Block polymer and photosensitive resin composition containing the block polymer

Abstract

To provide a block polymer for obtaining a photosensitive resin composition that has excellent dielectric properties and resolution, and further excellent crack resistance after heat cycle testing, and a photosensitive resin composition containing the block polymer. [Solution] A block polymer comprising a polyimide block derived from a dimer structure having a specific structure, and a polyamic acid block or polyimide block having a specific structure, and characterized by having residues derived from dimer amine and / or dimer isocyanate.

Description

Technical Field

[0001] The present invention relates to a block polymer and a photosensitive resin composition containing the block polymer.

Background Art

[0002] Conventionally, in the production of insulating films and semiconductor protective films for OLEDs using polyimide resins, a method has been adopted in which a photoresist film is additionally coated, then patterning treatment is performed, and then etching is performed with an organic solvent. However, this method has a complicated procedure and a problem of swelling of the resist pattern due to the organic solvent. Further, when using a negative photosensitive polyimide, an additional photoresist film is not required, so the process can be shortened, but there still remains a problem of a decrease in resolution due to swelling of the resist pattern by the organic solvent.

[0003] In recent years, in order to address such problems, the development of negative photosensitive polyimides has advanced by using an aqueous alkaline solution as an etching solution. However, even with this approach, there is a problem that uncrosslinked carboxyl groups and alcoholic hydroxyl groups remain in the exposed area, and it is difficult to ensure a high-quality resist pattern layer because these swell when developed with an aqueous alkaline solution. Therefore, the development of positive photosensitive polyimides that can simplify the process by directly applying a photosensitive resin and achieve high resolution by using an environmentally friendly aqueous alkaline solution instead of an organic solvent is actively underway.

[0004] Conventionally, positive photosensitive resin compositions have been developed in several combinations. For example, there are combinations of polyamic acid and diazonaphthoquinone, polyimide-polyamic acid block copolymer copolymer and diazonaphthoquinone, polyimide and diazonaphthoquinone, polybenzoxazole and diazonaphthoquinone, and chemically amplified polyamic acid ester and photoacid generator.

[0005] However, in conventional photosensitive compositions, when a polyimide-polyamic acid copolymer is used as a binder resin, polyamic acid has high solubility in alkaline aqueous solutions, while polyimide has very low solubility. This makes it difficult to adjust the solubility difference between the exposed and unexposed regions, and thus difficult to achieve high resolution.

[0006] Therefore, it is important to adjust the solubility in the exposed and unexposed regions of an alkaline aqueous solution, and this necessitates the development of positive-type photosensitive resin compositions that can achieve high resolution. On the other hand, in recent years, the range of applications and performance of semiconductors have improved, and cost reductions and advanced integration have progressed through the efficiency of manufacturing processes. As a result, semiconductor devices equipped with multilayer metal redistribution are attracting attention. The insulating film of this multilayer metal redistribution requires crack resistance against stress due to multilayering and a low dielectric constant to accommodate high integration. In addition, for high-speed wireless communication applications, a low dielectric loss tangent is important for the insulating film in order to suppress transmission loss.

[0007] To improve crack resistance, a method has been proposed in which a flexible alkylene oxide skeleton is introduced into the main chain of the polyimide (Patent Document 1). As a means of achieving a low dielectric constant, a method of using alicyclic polyimide has been proposed (Patent Document 2). Furthermore, to achieve low dielectric loss tangent, a soluble polyimide using dimeramine has been proposed as an adhesive layer (Patent Document 3). The inventors have investigated and found that these conventional technologies can be used for high-frequency wireless communication When fabricating multilayer wiring insulating films for signaling devices, for example, Patent Document 1 presented a problem where the water absorption of the alkylene oxide group improved, leading to a deterioration of the dielectric constant. Patent Document 2 had the problem of low elongation and insufficient crack resistance. Furthermore, Patent Document 3 failed to achieve sufficient exposure sensitivity, resulting in resolution issues. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2012-208360 [Patent Document 2] Japanese Patent Publication No. 2009-186861 [Patent Document 3] Japanese Patent Publication No. 2018-203959 [Overview of the project] [Problems that the invention aims to solve]

[0009] This disclosure is made in view of the above background and aims to provide a block polymer for obtaining a photosensitive resin composition that has excellent dielectric properties and resolution, and further excellent crack resistance (stress relaxation) after heat cycle testing, and a photosensitive resin composition containing the block polymer. [Means for solving the problem]

[0010] After diligent research by the inventors, we discovered that the problems of the present invention can be solved in the following embodiment, and thus completed the present invention.

