A negative photosensitive polyimide composition, a method for manufacturing a pattern, and an electronic component

Abstract

The present invention provides a negative photosensitive polyimide composition, a method for manufacturing a pattern, and an electronic component. 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, the polymerizable functional group including an unsaturated double bond or triple bond, and (d) a thermal crosslinking agent. The unexposed portion of the negative photosensitive polyimide composition of the present invention is easily soluble in an alkaline aqueous solution, while the exposed portion is insoluble in an alkaline aqueous solution, and thus can effectively reproduce 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 manufacturing a pattern, a cured product thereof, an interlayer insulating film, a surface protective film, and an electronic component. More specifically, it relates to a negative photosensitive polyimide composition capable of being developed with an alkaline aqueous solution without reducing sensitivity, having excellent resolution, and maintaining a good pattern shape, a method for manufacturing a pattern cured film using the composition, and an electronic component. Background Art

[0002] Conventionally, polyimide resins having excellent thermal stability, electrical insulation, and mechanical properties have generally been used for surface protective films and interlayer insulating films of semiconductor devices. Such a polyimide resin film is generally a solution of a polyimide precursor (polyamic acid) obtained by a polycondensation reaction of a tetracarboxylic dianhydride and a diamine in a polar solvent, which is coated by spin coating or the like and then thinned, and is formed by heating for dehydration and ring closure curing (see Non-Patent Document 1).

[0003] In recent years, photosensitive polyimides have been widely used in surface protective films, interlayer insulating films, etc. in the fields of semiconductor devices and integrated circuit packages due to their own photosensitive characteristics, which can simplify the pattern formation process and shorten the complicated pattern manufacturing process (see Patent Documents 1-3).

[0004] Conventionally, the development of the above-mentioned photosensitive polyimides has always used organic solvents such as N-methylpyrrolidone. However, due to environmental awareness in recent years and considering the treatment of waste liquid, it is considered that development with an alkaline aqueous solution has fewer problems. However, these photosensitive polyimide materials have poor solubility and it is difficult to form patterns (see Patent Documents 4-5). In addition, a negative photosensitive polyimide material that can be used for development with an alkaline aqueous solution must contain an alkali-soluble group, but it is difficult to effectively reproduce patterns after development of such a material (see Non-Patent Document 2). With the requirements of semiconductor devices for power consumption, polybenzoxazole materials have gradually attracted attention due to their lower dielectric constant and lower water absorption. However, materials that simultaneously have negativity and excellent alkaline developability have not been reported yet.

[0005] Therefore, in this field, it is desired to develop a photosensitive polyimide composition having both negativity and excellent alkaline developability.

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

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

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

[0009] Patent Document 4: Japanese Unexamined Patent Publication No. 54-109828.

[0010] Patent Document 5: Japanese Unexamined Patent Publication 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] Aiming at the deficiencies of the prior art, the object of the present invention is to provide a negative photosensitive polyimide composition, a method for manufacturing a pattern, and an electronic component. The present invention provides a negative photosensitive polyimide composition soluble in an alkaline aqueous solution and having a specific structure. Among them, the unexposed part of the negative photosensitive polyimide composition is easily soluble in the alkaline aqueous solution, while the exposed part to ultraviolet light is insoluble in the alkaline aqueous solution, so that fine patterns can be effectively replicated.

[0014] To achieve the object of this invention, the following technical solutions are adopted in the present invention:

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

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

[0017] (b) A photoinitiator for photopolymerization;

[0018] (c) A compound having a polymerizable functional group, and the polymerizable functional group includes an unsaturated double bond or triple bond;

[0019] (d) A thermal crosslinking agent.

[0020] In the present invention, the negative photosensitive polyimide composition simultaneously contains components (a), (b), (c) and (d), has negative characteristics and can be developed with an alkaline aqueous solution. The unexposed part of the negative photosensitive polyimide composition is easily soluble in the alkaline aqueous solution, while the exposed part to ultraviolet light is insoluble in the alkaline aqueous solution, so that fine patterns can be effectively replicated. In addition, the negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed part and the exposed part, and has good 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 the same or different each time it appears and is independently selected from hydrogen, CH 2 =CH-COOCH 2 CH 2 - or CH 2 =C(CH 3 )-COOCH 2 CH 2 -; U is a tetravalent organic group, V is a divalent organic group, and W is a tetravalent organic group.

[0024] Preferably, U is the same or different each time it appears and is independently selected from any one of the tetravalent organic groups represented by Formula 2:

[0025]

[0026] wherein R 1 -R 8 are both monovalent organic groups, independently selected from monovalent organic groups such as hydrogen, fluorine atom, methyl or trifluoromethyl, and X is a divalent group selected from oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 any one of them.

[0027] Preferably, V is the same or different each time it appears and is independently selected from any one of the divalent organic groups represented by Formula 3:

[0028]

[0029] wherein R 10 -R 20 are both monovalent organic groups, independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Y is a divalent group selected from oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 any one of them.

[0030] Preferably, W is the same or different each time it appears and is independently selected from any one of the tetravalent organic groups represented by Formula 4:

[0031]

[0032] wherein R 21 -R26 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Q is a divalent group selected from oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 in any one of them.

