CN116414000A

CN116414000A - Photosensitive polyimide composition, cured product, and electronic component

Info

Publication number: CN116414000A
Application number: CN202310402271.9A
Authority: CN
Inventors: 刘斌; 向文胜; 胡泽明; 张兵; 赵建龙; 谢立洋; 程晋广
Original assignee: Jiangsu Aisen Semiconductor Material Co ltd
Current assignee: Jiangsu Aisen Semiconductor Material Co ltd
Priority date: 2023-04-14
Filing date: 2023-04-14
Publication date: 2023-07-11

Abstract

The present invention relates to the technical field of photosensitive dielectric materials, and in particular, to a photosensitive polyimide composition, a cured product and an electronic component. A photosensitive polyimide composition having low-temperature crosslinking and low warp stress, which comprises the following components (a), (b) and (c): (a) a block polymer soluble in an aqueous alkaline solution; (b) a photosensitizer; (c) A thermal crosslinking agent, wherein the thermal crosslinking agent comprises a component (c 1) of an epoxy group-containing crosslinking agent and a component (c 2) of a CH-containing crosslinking agent ₂ OR cross-linking agent of OR. The photosensitive polyimide composition can realize low-temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical stability and high cohesiveness.

Description

Photosensitive polyimide composition, cured product, and electronic component

Technical Field

The present invention relates to the technical field of photosensitive dielectric materials, and in particular, to a photosensitive polyimide composition, a cured product and an electronic component.

Background

In recent years, in response to demands for reduction in heat load on the device, reduction in warpage of the device, and the like, there has been a demand for a positive photosensitive material which can be cured by firing at a low temperature of 250 ℃ or lower (more desirably 200 ℃ or lower) and which has high sensitivity and high resolution. Examples of the polyimide composition curable at low temperature include photosensitive polyimide compositions using a closed-loop polyimide, a photoacid generator, and a thermal crosslinking agent containing a hydroxymethyl group. However, these compositions have a problem of large warpage because of high shrinkage upon curing.

In order to achieve low warpage, a water-soluble photosensitive composition comprising a multicomponent block copolyimide comprising a specific diamine residue and acid dianhydride residue, a sensitizer and water is exemplified. However, the water-soluble photosensitive composition is poor in exposure sensitivity because it uses a material for forming a low linear expansion property, and is limited in use because it contains a large amount of water, and therefore it cannot be used for a surface protective film, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc. of a semiconductor element.

It can be seen that the photosensitive polyimide composition in the prior art cannot achieve low-temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical resistance and high adhesion at the same time.

In view of this, the present invention has been made.

Disclosure of Invention

The invention aims to provide a photosensitive polyimide composition, a cured product and an electronic component. The photosensitive polyimide composition provided by the embodiment of the invention can realize low-temperature curing, excellent exposure sensitivity, low warpage, low stress, high chemical stability and high cohesiveness.

The invention is realized in the following way:

in a first aspect, the present invention provides a photosensitive polyimide composition having low-temperature crosslinking and low warp stress, which contains the following components (a), (b) and (c):

(a) Block polymers soluble in aqueous alkaline solutions; the structural formula is shown in the following formula 1:

formula 1, wherein k+m=5 to 200, m/k=0.01 to 0.5; ar (Ar) ₁ Selected from 4-valent organic groups, ar ₂ Selected from 2-valent organic groups, ar ₃ Selected from 4-valent organic groups.

(b) A photosensitizer;

(c) A thermal crosslinking agent, wherein the thermal crosslinking agent comprises a component (c 1) of an epoxy group-containing crosslinking agent and a component (c 2) of a CH-containing crosslinking agent ₂ OR cross-linking agent of OR.

In a second aspect, the present invention provides a method for producing a pattern, comprising the steps of applying the low-temperature cross-linked, low-warp-stress photosensitive polyimide composition according to any one of the above embodiments to a support substrate, and drying, exposing, developing, and heating the support substrate;

preferably, the light source used in the exposure step is i-rays.

In a third aspect, the present invention provides a cured product obtained by curing the photosensitive polyimide composition having low-temperature crosslinking and low warp stress according to any one of the above embodiments;

Preferably, the cured product includes a surface protective film or an interlayer insulating film.

In a fourth aspect, the present invention provides an electronic component comprising the cured product according to the foregoing embodiment;

preferably, the cured product is used as a surface protective film or an interlayer insulating film.

The invention has the following beneficial effects: the photosensitive polyimide composition provided by the embodiment of the invention has the advantages that the part exposed to ultraviolet light is easy to dissolve in alkaline aqueous solution, and the part not exposed to ultraviolet light is insoluble in alkaline aqueous solution, so that fine patterns can be effectively duplicated. In addition, the photosensitive polyimide composition of the present invention is excellent in the dissolution rate ratio (contrast) of the unexposed portion to the exposed portion, and has good resolution, sensitivity, low warpage, low stress and low-temperature curability, and the film formed after curing has good chemical resistance and adhesion.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a schematic diagram of a semiconductor package structure according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The embodiment of the invention provides a photosensitive polyimide composition, which comprises the following components:

(a) Block polymers soluble in aqueous alkaline solutions; (b) a photosensitizer; (c) a thermal crosslinking agent; (d) a silane coupling agent.

