensitive resin, a common technical means is to add a curing catalyst or a crosslinking agent to the precursor solution to enhance the mechanical strength after low-temperature curing. However, the additional active monomers in the formula usually face the problem of balancing high reactivity and storage stability. Some technical documents disclose the relationship affecting the stability of the composition formula, but the research results are still difficult to meet the current production process requirements.

[0004] SUMMARY

[0005] The purpose of the present application is to overcome the defects of the prior art and provide a new negative photosensitive resin composition with good storage stability. The purpose of the present application is to provide a method for preparing an insulating film.

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

[0007] In a first aspect, the present application provides an initiator composition, comprising the following components by mass:

[0008] photoinitiator 0.1-10 parts; such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts;

[0009] co-photoinitiator 0.5-5 parts; such as 1 part, 2 parts, 3 parts, 4 parts

[0010] thermal initiator 0.5-10 parts; such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts;

[0011] The photoinitiator is a hydrogen abstraction type photoinitiator, the co-photoinitiator is a cationic photoinitiator, and the thermal initiator is a peroxide initiator.

[0012] The hydrogen abstraction type photoinitiator absorbs light energy, is excited and undergoes intersystem crossing to an excited triplet state, and undergoes bimolecular reaction with the co-photoinitiator, a hydrogen donor, to produce active radicals through electron transfer.

[0013] The cationic photoinitiator absorbs light energy to reach an excited state, and the molecule undergoes photolysis to produce super acid, i.e. super strong protonic acid.

[0014] The thermal initiator is a compound that is easily decomposed into radicals (i.e. primary radicals) by heat.

[0015] Further, the photoinitiator is selected from at least one of a benzophenone type photoinitiator, a thioxanthone type photoinitiator, and a quinone type photoinitiator.

[0016] Further, the main photoinitiator comprises at least one of the following technical features:

[0017] a1) the benzophenone type photoinitiator is selected from at least one of benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone, 2,4,6-trimethylbenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2-hydroxybenzophenone, 4-hydroxy-benzophenone, methyl o-benzoylbenzoate;

[0018] Preferably, the benzophenone type photoinitiator is selected from at least one of 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone

[0019] a2) the thioxanthone type photoinitiator is selected from at least one of 2-isopropylthioxanthone, 2,4-diethylthioxanthone;

[0020] Preferably, the thioxanthone type photoinitiator is selected from 2,4-diethylthioxanthone,

[0021] a3) the quinone type photoinitiator is selected from at least one of 2-ethylanthraquinone, DL-camphorquinone

[0022] Further, the co-photoinitiator is selected from at least one of iodonium salt, sulfonium salt, and quaternary ammonium salt.

[0023] Preferably, the co-photoinitiator is an onium salt composed of a cation composed of iodonium, sulfonium, or quaternary ammonium structure and an anion composed of a sulfonyl-containing structure.

[0024] Further, the co-initiator comprises at least one of the following technical features:

[0025] b1) the iodonium salt is selected from the following general structures I-1 and I-2

[0026] wherein R 11 is selected from C6-C 20 aromatic groups, R 12 is selected from C6-C 20 aromatic groups or C1-C 20 alkyl groups, or R 11 , R 12 form a five- or six-membered ring with the iodine ion, R 13 is selected from C6-C 20 aromatic groups, C1-C 10 alkyl groups, C1-C 10 halogenated alkyl groups or C1-C 15 imino groups, R 14 is selected from halogen atoms, C1-C 10 alkyl groups, C1-C 10 halogenated alkyl groups or C6-C 20 aromatic groups, R 15 is selected from C1-C 10 sulfonyl groups or C1-C 20 carbonyl groups, or R 14 , R 15 form a five- or six-membered ring with the nitrogen ion, the sulfonyl group;

[0027] Preferably, R 11 is selected from the following structures:

[0028] Preferably, R 12 is selected from the following structures:

[0029] Preferably, R 11 , R 12 form a five- or six-membered ring with the iodine ion (i.e. iodonium cation) are selected from the following structures:

[0030] Preferably, R 13 is selected from the following structures:

[0031] Preferably, R 14 is selected from the following structures:

[0032] Preferably, R 15 is selected from the following structures:

[0033] Preferably, said R 14 , R 15 form a five- or six-membered ring with the nitrogen ion, the sulfonyl group or the sulfoxyl group (i.e. the anion of the sulfonyl structure) is selected from the following structures:

[0034] Further preferably, said iodonium salt of general formula I-1 is selected from at least one of the following structures:

[0035] Preferably, said iodonium salt of general formula I-2 is selected from at least one of the following structures:

[0036] b2) said sulfonium salt is selected from the following general structures II-1 and II-2

[0037] wherein said R 21 is selected from C6-C 20 aromatic groups, R 22 , R 23 are each independently selected from C1-C 10 alkyl groups, C6-C 20 aromatic groups or C1-C 20 carbonyl groups, or R22, R 23 form a five- or six-membered ring with the sulfur ion; R 24 is selected from C6-C 20 aromatic groups, C1-C 10 alkyl groups, C1-C 10 haloalkyl groups or C1-C 15 imino groups, R 25 is selected from halogen atoms, C1-C 10 alkyl groups, C1-C 10 haloalkyl groups or C6-C 20 aromatic groups, R 26 is selected from C1-C 10 sulfonyl groups or C1-C 20 carbonyl groups, or R 25 , R 26 form a five- or six-membered ring with the nitrogen ion, the sulfonyl group or the sulfoxyl group;

[0038] Preferably, said R 21 is selected from the following structures:

[0039] Preferably, said R 22 , R 23 are each independently selected from the following structures:

[0040] Preferably, the R 22 , R 23 form a five- or six-membered ring with the sulfur ion selected from the following structures

[0041] Preferably, the R 24 , R 25 form a five- or six-membered ring with the sulfur ion selected from the following structures 26 , R 13 , R 14 form a five- or six-membered ring with the sulfur ion selected from the following structures 15 Further preferably, the sulfonium salt II-1 is selected from at least one of the following structures

[0042] Further preferably, the sulfonium salt II-2 is selected from at least one of the following structures

[0043] b3) the quaternary ammonium salt is selected from the following general structures III-1 and III-2:

[0044] wherein the R 31 , R 32 or R 33 are each independently selected from C1-C 10 alkyl or C6-C 20 aromatic groups, or the R 31 , R 32 form a five- or six-membered ring with the nitrogen ion, or the R 31 , R 32 , R 33 form a five- or six-membered ring or a bridged ring with the nitrogen ion, R 34 is selected from C6-C 20 aromatic groups, C1-C 10 alkyl, C1-C 10 haloalkyl or C1-C 15 imino, R 35 is selected from halogen atoms, C1-C 10 alkyl, C1-C 10 haloalkyl or C6-C 20 aromatic groups, R 36 is selected from C1-C 10 sulfonyl or C1-C 20 carbonyl, or the R 35 , R 36 form a five- or six-membered ring with the nitrogen ion, sulfonyl.

[0045] Preferably, the R 31 , R 32 or R33 each independently selected from the group consisting of:

[0046] Preferably, said R 31 , R 32 form a five- or six-membered ring with the nitrogen ion selected from the group consisting of:

[0047] Preferably, said R 31 , R 32 , R 33 form a five- or six-membered ring or a bridged ring (i.e. quaternary ammonium cation) with the nitrogen ion selected from the group consisting of:

[0048] Further preferably, said quaternary ammonium salt of general formula III-1 is selected from at least one of the following structures:

[0049] Preferably, said quaternary ammonium salt of general formula III-2 is selected from at least one of the following structures:

[0050] Further, said thermal initiator is selected from at least one of the group consisting of dibenzoyl peroxide, 1,1-di-tert-butylperoxy cyclohexane, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, dicumyl peroxide, di-tert-butylperoxy isopropylbenzene, di-tert-butyl peroxide, tert-butyl isopropylbenzene peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.

