Negative mixed phenolic resin composition as well as preparation method and application thereof

Abstract

The invention belongs to the field of semiconductor packaging materials and photoetching materials, and particularly relates to a negative mixed phenolic resin composition as well as a preparation method and application thereof. The negative mixed phenolic resin composition comprises a phenolic resin mixture, an initiator and an optional organic solvent I; the phenolic resin mixture comprises phenolic resin A with a structure as shown in a formula (1) and phenolic resin B with a structure as shown in a formula (2). The preparation method is characterized in that phenolic resin A and phenolic resin B with specific structures are designed and synthesized, and the grafting ratio of olefinic double bonds in the phenolic resin A and phenolic resin B is regulated and controlled, so that the obtained negative phenolic resin composition has low-temperature curing performance, good uniformity in a film thickness plane and chemical solvent resistance; and the requirements of a negative photoetching material and a semiconductor packaging material are met. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of semiconductor packaging materials and photolithography materials, and in particular relates to a negative mixed phenolic resin composition and a preparation method and application thereof. Background Art

[0002] Polyimide resins, polybenzoxazole resins, and polyamide-imide resins are widely used in semiconductor packaging materials due to their excellent properties such as heat resistance and mechanical properties, such as protective films and interlayer insulating films of semiconductor elements, insulating layers of organic electroluminescent elements, etc. Among them, polyimide resins with photosensitivity can also be used as raw materials for photolithography materials, which are divided into negative photolithography materials and positive photolithography materials (negative type has residual resin in the exposed part through exposure / development, and positive type has residual resin in the unexposed part through exposure / development). Negative photolithography materials have better reliability, higher sensitivity, and require less exposure, but the in-plane uniformity of film thickness is worse than that of positive photolithography materials, resulting in poor formation of the final photolithography pattern. At present, most semiconductor products require resin compositions with a thermal curing temperature below 250°C, while polyimide resins generally need to be cured at above 300°C to form films. When polyimide resins are cured at low temperatures, due to incomplete imidization, the formed cured film becomes brittle, its physical and mechanical properties decrease, its chemical solvent resistance deteriorates, cracks are easily generated, and the in-plane uniformity of the film thickness is also poor, which reduces the protective effect on semiconductor components (such as insulation protection, isolation from environmental influences, mechanical support, etc.). Therefore, it is urgent to find a resin composition with low-temperature curing characteristics and good in-plane uniformity of film thickness and chemical solvent resistance to meet the requirements of negative photolithography materials and semiconductor packaging materials. Summary of the invention

[0003] The purpose of the present invention is to provide a negative mixed phenolic resin composition and its preparation method and application, in view of the shortcomings of the existing resin composition when used as a photolithography material or a semiconductor packaging material, such as a high curing temperature, poor uniformity of film thickness in a plane and poor chemical solvent resistance, which leads to poor photolithography pattern formation effect and reduced protection of semiconductor elements.

[0004] In a first aspect, the present invention provides a negative mixed phenolic resin composition.

[0005] Specifically, the mixed phenolic resin composition comprises a phenolic resin mixture, an initiator and an optional organic solvent I; the phenolic resin mixture comprises a phenolic resin A having a structure as shown in formula (1) and a phenolic resin B having a structure as shown in formula (2);

[0006]

[0007] In formula (1) and formula (2), R1 is a hydrogen atom, C1 to C 10 C1~C 10 R2-R5, R8 and R9 are each independently a hydrogen atom or a C1-C 10 R6 and R7 are each independently a halogen atom, a hydrogen atom, a C1-C 10 C1~C 10 wherein part of X1 or X2 in the same molecular chain is a hydrogen atom, the remaining part of X1 or X2 is a group represented by formula (3), and the molar ratio of hydrogen atoms to the group represented by formula (3) in the same molecular chain is (1 to 3):1, E is a single bond, C1 to C 10 C1~C 10 alkylene, m1 and m5 are each independently an integer of 1 to 3, m2 and m6 are each independently an integer of 0 to 2, 2≤(m1+m2)≤4, 2≤(m5+m6)≤4, m3 and m4 are each independently an integer of 0 to 3, n1 and n2 are each independently an integer of 5 to 500; the grafting rates of the groups represented by formula (3) in the phenolic resin A and the phenolic resin B are each independently 25 to 50%;

[0008]

[0009] In formula (3), R 10 is a hydrogen atom or a C1-C5 alkyl group, and m7 is an integer of 1-3.

[0010] In a second aspect, the present invention provides a method for preparing the above-mentioned negative mixed phenolic resin composition, which comprises: mixing phenolic resin A, phenolic resin B, an initiator and optional organic solvent I, a sensitizer, a surfactant, a silane coupling agent, a dissolution control agent, and a polymerization inhibitor to obtain a negative mixed phenolic resin composition.

[0011] In a third aspect, the present invention further provides the use of the negative mixed phenolic resin composition in the field of photolithography materials and semiconductor packaging materials.

[0012] In a fourth aspect, the present invention provides a method for preparing a cured relief pattern, which comprises the following steps: S1. coating the above-mentioned negative mixed phenolic resin composition on a substrate to form a photosensitive resin layer; S2. exposing the photosensitive resin layer; S3. removing the unexposed resin portion by treating with a developer to obtain a relief pattern; S4. curing the relief pattern to obtain a cured relief pattern.