The photosensitive polyimide composition of the present invention has excellent sensitivity and resolution by increasing the dissolution rate ratio (dissolution contrast) of the exposed portion of the pattern and the unexposed portion with respect to the alkaline developer. And the portion of the photosensitive polyimide composition exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the portion not exposed to ultraviolet light is insoluble in an alkaline aqueous solution, thus enabling effective replication of fine patterns. Meanwhile, the photosensitive polyimide composition has the capability of being cured at a low temperature, and has low warpage, low stress and chemical resistance.

First, the following description will be made on one criterion that component (a) is soluble in an alkaline aqueous solution. A photosensitive composition obtained by dissolving the component (a) alone or together with other components in any solvent is spin-coated on a substrate such as a silicon wafer to form a coating film having a film thickness of about 5 μm, and the coating film is immersed in an aqueous tetramethylammonium hydroxide solution at 20 to 25 ℃ to form a uniform solution.

The alkaline aqueous solution refers to an aqueous tetramethylammonium hydroxide solution, an aqueous metal hydroxide solution, an aqueous organic ammonia solution, or the like.

In view of the solubility in an aqueous alkaline solution, the component (a) has a plurality of phenolic hydroxyl groups and a plurality of carboxyl groups.

The main chain skeleton of the component (a) adopts polyimide series and polyoxazole series polymer alternating block polymers, so that the photosensitive polyimide composition has better processing and heat resistance.

Further, the component (a) is more preferably a block copolymer of polyimide-polyhydroxyamide, and a polymer having a structural unit represented by the following formula 1, which utilizes alkali solubility of a phenolic hydroxyl group and a partial carboxyl group, good photosensitivity and film characteristics:

where k+m=5-200, e.g., 5, 10, 15, 20, 25, 35, 40, 50, 70, 75, 80, 85, 95, 100, 110, 120, 135, 150, 160, 175, 180, 185, 190, 195, 200, etc. any number between 5-200. m/k=0.01 to 0.5; for example, 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 0.5, etc. 0-0.5. Ar (Ar) ₁ Selected from 4-valent organic groups, ar ₂ Selected from 2-valent organic groups, ar ₃ Selected from 4-valent organic groups;

the amide structure containing a hydroxyl group represented by formula 1 can be finally converted into an oxazol body by curing dehydration ring closure, whereby the cured film has excellent chemical resistance, heat resistance, adhesion, and the like.

The solubility of the polymer in an alkaline aqueous solution is derived from a phenolic hydroxyl group and a carboxyl group, and therefore, it is preferable to contain a structure in a proportion of or above. More preferably: m is an amide unit containing a carboxyl group, and the molar ratio of m to k is m=1 to 33 mol%, and k=67 to 99 mol%. Too large an m-cell can result in a loss of film thickness in the exposed area, resulting in an inefficient replication of the pattern. Therefore, by adjusting the amounts of the alkali-soluble groups of the phenolic hydroxyl groups and the carboxyl groups, the dissolution rate of the polymer in the alkali aqueous solution is changed, and thus a photosensitive polyimide composition having an appropriate dissolution rate can be obtained.

The polymer m+k is the number of repeating structural units of component (a), and the value of m+k is 5 to 200. When m+k is less than 5, the viscosity of the composition is too small, resulting in the composition not being used as a thick film, and when m+k is greater than 200, the composition becomes insoluble in an alkaline aqueous solution.

Further, ar ₁ And is selected from any one of the 4-valent organic groups represented by the following formula 2, identically or differently at each occurrence:

wherein R is ₁ -R ₈ Are monovalent organic groups, R ₁ -R ₈ Each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; for example, R ₁ -R ₈ Each independently selected from any one of hydrogen, fluorine atom, methyl group and trifluoromethyl group; x is a divalent group, preferably, X is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group, and a carbonyl group; for example X is selected from oxygen atoms, methylene groupsSulfur atom, sulfonyl, carbonyl, C (CH) ₃ ) ₂ And C (CF) ₃ ) ₂ Any one of the following.

In formula 1, ar1 is a residue derived from tetracarboxylic dianhydride or a derivative thereof, preferably a 4-valent aromatic group, having an amide ester structure of tetracarboxylic dianhydride or a derivative thereof and diamine, preferably tetracarboxylic dianhydride or a derivative thereof having the structure wherein all of 4 binding sites are present on an aromatic ring, and examples of such tetracarboxylic dianhydride include: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyl tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride aromatic tetracarboxylic dianhydrides such as 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorene dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, and aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and 1,2,3, 4-cyclopentane tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

Ar ₂ And is selected from any one of the 2-valent organic groups represented by formula 3, identically or differently at each occurrence:

wherein R is ₉ -R ₂₀ Are monovalent organic groups, preferably R ₉ -R ₂₀ Each independently selected from hydrogen, halogen, C1-C5 substituted or unsubstituted alkylAny one of them; for example R ₉ -R ₂₀ Each independently selected from any one of hydrogen, fluorine atom, methyl group and trifluoromethyl group; y is a divalent group; y is selected from any one of oxygen atom, C1-C5 substituted or unsubstituted alkylene, sulfur atom, sulfonyl and carbonyl; for example Y is selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) ₃ ) ₂ And C (CF) ₃ ) ₂ Any one of the following.

Ar in formula 1 ₂ The amino acid residue derived from an amino acid, which is an amide structure formed by an amino acid and a diamine, is generally a 2-valent organic group, and is preferably a 2-valent aromatic group, and amino acid residues having a structure in which 2 binding sites are present on an aromatic ring are preferable, and examples of such amino acids include p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid. One kind of them may be used alone, or two or more kinds may be combined.