[0051] Preferably, said thermal initiator is selected from dicumyl peroxide, di-tert-butylperoxy isopropylbenzene, di-tert-butyl peroxide.

[0052] Preferably, said thermal initiator has a thermal decomposition temperature in the range of 110°C to 250°C, further preferably a thermal decomposition temperature in the range of 130°C to 180°C. In a second aspect, the present application provides a negative-working photosensitive resin composition comprising:

[0053] Further, said polyimide precursor comprises at least one of the following technical features:

[0054] c1) said polyimide precursor has a molecular weight in the range of 3000 to 80000; preferably a molecular weight in the range of 5000 to 50000, further preferably a molecular weight in the range of 30000 to 40000, such as 32300, 34700, 38900;

[0055] c2) said polyimide precursor comprises the following general structure formula IV: c2) said polyimide precursor comprises the following general structure formula IV:

[0056] wherein X is selected from a tetravalent organic group having a C6-C 30 aromatic structure; Y is selected from a divalent organic group having a C6-C 30 aromatic structure or a C1-C 20 alicyclic structure; R1and R2are each independently selected from a hydrogen atom or a C3-C 30 ethylenically unsaturated bond organic group, a urea group, a thiourea group.

[0057] Preferably, the X is selected from at least one of the following structures:

[0058] Preferably, the Y is selected from at least one of the following structures:

[0059] Preferably, the R1and R2are each independently selected from at least one of the following structures:

[0060] R3is an alkane structure having a carbon number of 1-8, and n is a positive integer of 1-8.

[0061] Preferably, when the end group of the polyimide precursor is an amino group, the end-capping agent is an anhydride-containing monomer selected from at least one of (meth)acrylic anhydride, (meth)norbornene anhydride, maleic anhydride, 4-methacryloyloxy trimellitic anhydride, phenylacetylene trimellitic anhydride, and 4-phenylacetylene phthalic anhydride.

[0062] Preferably, when the end group of the polyimide precursor is a carboxyl group, the end-capping agent is an amine-containing monomer selected from at least one of 3-aminophenol, 4-aminophenol, 3-aminophenyl ether, and 4-aminophenyl ether.

[0063] Further, the polymerization inhibitor is selected from at least one of hydroquinone, 4-methoxyphenol, tert-butyl hydroquinone, 1,4-benzoquinone, phenothiazine, N-nitrosodiphenylamine, 2,6-di-tert-butyl-4-methylphenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2,2,6,6-tetramethylpiperidinooxy, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxy, and N-tert-butyl-a-phenyl nitrone.

[0064] Preferably, the polymerization inhibitor is selected from at least one of N-tert-butyl-a-phenyl nitrone, 2,2,6,6-tetramethylpiperidinooxy, N-nitrosodiphenyl, 3,5-di-tert-butyl-4-hydroxytoluene, and hydroquinone.

[0065] Further, the cross-linking agent is selected from at least one of triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol or polyethylene glycol di(meth)acrylate; propylene glycol or polypropylene glycol di(meth)acrylate; glycerol di- or tri(meth)acrylate; cyclohexane di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; bisphenol A di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tri- or tetra(meth)acrylate; tricyclo[5.2.1.0,2,6]decane dimethanol di(meth)acrylate.

[0066] Preferably, the cross-linking agent is selected from tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate.

[0067] In a third aspect, the present application provides a method for preparing a patterned cured film, wherein the negative photosensitive resin composition according to any one of the above is dissolved in an organic solvent, and then exposed, developed and cured.