[0011] [1]: A block polymer having any of the structural units shown in the following general formulas (1) to (4), [ka] [ka] [ka] [ka] (In the formula, X1 and X3 are independently tetravalent tetracarboxylic acid residues in each repeating unit, X2 and X4 are independently divalent diamine residues in each repeating unit, and n, m, and l are positive integers.) The above X4 is a block polymer characterized by having a residue X4d derived from a dimer diamine and / or a dimer diisocyanate. [2]: The block polymer according to [1], characterized by having 1% by mass or more and less than 50% by mass of a residue X4d derived from a dimer diamine and / or a dimer diisocyanate with respect to all diamine residues in the block polymer. [3]: The block polymer according to [1] or [2], characterized in that the glass transition temperature of the polyimide block (A) derived from a dimer structure represented by the following general formula (5) or (6) constituting the block polymer is 100 °C or lower. [Chemical formula] [Chemical formula] (In the formula, X3 is a tetravalent tetracarboxylic acid residue independently for each repeating unit, X4 is a divalent organic group independently for each repeating unit, and the X3 and imide bonds are bonded to each other to form two imide rings. m is a positive integer.) [4]: Having the general formula (5) or (6), and the general formula (7) or (8), The block polymer according to any one of [I] to [3], characterized by satisfying the following formula. (TgB)-(TgA)≧100 °C TgA: The glass transition temperature of the polyimide block derived from a dimer structure represented by the following general formula (5) constituting the block polymer, or the polyamic acid block (A) derived from a dimer structure represented by the general formula (6) TgB: The glass transition temperature of the block (B) composed of the polyamic acid block represented by the following general formula (7) or the polyimide block represented by the general formula (8) constituting the block polymer [Chemical formula] [Chemical formula] <​[ka] [ka] (In the formula, X1 and X3 are independently tetravalent tetracarboxylic acid residues in each repeating unit, X2 and X4 are independently divalent diamine residues in each repeating unit, and n and m are positive integers.) [5]: The block polymer according to any one of [1] to [4], characterized in that in general formulas (1) to (4), X2 includes a diamine residue having a phenolic hydroxyl group and an aromatic diamine residue not having a phenolic hydroxyl group. [6]: The block polymer according to any one of [1] to [5], characterized in that in general formulas (1) to (4), X3 is a tetravalent tetracarboxylic acid residue having an alicyclic structure. [7]: A photosensitive resin composition comprising a block polymer and a photosensitive compound (C) as described in any of [1] to [6], characterized in that the block polymer is contained in 50% by mass or more and less than 100% by mass of 100% by mass of the resin composition excluding volatile components. [8]: The photosensitive resin composition according to [7], characterized in that the photosensitive compound (C) contains at least one compound represented by the following general formulas (9) to (12): [ka] [ka] [ka] [ka] In the general formulas (9) to (12) above, D is chemical formula (13) or hydrogen, and p is a positive integer. [ka] [9] The photosensitive resin composition according to [7] or [8] further comprising a curable compound (D).

[10] : A photosensitive resin composition according to any one of [7] to [9], further comprising an inorganic filler (E). [Effects of the Invention]

[0012] This disclosure provides excellent effects, such as offering block polymers and photosensitive resin compositions that exhibit superior dielectric properties and resolution, as well as superior crack resistance after heat cycle testing. [Modes for carrying out the invention]

[0013] The present disclosure will be described in detail below. It goes without saying that other embodiments are also included within the scope of this disclosure, insofar as they are consistent with the spirit of this disclosure. Furthermore, numerical ranges specified using "~" in this specification include the numerical values ​​before and after "~" as the lower and upper limits. Also, in this specification, "film" and "sheet" are synonymous and are not distinguished by thickness. Furthermore, unless otherwise noted, the various components mentioned in this specification may be used individually or in combination of two or more. The numerical values ​​described in this specification refer to values ​​obtained by the methods described in the [Examples] section below. In this specification, monomers may be referred to as monomers.

[0014] Block polymer The block polymer of the present invention has repeating units of any of the structures represented by general formulas (1) to (4), and the following X4 has a residue X4d derived from a dimer amine and / or dimer isocyanate. [ka] [ka] [ka] [ka] (In the formula, X1 and X3 are independently tetravalent tetracarboxylic acid residues in each repeating unit, X2 and X4 are independently divalent diamine residues in each repeating unit, and n, m, and l are positive integers.)

[0015] In this specification, a polyimide block or polyamic acid block derived from a dimer structure represented by the following general formula (5) or general formula (6) that constitutes a block polymer is referred to as block (A), and a polyamic acid block or polyimide block represented by the following general formula (7) or general formula (8) is referred to as block (B). [ka] [ka] [ka] [ka] (In the formula, X1 and X3 are independently tetravalent tetracarboxylic acid residues in each repeating unit, X2 and X4 are independently divalent diamine residues in each repeating unit, and n and m are positive integers.)

[0016] The block polymer can be diblock polymer, triblock polymer, or multiblock polymer, but multiblock polymer is preferred. Multiblock polymer is preferred because it can maintain polymeric properties while retaining a fine microphase separation structure, and can reduce defects based on poor microphase separation sites, thereby forming fine and minute repeating patterns.