[0013] The key to the present invention is to design and synthesize phenolic resin A and phenolic resin B with specific structures, and regulate the grafting ratio of olefinic double bonds in phenolic resin A and phenolic resin B. The negative phenolic resin composition obtained by compounding the phenolic resin mixed region with an initiator and an optional organic solvent not only has the performance of low-temperature curing, but also has good film thickness in-plane uniformity and chemical solvent resistance after film formation, so that when used as a photolithography material, it is beneficial to obtain a well-shaped cured relief pattern. When used as a semiconductor packaging material, low-temperature curing reduces possible damage to semiconductor elements. Good film thickness in-plane uniformity and chemical solvent resistance are beneficial to improving the protective effect of the film-forming resin layer on the semiconductor element (such as insulation protection, isolation from environmental influences, mechanical support, etc.). DETAILED DESCRIPTION

[0014] The negative mixed phenolic resin composition provided by the present invention comprises a phenolic resin mixture, an initiator and an optional organic solvent I; the phenolic resin mixture comprises a phenolic resin A having a structure as shown in formula (1) and a phenolic resin B having a structure as shown in formula (2).

[0015]

[0016] In formula (1) and formula (2), R1 is a hydrogen atom, C1 to C 10 C1~C 10 R2 to R5, R8 and R9 are each independently a hydrogen atom or a C1 to C3 alkyl group. 10 R6 and R7 are each independently a halogen atom, a hydrogen atom, a C1-C3 alkyl group. 10 C1~C 10 wherein part of X1 or X2 in the same molecular chain is a hydrogen atom, and the remaining part of X1 or X2 is a group represented by formula (3), and the molar ratio of hydrogen atoms to the group represented by formula (3) in the same molecular chain is (1-3):1, such as 1:1, 1.5:1, 2:1, 2.5:1, 3:1 or any value therebetween; and E is a single bond, C1-C 10 C1~C 10alkylene, preferably a hydrogen atom or a C1-C3 alkylene; m1 and m5 are each independently an integer of 1-3, such as 1, 2 or 3; m2 and m6 are each independently an integer of 0-2, such as 0, 1 or 2; 2≤(m1+m2)≤4, i.e., the value of m1+m2 can be 2, 3 or 4; 2≤(m5+m6)≤4, i.e., the value of m5+m6 can be 2, 3 or 4; m3 and m4 are each independently an integer of 0-3, such as 0, 1, 2 or 3; n1 and n2 are each independently an integer of 5-500, such as 5, 8, 10, 15, 20, 50, 100, 200, 300, 400, 500 or any integer therebetween. In formula (3), R 10 is a hydrogen atom or a C1-C5 alkyl group, and m7 is an integer of 1-3, such as 1, 2 or 3. The grafting rate of the group represented by formula (3) in the phenolic resin A and the phenolic resin B is independently 25-50%, such as 25%, 30%, 35%, 40%, 45%, 50% or any value therebetween. 10 Specific examples of the alkyl group of C1 to C3 include, but are not limited to, one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. Specific examples of the alkyl group of C1 to C3 include, but are not limited to, one of methyl, ethyl, n-propyl, and isopropyl. 10 Specific examples of the alkylene group include, but are not limited to, one of methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, isobutylene, n-pentylene, isopentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and n-decylene. Specific examples of the alkylene group of C1 to C3 include, but are not limited to, at least one of methylene, ethylene, n-propylene, and isopropylene. The halogen atom is one of fluorine, chlorine, bromine, or iodine. Specific examples of the alkyl group of C1 to C5 include, but are not limited to, one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, and neopentyl.

[0017] In the present invention, the weight average molecular weight of the phenolic resin A and the phenolic resin B is preferably independently 2000-200000 Daltons, such as 2000, 5000, 8000, 10000, 50000, 100000, 150000, 200000 Daltons or any value therebetween.

[0018] In the present invention, the mass ratio of the phenolic resin A to the phenolic resin B is preferably (0.4-2.5):1, such as 0.4:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1 or any ratio therebetween. This is more conducive to ensuring that the mixed phenolic resin composition has excellent mechanical properties and chemical solvent resistance after film formation.

[0019] In the present invention, the preparation method of the phenolic resin A is preferably as follows: a phenol compound I having a structure as shown in formula (4) is subjected to a first polymerization reaction with a polymer component having a structure as shown in formula (5), and the resulting polymer is subjected to a first nucleophilic substitution reaction with an olefinic epoxy compound having a structure as shown in formula (6). The resulting product is a phenolic resin A having a structure as shown in formula (1).

[0020] In the present invention, the preparation method of the phenolic resin B is preferably as follows: a phenolic compound II having a structure as shown in formula (7) is subjected to a second polymerization reaction with an aldehyde compound having a structure as shown in formula (5), and the resulting polymer is subjected to a second nucleophilic substitution reaction with an olefinic epoxy compound having a structure as shown in formula (6). The resulting product is a phenolic resin B having a structure as shown in formula (2).