[0068] Further, at least one of the following technical features is included:

[0069] d1) the organic solvent is selected from at least one of N-methylpyrrolidone and ethyl lactate; further, a mixed solvent of N-methylpyrrolidone and ethyl lactate is selected, preferably, the mass ratio of N-methylpyrrolidone and ethyl lactate is 4 / 1,

[0070] Further, the organic solvent is 400 parts by mass;

[0071] d2) the light source for exposure is a 100-3000W ultraviolet mercury lamp or an LED exposure machine;

[0072] d3) the developing solution is selected from at least one of cyclopentanone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, isopropyl alcohol;

[0073] d4) the curing temperature is 150-280°C;

[0074] d5) the curing time is 1-3 hours.

[0075] In a fourth aspect, the present application provides an insulating film formed by curing the negative photosensitive resin composition according to any one of the above.

[0076] Further, the thickness of the insulating film is 1-100um.

[0077] Compared with the prior art, the present application has the following beneficial effects:

[0078] The negative photosensitive resin composition of the present application includes an initiator composition, specifically a hydrogen abstraction type photoinitiator, a cationic type co-initiator, and a peroxide thermal initiator. The hydrogen abstraction type photoinitiator cooperates with the cationic photoinitiator, and compared with the conventional co-initiator (a tertiary amine type benzoate), the negative photosensitive resin composition has a significant improvement in storage stability and exposure sensitivity during the curing process.

[0079] And further, with the cooperation of the peroxide thermal initiator, the negative photosensitive resin composition has a further improvement in exposure sensitivity during the curing process, and the elongation at break of the cured pattern film is significantly improved.

[0080] And further, with the cooperation of the polymerization inhibitor, the storage stability of the negative photosensitive resin composition is significantly improved. DETAILED DESCRIPTION

[0081] Unless otherwise indicated, all parts and percentages contained in this application are on a weight basis, and all tests and characteristics are determined on the date of filing of this application. To the extent that any patent, patent application, or publication is cited in this application, the contents of all such citations are hereby incorporated by reference into this application, and their equivalents, and the same is true also of any other documents or archived information that can be cited in the prosecution history of the present application or of any patent issuing thereon. To the extent that definitions of specific terms are provided in this application, those definitions shall be understood to apply both to that term and to like terms throughout this application. In the event that any definition in this application conflicts with the meaning of a term in a document incorporated herein by reference, the definition that appears in this application controls.

[0082] Numerical ranges in this application are approximate, and thus can include values outside the stated limits, unless otherwise indicated. Numerical ranges include all values from and including the lower and the upper values, in increments of one unit, provided that there is a separation of at least two units between any lower value and any higher value. As an example, if a compositional, physical or other property, such as, for example, molecular weight, melt index, or the like, is from 100 to 1000, it is understood that individual values, such as 100, 101, 102, etc... and sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc... are expressly enumerated. For ranges containing values less than one or containing fractional numbers greater than one {such as 1.1, 1.5, etc...), "one unit" is considered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. For ranges containing single digit numbers greater than one {such as 1 to 5), "one unit" is typically considered to be 0.1. These are only examples of what is specifically enumerated herein, and the enumeration of numbers from the lowest value, through zero, to the highest value, in increments of one, is expressly stated to be provided. Numerical ranges included within this application are especially those of calcium-containing filler content, mixing temperature, and various characteristics and properties of these components.

[0083] When used with respect to chemical compounds, unless expressly stated 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 stated otherwise.

[0084] 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, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, excipients or compounds unless expressly stated otherwise. In contrast, the term "essentially consisting of" excludes any other components, steps or processes from the scope of any description of the term below, except those necessary for operational performance. The term "consisting of" does not include any components, steps or processes that are not specifically described or listed. Unless expressly stated otherwise, the term "or" refers to the listed members alone or in any combination thereof.

