Negative photosensitive polyimide composition, method for producing pattern and electronic component

Abstract

The present invention provides a negative photosensitive polyimide composition, a method for manufacturing a pattern, and an electronic component, wherein the negative photosensitive polyimide composition contains the following components (a), (b), (c), and (d): (a) a polymer soluble in an alkaline aqueous solution, (b) a photopolymerization initiator, (c) a compound having a polymerizable functional group, wherein the polymerizable functional group includes an unsaturated double bond or triple bond, and (d) a thermal crosslinking agent. The portion of the negative photosensitive polyimide composition of the present invention that is not exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the portion that has been exposed to ultraviolet light is insoluble in an alkaline aqueous solution, thereby being able to effectively replicate fine patterns. In addition, the negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed portion and the exposed portion, and has good resolution, adhesion, chemical resistance, and storage stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of photosensitive resins and relates to a negative photosensitive polyimide composition, a method for producing a pattern, a cured product thereof, an interlayer insulating film, a surface protective film, and an electronic component. More specifically, the present invention relates to a negative photosensitive polyimide composition that can be developed with an alkaline aqueous solution without reducing sensitivity, achieving excellent resolution, and maintaining a good shape of the pattern; a method for producing a pattern-cured film using the composition; and an electronic component. Background Art

[0002] Traditionally, surface protective films and interlayer insulating films for semiconductor devices have generally been made from polyimide resins, which offer excellent thermal stability, electrical insulation, and mechanical properties. These polyimide resin films are typically formed by applying a polyimide precursor (polyamic acid) solution obtained by polycondensing tetracarboxylic dianhydride and diamine in a polar solvent, coating the solution with spin coating or other methods, and then curing the solution by dehydration and ring closure by heating (see Non-Patent Document 1).

[0003] In recent years, photosensitive polyimide has been widely used in surface protection films, interlayer insulation films, etc. in the field of semiconductor devices and integrated circuit packaging due to its inherent photosensitive properties, which can simplify the pattern formation process and shorten the complicated pattern manufacturing process (see patent documents 1-3).

[0004] In the past, the development of above-mentioned photosensitive polyimide has adopted organic solvents such as N-Methylpyrrolidone always.But due to the environmental consciousness in recent years and considering the processing of waste liquid, it is believed that adopting alkaline aqueous solution development problem is less, but the solubility of these photosensitive polyimide materials is very poor, is difficult to form pattern (referring to patent documentation 4-5).In addition, the negative photosensitive polyimide material that can be used for alkaline aqueous solution development must comprise alkali soluble group, but this material is difficult to effectively replicate pattern (referring to non-patent documentation 2) after development.Along with the requirement of semiconductor device to power consumption, polybenzoxazole material has been gradually paid attention to because of its lower dielectric constant and lower water absorption.But, the material that possesses negativity and excellent alkali developability simultaneously is still not reported.

[0005] Therefore, in the art, it is desired to develop a photosensitive polyimide composition having both negative properties and excellent alkaline developability.

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 49-115541.

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 59-108031.

[0008] Patent Document 3: Japanese Patent Application Laid-Open No. 59-219330.

[0009] Patent Document 4: Japanese Patent Application Laid-Open No. 54-109828.

[0010] Patent Document 5: Japanese Patent Application Laid-Open No. 11-24268.

[0011] Non-patent document 1: Polyimide - Structure, Properties and Applications.

[0012] Non-patent document 2: Journal of Photopolymer Science and Technology, 1997, 10(1), 55-60. Summary of the Invention

[0013] To address the shortcomings of the prior art, the present invention provides a negative photosensitive polyimide composition, a method for producing a pattern, and an electronic component. The present invention provides a negative photosensitive polyimide composition having a specific structure and being soluble in alkaline aqueous solutions. The portion of the negative photosensitive polyimide composition not exposed to ultraviolet light is readily soluble in alkaline aqueous solutions, while the portion exposed to ultraviolet light is insoluble in alkaline aqueous solutions. This allows for the effective reproduction of fine patterns.

[0014] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0015] In a first aspect, the present invention provides a negative photosensitive polyimide composition, wherein the negative photosensitive polyimide composition comprises the following components (a), (b), (c) and (d):

[0016] (a) a polymer soluble in an alkaline aqueous solution;

[0017] (b) a photopolymerization initiator;

[0018] (c) a compound having a polymerizable functional group comprising an unsaturated double bond or triple bond;

[0019] (d) Thermal cross-linking agent.

[0020] In the present invention, the negative photosensitive polyimide composition comprises components (a), (b), (c), and (d), exhibits negative characteristics, and is developable with an alkaline aqueous solution. The portion of the negative photosensitive polyimide composition not exposed to ultraviolet light is readily soluble in an alkaline aqueous solution, while the portion exposed to ultraviolet light is insoluble in an alkaline aqueous solution. This allows for efficient reproduction of fine patterns. Furthermore, the negative photosensitive polyimide composition of the present invention exhibits an excellent dissolution rate ratio (contrast ratio) between the unexposed and exposed portions, and exhibits excellent resolution, adhesion, chemical resistance, and storage stability.

[0021] Preferably, the component (a) has a structural unit represented by formula 1,

[0022]

[0023] wherein R is selected from any one of hydrogen, CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2- at each occurrence, the same or different; U is a tetravalent organic group, V is a divalent organic group, and W is a trivalent organic group.

[0024] Preferably, W is selected from any one of the trivalent organic groups represented by Formula 2, the same or different each time it occurs:

[0025]

[0026] Wherein, R1-R3 are all monovalent organic groups, and are independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl.

[0027] Preferably, each occurrence of V is identical or different and is selected from any one of the divalent organic groups represented by Formula 3:

[0028]

[0029] Among them, R4-R 15 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; X is a divalent group, selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 or C(CF3)2.

[0030] Preferably, each occurrence of U is identical or different and is selected from any one of the tetravalent organic groups represented by Formula 4:

[0031]

[0032] Among them, R 16 -R 23 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Y is a divalent group, selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 or C(CF3)2.

[0033] Preferably, the component (a) has a structure shown in Formula 1-1:

[0034]

[0035] Among them, R 24Each occurrence is identically or differently selected from CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2-; U, V, and W have the same defined ranges as above; j+k is the number of repeating structural units of component (a), and the value of j+k is 3-200 (for example, 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200, etc.), preferably 5-100.

[0036] Preferably, the component (b) contains one or more compounds selected from Formula 5-1, Formula 5-2, Formula 6-1 and / or Formula 6-2.