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

[0034]

[0035] wherein, R 27 is the same or different each time it appears and is selected from CH 2 =CH-COOCH 2 CH 2 - or CH 2 =C(CH 3 )-COOCH 2 CH 2 -; U, V, W have the same defined ranges as described above; j + k is the number of repeating structural units of the component (a), and the value of j + k is 3 - 200 (such as 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 those shown in Formula 5-1, Formula 5-2, Formula 6-1 and / or Formula 6-2,

[0037]

[0038] In Formula 5-1, R 28 is an alkyl group having 1 - 12 carbon atoms, R 29 is selected from a hydrogen atom or an alkyl group having 1 - 12 carbon atoms, and R 30 and R 31 are each independently selected from any one of a hydrogen atom, an alkyl group having 1 - 12 carbon atoms, a phenyl group or a tolyl group;

[0039] In Formula 5-2, R 32 is selected from a hydrogen atom, -OH, -COOH, -OCH 2 OH, -O(CH 2 ) 2 OH, -COOCH 2 OH or -COO(CH 2 ) 2Any one of OH, R 33 and R 34 each independently selected from 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;

[0040]

[0041] In Formula 6-1, R 35 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 36 and R 37 each independently selected from a hydrogen atom, an alkyl group or an 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 38 and R 39 each independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer from 1 to 5 (such as 1, 2, 3, 4 or 5), s and t are each independently an integer from 0 to 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] wherein, R 40 is the same or different each time it appears and is selected from a hydrogen atom or a methyl group, R 41 is an alkylene group having 3 to 8 carbon atoms, R 42 is the same or different each time it appears and is selected from an alkylene group having 1 to 4 carbon atoms, and n is an integer from 2 to 5, such as 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 43 is the same or different each time it appears and is selected from a hydrogen atom or a monovalent organic group; R 44 is the same or different each time it appears and is selected from a hydrogen atom or a monovalent organic group, or R 44 combine with each other to form a ring structure which may have substituents;

[0049] In Formula 8-2, R 45 is selected from a hydrogen atom or a monovalent organic group, R 46selected from monovalent organic groups, d is an integer from 1 to 4 (e.g., 1, 2, 3, or 4), X is selected from a single bond or an organic group with a valence of 1 to 4 (e.g., monovalent, divalent, trivalent, or tetravalent), a is an integer from 1 to 4 (e.g., 1, 2, 3, or 4), b is an integer from 0 to 3 (e.g., 0, 1, 2, or 3), and when a is 2, 3, or 4, R 45 are the same or different, and when b is 2 or 3, R 46 are the 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 be methyl, ethyl, propyl, isopropyl, butyl, pentyl, octyl, heptyl, decyl, dodecyl, etc.

[0051] In the present invention, the cycloalkyl group having 4 to 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 to 10 carbon atoms may be cyclobutyl, cyclopentyl, cyclohexyl, etc.

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

[0053] As a preferred technical solution of the present invention, based on 100 parts by weight of the content of the component (a), the content of the component (b) may be 0.1 part by weight, 0.3 part by weight, 0.5 part by weight, 0.8 part 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) may 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) may 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 or a combination of at least two of (e) a solvent, (f) an alkoxysilane binder, (g) an antirust agent, or (h) a polymerization inhibitor.

[0055] Preferably, based on 100 parts by weight of the content 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 content 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, 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, 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, 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, 2 parts by weight, etc.

[0057] In a second aspect, the present invention provides a method for manufacturing a pattern, which includes the steps of coating the negative photosensitive polyimide composition described in the first aspect on a support substrate, and performing drying, exposure, development, and heat treatment.

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

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

[0060] In a fourth aspect, the present invention provides an electronic component formed with the cured product described in the third aspect 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 unexposed part of the negative photosensitive polyimide composition is easily soluble in the alkaline aqueous solution, while the exposed part is insoluble in the alkaline aqueous solution, so that fine patterns can be effectively replicated. In addition, the negative photosensitive polyimide composition of the present invention has an excellent dissolution rate ratio (contrast) between the unexposed part and the exposed part, and has good resolution, adhesion, chemical resistance, and storage stability. Description of the Drawings

[0063] Figure 1 It is a schematic diagram of the semiconductor package 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 implementation manners

[0065] Hereinafter, the implementation manners of the photosensitive resin composition, the method for manufacturing a cured pattern, the cured product, the interlayer insulating film, the surface protective film, the electronic component, etc. of the present invention will be described in detail. It should be noted that the present invention is not limited to the following implementation manners.

[0066] [Negative photosensitive polyimide 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 -CH 2 OR (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) of the pattern-exposed portion to the unexposed portion with respect to the alkaline developer.

[0069] Regarding the polymer soluble in an alkaline aqueous solution as component (a), from the viewpoints of processability and heat resistance, the main chain skeleton is preferably a polyimide-based or polyoxazole-based polymer, and specifically preferably an alternating block copolymer of the two types of polymers. In addition, component (a) may be a copolymer having two or more of the above main chain skeletons, or a mixture of two or more polymers.

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

[0071] The following describes a standard for component (a) to be soluble in an alkaline aqueous solution. A photosensitive composition obtained by dissolving 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 with a film thickness of about 5 μm. When the coating film is immersed in an aqueous solution of tetramethylammonium hydroxide at 20 - 25°C and can be dissolved to form a uniform solution, the component (a) used is soluble in the alkaline aqueous solution.

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

[0073]

[0074] wherein, each occurrence of R is the same or different and is independently selected from hydrogen, CH 2 =CH-COOCH 2 CH 2 -, or CH 2 =C(CH 3 )-COOCH 2 CH 2 -; U is a tetravalent organic group, V is a divalent organic group, and W is a tetravalent organic group.

[0075] The polyamide containing a hydroxyl group shown in Formula 1 can be finally converted into an oxazole body by curing and dehydrating to form a closed loop, and the part containing an amide ester can be finally converted into an imide by curing and eliminating small molecules. Thus, the cured film has excellent heat resistance, mechanical properties, and electrical properties.

[0076] In addition, the above-mentioned alkaline aqueous solution refers to an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of metal hydroxide, an aqueous solution of organic amine, etc.