[0021]

[0022] In formula (4) and formula (7), R1 is a hydrogen atom, C1 to C 10 C1~C 10 alkyl, preferably a hydrogen atom or a C1-C3 alkyl; m1 and m5 are each independently an integer of 1-3, such as 1, 2 or 3, m2 and m6 are each independently an integer of 0-2, such as 0, 1 or 2, 2≤(m1+m2)≤4, i.e., the value of m1+m2 can be 2, 3 or 4, 2≤(m5+m6)≤4, i.e., the value of m5+m6 can be 2, 3 or 4. In formula (5), R2-R5 are each independently a hydrogen atom or a C1-C 10 R6 and R7 are each independently a halogen atom, a hydrogen atom, a C1-C3 alkyl group. 10 C1~C 10 is an alkyl group, preferably a hydrogen atom or a C1-C3 alkyl group; E is a single bond, a C1-C 10 C1~C 10alkylene, preferably a hydrogen atom or a C1-C3 alkylene; Y1 and Y2 are each independently a hydroxyl group, a halogen group or a C1-C5 alkoxy group; m3 and m4 are each independently an integer of 0 to 3, such as 0, 1, 2 or 3. In formula (6), R 10 is a hydrogen atom or a C1-C5 alkyl group, and m7 is an integer of 1-3, such as 1, 2 or 3. 10 Alkyl, C1~C3 alkyl, C1~C 10 Specific examples of the alkylene group of C1 to C3, the alkylene group of C1 to C3, and the alkyl group of C1 to C5 are as described above, and are not repeated here one by one. The halogen atom may be one of fluorine, chlorine, bromine, or iodine. Specific examples of the alkoxy group of C1 to C5 include, but are not limited to, one of methoxy, ethoxy, propoxy, butoxy, and pentoxy.

[0023] In the present invention, the molar ratio of the phenol compound I to the polymer component is preferably 1:(0.9-1.2), such as 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2 or any value therebetween. The molar ratio of the phenol compound II to the aldehyde compound is preferably 1:(0.9-1.2), such as 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2 or any value therebetween.

[0024] In the present invention, the phenol compound I or phenol compound II can be any compound having a structure as shown in formula (4). The phenol compound I and phenol compound II are each independently selected from at least one of catechol, pyrocatechol, catechol, pyrocatechol, 1,2,4-pyrocatechol, m-methylphenol, p-methylphenol, p-trifluoromethylphenol, and o-trifluoromethylphenol.

[0025] In the present invention, the polymer component can be any compound having a structure as shown in formula (5), preferably at least one selected from 4,4'-bis(methoxymethyl)biphenyl, dichlorobenzyl biphenyl, and 4,4'-bis(hydroxymethyl)biphenyl. The aldehyde compound is preferably at least one selected from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and valeraldehyde.

[0026] In the present invention, the conditions of the first polymerization reaction and the second polymerization reaction can independently include: the temperature is preferably 20-250°C, such as 20°C, 40°C, 50°C, 80°C, 100°C, 150°C, 200°C, 250°C or any value therebetween, more preferably 40-200°C; the time is preferably 5-15h, such as 5h, 7h, 8h, 10h, 12h, 15h or any value therebetween.

[0027] In the present invention, the first polymerization reaction and / or the second polymerization reaction are preferably carried out in the presence of a catalyst. The catalyst may be selected from an acidic catalyst and / or a basic catalyst, preferably an acidic catalyst. Specific examples of the acidic catalyst include, but are not limited to, at least one of hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. Specific examples of the basic catalyst include, but are not limited to, at least one of sodium hydroxide, potassium hydroxide, ammonia water, ethylenediamine, triethanolamine, and barium hydroxide.

[0028] In the present invention, the first polymerization reaction and / or the second polymerization reaction are preferably carried out in the presence of an organic solvent II. Specific examples of the organic solvent II include, but are not limited to, at least one of bis(2-methoxyethyl) ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. The mass ratio of the organic solvent II to the raw material to be polymerized is preferably (20 to 1000):100, such as 20:100, 40:100, 60:100, 100:100, 200:100, 400:100, 500:100, 800:100, 1000:100 or any value therebetween, more preferably (60 to 500):100.

[0029] In the present invention, the first polymerization reaction and the second polymerization reaction may each independently include a purification treatment after the polymerization reaction. The purification treatment may be performed as follows: the mixture after the polymerization reaction is mixed with water or aliphatic lower alcohol, and the precipitate is the phenolic resin. According to the purification needs, the obtained precipitate may be mixed with water or aliphatic lower alcohol again, and reprecipitated, and the above steps may be repeated to improve the purity of the phenolic resin. The number of repetitions may be determined according to actual needs. The purification treatment may also be performed as follows: the mixture after the polymerization reaction is treated with an anion and / or cation exchange resin filled column to remove ionic impurities.

[0030] In the present invention, the conditions for the first nucleophilic substitution reaction and the second nucleophilic substitution reaction can independently include: the temperature is preferably 50-100°C, such as 50°C, 60°C, 70°C, 80°C, 90°C, 100°C or any value therebetween; the time is preferably 10-20h, such as 10h, 12h, 15h, 18h, 20h or any value therebetween.

[0031] In the present invention, the olefinic epoxy compound can be any compound having a structure as shown in formula (6), and specific examples thereof include but are not limited to at least one of glycidyl methacrylate, allyl glycidyl ether, and epoxybutyl methacrylate. The amount of the olefinic epoxy compound is preferably such that the grafting rate of the group shown in formula (3) in the phenolic resin A and the phenolic resin B is independently 25 to 50%. The grafting rate is the ratio of the reaction of the phenolic hydroxyl group in the phenolic resin with the olefinic epoxy compound.