[0037]

[0038] In formula 5-1, R 25 is an alkyl group having 1 to 12 carbon atoms, R 26 is selected from hydrogen or an alkyl group having 1 to 12 carbon atoms, R 27 and R 28 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group;

[0039] In formula 5-2, R 29 Any one selected from hydrogen, -OH, -COOH, -OCH2OH, -O(CH2)2OH, -COOCH2OH or -COO(CH2)2OH, R 30 and R 31 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, and a tolyl group.

[0040]

[0041] In formula 6-1, R 32 is selected from hydrogen or an alkyl group having 1 to 12 carbon atoms, R 33 and R 34 Each is independently selected from any one of a hydrogen atom, an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;

[0042] In formula 6-2, R 35 and R 36 Each is independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5 (e.g., 1, 2, 3, 4 or 5), s and t are each independently an integer of 0 to 3 (e.g., 0, 1, 2 or 3), and the sum of s and t is 3.

[0043] Preferably, the component (c) is selected from the compounds represented by formula 7-1 and / or formula 7-2,

[0044]

[0045] Among them, R 37 Each occurrence is identically or differently selected from a hydrogen atom or a methyl group, R 38 is an alkylene group having 3 to 8 carbon atoms, R 39 Each occurrence is identical or different and is selected from an alkylene group having 1 to 4 carbon atoms (e.g. 1, 2, 3 or 4), and n is an integer from 2 to 5, e.g. 2, 3, 4 or 5.

[0046] Preferably, the component (d) is selected from the compounds represented by formula 8-1 and / or formula 8-2,

[0047]

[0048] In formula 8-1, R 40 Each occurrence of R is identical or different and is selected from a hydrogen atom or a monovalent organic group; 41 are selected, identically or differently on each occurrence, from a hydrogen atom or a monovalent organic radical, or R 41 Combine with each other to form a ring structure;

[0049] In formula 8-2, R 42 is selected from a hydrogen atom or a monovalent organic group, R 43 is selected from a monovalent organic group, d is an integer of 1-4 (e.g., 1, 2, 3, or 4), X is selected from a single bond or an organic group with 1-4 valences (e.g., 1, 2, 3, or 4), a is an integer of 1-4 (e.g., 1, 2, 3, or 4), b is an integer of 0-3 (e.g., 0, 1, 2, or 3), when a is 2, 3, or 4, R 42 Same or different, when b is 2 or 3, R 43 Same or different.

[0050] In the present invention, the alkyl group having 1 to 12 carbon atoms may be an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms may include methyl, ethyl, propyl, isopropyl, butyl, pentyl, octyl, heptyl, decyl, dodecyl and the like.

[0051] In the present invention, the cycloalkyl group having 4-10 carbon atoms may be a cycloalkyl group having 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Examples of the cycloalkyl group having 4-10 carbon atoms may be cyclobutyl, cyclopentyl or cyclohexyl.

[0052] Preferably, based on 100 parts by weight of the component (a), the content of the component (b) is 0.1-10 parts by weight, the content of the component (c) is 1-50 parts by weight, and the content of the component (d) is 5-30 parts by weight.

[0053] As a preferred technical solution of the present invention, based on the content of the component (a) as 100 parts by weight, the content of the component (b) can be 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, etc., the content of the component (c) can be 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight or 50 parts by weight, etc., and the content of the component (d) can be 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight or 30 parts by weight, etc.

[0054] Preferably, the negative photosensitive polyimide composition further contains any one of (e) a solvent, (f) an alkoxysilane binder, (g) a rust inhibitor, or (h) a polymerization inhibitor, or a combination of at least two thereof.

[0055] Preferably, based on 100 parts by weight of the component (a), the content of the (e) solvent is 100-200 parts by weight, the content of the (f) alkoxysilane binder is 0.5-10 parts by weight, the content of the (g) rust inhibitor is 0.1-10 parts by weight, and the content of the (h) polymerization inhibitor is 0.1-2 parts by weight.

[0056] As a preferred technical solution of the present invention, based on 100 parts by weight of the component (a), the content of the (e) solvent can be 100 parts by weight, 130 parts by weight, 150 parts by weight, 180 parts by weight or 200 parts by weight, etc., the content of the (f) alkoxysilane binder can be 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight or 10 parts by weight, etc., the content of the (g) rust inhibitor can be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight or 10 parts by weight, and the content of the (h) polymerization inhibitor can be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight or 2 parts by weight, etc.

[0057] In a second aspect, the present invention provides a method for producing a pattern, comprising coating the negative photosensitive polyimide composition described in the first aspect on a supporting substrate, and performing the steps of drying, exposing, developing, and heating.

[0058] Preferably, the light source used in the exposure process is i-ray.

[0059] In a third aspect, the present invention provides a cured product formed by curing the negative photosensitive polyimide composition according to the first aspect.

[0060] In a fourth aspect, the present invention provides an electronic component comprising the cured product according to the third aspect formed as a surface protective film or an interlayer insulating film.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] The present invention provides a negative photosensitive polyimide composition that can be developed with an alkaline aqueous solution. The portion of the negative photosensitive polyimide composition not exposed to ultraviolet light is readily soluble in the alkaline aqueous solution, while the portion exposed to ultraviolet light is insoluble in the alkaline aqueous solution. This allows for efficient reproduction of fine patterns. Furthermore, the negative photosensitive polyimide composition of the present invention exhibits an excellent dissolution rate ratio (contrast ratio) between the unexposed and exposed portions, and exhibits excellent resolution, adhesion, chemical resistance, and storage stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 Schematic diagram of the semiconductor packaging structure of the present invention.

[0064] Among them, 1-Si substrate, 2-oxide layer, 3-wafer, 4-first passivation layer, 5-RDL, 6-second passivation layer, 7-Ni, 8-solder bump. DETAILED DESCRIPTION

[0065] Hereinafter, embodiments of the negative photosensitive resin composition, method for producing a cured pattern, cured product, interlayer insulating film, surface protective film, electronic component, etc. of the present invention will be described in detail.

[0066] [Negative photosensitive resin composition]

[0067] The negative photosensitive polyimide composition of the present invention contains (a) a polymer soluble in an alkaline aqueous solution, (b) a photopolymerization initiator, (c) a compound having a polymerizable functional group, and (d) a crosslinking agent having a -CH2OR (R is a hydrogen atom or a monovalent organic group) group.