[0077] In Formula 1, U is a tetravalent organic group, generally a residue derived from a tetra-carboxylic dianhydride or its derivative in the amide ester structure formed by a tetra-carboxylic dianhydride or its derivative and a diamine, preferably a tetravalent aromatic group, preferably a residue of a tetra-carboxylic dianhydride or its derivative having the following structure, with all four bonding sites existing on the aromatic ring. Examples of such tetra-carboxylic 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-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, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and other aromatic tetra-carboxylic dianhydrides, butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and other aliphatic tetra-carboxylic dianhydrides, etc. These can be used alone or in combination of two or more.

[0078] In Formula 1, V is a divalent organic group, generally a residue from an amino acid of an amide structure formed by an amino acid and a diamine, preferably a divalent aromatic group, preferably an amino acid residue having the following structure, and two binding sites are both on the aromatic ring. As such an amino acid, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, etc. can be cited. They can be used alone or in combination of two or more.

[0079] In Formula 1, W is a tetravalent organic group, generally a residue from a dihydroxydiamine of an amide structure formed by the reaction of a dihydroxydiamine with an amino acid, preferably a tetravalent aromatic group, and as its carbon number, preferably 6 - 40, more preferably a tetravalent aromatic group with 6 - 40 carbon atoms. As the above-mentioned tetravalent aromatic group, preferably a residue of a diamine having the following structure, and four binding sites are all on the aromatic ring, and two hydroxyl groups are each located at the ortho position to the binding of W. As such diamines, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)1,1,1,3,3,3-hexafluoropropane, bis(4-amino-3-hydroxyphenyl)1,1,1,3,3,3-hexafluoropropane, etc. can be cited. The residues of such diamines are not limited to these, and the residues of these compounds can be used alone or in combination of two or more.

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

[0081]

[0082] In Formula 1-1, R 27 is the same or different each time it appears and is selected from CH 2 =CH-COOCH 2 CH 2 - or CH 2 =C(CH 3 )-COOCH 2 CH 2-; 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, 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. When j + k is greater than 200, the composition becomes insoluble in alkaline aqueous solutions. When the structures represented by Formula 1 each contain greater than or equal to 10% by weight of fluorine atoms, during the development process with an alkaline aqueous solution, an appropriate degree of waterproofing is exhibited at the interface of the thin film, preventing penetration at the interface. However, when the fluorine atom content exceeds 20% by weight, the solubility in the alkaline aqueous solution decreases. Therefore, the fluorine atom content is preferably 10 - 20% by weight.

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

[0084] The terminal groups of the aromatic polyamide represented by Formula 1 become carboxylic acids or amines according to the input ratio of U, V, and W. If necessary, one or two capping agents can react with the polymer terminals to make one terminal or both terminals be saturated aliphatic groups, unsaturated aliphatic groups, carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, or mercapto groups, etc. At this time, the capping rate is preferably 30 - 100%.

[0085] Regarding the molecular weight of component (a), in terms of the weight-average molecular weight, it is preferably 3000 - 200000, more preferably 5000 - 100000. The molecular weight here is a value determined by gel permeation chromatography and converted from the standard polystyrene standard curve.

[0086] In the present invention, the polyamide having the structural unit represented by Formula 1 is generally first synthesized by acylating and hydrogenating nitrobenzoic acid and diamine containing a hydroxyl group to form a compound with terminal amino groups, then forming a polyamic acid structure through a polycondensation reaction with an acid anhydride, and then performing isoimide formation and esterification.

[0087] Specifically, in the first step, a dinitro compound containing a hydroxyl group can be prepared by reacting nitrobenzoic acid with diamine containing a hydroxyl group, and then hydrogenated to obtain a diamine compound 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 polyamic acid. In the third step, in the presence of a dehydrating agent, the polyamic acid is converted into polyisoimide, and the dehydrating agent here is preferably trifluoroacetic anhydride. In the fourth step, in combination with the property that isoimide has an acid anhydride, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is added for an esterification reaction to obtain the polymer represented by Formula 1.

[0088] The compound that generates free radicals upon irradiation with actinic rays as component (b) is a photoinitiator. Examples of actinic rays include ultraviolet rays such as i-rays, visible light, or radiation. As component (b), examples include oxime compounds, acylphosphine oxide compounds, acyl dialkyl methane compounds, etc. It is preferred to contain one or more compounds selected from the compounds represented by formula 5-1 and / or formula 5-2 (hereinafter referred to as component (b1)). Component (b1) is preferably a component with high sensitivity to actinic rays and is preferably a high-sensitivity photosensitizer.

[0089]

[0090] In formula 5-1, R 28 is an alkyl group having 1 to 12 carbon atoms, and R 29 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 30 and R 31 are each 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 32 is selected from any one of a hydrogen atom, -OH, -COOH, -OCH 2 OH, -O(CH 2 ) 2 OH, -COOCH 2 OH, or -COO(CH 2 ) 2 OH, and R 33 and R 34 are each 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.

[0092] As the compound represented by formula 5-1, the compound represented by the following formula 5-1-1 is exemplified, and its trade name is "IRGACURE OXE 02" manufactured by BASF.

[0093]

[0094] As the compound represented by formula 5-2, the compound represented by the following formula 5-2-1 is exemplified, and its trade name is "IRGACURE OXE 01" manufactured by BASF. Additionally, the compound represented by the following formula 5-2-2 is exemplified, and its trade name is "NCI-930" manufactured by ADEKA.

[0095]

[0096] In addition, component (b) preferably contains one or more compounds selected from the compounds represented by the following formula 6-1 and / or formula 6-2 (hereinafter referred to as component (b2)). Component (b2) is preferably a component with low sensitivity to actinic rays and is preferably a photosensitizer with standard sensitivity.

[0097]

[0098] In formula 6-1, R 35 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 36 and R 37 are each independently selected from any one of a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group;

[0099] In formula 6-2, R 38 and R 39 are each independently selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, m is an integer of 1 to 5 (for example, 1, 2, 3, 4 or 5), s and t are each independently an integer of 0 to 3 (for example, 0, 1, 2 or 3), and the sum of s and t is 3.