Ar ₃ And is selected from any one of the 4-valent organic groups represented by formula 4, identically or differently at each occurrence:

Wherein R is ₂₁ -R ₂₆ Are monovalent organic groups, and are each independently selected from any one of hydrogen, fluorine atoms, methyl groups or trifluoromethyl groups; q is a divalent group selected from oxygen atom, methylene group, sulfur atom, sulfone group, carbonyl group, C (CH) ₃ ) ₂ Or C (CF) ₃ ) ₂ Any one of the following.

Ar in formula 1 ₃ The 4-valent organic group is generally a residue derived from a dihydroxydiamine having an amide structure formed by reacting a hydroxyl-containing diamine with an amino acid, and is preferably a 4-valent aromatic group, and the carbon number of the residue is preferably 6 to 40, more preferably a 6 to 40-valent aromatic group. The above-mentioned 4-valent aromatic group is preferably a residue of a diamine having a structure in which 4 binding sites are all on an aromatic ring and 2 hydroxyl groups are each located at an ortho position to the bond with W. Examples of such diamines include 3,3'diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) 1, 3-hexafluoropropane bis (4-amino-3-hydroxyphenyl) 1, 3-hexafluoropropane, and the like. The residue of such diamine is not limited to these, and the residue of these compounds may be two or more kinds alone or in combination.

In addition, ar is not required to deteriorate heat resistance in order to improve adhesion to a substrate ₃ Part of the aliphatic group having a siloxane structure may be copolymerized, and preferably 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like may be selected.

The terminal group of the aromatic polyamide represented by formula 1 is according to Ar ₁ 、Ar ₂ And Ar is a group ₃ The ratio of (2) is carboxylic acid or amine. One or two kinds of blocking agents may be reacted with the polymer terminals as needed to make one terminal or both terminals each be a saturated aliphatic group, an unsaturated aliphatic group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or the like. In this case, the end capping rate is preferably 30 to 100%.

When the structures represented by formula 1 each contain 10% by weight or more of fluorine atoms, water repellency to a proper extent is exhibited at the interface of the film during development with an alkaline aqueous solution, preventing permeation at the interface. However, when the fluorine atom content exceeds 20% by weight, the solubility in an aqueous alkaline solution is reduced. The fluorine atom content is therefore preferably 10 to 20% by weight.

It should be noted that: (1) R is as described above ₁ -R ₂₆ The halogen mentioned in (b) is not limited to F, but may be bromine, chlorine, or the like.

(2) R is as described above ₁ -R ₂₆ The C1-C5 substituted or unsubstituted alkyl group mentioned in (1) may be a C1-C3 substituted or unsubstituted alkyl group, and may be, for example, an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, or the like, or a substituted alkyl group such as a trifluoromethyl group, a trifluoroethyl group, a difluoromethyl group, a trichloromethyl group, or the like.

(3) R is as described above ₁ -R ₂₆ The C1-C5 substituted or unsubstituted alkylene group mentioned in (a) may be a C1-C3 unsubstituted alkylene group such as methylene, ethylene, propylene or the like, or a C1-C3 substituted alkylene group such as halogen (fluorine, bromine, chlorine) substituted methylene, halogen substituted ethylene or the like.

The molecular weight of the component (a) is preferably 3000 to 200000, more preferably 5000 to 100000 in terms of weight average molecular weight. The molecular weight herein is a value measured by gel permeation chromatography and converted from a standard polystyrene standard curve.

In the invention, a block polymer with a structural unit shown in a formula 1 is generally obtained by preparing a diacid chloride compound by imidizing and then acylating and chloridizing dianhydride and amino benzoic acid polymer, condensing hydroxyl diamine and dianhydride into an oligomer, and polymerizing the oligomer with the prepared diacid chloride compound.

Specifically, in the first step, a compound having a polyimide structure of a terminal carboxyl group can be prepared by reacting aminobenzoic acid with dianhydride, and then a compound having a polyimide structure of a terminal acid chloride can be prepared by acid chlorination. And secondly, carrying out polycondensation reaction on a diamine compound containing hydroxyl and dianhydride to prepare the amino-terminated polyhydroxyamide oligomer. And thirdly, preparing the block polymer by condensation reaction of the terminal acyl chloride compound prepared in the first step and the terminal amino polyhydroxy amide.

In the embodiments of the present invention, for the quinone diazide compound, the diazide naphthoquinone-5-sulfonyl group and the diazide naphthoquinone-4-sulfonyl group may be preferably used. In the examples of the present invention, a diazidonaphthoquinone sulfonyl ester compound in which a diazidonaphthoquinone-5-sulfonyl group and a diazidonaphthoquinone-4-sulfonyl group are used together in the same molecule may be obtained, or a mixture of a diazidonaphthoquinone-5-sulfonyl ester compound and a diazidonaphthoquinone-4-sulfonyl ester compound may be used.

Wherein the component (b) quinone diazide compound more preferably contains an ester formed from a phenol compound and a diazide naphthoquinone-5-sulfonyl group. Thus, high sensitivity can be obtained under i-line exposure.

The content of the component (b) is preferably 5 to 20 parts by weight, more preferably 8 to 15 parts by weight, for example, 5 to 20 parts by weight, such as 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, and the like, based on 100 parts by weight of the component (a). By setting the content of the quinone diazide compound to the above range, higher sensitivity can be achieved, and further a sensitizer or the like can be added as needed.