[0068] The negative photosensitive polyimide composition of the present invention has excellent sensitivity and resolution by increasing the dissolution rate ratio (dissolution contrast) between the exposed portion of the pattern and the unexposed portion in an alkaline developer.

[0069] Regarding the alkaline aqueous solution-soluble polymer as component (a), from the viewpoints of processability and heat resistance, its main chain backbone is preferably a polyimide-based or polyoxazole-based polymer, and more specifically, an alternating block polymer of these two types of polymers is preferred. Component (a) may also be a copolymer having two or more of the above main chain backbones, or a mixture of two or more polymers.

[0070] From the viewpoint of solubility in an alkaline aqueous solution, the polymer soluble in an alkaline aqueous solution as component (a) is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both.

[0071] The following describes one criterion for component (a) being soluble in an alkaline aqueous solution. A photosensitive composition obtained by dissolving component (a) alone or in combination with other components in any solvent is spin-coated onto a substrate such as a silicon wafer to form a coating film having a thickness of approximately 5 μm. This coating film is then immersed in an aqueous solution of tetramethylammonium hydroxide at 20-25°C. Component (a) is soluble in an alkaline aqueous solution if it dissolves to form a uniform solution.

[0072] Component (a) is more preferably a copolymer of polyamide ester-polyhydroxyamide, a polymer having a structural unit represented by the following formula 1, utilizing the alkali solubility, good photosensitivity, and film properties of phenolic hydroxyl groups and part of carboxyl groups.

[0073]

[0074] wherein R is selected from any one of hydrogen, CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2- at each occurrence, the same or different; U is a tetravalent organic group, V is a divalent organic group, and W is a trivalent organic group.

[0075] The hydroxyl-containing polyamide shown in Formula 1 can be ultimately converted into an oxazole by curing dehydration ring closure, and the amide ester-containing part can be ultimately converted into an imide by curing to release small molecules. Thus, the cured film has excellent heat resistance, mechanical properties and electrical properties.

[0076] The alkaline aqueous solution mentioned above refers to a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, an organic amine aqueous solution, or the like.

[0077] In formula 1, U is a tetravalent organic group, generally a residue of a tetracarboxylic dianhydride or a derivative thereof having an amide ester structure formed by tetracarboxylic dianhydride or a derivative thereof and a diamine, preferably a tetravalent aromatic group, preferably a residue of a tetracarboxylic dianhydride or a derivative thereof having the following structure, wherein all four binding sites are present on the aromatic ring. Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3, 4-dicarboxyphenyl)ethane dianhydride, 1,1-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, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9 Aromatic tetracarboxylic dianhydrides such as bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; and aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0078] In Formula 1, V is a divalent organic group, generally a dicarboxylic acid residue having an amide structure formed by a dicarboxylic acid and a diamine. It is preferably a divalent aromatic group, preferably a dicarboxylic acid residue having the following structure, where both binding sites are present on the aromatic ring. Examples of such dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 4,4'-dicarboxydiphenyl ether, bis(4-carboxyphenyl)propane, and bis(4-carboxyphenyl)hexafluoropropane. These can be used alone or in combination of two or more.

[0079] In formula 1, W is a trivalent organic group, generally a residue of a hydroxydiamine having an amide structure formed by the reaction of a hydroxyl-containing diamine with a dicarboxylic acid, preferably a trivalent aromatic group, preferably 6-40 carbon atoms, more preferably a trivalent aromatic group having 6-40 carbon atoms. As the above-mentioned trivalent aromatic group, a residue of a diamine having the following structure is preferred, wherein all three binding sites are on the aromatic ring, and one hydroxyl group is each located at the ortho position to which W is bound. Examples of such diamines include 2,4-diaminophenol, 2,3-diaminophenol, 2,5-diaminophenol, 2,6-diaminophenol, and the like. The residues of such diamines are not limited to these, and the residues of these compounds may be present alone or in combination of two or more.

[0080] The solubility of the polymer in alkaline aqueous solution is derived from phenolic hydroxyl groups and carboxyl groups, so it is preferred to contain a structure of a certain proportion or more. More preferably, j is an amide unit containing a carboxyl group, and the molar ratio of j to k is j = 10-50 mol%, k = 50-90 mol%. The two structural units can be blended or copolymerized. In addition, an excessively large j unit will cause a certain film thickness loss in the exposed area, resulting in an inability to effectively replicate the pattern. Therefore, by adjusting the amount of alkali-soluble groups of phenolic hydroxyl groups and carboxyl groups, the dissolution rate of the polymer in alkaline aqueous solution changes, thereby obtaining a negative photosensitive resin composition with a moderate dissolution rate.

[0081]

[0082] In formula 1-1, R 24 Each occurrence is identically or differently selected from CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2-. j+k is the number of repeating structural units of the polymer of the present invention, preferably 3-200, more preferably 5-100. When j+k is less than 3, the viscosity of the composition is too small, resulting in the composition being unable to be used as a thick film, and when j+k is greater than 200, the composition becomes insoluble in alkaline aqueous solution. When the structures represented by Formula 1 each contain greater than or equal to 10% by weight of fluorine atoms, during development with an alkaline aqueous solution, an appropriate degree of waterproofing is exhibited at the interface of the film to prevent penetration at the interface. However, when the content of fluorine atoms exceeds 20% by weight, the solubility in alkaline aqueous solution is reduced. Therefore, the fluorine atom content is preferably 10-20% by weight.

[0083] In addition, in order to improve adhesion to the substrate, as long as the heat resistance is not damaged, the V part can be selected to copolymerize with a certain proportion of aliphatic groups with a siloxane structure, preferably 1-10 mol% of bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane, etc.

[0084] The terminal groups of the aromatic polyamide represented by Formula 1 are carboxylic acids or amines, depending on the ratio of U, V, and W. Optionally, one or two end-capping agents may react with the polymer ends to convert one or both ends into saturated aliphatic groups, unsaturated aliphatic groups, carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, or mercapto groups. In this case, the end-capping ratio is preferably 30-100%.

[0085] The molecular weight of component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, as a weight average molecular weight. The molecular weight herein is a value measured by gel permeation chromatography and converted from a standard polystyrene calibration curve.

[0086] In the present invention, the polyamide having the structural unit shown in Formula 1 is generally first synthesized by acylation of dicarboxylic acid and diamine containing hydroxyl groups to form a terminal amino compound, which is then reacted with an acid anhydride through a condensation reaction to form a polyamic acid structure, which is then subjected to isoimidization and then esterification to obtain the obtained product.