[0100] As the compound represented by formula 6-1, the compound represented by the following formula 6-1-1 is exemplified, and its trade name is "G-1820 (PDO)" manufactured by Lambson.

[0101]

[0102] As the compound represented by formula 6-2, the compound represented by the following formula 6-2-1 is exemplified, and its trade name is "IRGCURE TPO" manufactured by BASF. In addition, the compound represented by the following formula 6-2-2 can be exemplified, and its trade name is "IRGCURE819" manufactured by BASF.

[0103]

[0104] Component (b) can be used alone or in combination of two or more. It is preferably contained one or more selected from the group consisting of component (b1) and component (b2). More preferably, it contains component (b1) and component (b2). For component (b), relative to 100 parts by mass of component (a), the content of component (b1) is usually 0.05 to 5 parts by mass, preferably 0.05 to 1 part by mass, more preferably 0.15 to 0.6 part by mass; the content of component (b2) is usually 0.5 to 10 parts by mass, preferably 0.5 to 5 parts by mass.

[0105] 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 still more preferably 1.15 to 5.6 parts by mass.

[0106] The component (c) is selected from the compounds represented by Formula 7-1 and / or Formula 7-2.

[0107]

[0108] wherein R 40 is the same or different each time and is selected from a hydrogen atom or a methyl group, and R 41 is an alkylene group having 3 to 8 carbon atoms, and R 42 is the same or different each time and is selected from an alkylene group having 1 to 4 carbon atoms, and n is an integer of 2 to 5.

[0109] As the component (c), specifically, 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, 1,6-hexanediol dimethacrylate, etc. can be mentioned. One kind can be used alone, or two or more kinds can be combined.

[0110] Relative to 100 parts by mass of the component (a), the blending amount of the component (c) is preferably 5 to 50 parts by mass, more preferably 10 to 35 parts by mass. Within the above range, good adhesiveness can be exhibited.

[0111] As the component (d), it is a crosslinking agent having a —CH 2 OR (R is a hydrogen atom or a monovalent organic group) group. In the heat treatment step after coating, exposing, and developing the photosensitive polymer composition of the present invention, it reacts with the polymer as the component (a) to crosslink, or a compound that polymerizes itself during the heat treatment step. In addition, the crosslinking agent as the component (d) has an affinity for an alkaline aqueous solution and can increase the dissolution rate in the alkaline aqueous solution.

[0112] In the present invention, the component (d) is a crosslinking agent having a —CH 2 OR (R is a hydrogen atom or a monovalent organic group) group in its structure. As long as one or more of such groups are present in the compound, but preferably two or more are present. Among them, the component (d) is selected from the compounds represented by the following Formula 8-1 and / or Formula 8-2.

[0113]

[0114] In Formula 8-1, R 43Each occurrence is the same as or different from a hydrogen atom or a monovalent organic group; R 44 Each occurrence is the same as or different from a hydrogen atom or a monovalent organic group, or R 44 Combine with each other to form a ring structure which may have substituents.

[0115] In Formula 8-2, R 45 Is selected from a hydrogen atom or a monovalent organic group, R 46 Is selected from a monovalent organic group, d is an integer from 1 to 4, X is selected from a single bond or a 1-4 valent organic group, a is an integer from 1 to 4, b is an integer from 0 to 3, when a is 2, 3 or 4, R 45 Are the same as or different from each other, when b is 2 or 3, R 46 Are the same as or different from each other.

[0116] The following shows specific examples of the compound represented by Formula 8-1. In addition, these compounds can be used alone or in combination of two or more.

[0117]

[0118] In Formula 8-1-1, R 48 Each occurrence is the same as or different 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 the same as or different from an alkyl group having 1 to 10 carbon atoms.

[0119] In addition, in Formula 8-2, as the 1-4 valent organic group of X, an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 10 carbon atoms (such as ethylene, etc.), an arylene group having 6 to 30 carbon atoms (such as phenylene, etc.), or a group obtained by substituting a part or all of the hydroxy hydrogen atoms of these with halogen atoms such as fluorine atoms can be cited. These groups may further contain a phenyl group, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc. R 45 Is preferably hydrogen, an alkyl group or an alkenyl group. The alkyl group or alkenyl group preferably has 1 to 20 carbon atoms. R 46 Is preferably an alkyl group, an alkenyl group, an alkoxyalkyl group or a hydroxymethyl group, and preferably has 1 to 20 carbon atoms.

[0120] The purity of the compound represented by the above Formula 8-2 is preferably 75% or more, more preferably 85% or more. When the purity is 85% or more, its storage stability is excellent and the crosslinking reaction of the resin composition can be sufficiently carried out. In addition, since the unreacted groups that become water-absorbing groups can be reduced, the water absorption of the resin composition can be lowered. As a method for obtaining a high-purity thermal crosslinking agent, recrystallization, distillation, etc. can be cited. The purity of the thermal crosslinking agent can be determined by liquid chromatography.

[0121] Specific examples of the compound represented by Formula 8-2 below are shown. In addition, these compounds can be used alone or in combination of two or more.

[0122]

[0123] With respect to 100 parts by mass of the resin of component (a), the content of the thermal crosslinking agent of component (d) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. When it is 5 parts by weight or more, the crosslinking density of the cured film increases, and the chemical resistance is high. Furthermore, when it is 10 parts by mass or more, the chemical resistance is even higher, and at the same time, higher mechanical properties can be obtained. In addition, from the viewpoints of the storage stability and mechanical strength of the composition, it is preferably 30 parts by mass or less.

[0124] The resin composition of the present invention further contains (e) a solvent, preferably an organic solvent. For example, γ-butyrolactone, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl sulfoxide, hexamethylphosphoric triamide, dimethylimidazolinone, tetraethylurea, tetramethylurea, ethyl lactate, 3-methoxy-N,N-dimethylpropionamide, N-acetyl-ε-caprolactam and other polar solvents can be mentioned.