The photosensitive polyimide composition of the present invention may contain (c) a thermal crosslinking agent for the purpose of easily obtaining a cured film. As component (c 1), a crosslinking agent having an epoxy group, and as component (c 2), a crosslinking agent having-CH ₂ A crosslinking agent having an OR (R is a hydrogen atom OR a 1-valent organic group) group, which is crosslinked by reacting with the polymer as the component (a) in the heat treatment step after the photosensitive polymer composition of the present invention is applied, exposed and developed, OR which is a compound which is self-polymerized in the heat treatment step. In addition, the crosslinking agent as the component (c 2) has affinity for the alkaline aqueous solution, and can increase the dissolution rate of the alkaline aqueous solution.

In the present invention, the component (c 1) is a crosslinking agent having an epoxy group in its structure. Wherein component (c 1) is selected from the group consisting of compounds represented by the following formula 5-1,

Wherein U is selected from divalent organic groups containing alicyclic or aromatic rings; specific examples of the compound represented by the following formula 5-1 include, for example, epiclon (registered trademark) 850-S, epiclon HP-4032, epiclon HP-7200, epiclon HP-820, epiclon HP-4700, epiclon EXA-4710, epiclon HP-4770, epiclon EXA-859CRP, epiclon EXA-4810, epiclon EXA-4850, epiclon EXA-4816, epiclon EXA-4822 (above, trade name, dainippon Ink and Chemicals, manufactured by Inc.), rikaresin (registered trademark) BPO-20E, rikaresin BEO-60E (above, trade name, manufactured by New Japanese chemical Co., ltd.), EP-4003S, EP-4000S (above, trade name, manufactured by ADEKA) and the like. They may be used alone or in combination of 2 or more. In addition, two or more of these compounds may be used singly or in combination.

In the present invention, component (c 2) is a compound having a structure of-CH ₂ OR (R is a hydrogen atom OR a 1-valent organic group). The number of the groups in the compound may be one or more, but is preferably two or more. Wherein component (c 2) is selected from the compounds represented by the following formula 5-2.

Wherein R is ₂₉ Selected from hydrogen atoms or monovalent organic radicals, R ₃₀ Selected from monovalent organic groups, n is an integer from 1 to 4, and X is selected from single bonds or organic groups of 1 to 4 valences. a is an integer of 1 to 4, b is an integer of 0 to 3, when a is 2, 3 or 4, R ₂₉ Identical or different, R when b is 2 or 3 ₃₀ The same or different.

Specific examples of the compounds represented by the formula 5-2 are shown below, and these compounds may be used singly or in combination.

Examples of the 1-4 valent organic group of X in the formula 5-2 include an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms (e.g., ethylene group, etc.), an arylene group having 6 to 30 carbon atoms (e.g., phenylene group, etc.), or a group obtained by substituting some or all of these hydroxyl hydrogen atoms with halogen atoms such as fluorine atoms, and these groups may further contain phenyl groups, sulfone groups, carbonyl groups, ether linkages, thioether linkages, amide linkages, etc. R is R ₂₉ Preferably hydrogen, alkyl or alkenyl. The number of carbon atoms of the alkyl group or alkenyl group is preferably 1 to 20.R is R ₃₀ Preferably alkyl, alkenyl, alkoxyalkyl or hydroxymethyl, and the number of carbon atoms is preferably 1 to 20.

The purity of the compound represented by the above formula 5-2 is preferably 75% or more, more preferably 85% or more. When the purity is 85% or more, the storage stability is excellent, and the crosslinking reaction of the polyimide composition can be sufficiently performed. Further, since unreacted groups which become water-absorbent groups can be reduced, the water absorption of the polyimide composition can be reduced. Examples of the method for obtaining the high-purity thermal crosslinking agent include recrystallization and distillation. The purity of the thermal crosslinking agent can be determined by liquid chromatography.

The content of the thermal crosslinking agent in the component (c) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the polyimide in the component (a). When the amount is 5 parts by weight or more, the crosslinking density of the cured film is increased, the chemical resistance is high, and the cured film has low curing warpage properties, and when it is 10 parts by weight or more, the chemical resistance is higher, the low curing warpage properties are better, and at the same time, higher mechanical properties can be obtained. In addition, from the viewpoint of the storage stability and mechanical strength of the composition, it is preferably 30 parts by mass or less.

Further, the content of c1 is any value between 5 and 15 parts by weight, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.; the content of c2 is any number between 0.1 and 15 parts, for example, 0.1f part, 0.5 part, 1 part, 2 parts, 5 parts, 7 parts, 8 parts, 10 parts, 13 parts, 14 parts, 15 parts, and the like.

The photosensitive polyimide composition having low-temperature crosslinking and low warp stress of the present invention further contains (d) a solvent, preferably an organic solvent. For example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons and the like can be used. Specifically, examples thereof include: polar solvents such as gamma-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylsulfoxide, hexamethylphosphoric triamide, dimethylimidazolidinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N, N-dimethylpropaneamide, and N-acetyl-epsilon-caprolactam. It is also possible to use: acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methylene chloride, 1, 2-dichloroethane, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate, and the like. The component (d) may be used alone or in combination of two or more.

When the component (d) is contained, the blending amount of the component (d) is preferably 50 to 1000 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the component (a). For example, 50 parts, 60 parts, 70 parts, 100 parts, 150 parts, 200 parts, 300 parts, 400 parts, 500 parts, 600 parts, 700 parts, 800 parts, 900 parts and 1000 parts of any number between 50 and 1000 parts of the peak.