[0087] Specifically, in the first step, a diamine compound containing a hydroxyl group can be prepared by reacting a dicarboxylic acid with a diamine containing a hydroxyl group. In the second step, the diamine compound synthesized in the first step is subjected to a polycondensation reaction with an acid anhydride to prepare a polyamic acid. In the third step, the polyamic acid is converted into a polyisoimide in the presence of a dehydrating agent, wherein the dehydrating agent is preferably trifluoroacetic anhydride. In the fourth step, hydroxyethyl acrylate or hydroxyethyl methacrylate is added to carry out an esterification reaction, taking into account the characteristics of the isoimide as an acid anhydride, to obtain the polymer described in Formula 1.

[0088] The compound that generates free radicals by irradiation with active light as component (b) is a photoinitiator. Active light can include ultraviolet rays such as i-rays, visible light or radiation. As component (b), oxime compounds, acylphosphine oxide compounds, acyldialkylmethane compounds, etc. are listed. It is preferred to contain one or more compounds (hereinafter referred to as component (b1)) selected from the group consisting of compounds represented by formula 5-1 and / or formula 5-2. Component (b1) is preferably a component with high sensitivity to active light, and is preferably a highly sensitive photosensitizer.

[0089]

[0090] In formula 5-1, R 25 is an alkyl group having 1 to 12 carbon atoms, R 26 is selected from hydrogen or an alkyl group having 1 to 12 carbon atoms, R 27 and R 28 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group;

[0091] In formula 5-2, R 29Any one selected from hydrogen, -OH, -COOH, -OCH2OH, -O(CH2)2OH, -COOCH2OH or -COO(CH2)2OH, R 30 and R 31 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, and a tolyl group.

[0092] Examples of the compound represented by Formula 5-1 include the compound represented by the following Formula 5-1-1, and its trade name is "IRGACURE OXE 02" manufactured by BASF.

[0093]

[0094] Examples of the compound represented by formula 5-2 include the compound represented by formula 5-2-1 below, whose trade name is "IRGACURE OXE 01" manufactured by BASF, and the compound represented by formula 5-2-2 below, whose trade name is "NCI-930" manufactured by ADEKA.

[0095]

[0096]

[0097] Component (b) preferably contains one or more compounds selected from the compounds represented by Formula 6-1 and / or Formula 6-2 below (hereinafter referred to as component (b2)). Component (b2) preferably has low sensitivity to active light and is preferably a photosensitizer of standard sensitivity.

[0098]

[0099] In formula 6-1, R 32 is selected from hydrogen or an alkyl group having 1 to 12 carbon atoms, R 33 and R 34 Each is independently selected from any one of a hydrogen atom, an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;

[0100] In formula 6-2, R 35 and R 36 Each is independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5 (eg, 1, 2, 3, 4 or 5), s and t are each independently an integer of 0 to 3, and the sum of s and t is 3.

[0101] Examples of the compound represented by Formula 6-1 include the compound represented by the following Formula 6-1-1, whose trade name is "G-1820 (PDO)" manufactured by Lambson.

[0102]

[0103] Examples of the compound represented by formula 6-2 include the compound represented by formula 6-2-1 below, whose trade name is "IRGCURE TPO" manufactured by BASF. Also, examples include the compound represented by formula 6-2-2 below, whose trade name is "IRGCURE 819" manufactured by BASF.

[0104]

[0105]

[0106] Component (b) can be used alone or in combination of two or more. Preferably, it comprises one or more selected from the group consisting of component (b1) and component (b2). More preferably, it comprises component (b1) and component (b2). For component (b), the content of component (b1) is generally 0.05-5 parts by mass, preferably 0.05-1 parts by mass, and more preferably 0.15-0.6 parts by mass, relative to 100 parts by mass of component (a); the content of component (b2) is generally 0.5-10 parts by mass, and preferably 0.5-5 parts by mass.

[0107] When components (b1) and (b2) are contained, the total amount of the two components is preferably 0.6 to 11 parts by mass, more preferably 1 to 6 parts by mass, and even more preferably 1.15 to 5.6 parts by mass.

[0108] The component (c) is selected from the compounds represented by formula 7-1 and / or formula 7-2,

[0109]

[0110] Among them, R 37 Each occurrence is identically or differently selected from a hydrogen atom or a methyl group, R 38 is an alkylene group having 3 to 8 carbon atoms, R 39 Each occurrence is identical or different and is selected from alkylene groups having 1 to 4 carbon atoms, and n is an integer of 2 to 5.

[0111] Specific examples of component (c) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate. These may be used alone or in combination of two or more.

[0112] The amount of component (c) added is preferably 5 to 50 parts by mass, more preferably 10 to 35 parts by mass, relative to 100 parts by mass of component (a). Within the above range, good adhesiveness can be exhibited.

[0113] Component (d) is a crosslinking agent having a -CH2OR (R is a hydrogen atom or a monovalent organic group) group. During the heat treatment step following coating, exposure, and development of the photosensitive polymer composition of the present invention, the crosslinking agent reacts with the polymer of component (a) to form a crosslink, or the crosslinking agent polymerizes itself during the heat treatment step. Furthermore, the crosslinking agent of component (d) has an affinity for alkaline aqueous solutions and can increase the dissolution rate in alkaline aqueous solutions.

[0114] In the present invention, component (d) is a crosslinking agent having a -CH2OR (R is a hydrogen atom or a monovalent organic group) group in its structure. The compound may have at least one of these groups, but preferably has at least two. Component (d) is selected from compounds represented by the following formula 8-1 and / or formula 8-2:

[0115]

[0116] In formula 8-1, R 40 Each occurrence of R is identical or different and is selected from a hydrogen atom or a monovalent organic group; 41 are selected, identically or differently on each occurrence, from a hydrogen atom or a monovalent organic radical, or R 41 Combine with each other to form a ring structure;

[0117] In formula 8-2, R 42 is selected from a hydrogen atom or a monovalent organic group, R 43 is selected from a monovalent organic group, d is an integer of 1-4, X is selected from a single bond or a 1-4 valent organic group, a is an integer of 1-4, b is an integer of 0-3, when a is 2, 3 or 4, R 42 Same or different, when b is 2 or 3, R 43 Same or different.

[0118] Specific examples of the compound represented by Formula 8-1 are shown below. These compounds may be used alone or in combination of two or more.