[0125] 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 component (e) is included, the blending amount of component (e) is preferably 50 to 1000 parts by mass, more preferably 100 to 200 parts by mass, with respect to 100 parts by mass of component (a).

[0126] 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-isocyanatopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, ethyl carbamate triethoxysilylpropyl ester, 3-(triethoxysilyl)propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.

[0127] When an organosilane compound is included, the adhesion between the cured photosensitive resin composition and the substrate can be improved. When an organosilane compound is contained, the content of the organosilane compound is preferably 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the component (a).

[0128] From the viewpoint of further improving the rust prevention property, the photosensitive resin composition of the present invention may also contain a rust inhibitor. Examples of the rust inhibitor include: 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino-tetrazole, etc. These tetrazole compounds may also be their water-soluble salts.

[0129] When a rust inhibitor is included, the content 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).

[0130] In addition, the photosensitive resin composition of the present invention may contain a polymerization inhibitor. As the 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. When a polymerization inhibitor is included, the content is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, relative to 100 parts by mass of the component (a).

[0131] The present invention may further contain a surfactant to improve the coatability with a substrate. Examples of the surfactant include fluorosurfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Limited), Megafac (trade name, manufactured by DIC Corporation), Surflon (trade name, manufactured by Asahi Glass Co., Ltd.); silicone surfactant 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.), BYK (trade name, manufactured by BYK-Chemie GmbH); acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

[0132] Next, a method for manufacturing the photosensitive resin composition of the present invention will be described. For example, by uniformly mixing the above components (a) to (d), components (e) to (h) used as needed, a surfactant, etc., a photosensitive resin composition can be obtained. Examples of the dissolution method include stirring and heating. When heating is performed, it is preferable to set the heating temperature within a range that does not damage the performance of the resin composition, usually from room temperature to 80°C. In addition, the dissolution order of each component is not particularly limited. For example, it includes a method of dissolving in order from a compound with low solubility. In addition, for components such as surfactants and some adhesion improvers that are likely to generate bubbles during stirring and dissolution, the addition can be performed last after dissolving other components to prevent poor dissolution of other components caused by the generation of bubbles.

[0133] The obtained photosensitive resin composition is preferably filtered using a filter to remove impurities and particles. The pore size of the filter is 0.5 to 0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited thereto. The materials of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred. When the photosensitive resin composition contains inorganic particles, it is preferable to use a filter with a pore size larger than the particle size of these inorganic particles.

[0134] [Cured product]

[0135] The cured product of the present invention can be obtained by curing the above-described negative photosensitive polyimide composition. The cured product of the present invention can be used as a patterned cured film or as an unpatterned cured film.

[0136] A method for manufacturing a pattern-cured film, for example, includes: a step of coating the above-mentioned negative photosensitive polyimide composition on a substrate and drying 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 aqueous alkali solution to form a patterned resin film (development step); and a step of heating the patterned resin film (heating step). A method for manufacturing a non-patterned cured film, for example, includes the above-mentioned film-forming step and heating step. An exposure step may also be further included.

[0137] In the film-forming step, for example, the above-mentioned negative photosensitive polyimide composition is coated on a support substrate such as a metal substrate (e.g., Cu), a glass substrate, a semiconductor, a metal oxide insulator (e.g., TiO 2 , SiO 2 , etc.), or silicon nitride by an immersion method, a spray method, a screen printing method, a spin coating method, etc. From the viewpoint of operability, the coated negative photosensitive polyimide composition can also be dried by heating (e.g., at 90 to 150 °C for 1 to 5 minutes) using a hot plate, an oven, etc. and then used. The support substrate can also be cleaned with acetic acid or the like before coating. The film thickness of the obtained photosensitive resin film is preferably 5 to 20 μm.

[0138] In the exposure step, for example, the above-mentioned actinic rays are irradiated through a mask onto the photosensitive resin film formed on the substrate. From the viewpoint of the transparency of component (a), irradiation with i-rays can be suitably used. After exposure, post-exposure baking (PEB) can also be performed as needed. The temperature of the post-exposure baking is preferably 70 °C to 140 °C, and the time of the post-exposure baking is preferably 1 minute to 5 minutes.

[0139] In the development step, for example, the exposed portion of the photosensitive resin film after the exposure step is removed with a developer to pattern the photosensitive resin film. As the developer, in the case of an alkali-soluble photosensitive resin composition, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), etc. 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 mixed in a range preferably of 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 called a patterned resin film.

[0140] In the heating process, by heating the patterned resin film or photosensitive resin film, the photosensitive resin composition can be cured. In particular, the film obtained by curing the patterned resin film is called a patterned cured film. The heating temperature is preferably 100 to 500 °C, and from the viewpoint of sufficiently preventing damage to electronic components caused by heat, 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, and more preferably 30 minutes to 3 hours. Multi-stage heating can also be performed. The heat treatment can be carried out, for example, using an oven such as a quartz tube furnace, a hot plate, a rapid thermal anneal furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. In addition, either the atmosphere or an inert atmosphere such as nitrogen can be selected, but an inert atmosphere such as nitrogen is preferred because oxidation of the pattern can be prevented when carried out under nitrogen.

[0141] The cured product of the present invention can be used as an interlayer insulating film or a surface protective film, etc.

[0142] The interlayer insulating film and surface protective film of the present invention can be used for electronic components, etc., and the electronic components of the present invention can be used for semiconductor devices, etc. The semiconductor device can be used for various electronic devices, etc., and a schematic diagram of the semiconductor package structure of the present invention is as Figure 1 shown.

[0143] Thereby, excellent rust prevention effect and adhesion effect are shown on the support substrate (especially copper substrate, copper alloy substrate), and discoloration of the cured film and the support substrate (especially copper substrate, copper alloy substrate) can be suppressed.