[0085] Example

[0086] The embodiments of the present invention will be described in detail below. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0087] It should be noted that the measurement methods in the examples and comparative examples are as follows:

[0088] 1. Synthesis of polyimide precursor A

[0089] Synthesis of polyimide precursor A1

[0090] To a four-necked flask under nitrogen protection, 4,4'-diphenyl ether dianhydride 62.04 g (0.2 mol), hydroxyethyl methacrylate 52.04 g (0.4 mol) and pyridine 31.64 g (0.4 mol) were added and dissolved using 120 g of γ-butyrolactone, and the reaction was stirred for 4 hours. The reaction vessel was transferred to an ice water bath (0-10°C), and 1-hydroxybenzotriazole 51.35 g, N,N'-dicyclohexyl carbodiimide 82.53 g were dissolved in 80 g of γ-butyrolactone and added dropwise to the reaction bottle in half an hour. After the reaction exothermic ended, 4,4'-diamino diphenyl ether 38.05 g (0.19 mol) was dispersed in 150 g of γ-butyrolactone and added to the reaction and the reaction was continued to stir for 2 hours. The reaction liquid was filtered to obtain the filtrate, which was diluted with 2-methyltetrahydrofuran and precipitated in deionized water, filtered, and dried in a 50°C oven under vacuum for 72 hours to obtain a light yellow solid powder A1 with a weight average molecular weight of 38900.

[0091] Synthesis of polyimide precursor A2

[0092] Except that 4,4'-diphenyl ether dianhydride 62.04 g (0.2 mol) in the synthesis of polyimide precursor A1 was changed to 3,3',4,4'-biphenyl tetracarboxylic dianhydride 58.84 g (0.2 mol), the rest was reacted and treated according to the synthesis method in polyimide precursor A1 to obtain a light yellow solid powder A2 with a weight average molecular weight of 35400.

[0093] Synthesis of polyimide precursor A3

[0094] Except that 4,4'-diphenyl ether dianhydride 62.04 g (0.2 mol) in the synthesis of polyimide precursor A1 was changed to 4,4'-diphenyl ether dianhydride 31.02 g (0.1 mol) and phthalic anhydride 21.81 g (0.1 mol), the rest was reacted and treated according to the synthesis method in polyimide precursor A1 to obtain a light yellow solid powder A3 with a weight average molecular weight of 32300.

[0095] Synthesis of polyimide precursor A4

[0096] Except that 4,4'-diamino diphenyl ether 38.05 g (0.19 mol) in the synthesis of polyimide precursor A1 was changed to 4,4'-diamino-2,2'-dimethyl diphenyl 41.67 g (0.19 mol), the rest was reacted and treated according to the synthesis method in polyimide precursor A1 to obtain a light yellow solid powder A4 with a weight average molecular weight of 40100.

[0097] Synthesis of polyimide precursor A5

[0098] Except that 4,4'-diaminodiphenyl ether 38.05 g (0.19 mol) in the synthesis of polyimide precursor Al was changed to 4,4'-diaminodiphenyl ether 20.02 g (0.1 mol) and p-phenylenediamine 9.72 g (0.09 mol), the rest was reacted and treated according to the synthesis method of polyimide precursor Al, and a light yellow solid powder A5 was obtained, and the weight average molecular weight was 34700.

[0099] II. Composition of the negative photosensitive resin composition

[0100] 1. Polyimide precursor A, 100 parts

[0101] Polyimide precursors Al to A5;

[0102] 2. Photoinitiator B, 3 parts

[0103] B1: 4,4'-bis(diethylamino)benzophenone

[0104] B2: 2,4-diethylthioxanthone

[0105] B3: 2-ethylanthraquinone

[0106] B4: DL-camphorquinone

[0107] 3. Co-initiator C, 0.5-5 parts

[0108] Co-initiator C'1: methyl 4-dimethylaminobenzoate

[0109] 4. Polymerization inhibitor D, 0.1 parts

[0110] D1: N-tert-butyl-a-phenyl nitrone

[0111] D2: 2,2,6,6-tetramethylpiperidine oxide

[0112] D3: N-nitrosodiphenylamine

[0113] D4: 3,5-di-tert-butyl-4-hydroxytoluene

[0114] D5: hydroquinone

[0115] 5. Thermal initiator E, 2 parts

[0116] E1: dicumyl peroxide

[0117] E2: di-tert-butyl peroxide isopropyl benzene

[0118] E3: di-tert-butyl peroxide

[0119] 6. Crosslinking agent F, 20 parts

[0120] F1: tetraethylene glycol dimethacrylate

[0121] F2: trimethylolpropane trimethacrylate

[0122] F3: pentaerythritol tetramethacrylate

[0123] In addition to the above ingredients, the negative photosensitive resin composition is added with the following substances (100 parts in total relative to the polyimide precursor A):