[0119]

[0120] In formula 8-1-1, R 48 Each occurrence is identical or different and is selected from an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, R 49 Each occurrence is identical or different and is selected from alkyl groups having 1 to 10 carbon atoms.

[0121] In formula 8-2, as the 1-4 valent organic group of X, there can be mentioned an alkyl group having 1-10 carbon atoms, an alkylene group having 2-10 carbon atoms (such as ethylene), an arylene group having 6-30 carbon atoms (such as phenylene), or a group obtained by replacing part or all of the hydrogen atoms of these hydroxy groups with halogen atoms such as fluorine atoms, and these groups may further include a phenyl group, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc. 42 It is preferably hydrogen, alkyl or alkenyl. The number of carbon atoms in the alkyl or alkenyl group is preferably 1-20. 43 It is preferably an alkyl group, an alkenyl group, an alkoxyalkyl group or a hydroxymethyl group, and the number of carbon atoms is preferably 1-20.

[0122] The purity of the compound represented by formula 8-2 is preferably 75% or greater, more preferably 85% or greater. A purity of 85% or greater provides excellent storage stability, allowing for sufficient crosslinking of the resin composition. Furthermore, since the number of unreacted groups that become hygroscopic groups can be reduced, the water absorption of the resin composition can be reduced. Methods for obtaining high-purity thermal crosslinkers include recrystallization and distillation. The purity of the thermal crosslinker can be determined using liquid chromatography.

[0123] Specific examples of the compound represented by Formula 8-2 are shown below. These compounds may be used alone or in combination of two or more.

[0124]

[0125] The thermal crosslinking agent content of component (d) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of the resin in component (a). A content of 5 parts by mass or more increases the crosslinking density of the cured film, improving chemical resistance. Furthermore, a content of 10 parts by mass or more further improves chemical resistance and achieves higher mechanical properties. Furthermore, from the perspectives of storage stability and mechanical strength of the composition, a content of 30 parts by mass or less is preferably used.

[0126] The resin composition of the present invention further contains (e) a solvent, preferably an organic solvent. Examples thereof include polar solvents such as γ-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylsulfoxide, hexamethylphosphoric triamide, dimethylimidazolidinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N,N-dimethylpropaneamide, and N-acetyl-ε-caprolactam.

[0127] In addition, as component (e), for example, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc. can be used. Specifically, for example, 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, dichloromethane, 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, etc. can be used. Component (e) can be used alone or in combination of two or more. When the component (e) is contained, the amount of the component (e) added is preferably 50 to 1000 parts by mass, more preferably 100 to 200 parts by mass, relative to 100 parts by mass of the component (a).

[0128] The resin composition of the present invention further contains (f) an adhesion promoter, which is generally an organosilane compound. Examples of the organosilane compound include: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane. , 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, triethoxysilylpropylethyl carbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(l,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0129] When an organosilane compound is contained, the adhesion between the photosensitive resin composition and 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, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of component (a).

[0130] To further enhance rust resistance, the photosensitive resin composition of the present invention may also contain a rust inhibitor. Examples of rust inhibitors include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-carboxymethyl-5-amino-tetrazole. These tetrazole compounds may also be water-soluble salts thereof.

[0131] When the rust preventive agent is included, the content thereof is preferably 1 to 10 parts by mass, more preferably 0.5 to 4.0 parts by mass, relative to 100 parts by mass of the component (a).

[0132] The photosensitive resin composition of the present invention may also contain a polymerization inhibitor. Known compounds such as 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide can be used as the polymerization inhibitor. When the polymerization inhibitor is included, the content is preferably 0.05 to 5.0 parts by mass, and more preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of component (a).

[0133] The present invention may further contain a surfactant to improve coating properties with the substrate. Examples of the surfactant include fluorine-based surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), and Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Polyflow, Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and BYK (trade name, manufactured by BYK-Chemie GmbH); and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

[0134] Next, the method for producing the photosensitive resin composition of the present invention will be described. For example, a photosensitive resin composition can be obtained by uniformly mixing the above-mentioned components (a) to (d) and the components (e) to (h) used as needed, a surfactant, etc. As the dissolution method, stirring and heating can be mentioned. When heating, it is preferred to set the heating temperature within a range that does not damage the performance of the resin composition, usually room temperature to 80°C. In addition, the order in which the components are dissolved is not particularly limited, and for example, a method of dissolving in sequence starting from compounds with low solubility is included. In addition, for components such as surfactants and some adhesion improvers that are prone to generate bubbles when stirred and dissolved, poor dissolution of other components caused by the generation of bubbles can be prevented by adding them last after dissolving other components.

[0135] The resulting photosensitive resin composition is preferably filtered through a filter to remove impurities and particles. The filter pore size is 0.5 to 0.02 μm, including, but not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, and 0.02 μm. Filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), with polyethylene and nylon being preferred. If the photosensitive resin composition contains inorganic particles, a filter with a pore size larger than the particle size of these inorganic particles is preferably used.

[0136] [cured material]

[0137] The cured product of the present invention can be obtained by curing the negative photosensitive polyimide composition. The cured product of the present invention can be used as a patterned cured film or a non-patterned cured film.

[0138] The method for producing a patterned cured film, for example, comprises: a step of coating the negative photosensitive polyimide composition on a substrate and drying it to form a photosensitive resin film (film forming step); a step of exposing the photosensitive resin film (exposure step); a step of developing the exposed photosensitive resin film with an alkaline aqueous solution to form a patterned resin film (development step); and a step of heating the patterned resin film (heating step). A method for producing a non-patterned cured film, for example, comprises the film forming step and the heating step. An exposure step may also be further included.

[0139] In the film forming process, the negative photosensitive polyimide composition is applied to a supporting substrate such as a Cu substrate, a glass substrate, a semiconductor, a metal oxide insulator (e.g., TiO2, SiO2, etc.), or silicon nitride by, for example, dipping, spraying, screen printing, or spin coating. From the perspective of workability, the applied negative photosensitive polyimide composition may be dried by heating using a hot plate, oven, or the like (e.g., 90-150°C for 1-5 minutes) before use. The supporting substrate may also be cleaned with acetic acid or the like before coating. The resulting photosensitive resin film preferably has a thickness of 5-20 μm.

[0140] In the exposure process, for example, the photosensitive resin film formed on the substrate is irradiated with the above-mentioned active light through a mask. From the perspective of the transparency of component (a), irradiation with i-rays can be preferably used. After exposure, post-exposure heating (PEB) can also be performed as needed. The temperature of post-exposure heating is preferably 70°C to 140°C, and the time of post-exposure heating is preferably 1 minute to 5 minutes.