[0144] As the above semiconductor device, for example, semiconductor packages such as wafer-level chip scale package (WLCSP), fan-out wafer-level package (FOWLP), etc. can be cited. In addition, the interlayer insulating film and surface protective film of the present invention can also be used for a circuit formation substrate, and the above circuit formation substrate can be used for a suspension for a hard disk drive, a flexible wiring board, etc.

[0145] [Examples]

[0146] Examples, etc. are given below to illustrate the present invention, but the present invention is not limited by these examples. It should be noted that the evaluation of the resin and photosensitive resin composition in the examples and comparative examples was carried out by the following methods.

[0147] The abbreviated names of the compounds, additives, and solvents shown in the following examples and comparative examples are as described below.

[0148] PNDC: p-nitrobenzoyl chloride

[0149] Bis-AP-AF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0150] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0151] ODPA: 4,4'-oxydiphthalic anhydride

[0152] DMAP: 4,4'-diamino-2,2'-dimethylbiphenyl

[0153] TFAA: trifluoroacetic anhydride

[0154] HEMA: 2-hydroxyethyl methacrylate

[0155] MAP: m-aminophenol

[0156] NMP: N-methyl-2-pyrrolidone

[0157] GBL; γ-butyrolactone

[0158] TMAH: tetramethylammonium hydroxide

[0159] DCC: dicyclohexylcarbodiimide

[0160] Synthesis Example 1: Preparation of diamine containing hydroxyl group

[0161] Under a dry nitrogen stream, 18.3 g (0.05 mol) of Bis-AP-AF was dissolved in 100 g of acetone, and then the resulting solution was cooled to -10°C. Subsequently, a 50 g acetone solution of 18.56 g (0.1 mol) of PNDC was added dropwise thereto such that the temperature of the reaction solution did not exceed 0°C. After the addition was completed, the mixture was returned to room temperature, and the precipitated white solid was filtered out and dried in vacuo at 50°C.

[0162] 30 g of the solid was added to a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, 2 g of 5% palladium-carbon was added, and hydrogen was introduced thereto with a balloon, and a reduction reaction was carried out at room temperature. After about 2 hours, when it was confirmed that the balloon did not further shrink, the reaction was terminated. After the reaction was completed, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure to obtain a diamine compound (I), and the obtained solid was directly used in the reaction.

[0163]

[0164] Synthesis Example 2: Synthesis of Polymer A

[0165] Under a dry nitrogen stream, 13.29 g (0.022 mol) of the diamine (I) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. 9.31 g (0.030 mol) of ODPA and 14 g of NMP were added thereto, and the reaction was carried out at 20 °C for 1 hour, and then continued at 40 °C for 2 hours. Then, 0.65 g (0.006 mol) of MAP as a capping agent was added, and the reaction was continued at 40 °C for 1 hour. Thereafter, 6.84 g (0.06 mol) of TFAA was 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 measured, and the test methods are as follows:

[0166] (1) Measurement of molecular weight

[0167] The number-average molecular weight was determined by gel permeation chromatography (GPC) method under the following conditions by converting with standard polystyrene. The number-average molecular weight of Polymer A was 39,000. The measurement was carried out using a solution of 0.5 mg of A and 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0168] Measurement device: L4000UV manufactured by Hitachi, Ltd.

[0169] Pump: L6000 manufactured by Hitachi, Ltd.

[0170] C-R4A Chromatopac manufactured by Shimadzu Corporation

[0171] Measurement conditions: Chromatographic column Gelpack GL-S300MDT-5 × 2 columns

[0172] Eluent: THF / DMF = 1 / 1 (volume ratio), LiBr (0.03 mol / L), H 3 PO 4 (0.06 mol / L)

[0173] Flow rate: 1.0 mL / min, detector: UV270 nm

[0174] (2) Measurement of esterification rate

[0175] In addition, NMR measurement was carried out under the following conditions to calculate the esterification rate of A (the reaction esterification rate of the carboxyl group of ODPA with HEMA was 80 mol% relative to all the carboxyl groups of the polyamic acid (the remaining 20 mol% was carboxyl group).

[0176] Measurement equipment: AV400M manufactured by Bruker BioSpin

[0177] Magnetic field strength: 400 MHz

[0178] Reference substance: Tetramethylsilane (TMS)

[0179] Solvent: Dimethyl sulfoxide (DMSO)

[0180] Synthesis Example 3: Synthesis of Polymer B

[0181] Under a dry nitrogen stream, 13.29 g (0.022 mol) of the diamine (I) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. 9.31 g (0.030 mol) of ODPA and 14 g of NMP were added thereto, and the reaction was carried out at 20 °C for 1 hour, and then continued at 40 °C for 2 hours. Then, 0.65 g (0.006 mol) of MAP as a capping agent was added, 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 was measured to be 38,000 and the esterification rate was 0% by the method of Synthesis Example 2.

[0182] Synthesis Example 4: Synthesis of Polymer C

[0183] Under a dry nitrogen stream, 4.67 g (0.022 mol) of DMAP and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. 21.4 g (0.030 mol) of ODPA and 14 g of NMP were added thereto, and the reaction was carried out at 20 °C for 1 hour, and then continued at 40 °C for 2 hours. Then, 0.65 g (0.006 mol) of MAP as a capping agent was added, and the reaction was continued at 40 °C for 1 hour. Thereafter, 6.84 g (0.06 mol) of TFAA was 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 C. The number average molecular weight was measured to be 38,000 and the esterification rate was 80% by the method of Synthesis Example 2.

[0184] Examples 1-10 and Comparative Examples 1-2

[0185] The photosensitive resin compositions of Examples 1-10 and Comparative Examples 1-2 were prepared according to the components and compounding amounts shown in Tables 1 and 2. The compounding amounts in Tables 1 and 2 are the mass parts of each component relative to 100 mass parts of component (a).