[0032] In the present invention, the first nucleophilic substitution reaction and / or the second nucleophilic substitution reaction are preferably carried out in the presence of an organic solvent III. Specific examples of the organic solvent III include, but are not limited to, at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, and diethylene glycol dimethyl ether. The mass ratio of the organic solvent III to the phenolic resin is preferably (100-1000):100, such as 100:100, 200:100, 400:100, 500:100, 800:100, 1000:100 or any value therebetween, more preferably (180-500):100.

[0033] In the present invention, the first nucleophilic substitution reaction and the second nucleophilic substitution reaction may each independently include a purification treatment after the first nucleophilic substitution reaction. The steps of the purification treatment are the same as those described above and will not be described in detail here.

[0034] In the present invention, the mass ratio of the phenolic resin mixture to the initiator and the organic solvent I is preferably 100:(0.1-10):(100-1000). Taking the mass of the phenolic resin mixture as 100 parts by weight, the mass of the initiator is preferably 0.1-10 parts by weight, such as 0.1, 0.5, 1, 2, 5, 8, 10 parts by weight or any value therebetween; the mass of the organic solvent I is preferably 100-1000 parts by weight, such as 100, 200, 500, 800, 1000 parts by weight or any value therebetween, more preferably 125-500 parts by weight.

[0035] In the present invention, the initiator is preferably selected from at least one of benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzoin derivatives, and oxime derivatives. Specific examples of the benzophenone derivatives include, but are not limited to, at least one of benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone. Specific examples of the acetophenone derivatives include, but are not limited to, at least one of 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone. Specific examples of the thioxanthone derivatives include, but are not limited to, at least one of thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone. Specific examples of the benzyl derivatives include, but are not limited to, at least one of benzyl, benzyl dimethyl ketal, and benzyl-β-methoxyethyl acetal. The benzoin derivative is selected from benzoin and / or benzoin methyl ether. The oxime lipid derivative is 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime.

[0036] In the present invention, the organic solvent I is preferably selected from at least one of amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Specific examples include, but are not limited to, at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, methyl isobutyl ketone, cyclopentanone, cyclohexanone, butyl acetate, diethyl oxalate, ethyl lactate, methyl lactate, butyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, phenylene glycol, tetrahydrofurfuryl alcohol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, anisole, hexane, heptane, and xylene. The organic solvent I is more preferably at least one of dimethyl sulfoxide, tetramethyl urea, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, and tetrahydrofurfuryl alcohol, which is more conducive to improving the solubility of the phenolic resin and the stability of the resin composition.

[0037] In the present invention, the negative type mixed phenolic resin composition preferably further comprises at least one of a sensitizer, a surfactant, a silane coupling agent, a dissolution control agent, and a polymerization inhibitor. The mass ratio of the phenolic resin mixture to the sensitizer, the surfactant, the silane coupling agent, the dissolution control agent, and the polymerization inhibitor is 100:(0.01-10):(0.01-10):(0.01-15):(0.01-10):(0.01-5). Taking the mass of the phenolic resin mixture as 100 parts by weight, the mass of the sensitizer is preferably 0.01 to 10 parts by weight, such as 0.01, 0.05, 0.1, 0.5, 1, 2, 5, 8, 10 parts by weight or any value therebetween; the mass of the surfactant is preferably 0.01 to 10 parts by weight, such as 0.01, 0.05, 0.1, 0.5, 1, 2, 5, 8, 10 parts by weight or any value therebetween; the mass of the silane coupling agent is preferably 0.01 to 15 parts by weight, such as 0 .01, 0.05, 0.1, 0.5, 1, 2, 5, 8, 10, 12, 15 parts by weight or any value therebetween; the mass of the dissolution control agent is preferably 0.01-10 parts by weight, such as 0.01, 0.05, 0.1, 0.5, 1, 2, 5, 8, 10 parts by weight or any value therebetween; the mass of the polymerization inhibitor is preferably 0.01-5 parts by weight, such as 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5 parts by weight or any value therebetween.

[0038] In the present invention, the sensitizer can be a conventional choice in the art, preferably at least one selected from Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, and 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone.

[0039] In the present invention, the surfactant may be a conventional surfactant in the art, and is preferably a non-ionic surfactant of polyethylene glycol and / or its derivatives.

[0040] In the present invention, the silane coupling agent can be a conventional choice in the art, preferably at least one selected from phenylsilanetriol, trimethoxyphenylsilane, trimethoxy(p-tolyl)silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, and triphenylsilanol.

[0041] In the present invention, the dissolution control agent is preferably a (meth) acrylic compound, and specific examples thereof include but are not limited to at least one of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, and 1,3-butanediol dimethacrylate.

[0042] In the present invention, the polymerization inhibitor is preferably at least one selected from hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0043] The preparation method of the negative mixed phenolic resin composition provided by the present invention comprises: mixing phenolic resin A, phenolic resin B, an initiator and an optional organic solvent I, a sensitizer, a surfactant, a silane coupling agent, a dissolution control agent and a polymerization inhibitor to obtain the negative mixed phenolic resin composition.

[0044] The method for preparing a solidified relief pattern provided by the present invention comprises the following steps: S1. coating the negative mixed phenolic resin composition provided by the present invention on a substrate to form a photosensitive resin layer; S2. exposing the photosensitive resin layer; S3. removing the resin in the unexposed part by treating with a developer to obtain a relief pattern; S4. solidifying the relief pattern to obtain a solidified relief pattern. The temperature of the solidification treatment is preferably 150 to 250°C, such as 150°C, 180°C, 200°C, 220°C, 250°C or any value therebetween.