[0124] γ-glycidoxypropyltrimethoxysilane, 2 parts

[0125] mixed solvent of mass ratio of N-methylpyrrolidone / ethyl lactate = 4 / 1, 200 parts

[0126] Example 1

[0127] A negative photosensitive resin composition includes the following components in mass parts:

[0128] The above negative photosensitive resin composition, 2 parts of γ-glycidoxypropyltrimethoxysilane, and 200 parts of a mixed solvent of N-methylpyrrolidone / ethyl lactate = 4 / 1 are fully dissolved to form a solution of the negative photosensitive resin composition.

[0129] Method for preparing a patterned cured film

[0130] The above solution is spin-coated on a silicon wafer, and a 10-μm thin film is formed after baking at 100°C for 4 minutes using a contact hot plate. Pattern exposure is performed using a UV mercury lamp exposure machine with a power of 200 W, and the exposed silicon wafer is left to stand at room temperature for 30 minutes, and then developed in a developer. The patterned film after development is cured in a nitrogen oven at a temperature increasing rate of 5°C per minute from room temperature to 150°C for 0.5 hours and to 230°C for 3 hours, and then cooled to room temperature at a rate of 2°C per minute, to obtain a patterned cured film. The specific storage stability, sensitivity, and elongation at break are shown in Table 2 below.

[0131] According to the method for preparing a patterned cured film of Example 1, the specific components and proportions of the related examples and comparative examples of Examples 2-26 and Comparative Examples 1-4 are implemented without changing the γ-glycidoxypropyltrimethoxysilane and the mixed solvent of N-methylpyrrolidone / ethyl lactate = 4 / 1, as shown in Table 1 below.

[0132] Table 1 Specific components and proportions of examples and comparative examples

[0133] Note that the test methods for storage stability, sensitivity, and elongation at break in the examples and comparative examples are as follows.

[0134] Storage stability:

[0135] The initial viscosity of the prepared negative photosensitive resin composition solution was measured at room temperature using a Brookfield viscometer, after which the solution was filled into a brown glass bottle, sealed, and placed in a constant-temperature oven at 50°C for aging. Further, the viscosity of the composition during aging was measured once a day using a Brookfield viscometer, and the number of days for which the viscosity could be maintained with a change of less than 5% compared to the initial viscosity was counted. Time greater than 7 days: excellent; time less than 7 days but greater than or equal to 5 days: good; time less than 5 days: poor.

[0136] Sensitivity:

[0137] The film thickness after development was measured for each grid, and the development residual film thickness ratio was the film thickness after development T1 / the original film thickness before development T0. The exposure amount at which the development residual film thickness ratio was just greater than or equal to 85% was taken as the minimum exposure energy. If the minimum exposure energy was less than or equal to 150 mJ, the sensitivity was determined to be excellent; if the minimum exposure energy was greater than 150 mJ but less than or equal to 300 mJ, the sensitivity was determined to be good; and if the minimum exposure energy was greater than 300 mJ, the sensitivity was determined to be poor.

[0138] Elongation at break:

[0139] The formed cured film was cut into a tensile sample, which was placed in an environment of 23°C and 50% relative humidity for 12 hours or more, after which a universal tensile testing machine was used to measure the elongation at break. Elongation at break greater than or equal to 50%: excellent; elongation at break less than 50% but greater than or equal to 20%: good; elongation at break less than 20%: poor.