The polyimide composition of the present invention further contains (e) an alkoxysilane binder, and examples of the organosilane compound include: gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, vinyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-acryloxypropyl trimethoxysilane, gamma-ureidopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, bis (2-hydroxyethyl) -3-aminopropyl triethoxysilane, triethoxysilylpropyl ethyl carbamate, 3- (triethoxysilyl) propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, 3-triethoxysilyl-N- (l, 3-dimethylbutylidene) propylamine, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, and the like.

When the organic silane compound is contained, the adhesion of the photosensitive polyimide composition to the substrate after curing can be improved. When the organosilane compound is contained, the content of the organosilane compound is more preferably 0.5 to 15 parts by mass, still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the component (a). For example, 0.5 to 15 parts such as 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 1 part, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts.

The invention may further comprise (f) a leveling agent, which may be a surfactant, thereby improving the coatability with the substrate. Examples of the surfactant include fluorine-based surfactants such as fluoroad (trade name, manufactured by Sumitomo 3M (Co., ltd.), megafac (trade name, manufactured by DIC (Co., ltd.), surflon (trade name, manufactured by Asahi Kabushiki Kaisha); organosiloxane surfactants such as KP341 (trade name, manufactured by Xinyue chemical industry Co., ltd.), DBE (trade name, manufactured by Chisso Corporation), polyflow, glanol (trade name, manufactured by Kagaku chemical Co., ltd.), BYK (trade name, manufactured by BYK-Chemie GmbH); and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyowa Kagaku Co., ltd.).

Next, a method for producing a photosensitive polyimide composition having low-temperature crosslinking and low warp stress according to an embodiment of the present invention will be described. For example, the photosensitive polyimide composition can be obtained by uniformly mixing the above-mentioned components (a) to (c) and, if necessary, the components (d) to (f) and the like. The dissolution method includes stirring and heating. When heating is performed, the heating temperature is preferably set within a range that does not deteriorate the performance of the photosensitive polyimide composition, and is usually room temperature to 80 ℃. The dissolution order of the components is not particularly limited, and includes, for example, a method of sequentially dissolving compounds having low solubility. In addition, as for the components such as the surfactant and a part of the adhesion improver which are liable to generate bubbles when dissolved by stirring, it is possible to prevent dissolution failure of other components due to generation of bubbles by adding them last after dissolving other components.

The photosensitive polyimide composition thus obtained is preferably filtered using a filter to remove impurities and particles. The filter pore size is 0.5 to 0.02. Mu.m, for example, but not limited to, 0.5. Mu.m, 0.2. Mu.m, 0.1. Mu.m, 0.05. Mu.m, 0.02. Mu.m, etc. The filter material includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., preferably polyethylene or nylon. When inorganic particles are contained in the photosensitive polyimide composition, a filter having a larger pore diameter than the particle diameter of the inorganic particles is preferably used.

The cured product provided by the embodiment of the invention can be obtained by curing the photosensitive polyimide composition with low-temperature crosslinking and low warping stress. The cured product of the present invention can be used as a patterned cured film or an unpatterned cured film.

The method for producing a pattern cured film includes: a step (film forming step) of forming a photosensitive polyimide film by applying the photosensitive polyimide composition on a substrate and drying the composition; a step of exposing the photosensitive polyimide film (exposure step); a step (developing step) of developing the photosensitive polyimide film after exposure with an aqueous alkali solution to form a patterned polyimide film; and a step of heating the patterned polyimide film (heating step). The method for producing the unpatterned cured film includes, for example, the film forming step and the heating step. The method may further comprise an exposure step.

In the film forming step, the photosensitive polyimide composition is applied to a metal substrate such as Cu, a glass substrate, a semiconductor, or a metal oxide insulator (e.g., tiO) by, for example, dipping, spraying, screen printing, spin coating, or the like ₂ 、SiO ₂ Etc.), silicon nitride, etc. From the viewpoint of handleability, the applied photosensitive polyimide composition may be dried by heating (for example, 90 to 150 ℃ for 1 to 5 minutes) using a hot plate, an oven, or the like. The support substrate may be cleaned with acetic acid or the like before coating. The thickness of the photosensitive polyimide film is preferably 5 to 20. Mu.m.

In the exposure step, for example, the photosensitive polyimide film formed on the substrate is irradiated with the active light beam through a mask. From the viewpoint of transparency of the component (a), irradiation with i-rays can be suitably used. After exposure, post-exposure heating (PEB) may be performed as needed. The post-exposure heating temperature is preferably 70 to 140℃and the post-exposure heating time is preferably 1 to 5 minutes.

In the developing step, for example, the exposed portion of the photosensitive polyimide film after the exposing step is removed with a developing solution, thereby patterning the photosensitive polyimide film. In the case of the alkali-soluble photosensitive polyimide composition, for example, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) or the like can be suitably used as the developer. The alkali concentration of these aqueous solutions is preferably set to 0.1 to 10 mass%. Further, alcohols or surfactants may be added to the developer. These may be blended in a range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the developer. The patterned photosensitive polyimide film is referred to as a patterned polyimide film.

In the heating step, the patterned polyimide film or the photosensitive polyimide film is heated to cure the photosensitive polyimide composition. Particularly, a film obtained by curing a patterned polyimide film is called a patterned cured film. The heating temperature is preferably 100 to 500 ℃, and from the viewpoint of sufficiently preventing damage to the electronic component caused by heat, it is preferably 250 ℃ or less, more preferably 225 ℃ or less, and still more preferably 140 to 210 ℃. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating may also be performed. The heat treatment may be performed using, for example, an oven such as a quartz tube oven, a hot plate, a rapid annealing furnace (rapid thermal anneal), a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, or a microwave curing furnace. In addition, although either the atmosphere or an inert atmosphere such as nitrogen may be selected, the inert atmosphere such as nitrogen is preferable because oxidation of the pattern can be prevented when the pattern is performed under nitrogen.