[0045] In addition, the terms "first", "second", "Ⅰ", "Ⅱ", and "Ⅲ" are used for descriptive purposes only and should not be understood as a limitation on the number or type of technical features or an indication or suggestion of their importance.

[0046] The present invention will be described in detail below through specific embodiments.

[0047] Preparation Example 1 Preparation of phenolic resin A-1

[0048] S1. First, a 1L three-necked flask with a Dean-Stark water separator was replaced with nitrogen. Then, in the flask, 113.8 g (1.033 mol) of resorcinol, 278.66 g (1.15 mol) of 4,4'-bis(methoxymethyl)biphenyl, 3.81 g (0.02 mol) of p-toluenesulfonic acid, and 150 g of propylene glycol monomethyl ether (PGME) were mixed and stirred at 60°C to dissolve the solid substances uniformly to obtain a mixed solution. The mixed solution was then heated in an oil bath. The liquid was heated to 80°C and reacted under this condition for 12 hours; after the reaction, the reaction container was cooled in the atmosphere, 50 g of PGME was added thereto and stirred, and the above-mentioned reaction dilution liquid was dropwise added into 8 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, properly washed and dehydrated, and then vacuum dried to obtain a resin polymer F1 with a yield of 80%. The weight average molecular weight of the resin polymer was 12200 Daltons obtained by gel permeation chromatography (GPC) through standard polystyrene conversion.

[0049] S2. Add 165g of resin polymer F1 and 300g of γ-butyrolactone solvent to a 1L three-necked flask, mix and stir at 60°C to dissolve the resin, then drop 135.04g (0.95mol) of glycidyl methacrylate (GMA) thereinto, raise the temperature to 80°C for reaction for 12h after the reaction, cool the reaction vessel in the atmosphere after the reaction, add 50g of γ-butyrolactone thereto and stir, drop the above reaction dilution into 8L of water under high-speed stirring to disperse and precipitate the resin, and recover it, wash it with water appropriately, dehydrate it and then perform vacuum drying to obtain phenolic resin A-1 with a yield of 75%, and use gel permeation chromatography (GPC) to convert it to standard polystyrene to obtain a weight average molecular weight of phenolic resin A-1 of 19300 Daltons, and the grafting rate of GMA in phenolic resin A-1 (the ratio of phenolic hydroxyl groups in phenolic resin to GMA reaction) is 41%.

[0050] Preparation Example 2 Preparation of phenolic resin A-2

[0051] Phenolic resin A-2 was prepared according to the method of Preparation Example 1, except that the amount of glycidyl methacrylate (GMA) added in step S2 was 89.55 g (0.63 mol), and the other conditions were the same as those in Preparation Example 1. Phenolic resin A-2 was obtained with a yield of 77%. The weight average molecular weight of phenolic resin A-2 was 14400 Daltons as calculated by gel permeation chromatography (GPC) through standard polystyrene conversion, and the grafting rate of GMA in phenolic resin A-2 (the ratio of the reaction of phenolic hydroxyl groups in the phenolic resin with GMA) was 32%.

[0052] Preparation Example 3 Preparation of phenolic resin A-3

[0053] S1. Resin polymer F2 was prepared according to the method of step S1 in Preparation Example 1, except that 263.71 g (1.05 mol) of diphenylbenzyl chloride was used instead of 278.66 g (1.15 mol) of 4,4'-bis(methoxymethyl)biphenyl. The other conditions were the same, and the resin polymer F2 was obtained with a yield of 80%. The weight average molecular weight of the resin polymer F2 was 14200 Daltons obtained by gel permeation chromatography (GPC) through standard polystyrene conversion.

[0054] S2. Phenolic resin A-3 was prepared according to the method of step S2 in Preparation Example 1, except that 165 g of resin polymer F2 was used instead of resin polymer F1. The other conditions were the same, and phenolic resin A-3 was obtained with a yield of 75%. The weight average molecular weight of phenolic resin A-3 was 21,500 Daltons as calculated by gel permeation chromatography (GPC) through standard polystyrene conversion, and the grafting rate of GMA in phenolic resin A-3 (the ratio of phenolic hydroxyl groups in phenolic resin to GMA reaction) was 41%.

[0055] Preparation Example 4 Preparation of Phenolic Resin A-4

[0056] Phenolic resin A-4 was prepared according to the method of Preparation Example 3, except that the amount of glycidyl methacrylate (GMA) added in step S2 was 89.55 g (0.63 mol), and the other conditions were the same as those in Preparation Example 3. Phenolic resin A-4 was obtained with a yield of 77%. The weight average molecular weight of phenolic resin A-4 was 17300 Daltons as calculated by gel permeation chromatography (GPC) through standard polystyrene conversion, and the grafting rate of GMA in phenolic resin A-4 (the ratio of the reaction of phenolic hydroxyl groups in the phenolic resin with GMA) was 32%.

[0057] Preparation Example 5 Preparation of Phenolic Resin B-1

[0058] S1. Resin polymer F3 was prepared according to the method of step S1 in Preparation Example 1, except that 77.9 g (0.95 mol) of formaldehyde solution (37%) was used instead of 278.66 g (1.15 mol) of 4,4'-bis(methoxymethyl)biphenyl, and the amount of propylene glycol monomethyl ether (PGME) added was 140 g. Other conditions were the same, and resin polymer F3 was obtained with a yield of 70%. The weight average molecular weight of resin polymer F3 was 11200 Daltons obtained by gel permeation chromatography (GPC) through standard polystyrene conversion.