[0141] In the developing process, for example, the exposed portion of the photosensitive resin film after the exposure process is removed with a developer, thereby patterning the photosensitive resin film. As a developer, in the case of an alkali-soluble photosensitive resin composition, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) can be suitably used. The alkali concentration of these aqueous solutions is preferably set to 0.1 to 10% by mass. Furthermore, alcohols or surfactants can also be added to the above-mentioned developer and used. They can be respectively coordinated 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 resin film is referred to as a patterned resin film.

[0142] In the heating process, the photosensitive resin composition can be cured by heating the pattern resin film or the photosensitive resin film. In particular, the film obtained by curing the pattern resin film is called a pattern cured film. The heating temperature is preferably 100 to 500°C. From the viewpoint of fully preventing heat damage to electronic components, it is preferably less than or equal to 250°C, more preferably less than or equal to 225°C, and further preferably 140 to 210°C. The heating time is preferably 20 minutes to 6 hours, more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. The heat treatment can be performed using, for example, a quartz tube furnace, a hot plate, a rapid thermal annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. In addition, any one of the atmosphere or an inert atmosphere such as nitrogen can be selected, but when carried out under nitrogen, oxidation of the pattern can be prevented, so an inert atmosphere such as nitrogen is preferred.

[0143] The cured product of the present invention can be used as an interlayer insulating film, a surface protective film, or the like.

[0144] The interlayer insulating film and surface protective film of the present invention can be used in electronic components, etc. The electronic components of the present invention can be used in semiconductor devices, etc. The semiconductor devices can be used in various electronic devices, etc. The semiconductor package structure diagram of the present invention is shown in FIG. Figure 1 shown.

[0145] This exhibits excellent rust prevention and adhesion effects on a supporting substrate (particularly a copper substrate or a copper alloy substrate), and can suppress discoloration of the cured film and the supporting substrate (particularly a copper substrate or a copper alloy substrate).

[0146] Examples of the semiconductor device include semiconductor packages such as wafer-level chip scale packages (WLCSP) and fan-out wafer-level packages (FOWLP). Furthermore, the interlayer insulating film and surface protective film of the present invention can also be used in circuit formation substrates, which can be used in hard disk drive suspensions, flexible wiring boards, and the like.

[0147] [Example]

[0148] The present invention will be described below with reference to Examples, etc., but the present invention is not limited to these Examples. The resins and photosensitive resin compositions in Examples and Comparative Examples were evaluated by the following methods.

[0149] The abbreviated names of the compounds, auxiliary agents and solvents shown in the following Examples and Comparative Examples are as follows.

[0150] IPDC: Isophthaloyl dichloride

[0151] 4-NAP: 2-amino-4-nitrophenol

[0152] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0153] ODPA: 4,4'-oxydiphthalic anhydride

[0154] DMAP: 4,4'-diamino-2,2'-dimethylbiphenyl

[0155] TFAA: trifluoroacetic anhydride

[0156] HEMA: Hydroxyethyl Methacrylate

[0157] MAP: meta-aminophenol

[0158] NMP: N-methyl 2-pyrrolidone

[0159] GBL; γ-butyrolactone

[0160] TMAH: Tetramethylammonium hydroxide

[0161] DCC: dicyclohexylcarbodiimide

[0162] Synthesis Example 1: Preparation of diamine containing hydroxyl groups

[0163] Under a dry nitrogen stream, 30.8 g (0.2 mol) of 4-NAP was dissolved in 200 mL of acetone, and the resulting solution was cooled to -10°C. Subsequently, a solution of 22.4 g (0.11 mol) of IPDC in 200 mL of acetone was added dropwise so that the temperature of the reaction solution did not exceed 0°C. After the addition was complete, the reaction mixture was returned to room temperature, and the precipitated white solid was filtered out and dried in vacuo at 50°C.

[0164] 30 g of the solid was added to a 1000 mL three-necked flask and dispersed in 800 mL of methyl melting agent. 3 g of 5% palladium on carbon was added and the temperature was raised to 60°C. 7 g of hydrazine hydrate was slowly added dropwise and stirred at 60°C for 1 hour. After stirring, the catalyst was removed by filtration, the mixture was concentrated under reduced pressure to 200 mL, poured into 1.5 L of water, and the precipitate was collected. The precipitate was then vacuum dried at 50°C for 20 hours to obtain diamine compound (I). The obtained solid was used directly in the reaction.

[0165]

[0166] Synthesis Example 2: Synthesis of Polymer A

[0167] Under a dry nitrogen flow, 8.31 g (0.022 mol) of diamine (I) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP, and 9.31 g (0.030 mol) of ODPA and 14 g of NMP were added thereto, and the mixture was reacted at 20°C for 1 hour, and then the reaction was continued at 40°C for 2 hours. 0.65 g (0.006 mol) of MAP was then added as a capping agent, and the reaction was continued at 40°C for 1 hour. 6.84 g (0.06 mol) of TFAA was then added, and the reaction was continued at 40°C for 4 hours. Thereafter, 7.81 g (0.06 mol) of HEMA was added dropwise, and the reaction was continued at 40°C for 4 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer A. The molecular weight and esterification rate of polymer A were determined as follows:

[0168] (1) Determination of molecular weight

[0169] The number average molecular weight was determined using gel permeation chromatography (GPC) under the following conditions using standard polystyrene conversion. The number average molecular weight of polymer A was 42,000. The measurement was performed using 1 mL of a solution containing 0.5 mg of polymer A and a solvent of tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio).

[0170] Measuring device: L4000UV detector manufactured by Hitachi, Ltd.

[0171] Pump: L6000 manufactured by Hitachi Manufacturing Co., Ltd.