[0186] Each of the components used is described below.

[0187] Component (b): Photoinitiator

[0188] b1: IRUGCURE OXE 02 (manufactured by BASF, acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime))

[0189] b2: G-1820(PDO) (manufactured by Lambson Co., Ltd., 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime)

[0190] Component (c): Polymerizable monomer

[0191] c1: Tetraethylene glycol dimethacrylate

[0192] c2: Pentaerythritol tetraacrylate

[0193] Component (d): Thermal crosslinking agent

[0194]

[0195] Component (e): Solvent

[0196] e1: GBL (γ-butyrolactone)

[0197] e2: NMP (N-methyl-2-pyrrolidone)

[0198] Component (f): Silane coupling agent

[0199] f1: γ-ureidopropyltriethoxysilane

[0200] f2: Vinyltriethoxysilane

[0201] Component (g): Rust inhibitor

[0202] g1: 5-aminotetrazole

[0203] Component (h): Polymerization inhibitor

[0204] h1: Nitrosodiphenylamine

[0205] Table 1

[0206]

[0207] Table 2

[0208]

[0209] The photosensitive resin compositions prepared in the examples and comparative examples were evaluated for their properties as follows:

[0210] (1) Preparation of the developed film

[0211] The photosensitive resin compositions (varnishes) prepared in the examples and comparative examples were spin-coated on 8-inch silicon wafers, and then heat-treated (pre-baked) at 120 °C for 2 minutes using a hot plate (manufactured by Tokyo Electron Ltd., coating and developing apparatus Mark-7) to prepare a pre-baked film with a thickness of 2.5 μm. Using an i-line stepper (manufactured by Nikon Corporation, NSR-2005i9C), the obtained pre-baked film was exposed with an exposure amount of 50 - 400 mJ / cm 2 and a step of 10 mJ / cm 2 . After exposure, for the negative photosensitive resin composition, it was baked at 100 °C for 1 minute after exposure. After exposure and baking of the negative photosensitive resin composition, it was developed for 60 seconds using a 2.38 wt% aqueous solution of tetramethylammonium (TMAH) (manufactured by Mitsubishi Gas Chemical Co., Ltd., ELM-D), and then rinsed with pure water to obtain the developed film.

[0212] (2) Method for measuring film thickness

[0213] For the film thickness after pre-baking and after development, a light interference film thickness measuring device LAMBDA ACE STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used for measurement with a refractive index of 1.63.

[0214] (3) Calculation of the developed film loss amount

[0215] The developed film loss amount was calculated according to the following formula. Since the film thickness after pre-baking was 2.5 μm, the developed film loss amount was preferably less than 0.50 μm. The case where the developed film loss amount was less than 0.50 μm was judged as "A", the case where it was 0.51 - 0.59 μm was judged as "B", and the case where it was 0.60 μm or more was judged as "C".

[0216] Developed film loss amount (μm) = Film thickness after pre-baking - Film thickness after development. The results are shown in Table 3.

[0217] (4) Evaluation of the residual film ratio after curing

[0218] In the production of the above-mentioned cured product, Filmetrics (manufactured by Filmetrics, Inc.) was used to measure the film thickness after heating on a hot plate at 110 °C for 4 minutes and the film thickness after curing (the same applies to the measurement of the film thickness). The film thickness after curing, 10 μm, was divided by the film thickness after heating on a hot plate at 110 °C for 4 minutes, and then converted into a percentage to obtain the residual film rate after curing. The results are shown in Table 3.

[0219] (5) Sensitivity evaluation

[0220] After exposure and development, the exposure dose (referred to as the optimum exposure dose Eop) for forming a 20-μm line-and-space pattern (1L / 1S) with a 1-to-1 width was used as the sensitivity. If Eth is 200 mJ / cm 2 or less, it can be judged as high sensitivity. More preferably, it is 150 mJ / cm 2 or less. The results are shown in Table 3.

[0221] (6) Chemical resistance evaluation

[0222] GTN-68P (manufactured by Senju Metal Industry Co., Ltd.) was applied to the above-mentioned cured product using a pipette. The coated cured product was placed on a hot plate at 245 °C and held for 1 minute. After that, the cured product was removed from the hot plate and cooled to room temperature. The cooled cured product was washed with isopropyl alcohol and dried, and then the film thickness was measured.

[0223] The film thickness change rate (%) was calculated based on the film thickness change before and after the application of GTN-68P. If the value is positive, it means the film expands; if the value is negative, it means the film dissolves. The results are shown in Table 3.

[0224] (7) Adhesion evaluation

[0225] Using the above-mentioned production method of the cured product, a cured product was produced on a Cu substrate. The obtained cured product was divided into 100 small pieces by using a crosscut guide (manufactured by COAT-TECH Co., Ltd.) and cutting 10×10 checkerboard-shaped cuts with a shear knife.

[0226] An adhesive tape (manufactured by 3M Japan Ltd.) was attached to the above-mentioned cured product, and then the adhesive tape was peeled off. The adhesion 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.

[0227] A: The remaining grids are 100 - 80.

[0228] B: The remaining grids are less than 80.

[0229] The results are shown in Table 3.

[0230] Table 3

[0231]

[0232]

[0233] Industrial applicability

[0234] As can be seen from Table 3, the photosensitive resin compositions provided in Examples 1-10 of the present invention all have a small development film loss amount, a low residual film rate after curing (58%-81%), and excellent chemical resistance and adhesiveness. Compared with the examples, Comparative Example 1 has a higher development film loss amount, a higher residual film rate after curing, and poor chemical resistance. And Comparative Example 2 cannot be developed.