[0059] S2. Add 80g of resin polymer F3 and 160g of γ-butyrolactone solvent to a 1L three-necked flask, mix and stir at 60°C to dissolve the resin, then drop 71.07g (0.50mol) of glycidyl methacrylate (GMA) thereinto, raise the temperature to 80°C for reaction for 12h, cool the reaction vessel in the atmosphere after the reaction, add another 30g of γ-butyrolactone thereinto and stir, drop the above reaction dilution into 6L of water under high-speed stirring to disperse and precipitate the resin, and recover it, wash it with water appropriately, dehydrate it and then perform vacuum drying to obtain phenolic resin B-1 with a yield of 77%, and use gel permeation chromatography (GPC) to convert it to standard polystyrene to obtain a weight average molecular weight of phenolic resin B-1 of 19100 Daltons, and the grafting rate of GMA in phenolic resin B-1 (the ratio of phenolic hydroxyl groups in phenolic resin to GMA reaction) is 43%.

[0060] Preparation Example 6 Preparation of Phenolic Resin B-2

[0061] 80 g of resin polymer F3 and 160 g of γ-butyrolactone solvent were added to a 1 L three-necked flask, and the mixture was stirred at 60° C. to dissolve the resin. Then, 35.54 g (0.35 mol) of glycidyl methacrylate (GMA) was added dropwise thereto. After the addition was completed, the temperature was raised to 80° C. to react for 12 h. After the reaction was completed, the reaction vessel was cooled in the atmosphere, and 50 g of γ-butyrolactone was added thereto and stirred. The reaction dilution was added dropwise to 6 L of water under high-speed stirring to disperse and precipitate the resin, which was recovered, properly washed with water, dehydrated, and vacuum dried to obtain phenolic resin B-2 with a yield of 77%. The weight average molecular weight of phenolic resin B-2 was 15,300 Daltons as converted by gel permeation chromatography (GPC) according to standard polystyrene, and the grafting rate of GMA in phenolic resin B-2 (the ratio of the reaction of phenolic hydroxyl groups in the phenolic resin with GMA) was 28%.

[0062] Preparation Example 7 Preparation of Phenolic Resin A-5

[0063] S1. Resin polymer F4 was prepared according to the method of Preparation Example 1, except that 168.5 g (1.033 mol) of trifluoromethylphenol was used instead of 113.8 g (1.033 mol) of resorcinol. The other conditions were the same, and resin polymer F4 was obtained with a yield of 75%. The weight average molecular weight of the resin polymer was 9400 Daltons after conversion to standard polystyrene using gel permeation chromatography (GPC).

[0064] S2. Phenolic resin A-5 was prepared according to the method of Preparation Example 1, except that the added amount of glycidyl methacrylate (GMA) was 46.91 g (0.33 mol). The other conditions were the same, and phenolic resin A-5 was obtained with a yield of 75%. The weight average molecular weight of phenolic resin A-1 was obtained by gel permeation chromatography (GPC) and converted to standard polystyrene, which was 10,900 Daltons. The grafting rate of GMA in phenolic resin A-1 (the ratio of the reaction of phenolic hydroxyl groups in the phenolic resin with GMA) was 28%.

[0065] Comparative Preparation Example 1 Preparation of Reference Phenolic Resin DA-1

[0066] 165g of resin polymer F1 and 380g of solvent γ-butyrolactone were added to a 1L three-necked flask, mixed and stirred at 60°C to dissolve the resin, and then 191.9g (1.35mol) of glycidyl methacrylate (GMA) was added dropwise thereto. After the addition was completed, the temperature was raised to 80°C for reaction for 12h. After the reaction was completed, the reaction vessel was cooled in the atmosphere, and 50g of γ-butyrolactone was added thereto and stirred. The above reaction dilution was added dropwise to 8L of water under high-speed stirring to disperse and precipitate the resin, and it was recovered, properly washed with water, dehydrated and vacuum dried to obtain a reference phenolic resin DA-1 with a yield of 76%. The weight average molecular weight of the reference phenolic resin DA-1 was 26600 Daltons by gel permeation chromatography (GPC) and converted to standard polystyrene, and the grafting rate of GMA in the reference phenolic resin DA-1 (the ratio of the phenolic hydroxyl group in the phenolic resin to the reaction of GMA) was 55%.

[0067] Comparative Preparation Example 2 Preparation of Reference Phenolic Resin DB-1

[0068] 80g of resin polymer F3 and 160g of solvent γ-butyrolactone were added to a 1L three-necked flask, mixed and stirred at 60°C to dissolve the resin, and then 49.75g (0.25mol) of glycidyl methacrylate (GMA) was added dropwise thereto. After the addition was completed, the temperature was raised to 80°C for reaction for 12h. After the reaction was completed, the reaction vessel was cooled in the atmosphere, and 50g of γ-butyrolactone was added thereto and stirred. The above reaction dilution was added dropwise to 6L of water under high-speed stirring to disperse and precipitate the resin, and it was recovered, properly washed with water, and vacuum dried after dehydration to obtain a reference phenolic resin DB-1 with a yield of 74%. The weight average molecular weight of the reference phenolic resin DB-1 obtained by gel permeation chromatography (GPC) was 12100 Daltons by standard polystyrene conversion, and the grafting rate of GMA in the reference phenolic resin DB-1 (the ratio of the phenolic hydroxyl group in the phenolic resin to the reaction of GMA) was 18%.