[0017] The block polymer preferably contains 1% by mass or more and less than 50% by mass of residue X4d derived from dimer amine and / or dimer isocyanate relative to the total diamine residues in the block polymer. A range of 8 to 45% by mass is more preferable. This range allows for improved dielectric properties and crack resistance while maintaining resolution.

[0018] <Block (A)> In the present invention, block (A) is a polyimide block or polyamic acid block derived from a dimer structure, and is of general formula (5): [ka] General formula (6): [ka] (In the formula, X3 is a tetravalent tetracarboxylic acid residue, independently of each repeating unit, and X4 is a divalent organic group, independently of each repeating unit, with X3 and the imide bond bonding to each other to form two imide rings. m is a positive integer.) It has repeating units of the structure shown. Block (A) also has residue X4d derived from a dimer amine and / or dimer isocyanate. Block (A) can be obtained by the method described below.

[0019] Dimer amines can be obtained, for example, by converting the carboxyl group of a dimer acid to an amino group. Dimer isocyanates can be obtained, for example, by converting the carboxyl group of a dimer acid to an isocyanate group. Here, dimer acid refers to a dimer or hydrogenated product of an unsaturated aliphatic carboxylic acid. For example, dimer acids can be obtained by dimerizing natural fatty acids such as soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids, or unsaturated fatty acids such as linolenic acid, linoleic acid, oleic acid, erucic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, stearolic acid, vaccenic acid, gadoleic acid, eicosenoic acid, brassic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid, eleostearic acid, meadic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, cetoleic acid, adrenalineic acid, bosopentaenoic acid, osbondic acid, sardine acid, tetracosapentaenoic acid, eicosapentaenoic acid, docosahexaenoic acid, and herringic acid. The degree of unsaturation may be reduced by hydrogenating the unsaturated bonds as needed. Dimer amines and dimer isocyanates with reduced unsaturation are preferable in terms of oxidation resistance (especially discoloration at high temperatures) and suppression of gelation during synthesis.

[0020] Dimer acids are preferably compounds with 20 to 60 carbon atoms, more preferably compounds with 24 to 56 carbon atoms, even more preferably compounds with 28 to 48 carbon atoms, and even more preferably compounds with 36 to 44 carbon atoms. Dicarboxylic acid compounds having a branched structure obtained by the Diels-Alder reaction of fatty acids are preferred. The branched structure is preferably an adipose chain or a ring structure, with a ring structure being more preferred. The ring structure is preferably one or more aromatic rings or alicyclic structures, with an alicyclic structure being more preferred. If there are two ring structures, the two rings may be independent or continuous. Dimer amines and dimer isocyanates can be one or more compounds. Alicyclic structures may have one or more double bonds within the ring, or may not have double bonds. A method for converting the carboxyl group of a dimer acid to an amino group is, for example, to amidate the carboxylic acid, aminate it by Hoffmann rearrangement, and then distill and purify it. Furthermore, one method for converting the carboxyl group of a dimer acid to a diisocyanate group is to convert a carboxylic acid to an isocyanate via a Curtius rearrangement.

[0021] The amino group in the dimer amine, or the isocyanate group in the dimer isocyanate, may be directly bonded to the ring structure, but from the viewpoint of improving solubility and flexibility, it is preferable that the amino group is bonded to the ring structure via an aliphatic chain. The number of carbon atoms between the amino group or isocyanate group and the ring structure is preferably 2 to 25. Suitable examples of aliphatic chains include linear hydrocarbon groups such as alkylene groups. As a preferred example, a compound in which the two amino groups or isocyanate groups are each bonded to the ring structure via alkylene groups can be cited.

[0022] The following chemical formulas (d1) to (d4) are examples of dimer acids (polybasic acids) used to obtain dimer amines or dimer isocyanates. These are just examples, and dimer acids are not limited to the structures shown below.

[0023] [ka]

[0024] The dimer amine and dimer isocyanate are preferably compounds having 20 to 60 carbon atoms, more preferably compounds having 24 to 56 carbon atoms, even more preferably compounds having 28 to 48 carbon atoms, and even more preferably compounds having 36 to 44 carbon atoms. These carbon number configurations are preferred from the viewpoint of availability.

[0025] Commercially available dimer amines include, for example, "Priamine 1071," "Priamine 1073," "Priamine 1074," and "Priamine 1075" from Croda Japan, and "Versamin 551" from BASF Japan. Dimer amines can be used alone or in combination of two or more types.

[0026] As described above, X4 in general formula (5) or general formula (6) is a divalent organic group, which may have an independent structure for each repeating unit. As described above, diamines and diisocyanates are examples of organic compounds used in polymerization to obtain X2. At least a portion of X4 is residue X4d derived from dimer amines and / or dimer isocyanates.