[0140] Table 2 Specific properties of examples and comparative examples

[0141] It can be found from Comparative Example 1, Examples 16 to 18, Comparative Example 1, and Comparative Example 4 that the auxiliary initiator proposed in the present application has a significant effect on improving the sensitivity and stability of the resin composition compared to the conventional auxiliary initiator (methyl 4-dimethylamino benzoate); it can be found from Comparative Example 2, Examples 19 to 12, and Comparative Example 2 that component D (a polymerization inhibitor) has a significant effect on improving the storage stability of the resin composition; it can be found from Comparative Example 2, Examples 23 and 24, and Comparative Example 3 that component E (a thermal initiator) has a significant effect on improving the elongation at break of the cured resin composition and can improve the sensitivity. In addition, it can be found from Comparative Examples A1 to A7 that the use of different types of resin in combination can also achieve a result that takes into account the sensitivity, storage stability, and elongation at break.

[0142] An insulating film was obtained by using the composition of Examples 1 to 26 and the method of Example 1 to produce a patterned film, and was cured to obtain an insulating film of 1 to 100 μm.

[0143] These insulating films can be used as insulating layers of chips, substrates, printed circuit boards, and display panels.

Claims

1. An initiator composition, characterized in that The invention comprises the following components in parts by weight: 0.1-10 parts of photoinitiator; 0.5-5 parts of co-photoinitiator; 0.5-10 parts of thermal initiator; Wherein, the photoinitiator is a hydrogen abstraction photoinitiator, the auxiliary photoinitiator is a cationic photoinitiator, and the thermal initiator is a peroxide initiator.

2. The initiator composition according to claim 1, characterized in that The photoinitiator is selected from at least one of benzophenone photoinitiators, thioxanthone photoinitiators, and quinone photoinitiators.

3. The initiator composition according to claim 2, characterized in that The photoinitiator includes at least one of the following technical features: a1) the benzophenone photoinitiator is selected from at least one of benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone, 2,4,6-trimethylbenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 2-hydroxybenzophenone, 4-hydroxy-benzophenone, and methyl o-benzoylbenzoate; a2) the thioxanthone photoinitiator is selected from at least one of 2-isopropylthioxanthone and 2,4-diethylthiazolone; a3) The quinone photoinitiator is selected from at least one of 2-ethylanthraquinone and DL-camphorquinone.

4. The initiator composition according to claim 1, characterized in that The auxiliary photoinitiator is selected from at least one of iodonium salts, sulfonium salts and quaternary ammonium salts.

5. The initiator composition according to claim 4, characterized in that The co-photoinitiator includes at least one of the following technical features: b1) The iodonium salt is selected from the following structural formula I-1 or I-2: Among them, the R 11 Selected from C6-C 20 The aromatic group, R 12 Selected from C6-C 20 aromatic or C1-C 20 Carbonyl, or R 11 、R 12 Form a five-membered ring or a six-membered ring with iodide ion, R 13 Selected from C6-C 20 Aromatic groups, C1-C 10 Alkyl, C1-C 10 haloalkyl or C1-C 15 The imino group, R 14 Selected from halogen atoms, C1-C 10 Alkyl, C1-C 10 haloalkyl or C6-C 20 The aromatic group, R 15 Selected from C1-C 10 Sulfonyl or C1-C 20 Carbonyl, or R 14 、R 15 Form a five-membered ring or a six-membered ring with a nitrogen ion or a sulfonyl group; b2) The sulfonium salt is selected from the following structural formula II-1 or formula II-2: Among them, the R 21 Selected from C6-C 20 The aromatic group, R 22 、R 23 Each independently selected from C1-C 10 Alkyl, C6-C 20 aromatic or C1-C 20 Carbonyl, or R 22 、R 23 Form a five-membered ring or a six-membered ring with the sulfide ion; R 24 Selected from C6-C 20 Aromatic groups, C1-C 10 Alkyl, C1-C 10 haloalkyl or C1-C 15 The imino group, R 25 Selected from halogen atoms, C1-C 10 Alkyl, C1-C 10 haloalkyl or C6-C 20 The aromatic group, R 26 Selected from C1-C 10 Sulfonyl or C1-C 20 Carbonyl, or R 25 、R 26 Form a five-membered ring or a six-membered ring with a nitrogen ion or a sulfonyl group; b3) The quaternary ammonium salt is selected from the following structural formula III-1 or formula III-2: Among them, the R 31 、R 32 or R 33 Each independently selected from C1-C 10 Alkyl or C6-C 20 The aromatic group, or R 31 、R 32 Form a five-membered ring or a six-membered ring with the nitrogen ion, or R 31 、R 32 、R 33 Form a five-membered ring, a six-membered ring or a bridged ring with the nitrogen ion, R 34 Selected from C6-C 20 Aromatic groups, C1-C 10 Alkyl, C1-C 10 haloalkyl or C1-C 15 The imino group, R 35 Selected from halogen atoms, C1-C 10 Alkyl, C1-C 10 haloalkyl or C6-C 20 The aromatic group, R 36 Selected from C1-C 10 Sulfonyl or C1-C 20 Carbonyl, or R 35 、R 36 It forms a five-membered or six-membered ring with nitrogen ion and sulfonyl group.