The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.

The interlayer insulating film and the surface protective film of the present invention can be used for electronic components and the like, and the electronic components of the present invention can be used for semiconductor devices and the like. The semiconductor device can be used for various electronic equipment and the like, and a schematic view of the semiconductor package structure of the present invention is shown in fig. 1.

This gives excellent rust preventing effect and adhesion effect to the support substrate (particularly copper substrate and copper alloy substrate), and can suppress discoloration of the cured film and the support substrate (particularly copper substrate and copper alloy substrate).

Examples of the semiconductor device include a semiconductor package such as a Wafer Level Chip Size Package (WLCSP) and a fan-out wafer level package (FOWLP). The interlayer insulating film and the surface protective film of the present invention can be used for a circuit-forming substrate which can be used for a suspension for a hard disk drive, a flexible wiring board, or the like.

The features and capabilities of the present invention are described in further detail below in connection with the examples.

The following examples and comparative examples are given by the simplified names of compounds, auxiliaries and solvents.

Bis-AP-AF:2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane

4-ABA para aminobenzoic acid

SiDA:1, 3-bis (3-aminopropyl) tetramethyldisiloxane

ODPA:4,4' -Oxyphthalic anhydride

MAP: m-aminophenol

NMP: n-methyl-2-pyrrolidone

GBL; gamma-butyrolactone

TMAH: tetramethyl ammonium hydroxide

SOCl ₂ : thionyl chloride

Synthesis example 1

The embodiment provides a preparation method of a compound containing an imide structure and containing end acyl chloride, which comprises the following steps:

13.71g (0.1 mol) of 4-ABA are dissolved in 100g of tetrahydrofuran under a stream of dry nitrogen, and the resulting solution is subsequently cooled to-10 ℃. Subsequently, 15.51g (0.05 mol) of ODPA was added, and the mixture was reacted at 0℃for 4 hours. 13.09g (0.11 mol) of SOCl are then added dropwise thereto ₂ After the completion of the dropwise addition, the reaction was carried out at 0℃for 1 hour, and thereafter the solution was concentrated by distillation under reduced pressure to obtain a compound (I) containing an imide structure as a terminal acid chloride.

Compounds containing imide structures as terminal acyl chlorides (I)

Synthesis example 2

The embodiment provides a method for synthesizing a polymer A, which comprises the following steps:

under a dry nitrogen stream, 32.96g (0.09 mol) of Bis-AP-AF was dissolved in 132g of NMP, 6.2g (0.02 mol) of ODPA was added thereto together with 25g of NMP, and reacted at 20℃for 3 hours, after which 2.18g (0.02 mol) of MAP as a blocking agent and 12.66g of pyridine were added, and then the system was cooled to-10℃and a solution of 46.8g (0.08 mol) of Compound (I) dissolved in 187g of NMP was added dropwise, and after completion of the dropwise addition, the reaction was continued at-10℃for 1 hour. After the reaction was completed, the solution was poured into 4L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer A. Polymer A was subjected to molecular weight measurement and had a molecular weight of 22000.

The molecular weight test method is as follows:

the number average molecular weight was determined under the following conditions by Gel Permeation Chromatography (GPC) based on standard polystyrene conversion. The number average molecular weight of polymer A was 40,000. The measurement was performed using 1mL of a solution with respect to 0.5mg a of the solvent [ Tetrahydrofuran (THF)/Dimethylformamide (DMF) =1/1 (volume ratio) ].

Measurement device: l4000UV manufactured by Hitachi of Detector Co., ltd

And (3) a pump: l6000 manufactured by Hitachi Co., ltd

C-R4A Chromatopac manufactured by Shimadzu corporation

Measurement conditions: chromatographic column Gelpack GL-S300 MDT-5X 2

Eluent: THF/DMF=1/1 (volume ratio), liBr (0.03 mol/L), H ₃ PO ₄ (0.06 mol/L) flow rate: 1.0mL/min, detector: UV270nm

Synthesis example 3

The present example provides a method for synthesizing polymer B, specifically as follows:

under a dry nitrogen stream, 32.96g (0.09 mol) of Bis-AP-AF was dissolved in 132g of NMP, 7.76g (0.025 mol) of ODPA was added thereto together with 31g of NMP, and reacted at 20℃for 3 hours, after which 2.18g (0.02 mol) of MAP as a blocking agent and 11.9g of pyridine were added, and then the system was cooled to-10℃and a solution of 43.88g (0.075 mol) of Compound (I) dissolved in 175g of NMP was added dropwise, and after completion of the dropwise addition, the reaction was continued at-10℃for 1 hour. After the reaction was completed, the solution was poured into 4L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer B. Polymer B was subjected to molecular weight measurement and had a molecular weight of 21000. Structurally, m/k=25/75.