[0069] Comparative Preparation Example 3 Preparation of Reference Phenolic Resin DA-2

[0070] Reference phenolic resin DA-2 was prepared according to the method of Preparation Example 1, except that step S2 was not performed, and the resin polymer F1 prepared in step S1 was directly used as the final product, which was recorded as reference phenolic resin DA-2.

[0071] Comparative Preparation Example 4 Preparation of Reference Phenolic Resin DB-2

[0072] Reference phenolic resin DB-2 was prepared according to the method of Preparation Example 5, except that step S2 was not performed, and the resin polymer F3 prepared in step S1 was directly used as the final product, which was recorded as reference phenolic resin DB-2.

[0073] Examples 1 to 8 and Comparative Examples 1 to 5

[0074] Preparation method of negative mixed phenolic resin composition: after phenolic resin A, phenolic resin B, initiator, dissolution control agent, and organic solvent are mixed to form a uniform solution, the solution is filtered with a membrane filter with a pore size of 1 μm to prepare a negative mixed phenolic resin composition. Examples 1 to 8 and Comparative Examples 1 to 5 are respectively prepared according to the components and amounts shown in Table 1 to obtain negative mixed phenolic resin compositions. Among them, C1 is a photopolymerization initiator: Michler's ketone, C2 is a photopolymerization initiator: 4,4'-bis(diethylamino)benzophenone, D1 is a dissolution control agent: propylene glycol monomethyl ether acetate, D2 is a dissolution control agent: di(methyl)acrylate, and the organic solvents are all γ-butyrolactone.

[0075] Table 1

[0076]

[0077] Test Case

[0078] The negative mixed phenolic resin compositions prepared in the above examples and comparative examples were tested for in-plane uniformity of film thickness and chemical resistance according to the following methods. The results are shown in Table 2.

[0079] (1) Film thickness in-plane uniformity test: A negative type mixed phenolic resin composition was spin-coated on a silicon wafer and heated on a hot plate at 120°C for 3 minutes to obtain a coating film with a thickness of 10 μm. The coating film was measured for film thickness at 39 points in the film surface using a non-contact film thickness measuring instrument (Nanometrics, NanoSpec / AFT 5100 model), and the average value and the difference between the maximum and minimum film thicknesses were calculated. The difference between the maximum and minimum film thicknesses at this time was used as an indicator of film thickness in-plane uniformity.

[0080] (2) Chemical solvent resistance test: A phenolic resin coating film was prepared according to the method in (1). The coating film was irradiated with 200 mJ / cm2 using an iline lithography machine using a mask with a test pattern. 2 The coating formed on the wafer is exposed with energy of 100°C. Subsequently, cyclopentanone is used to carry out spray development with a developer. The unexposed portion is then rinsed with propylene glycol methyl ether acetate to remove the unexposed portion, thereby obtaining a relief pattern of a polyimide precursor. The silicon wafer substrate having the relief pattern is cured at 230°C for 1 hour in a nitrogen atmosphere using a temperature-raising program curing furnace, thereby obtaining a phenolic resin cured film about 8 μm thick.

[0081] The obtained phenolic resin cured film was immersed in a solution (containing 40 wt% of 3-methoxy-3-methyl-1-butanol and 60 wt% of dimethyl sulfoxide) at 100°C for 1 hour, washed with water and air-dried, and then the chemical resistance of the phenolic resin cured film was evaluated by film thickness measurement and observation under an optical microscope.

[0082] For the cured film after immersion, the case where the thickness change of the cured film relative to the film thickness before immersion was within ±1% and no cracks were generated was evaluated as "++", the case where the thickness change of the cured film was within ±3% and no cracks were generated was evaluated as "+", the case where the thickness change of the cured film was within ±5% and no cracks were generated was evaluated as "-", and the case where the thickness change of the cured film exceeded ±5% or cracks were generated was evaluated as "--".

[0083] Table 2

[0084]

[0085]

[0086] It can be seen from the results in Table 1 that, compared with Comparative Examples 1 to 5, the negative phenolic resin compositions provided by Examples 1 to 9 of the present invention have better in-plane uniformity of film thickness, and the cured films after low-temperature curing (below 250° C.) have better chemical solvent resistance.

[0087] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A negative mixed phenolic resin composition, characterized in that: The negative type mixed phenolic resin composition comprises a phenolic resin mixture, an initiator and an optional organic solvent I; the phenolic resin mixture comprises a phenolic resin A having a structure as shown in formula (1) and a phenolic resin B having a structure as shown in formula (2); In formula (1) and formula (2), R1 is a hydrogen atom, C1 to C 10 C1~C 10 R2-R5, R8 and R9 are each independently a hydrogen atom or a C1-C 10 R6 and R7 are each independently a halogen atom, a hydrogen atom, a C1-C 10 C1-C 10 wherein part of X1 or X2 in the same molecular chain is a hydrogen atom, the remaining part of X1 or X2 is a group represented by formula (3), and the molar ratio of hydrogen atoms to the group represented by formula (3) in the same molecular chain is (1 to 3):1, E is a single bond, C1 to C 10 C1~C 10 alkylene, m1 and m5 are each independently an integer of 1 to 3, m2 and m6 are each independently an integer of 0 to 2, 2≤(m1+m2)≤4, 2≤(m5+m6)≤4, m3 and m4 are each independently an integer of 0 to 3, n1 and n2 are each independently an integer of 5 to 500; the grafting rates of the groups represented by formula (3) in the phenolic resin A and the phenolic resin B are each independently 25 to 50%; In formula (3), R 10 is a hydrogen atom or a C1-C5 alkyl group, and m7 is an integer of 1-3.

2. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The weight average molecular weights of the phenolic resin A and the phenolic resin B are independently 2000 to 200000 Daltons; preferably, the mass ratio of the phenolic resin A to the phenolic resin B is (0.4 to 2.5):

1.

3. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The preparation method of the phenolic resin A is as follows: a phenolic compound I having a structure as shown in formula (4) is subjected to a first polymerization reaction with a polymer component having a structure as shown in formula (5), and the resulting polymer is subjected to a first nucleophilic substitution reaction with an olefinic epoxy compound having a structure as shown in formula (6), and the resulting product is a phenolic resin A having a structure as shown in formula (1); The preparation method of the phenolic resin B is as follows: a phenolic compound II having a structure as shown in formula (7) is subjected to a second polymerization reaction with an aldehyde compound having a structure as shown in formula (5), and the resulting polymer is subjected to a second nucleophilic substitution reaction with an olefinic epoxy compound having a structure as shown in formula (6), and the resulting product is a phenolic resin B having a structure as shown in formula (2); In formula (4) and formula (7), R1 is a hydrogen atom, C1 to C 10 C1-C 10 alkyl, m1 and m5 are each independently an integer of 1 to 3, m2 and m6 are each independently an integer of 0 to 2, 2≤(m1+m2)≤4, 2≤(m5+m6)≤4; In formula (5), R2 to R5 are each independently a hydrogen atom or a C1 to C 10 R6 and R7 are each independently a halogen atom, a hydrogen atom, a C1-C 10 C1~C 10 Alkyl, E is a single bond, C1~C 10 C1~C 10 alkylene, Y1 and Y2 are each independently hydroxyl, halogen or C1-C5 alkoxy, m3 and m4 are each independently an integer of 0-3; In formula (6), R 10 is a hydrogen atom or a C1-C5 alkyl group, and m7 is an integer of 1-3.

4. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The molar ratio of the phenol compound I to the polymer component is 1:(0.9-1.2); Preferably, the molar ratio of the phenol compound II to the aldehyde compound is 1:(0.9-1.2); Preferably, the phenol compound I and the phenol compound II are each independently selected from at least one of resorcinol, phloroglucinol, catechol, pyrogallol, 1,2,4-pyrogallol, m-methylphenol, p-methylphenol, p-trifluoromethylphenol, and o-trifluoromethylphenol; Preferably, the polymer component is selected from at least one of 4,4'-bis(methoxymethyl)biphenyl, dichlorobenzyl biphenyl, and 4,4'-bis(hydroxymethyl)biphenyl; Preferably, the aldehyde compound is selected from at least one of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde.

5. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The conditions of the first polymerization reaction and the second polymerization reaction independently include: a temperature of 20 to 250° C. and a time of 5 to 15 hours; Preferably, the conditions of the first nucleophilic substitution reaction and the second nucleophilic substitution reaction independently include: a temperature of 50 to 100° C. and a time of 10 to 20 h; Preferably, the first polymerization reaction and / or the second polymerization reaction is carried out in the presence of a catalyst; Preferably, the catalyst is selected from an acidic catalyst and / or a basic catalyst; Preferably, the amount of the olefinic epoxy compound used is such that the grafting ratio of the group represented by formula (3) in the phenolic resin A and the phenolic resin B is independently 25 to 50%.

6. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The mass ratio of the phenolic resin mixture to the initiator and the organic solvent I is 100:(0.1-10):(100-1000); Preferably, the initiator is selected from at least one of benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzil derivatives, benzoin derivatives, and oxime derivatives; Preferably, the organic solvent I is selected from at least one of amides, sulfoxides, ureas, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons.

7. The negative type mixed phenolic resin composition according to claim 1, characterized in that: The negative mixed phenolic resin composition also includes at least one of a sensitizer, a surfactant, a silane coupling agent, a dissolution controller, and a polymerization inhibitor; preferably, the mass ratio of the phenolic resin mixture to the sensitizer, the surfactant, the silane coupling agent, the dissolution controller, and the polymerization inhibitor is 100:(0.01~10):(0.01~10):(0.01~15):(0.01~10):(0.01~5).

8. The method for preparing a negative type mixed phenolic resin composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing phenolic resin A, phenolic resin B, initiator, optional organic solvent I, sensitizer, surfactant, silane coupling agent, dissolution control agent and polymerization inhibitor to obtain a negative mixed phenolic resin composition.

9. Use of the negative mixed phenolic resin composition according to any one of claims 1 to 7 in the fields of photolithography materials and semiconductor packaging materials.

10. A method for preparing a solidified relief pattern, characterized in that: The preparation method comprises the following steps: S1. coating the negative mixed phenolic resin composition according to any one of claims 1 to 7 on a substrate to form a photosensitive resin layer; S2. exposing the photosensitive resin layer; S3. removing the resin of the unexposed part by treating with a developer to obtain a relief pattern; S4. curing the relief pattern to obtain a cured relief pattern; Preferably, the curing temperature is 150-250°C.

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