[0172] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0173] Measurement conditions: Gelpack GL-S300MDT-5 x 2 columns

[0174] Eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03 mol / L), H3PO4 (0.06 mol / L)

[0175] Flow rate: 1.0 mL / min, detector: UV 270 nm

[0176] (2) Determination of esterification rate

[0177] In addition, NMR measurement was performed under the following conditions to calculate the esterification rate of A (the esterification rate of the reaction between the carboxyl groups of ODPA and HEMA was 80 mol% relative to all the carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

[0178] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0179] Magnetic field strength: 400MHz

[0180] Reference substance: Tetramethylsilane (TMS)

[0181] Solvent: dimethyl sulfoxide (DMSO)

[0182] Synthesis Example 3: Synthesis of Polymer B

[0183] Under a dry nitrogen flow, 8.31 g (0.022 mol) of diamine (I) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP, and 9.31 g (0.030 mol) of ODPA and 14 g of NMP were added thereto. The mixture was reacted at 20°C for 1 hour and then at 40°C for 2 hours. 0.65 g (0.006 mol) of MAP was then added as a capping agent, and the reaction was continued at 40°C for 1 hour. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer B. The number average molecular weight measured by the method of Synthesis Example 2 was 38,000, and the esterification rate was 0%.

[0184] Synthesis Example 4: Synthesis of Polymer C

[0185] Under a dry nitrogen flow, 4.67 g (0.022 mol) of DMAP and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP, and 21.4 g (0.030 mol) of ODPA and 14 g of NMP were added thereto. The mixture was reacted at 20°C for 1 hour, and then continued to react at 40°C for 2 hours. 0.65 g (0.006 mol) of MAP was then added as a capping agent, and the reaction was continued at 40°C for 1 hour. 6.84 g (0.06 mol) of TFAA was then added, and the reaction was continued at 40°C for 4 hours. 7.81 g (0.06 mol) of HEMA was then added dropwise, and the reaction was continued at 40°C for 4 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80°C for 72 hours to obtain polymer C. The number average molecular weight measured by the method of Synthesis Example 2 was 38,000, and the esterification rate was 80%.

[0186] Examples 1-10 and Comparative Examples 1-2

[0187] The photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-2 were prepared according to the components and blending amounts shown in Tables 1 and 2. The blending amounts in Tables 1 and 2 are parts by mass of each component per 100 parts by mass of component (a).

[0188] The components used are as follows.

[0189] Component (b): Photoinitiator

[0190] b1: IRUGCURE OXE 02 (manufactured by BASF, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime))

[0191] b2: G-1820 (PDO) (manufactured by Lambson Corporation, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime)

[0192] Component (c): polymerizable monomer

[0193] c1: Tetraethylene glycol dimethacrylate

[0194] c2: Pentaerythritol tetraacrylate

[0195] Component (d): thermal crosslinking agent

[0196]

[0197] Component (e): solvent

[0198] e1: GBL (γ-butyrolactone)

[0199] e2: NMP (N-methyl-2-pyrrolidone)

[0200] Component (f): Silane coupling agent

[0201] f1: γ-ureapropyltriethoxysilane

[0202] f2: vinyltriethoxysilane

[0203] Ingredient (g): Rust inhibitor

[0204] g1: 5-aminotetrazoline

[0205] Ingredient (h): polymerization inhibitor

[0206] h1: Nitrosodiphenylamine

[0207] Table 1

[0208]

[0209] Table 2

[0210]

[0211] The performance of the photosensitive resin compositions prepared in the examples and comparative examples was evaluated as follows:

[0212] (1) Preparation of developing film

[0213] The photosensitive resin composition (varnish) prepared in the examples and comparative examples was spin-coated on an 8-inch silicon wafer and then heat-treated (prebaked) at 120°C for 2 minutes using a hot plate (coating and developing device Mark-7 manufactured by Tokyo Electron Ltd.) to form a prebaked film with a thickness of 2.5 μm. An i-line stepper (NSR-2005i9C manufactured by Nikon Corporation) was used to heat the film at a rate of 50 to 400 mJ / cm 2 Exposure, 10mJ / cm 2 The obtained prebaked film was exposed in steps of . After exposure, for a negative photosensitive resin composition, exposure was performed at 100°C for 1 minute and then baked. After the negative photosensitive resin composition was post-exposure baked, it was developed for 60 seconds using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution (ELM-D manufactured by Mitsubishi Gas Chemical Co., Ltd.), and then rinsed with pure water to obtain a developed film.

[0214] (2) Film thickness measurement method

[0215] The film thickness after prebaking and after development was measured using an optical interference film thickness measuring apparatus LAMBDA ACE STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. at a refractive index of 1.63.

[0216] (3) Calculation of developing film loss

[0217] The developed film loss was calculated using the following formula. Since the film thickness after prebaking is 2.5 μm, the developed film loss is preferably less than 0.50 μm. A developed film loss of less than 0.50 μm was designated "A," a developed film loss of 0.51 to 0.59 μm was designated "B," and a developed film loss of 0.60 μm or greater was designated "C."

[0218] The results are shown in Table 3: Developed film loss (μm) = film thickness after prebaking - film thickness after development.

[0219] (4) Evaluation of residual film rate after curing

[0220] In the production of the above-mentioned cured product, the film thickness after heating on a 110°C hot plate for 4 minutes and the film thickness after curing were measured using a Filmetrics instrument (manufactured by Filmetrics) (the film thickness measurement is the same below). The film thickness after curing (10 μm) was divided by the film thickness after heating on a 110°C hot plate for 4 minutes, and the result was converted into a percentage to determine the residual film ratio after curing. The results are shown in Table 3.

[0221] (5) Sensitivity evaluation

[0222] After exposure and development, the exposure dose (called the optimal exposure dose Eop) that forms a 20μm line and space pattern (1L / 1S) with a width of 1:1 is used as the sensitivity. If Eth is 200mJ / cm 2 Below, it can be judged as high sensitivity. More preferably, it is 150mJ / cm 2 The results are shown in Table 3 below.

[0223] (6) Chemical resistance evaluation

[0224] GTN-68P (manufactured by Senju Metal Industry Co., Ltd.) was applied to the cured product using a pipette. The coated product was placed on a hot plate at 245°C for 1 minute. The product was then removed from the hot plate and cooled to room temperature. The cooled product was rinsed with isopropyl alcohol, dried, and the film thickness was measured.

[0225] The film thickness change rate (%) was calculated based on the film thickness change before and after GTN-68P coating. A positive value indicates film expansion, while a negative value indicates film dissolution. The results are shown in Table 3.

[0226] (7) Adhesion evaluation

[0227] A cured product was produced on a Cu substrate using the above-described method for producing a cured product. The cured product was then cut into 10×10 grids using a crosscut guide (manufactured by COAT-TECH Co., Ltd.) with a shear blade, thereby dividing the cured product into 100 small pieces.

[0228] An adhesive tape (manufactured by 3M Japan Co., Ltd.) was attached to the cured product, and the adhesive tape was peeled off. The adhesiveness was evaluated as follows based on the number of small pieces of the cured product peeled off from the substrate when the adhesive tape was peeled off.