6. The initiator composition according to claim 1, characterized in that The thermal initiator is selected from at least one of dibenzoyl peroxide, 1,1-di-tert-butylperoxycyclohexane, tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, diisopropyl benzene peroxide, di-tert-butyl peroxide, isopropyl benzene peroxide, di-tert-butyl peroxide, tert-butyl isopropyl benzene peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

7. A negative photosensitive resin composition, characterized in that The composition comprises the following components in parts by weight:

8. The negative photosensitive resin composition according to claim 7, characterized in that The polyimide precursor includes at least one of the following technical features: c1) the molecular weight of the polyimide precursor is 3000-80000; c2) The polyimide precursor comprises the following structural formula IV: wherein X is selected from C6-C 30 Aromatic tetravalent organic group; Y is selected from C6-C 30 Aromatic or C1-C 20 A divalent alicyclic organic group; R1 and R2 are each independently selected from a hydrogen atom or a C3-C 30 Organic groups with ethylenically unsaturated bonds, urea groups, and thiourea groups.

9. The negative photosensitive resin composition according to claim 7, characterized in that The polymerization inhibitor is selected from at least one of hydroquinone, 4-methoxyphenol, tert-butylhydroquinone, 1,4-benzoquinone, phenothiazine, N-nitrosodiphenylamine, 2,6-di-tert-butyl-4-methylphenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2,2,6,6-tetramethylpiperidinol, 4-hydroxy-2,2,6,6-tetramethylpiperidinol, and N-tert-butyl-a-phenylnitrone.

10. The negative photosensitive resin composition according to claim 7, characterized in that: The crosslinking agent is selected from at least one of triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol or polyethylene glycol di(meth)acrylate; propylene glycol or polypropylene glycol di(meth)acrylate; glycerol di- or tri(meth)acrylate; cyclohexane di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; bisphenol A di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tri- or tetra(meth)acrylate; and tricyclo[5.2.1.0,2,6]decanedimethanol di(meth)acrylate.

11. A method for preparing a patterned cured film, characterized in that: The negative photosensitive resin composition according to any one of claims 7 to 10 is dissolved in an organic solvent, and subjected to exposure, development and curing.

12. The method for preparing a patterned cured film according to claim 11, wherein: Include at least one of the following technical features: d1) the organic solvent is at least one selected from N-methylpyrrolidone and ethyl lactate; d2) the exposure light source is selected from a 100-3000W ultraviolet mercury lamp or an LED exposure machine; d3) the developer is selected from at least one of cyclopentanone, propylene glycol monomethyl ether acetate, N,N-dimethylformamide, and isopropyl alcohol; d4) the curing temperature is 150 to 280° C.; d5) The curing time is 1 to 3 hours.

13. An insulating film, characterized in that: It is formed by curing the negative photosensitive resin composition described in any one of claims 7 to 10.

Images