[0235] The photosensitive resin composition of the present invention can be used for interlayer insulating films, covering coatings, surface protective films, etc., and the interlayer insulating films, covering coatings or surface protective films of the present invention can be used for electronic components, etc.

[0236] The above has described in detail several embodiments and / or examples of the present invention, but those skilled in the art can easily make many changes to these exemplified embodiments and / or examples without substantially departing from the new teachings and effects of the present invention. Therefore, these many changes are also included in the scope of the present invention.

Claims

1. A negative photosensitive polyimide composition, characterized in that, the negative photosensitive polyimide composition is composed of the following components (a), (b), (c), (d), (e), (f), (g) and (h): (a) A polymer soluble in an alkaline aqueous solution; (b) A photopolymerization initiator; (c) A compound having a polymerizable functional group, the polymerizable functional group including an unsaturated double bond or triple bond; (d) A thermal crosslinking agent; (e) A solvent; (f) An alkoxysilane binder; (g) An anti-rust agent; (h) A polymerization inhibitor; the component (a) has a structural unit shown in Formula 1, Formula 1 wherein, each occurrence of R is the same or different and is independently selected from CH 2 =CH-COOCH 2 CH 2 -, or CH 2 =C(CH 3 )-COOCH 2 CH 2 -; U is a tetravalent organic group, V is a divalent organic group, and W is a tetravalent organic group; W is the same or different each time it appears and is optionally selected from any one of the tetravalent organic groups shown in Formula 4: Formula 4 Among them, R 21 -R 26 are all monovalent organic groups, each independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Q is a divalent group, selected from oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 any one of them; V is the same or different each time it appears and is optionally selected from any one of the divalent organic groups shown in Formula 3: Formula 3 Among them, R 10 -R 20 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 oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 any one of them; the component (c) is selected from the compounds shown in Formula 7-1 and / or Formula 7-2, Among them, R 40 is the same or different each time it appears and is selected from a hydrogen atom or a methyl group, R 41 is an alkylene group having 3 to 8 carbon atoms, R 42 is the same or different each time it appears and is selected from an alkylene group having 1 to 4 carbon atoms, and n is an integer of 2 to 5.

2. The negative photosensitive polyimide composition according to claim 1, characterized in that, the component (a) has a structure shown in Formula 1-1: Formula 1-1 wherein, R 27 is the same as or different from each occurrence and is selected from CH 2 =CH-COOCH 2 CH 2 -, or CH 2 =C(CH 3 )-COOCH 2 CH 2 -; U is a tetravalent organic group, V is a divalent organic group, and W is a tetravalent organic group; W is the same or different each time it appears and is optionally selected from any one of the tetravalent organic groups shown in Formula 4: Formula 4 wherein, R 21 -R 26 are each a monovalent organic group, independently selected from any one of hydrogen, fluorine atom, methyl or trifluoromethyl; Q is a divalent group selected from any one of oxygen atom, methylene, sulfur atom, sulfone group, carbonyl group, C(CH 3 ) 2 or C(CF 3 ) 2 ; V is the same or different each time it appears and is optionally selected from any one of the divalent organic groups shown in Formula 3: Formula 3 wherein, R 10 -R 20 are each a monovalent organic group, 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(CH 3 ) 2 or C(CF 3 ) 2 ; j + k is the number of repeating structural units of the 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, U is the same or different each time it appears and is optionally selected from any one of the tetravalent organic groups shown in Formula 2: Formula 2 Among them, R 1 -R 8 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(CH 3 ) 2 or C(CF 3 ) 2 .

5. The negative photosensitive polyimide composition according to claim 1, characterized in that, the component (b) contains one or more compounds selected from Formula 5-1, Formula 5-2, Formula 6-1 and / or Formula 6-2, In Formula 5-1, R 28 is an alkyl group having 1 to 12 carbon atoms, R 29 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 30 and R 31 are each 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 32 is selected from any one of a hydrogen atom, -OH, -COOH, -OCH 2 OH, -O(CH 2 ) 2 OH, -COOCH 2 OH or -COO(CH 2 ) 2 OH; R 33 and R 34 are each 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 35 is selected from a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 36 and R 37 are each independently selected from any one of a hydrogen atom, an alkyl 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 38 and R 39 are each 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.

6. The negative photosensitive polyimide composition according to claim 1, characterized in that, the component (d) is selected from the compounds shown in Formula 8-1 and / or Formula 8-2, In Formula 8-1, R 43 is the same as or different from each other and is independently selected from a hydrogen atom or a monovalent organic group each time it appears; R 44 is the same as or different from each other and is independently selected from a hydrogen atom or a monovalent organic group each time it appears, or R 44 combines with each other to form a ring structure; In Formula 8-2, R 45 is selected from a hydrogen atom or a monovalent organic group, R 46 is selected from a monovalent organic group, d is an integer from 1 to 4, X is selected from a single bond or a 1- to 4-valent organic group, a is an integer from 1 to 4, b is an integer from 0 to 3, and when a is 2, 3, or 4, R 45 are the same or different, and when b is 2 or 3, R 46 are the same or different.

7. The negative photosensitive polyimide composition according to claim 1, characterized in that, 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.

8. The negative photosensitive polyimide composition according to claim 1, 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 anti-rust agent is 0.1 - 10 parts by weight, and the content of the polymerization inhibitor is 0.1 - 2 parts by weight.

9. A method for manufacturing a pattern, characterized in that, The manufacturing method includes the steps of coating the negative photosensitive polyimide composition according to any one of claims 1-8 on a support substrate, and performing drying, exposure, development, and heat treatment.

10. The manufacturing method according to claim 9, wherein, the light source used in the exposure step is i-ray.

11. A cured product, wherein, the cured product is formed by curing the negative photosensitive polyimide composition according to any one of claims 1-8.

12. An electronic component, wherein, the electronic component is formed with the cured product according to claim 11 as a surface protective film or an interlayer insulating film.

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