Synthesis example 4

The present example provides a method for synthesizing polymer C, specifically as follows:

under a dry nitrogen stream, 32.96g (0.09 mol) of Bis-AP-AF was dissolved in 132g of NMP, 10.2g (0.033 mol) of ODPA was added thereto together with 41g of NMP, and reacted at 20℃for 3 hours, after which 2.18g (0.02 mol) of MAP as a blocking agent and 10.6g of pyridine were added, and then the system was cooled to-10℃and 39.2g (0.067 mol) of Compound (I) was added dropwise to a solution of 156g of NMP, and after completion of the addition, the reaction was continued at-10℃for 1 hour. After the reaction was completed, the solution was poured into 4L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer C. Polymer C was subjected to molecular weight measurement and had a molecular weight of 21000. Structurally, m/k=33/67.

Synthesis example 5

The present example provides a method for synthesizing polymer D, specifically as follows:

32.96g (0.09 mol) of Bis-AP-AF and 2.18g (0.02 mol) of MAP as a capping agent were dissolved in 132g of NMP under a dry nitrogen stream, 31.02g (0.1 mol) of ODPA and 124g of NMP were added thereto, and reacted at 20℃for 3 hours, after the completion of the reaction, the solution was poured into 4L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80℃for 72 hours to give polymer D. Polymer D was subjected to molecular weight measurement and had a molecular weight of 23000.

Examples 1 to 10 and comparative examples 1 to 2

Photosensitive resin compositions of examples 1 to 10 and comparative examples 1 to 2 were prepared according to the components and blending amounts shown in Table 1. The amounts shown in tables 1 to 2 are parts by mass of each component per 100 parts by mass of component (a).

The components used are as follows.

Component (b): photosensitizers

Component (c): thermal crosslinking agent

Component (d): solvent(s)

d1: GBL (gamma-butyrolactone)

d2: EL (ethyl lactate)

Component (e): silane coupling agent

e1: gamma-ureidopropyltriethoxysilane

e2: vinyl triethoxysilane

TABLE 1

TABLE 2

The photosensitive resin compositions prepared in examples and comparative examples were subjected to performance evaluation by the following methods:

(1) Production of developing film

The photosensitive resin compositions (varnishes) produced in examples and comparative examples were spin-coated on 8-inch silicon wafers, and then heat-treated (prebaked) at 120℃for 3 minutes using a hot plate (manufactured by Tokyo Electron Ltd., coating and developing apparatus Mark-7) to produce prebaked films having a thickness of 6. Mu.m. Using an i-line stepper (manufactured by Nikon Corporation, NSR-2005i 9C) at a rate of 50 to 400mJ/cm ² Exposure of 10mJ/cm ² The resulting pre-baked film is exposed to light. After exposure, the photosensitive resin composition was baked after exposure to 100℃for 1 minute. After the photosensitive resin composition was subjected to post-exposure baking, it was developed with a 2.38 wt% aqueous solution of Tetramethylammonium (TMAH) (manufactured by mitsubishi gas chemistry, ELM-D) for 90 seconds, and then rinsed with pure water to obtain a developed film.

(2) Method for measuring film thickness

The film thicknesses after pre-baking and development were measured at refractive indices of 1.63 using a light interference film thickness measuring device LAMBDA ACE STM-602 manufactured by Dainippon Screen mfg.Co., ltd.

(3) Calculation of developing film loss amount

The amount of loss of the developing film was calculated according to the following formula. Since the film thickness after prebaking is 6 μm, the loss amount of the developing film is preferably less than 1 μm. A case where the loss amount of the developing film was less than 1 μm was judged as "A", a case where 1 to 1.5 μm was judged as "B", and a case where 2 μm or more was judged as "C".

Development film loss amount (μm) =film thickness after prebaking-film thickness after development. The results are shown in Table 3.

(4) Measurement of warp

The varnish was applied by spin coating using an application developing device ACT-8, prebaked to a film thickness of 10 μm after 3 minutes of prebaking at 120 ℃ and then heated to 200 ℃ at a rate of 3.5 ℃/min for 1 hour at 200 ℃ using an inert oven under conditions of an oxygen concentration of 20ppm or less. When the temperature was 50℃or lower, the wafer was taken out, and the cured film was measured by using a pressure device FLX2908 (manufactured by KLA Tencor Co.). As a result, the case of 35MPa or more was regarded as insufficient (D), the case of 30MPa or more and less than 35MPa was regarded as good (C), the case of 20MPa or more and less than 30MPa was regarded as better (B), and the case of less than 20MPa was regarded as best (A).

(5) Sensitivity evaluation

After exposure and development, an exposure amount (referred to as an optimal exposure amount Eop) of a line and space pattern (1L/1S) of 20 μm was formed with a width of 1 to 1 as sensitivity. If the Eth is 200mJ/cm ² Hereinafter, it can be determined as high sensitivity. More preferably 150mJ/cm ² The following is given. The results are shown in Table 3.

(6) Evaluation of chemical resistance

The cured product was applied by pipette. The coated cured product was placed on a nitrogen oven at 200 ℃ and held for 60 minutes. After which it was cooled to room temperature. The cooled solidified product was washed with a 25% naoh aqueous solution, and dried, and then the film thickness was measured.

The film thickness change rate (%) was calculated from the film thickness change. If the value is positive, this means that the membrane swells, and if the value is negative, this means that the membrane dissolves. The results are shown in Table 3.

(7) Evaluation of adhesion

With the above method for producing a cured product, a cured product was produced on a Cu substrate, and the obtained cured product was cut into 10×10 checkered cuts by a shearing blade using a cross cut guide (manufactured by COAT-TECH corporation), thereby dividing the cured product into 100 pieces.

An adhesive tape (manufactured by 3M japan corporation) was attached to the cured product, and the adhesive tape was peeled off. The adhesiveness was evaluated as follows based on the number of chips of the cured product peeled from the substrate when the adhesive tape was peeled off.