[0229] A: The number of remaining grids is 100 to 80.

[0230] B: The number of remaining grids is less than 80.

[0231] The results are shown in Table 3.

[0232] Table 3

[0233]

[0234]

[0235] As shown in Table 3, the photosensitive resin compositions provided in Examples 1-10 of the present invention all exhibited minimal developing film loss, low residual film rates after curing (55%-78%), and excellent chemical resistance and adhesion. Compared to the Examples, Comparative Example 1 exhibited higher developing film loss, a higher residual film rate after curing, and poorer chemical resistance. Comparative Example 2 was undevelopable.

[0236] Industrial applicability

[0237] The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat, a surface protective film, and the like. The interlayer insulating film, the cover coat, or the surface protective film of the present invention can be used for electronic components and the like.

[0238] While several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art can readily incorporate numerous modifications to these illustrative embodiments and / or examples without materially departing from the novel teachings and effects of the present invention. Therefore, these modifications are also encompassed within the scope of the present invention.

Claims

1. A negative photosensitive polyimide composition, characterized in that: The negative photosensitive polyimide composition contains the following components (a), (b), (c) and (d): (a) a polymer soluble in an alkaline aqueous solution; (b) a photopolymerization initiator; (c) a compound having a polymerizable functional group, wherein the polymerizable functional group includes an unsaturated double bond or triple bond; (d) thermal crosslinking agent; Based on 100 parts by weight of the component (a), the content of the component (b) is 0.1-10 parts by weight, the content of the component (c) is 1-50 parts by weight, and the content of the component (d) is 5-30 parts by weight; The component (a) has a structural unit represented by formula 1, wherein R is selected from any one of hydrogen, CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2- at each occurrence, the same or different; U is a 4-valent organic group, V is a 2-valent organic group, and W is a 3-valent organic group; The W is selected from any one of the trivalent organic groups shown in Formula 2, the same or different each time it appears. Wherein, R1-R3 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; The component (b) contains components (b1) and (b2), wherein (b1) contains one or more compounds selected from the group consisting of Formula 5-1 and / or Formula 5-2, and (b2) contains one or more compounds selected from the group consisting of Formula 6-1 and / or Formula 6-2. In formula 5-1, R 25 is an alkyl group having 1 to 12 carbon atoms, R 26 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 27 and R 28 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group; In formula 5-2, R 29 Any one selected from hydrogen, -OH, -COOH, -OCH2OH, -O(CH2)2OH, -COOCH2OH or -COO(CH2)2OH, R 30 and R 31 Each is independently selected from any one of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group; In formula 6-1, R 32 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 33 and R 34 Each is independently selected from any one of a hydrogen atom, an alkyl group or alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group; In formula 6-2, R 35 and R 36 Each is independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5, s and t are each independently an integer of 0 to 3, and the sum of s and t is 3; The component (c) is selected from compounds represented by Formula 7-1 and / or Formula 7-2, Among them, R 37 are selected, identically or differently, on each occurrence from a hydrogen atom or a methyl group, R 38 is an alkylene group having 3 to 8 carbon atoms, R 39 Each occurrence is identical or different and is selected from an alkylene group having 1 to 4 carbon atoms, and n is an integer from 2 to 5; The component (d) is selected from the compounds represented by Formula 8-1 and / or Formula 8-2, In formula 8-1, R 40 Each occurrence of R is identically or differently selected from a hydrogen atom or a monovalent organic radical; 41 are selected, identically or differently on each occurrence, from a hydrogen atom or a monovalent organic radical, or R 41 Combine with each other to form a ring structure; In formula 8-2, R 42 is selected from a hydrogen atom or a monovalent organic group, R 43 is selected from a monovalent organic group, d is an integer of 1-4, X is selected from a single bond or a 1-4 valent organic group, a is an integer of 1-4, b is an integer of 0-3, when a is 2, 3 or 4, R 42 Same or different, when b is 2 or 3, R 43 Same or different.

2. The negative photosensitive polyimide composition according to claim 1, characterized in that: The component (a) has a structure shown in Formula 1-1: Among them, R 24 Each occurrence is identically or differently selected from CH2=CH-COOCH2CH2- or CH2=C(CH3)-COOCH2CH2-; U is a 4-valent organic group, V is a 2-valent organic group, and W is a 3-valent organic group; Each time W appears, it is the same or different and is selected from any one of the trivalent organic groups shown in Formula 2: Wherein, R1-R3 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; j+k is the number of repeating structural units of component (a), and the value of j+k is 3-200.

3. The negative photosensitive polyimide composition according to claim 2, characterized in that: The value of j+k is 5-100.

4. The negative photosensitive polyimide composition according to claim 1 or 2, characterized in that: V is selected from any one of the divalent organic groups represented by Formula 3, the same or different at each occurrence: Among them, R4-R 15 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; X is a divalent group, selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 or C(CF3)2.

5. The negative photosensitive polyimide composition according to claim 1 or 2, characterized in that: U is selected from any one of the 4-valent organic groups represented by formula 4, the same or different at each occurrence: Among them, R 16 -R 23 They are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Y is a divalent group, selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH3)2 or C(CF3)2.

6. The negative photosensitive polyimide composition according to claim 1, characterized in that: The negative photosensitive polyimide composition further contains any one of a solvent, an alkoxysilane binder, a rust inhibitor or a polymerization inhibitor, or a combination of at least two of them.

7. The negative photosensitive polyimide composition according to claim 6, characterized in that: Based on 100 parts by weight of the component (a), the content of the solvent is 100-200 parts by weight, the content of the alkoxysilane binder is 0.5-10 parts by weight, the content of the rust inhibitor is 0.1-10 parts by weight, and the content of the polymerization inhibitor is 0.1-2 parts by weight.

8. A method for manufacturing a graphic, characterized in that: The manufacturing method comprises the steps of coating the negative photosensitive polyimide composition according to any one of claims 1 to 7 on a supporting substrate, and performing drying, exposure, development and heating treatment.

9. The manufacturing method according to claim 8, characterized in that: The light source used in the exposure process is i-ray.

10. A solidified product, characterized in that: The cured product is formed by curing the negative photosensitive polyimide composition according to any one of claims 1 to 7.

11. An electronic component, characterized in that: The electronic component includes the cured product according to claim 10 as a surface protection film or an interlayer insulating film.

Images