A: the residual lattice is 100 to 80.

B: the remaining lattice is less than 80.

The results are shown in Table 3.

TABLE 3 Table 3

As can be seen from Table 3, the photosensitive resin compositions provided in examples 1 to 10 of the present invention each have a small loss amount of the developing film, excellent low warp stress, and excellent chemical resistance. The warp stress of comparative example 1 is higher than that of the example. Whereas comparative example 2 is inferior in sensitivity and chemical resistance.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A photosensitive polyimide composition having low-temperature crosslinking and low warp stress, which comprises the following components (a), (b) and (c):

formula 1, wherein k+m=5 to 200, m/k=0.01 to 0.5; ar (Ar) ₁ Selected from 4-valent organic groups, ar ₂ Selected from 2-valent organic groups, ar ₃ Selected from 4-valent organic groups;

(b) A photosensitizer;

2. The photosensitive polyimide composition having low-temperature crosslinking and low warp stress according to claim 1, wherein Ar ₁ And is selected from any one of the 4-valent organic groups represented by formula 2, identically or differently at each occurrence:

wherein R is ₁ -R ₈ Are monovalent organic groups, X is a divalent group,

preferably, R ₁ -R ₈ Each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R ₁ -R ₈ Each independently selected from any one of hydrogen, fluorine atom, methyl group and trifluoromethyl group;

preferably, X is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group, and a carbonyl group;

preferably, X is selected from the group consisting of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C (CH) ₃ ) ₂ And C (CF) ₃ ) ₂ Any one of them;

preferably Ar ₂ And is selected from any one of the 2-valent organic groups represented by formula 3, identically or differently at each occurrence:

wherein R is ₉ -R ₂₀ Are monovalent organic groups, and Y is a divalent group;

preferably, R ₉ -R ₂₀ Each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R ₉ -R ₂₀ Each independently selected from any one of hydrogen, fluorine atom, methyl group and trifluoromethyl group;

preferably, Y is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group, and a carbonyl group;

preferably, Y is selected from the group consisting of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C (CH) ₃ ) ₂ And C (CF) ₃ ) ₂ Any one of them;

preferably Ar ₃ And is selected from any one of the 4-valent organic groups represented by formula 4, identically or differently at each occurrence:

wherein R is ₂₁ -R ₂₆ Are monovalent organic groups, and Q is a divalent group;

preferably, R ₂₁ -R ₂₆ Each independently selected from any one of hydrogen, halogen, C1-C5 substituted or unsubstituted alkyl; preferably, R ₂₁ -R ₂₆ Each independently selected from any one of hydrogen, fluorine atom, methyl group and trifluoromethyl group;

preferably, Q is selected from any one of an oxygen atom, a C1-C5 substituted or unsubstituted alkylene group, a sulfur atom, a sulfone group, and a carbonyl group;

preferably, Q is selected from the group consisting of an oxygen atom, a methylene group, a sulfur atom, a sulfone group, a carbonyl group, C (CH) ₃ ) ₂ And C (CF) ₃ ) ₂ Any one of them;

preferably, the weight average molecular weight of the component (a) is 3000-200000, preferably 5000-100000.

3. The photosensitive polyimide composition having low-temperature crosslinking and low warp stress according to claim 1, wherein the component (b) is a quinone diazide compound.

4. The photosensitive polyimide composition having low-temperature crosslinking and low warp stress as claimed in claim 1, wherein the component (c) is selected from the group consisting of compounds represented by formula 5,

wherein, in formula 5-1, U is selected from divalent organic groups containing alicyclic or aromatic rings;

in formula 5-2, R ₂₉ Selected from hydrogen atoms or monovalent organic radicals, R ₃₀ Selected from monovalent organic groups, n is an integer from 1 to 4, X is selected from single bonds or organic groups of 1 to 4 valences; a is an integer of 1 to 4, b is an integer of 0 to 3, when a is 2, 3 or 4, R ₂₉ Identical or different, R when b is 2 or 3 ₃₀ The same or different.

5. The photosensitive polyimide composition having low-temperature crosslinking and low warp stress as claimed in any one of claims 1 to 4, wherein the content of the component (b) is 5 to 20 parts by weight and the content of the component (c) is 5 to 30 parts by weight, based on 100 parts by weight of the content of the component (a), wherein the content of c1 is 5 to 15 parts by weight and the content of c2 is 0.1 to 15 parts by weight.

6. The photosensitive polyimide composition with low-temperature crosslinking and low warp stress according to any one of claims 1 to 4, further comprising any one or a combination of at least two of a solvent, an alkoxysilane binder or a leveling agent.

7. The photosensitive polyimide composition having low-temperature crosslinking and low warp stress as claimed in claim 6, wherein the solvent is contained in an amount of 100 to 200 parts by weight, the alkoxysilane binder is contained in an amount of 0.5 to 10 parts by weight, and the leveling agent is contained in an amount of 100 to 1000ppm based on 100 parts by weight of the component (a).

8. A method for producing a pattern, comprising the steps of applying the low-temperature cross-linked, low-warp-stress photosensitive polyimide composition according to any one of claims 1 to 7 to a support substrate, and drying, exposing, developing and heating the support substrate;

preferably, the light source used in the exposure step is i-rays.

9. A cured product obtained by curing the photosensitive polyimide composition having low-temperature crosslinking and low warp stress according to any one of claims 1 to 7;

10. An electronic component comprising the cured product according to claim 9;