[0027] The proportion of X4d having a dimer structure is preferably 60 to 100 mol% when the total amount of X4 constituting block (A) is considered to be 100 mol%. This range allows for a good balance of heat resistance, dielectric properties, and crack resistance. A more preferable range is 70 to 100 mol%, and an even more preferable range is 90 to 100 mol%. The proportion of X4d having a dimer structure can be determined from the content (mol%) of monomers in which X4d having a dimer structure is a residue, relative to 100 mol% of the total monomers that become X4 residues among the raw material monomers used in the synthesis of polyimide block (B).

[0028] Other diamine compounds other than the monomer that forms the residue X4d having the dimer structure described above in general formula (5) or general formula (6) of block (A) are not particularly limited. Specifically, these include aliphatic groups (which may contain unsaturated bonds, linear hydrocarbon structures and / or alicyclic hydrocarbon structures), aromatic rings, and diamine compounds in any combination thereof, which may have substituents.

[0029] Other diamine compounds besides the dimer structure may be used in combination, such as aliphatic diamines, aromatic diamines, alicyclic diamines, polyether diamines, and siloxane diamines, as exemplified below. However, aliphatic diamines, alicyclic diamines, polyether diamines, and siloxane diamines are preferred to prevent the glass transition temperature of block (A) from becoming too high.

[0030] [ka]

[0031] [ka] (l is an integer between 1 and 3)

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] Specific examples of polyetherdiamines include the following commercially available products. For example, the "JEFFAMINE D series" commercially available from Huntsman, Inc. in the United States includes varieties such as D-230, D-400, D-2000, and D-4000 as polyoxypropylenediamines. The JEFFAMINE ED series also includes polyetherdiamines such as ED-600, ED-900, and ED-2003. These are all polyetherdiamines with different molecular weights and numbers of amine functional groups, and they have a polyether structure modified at the ends with amino groups.

[0036] Specific examples of siloxanediamines include the following commercially available products. For example, Shin-Etsu Chemical Co., Ltd. offers "KF-8010" with an amine equivalent of 430, "X-22-161A" with an amine equivalent of 800, "X-22-161B" with an amine equivalent of 1500, "KF-8012" with an amine equivalent of 2200, "KF-8008" with an amine equivalent of 5700, "X-22-9409" with an amine equivalent of 700, and "X-22-1660B-3" with an amine equivalent of 2200. Additionally, Toray Dow Corning Co., Ltd. offers "BY-16-853U" with an amine equivalent of 460, "BY-16-853" with an amine equivalent of 650, and "BY-16-853B" with an amine equivalent of 2200, which can also be used.

[0037] Preferred examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine. Furthermore, substituents may be introduced at any position in these compounds.

[0038] As described above, X3 in general formula (5) or general formula (6) is a tetravalent tetracarboxylic acid residue, each repeating unit having an independent structure. The tetracarboxylic acids used in polymerization to obtain X3 are not particularly limited. Aromatic tetracarboxylic acids containing an aromatic group, aliphatic tetracarboxylic acids containing an aliphatic group, and tetracarboxylic acids containing both an aromatic and aliphatic group are preferably used as tetracarboxylic acids. An aliphatic group is a hydrocarbon group that is linear, branched, cyclic (alicyclic structure), or a combination thereof. The aliphatic group may contain an unsaturated bond. The aliphatic group may also contain heteroatoms such as nitrogen, oxygen, sulfur, selenium, fluorine, chlorine, and bromine. Tetracarboxylic acids may be used alone or in combination of two or more. The above examples of monomers may also have substituents as appropriate. Examples of substituents include alkyl groups, halogen atoms, nitro groups, cyano groups, etc.

[0039] Examples of tetracarboxylic dianhydrides used in the present invention include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, and 4,4'-[propane-2,2-diyrbis(1,4-phenyleneoxy)]diphthalic acid dianhydride. Water, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1,4,5, 8-Naphthalenetetracarboxylic anhydride, 2,3,6,7-Naphthalenetetracarboxylic anhydride, 9,9'-Bis[4-(3,4-Dicarboxyphenoxy)phenyl]fluorenic acid dianhydride, 9,9'-Bis(3,4-Dicarboxyphenoxy)fluorenic acid dianhydride, 1',2'-Dianhydride; 4,4'-[4,4'-(Propane-2,2-Diyl)Diphenoxy]Diphthalic acid dianhydride, 4-(2,5-Dioxotetrahydrofuran-3-yl)-1,2,3,4-Tetrahydronaph Talene-1,2-dicarboxylic acid anhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2.2.Examples include octane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 7-methyl-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 7-tert-butyl-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, and 7-tert-bitoxy-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride. Tetracarboxylic acid dianhydrides are not limited to those described above and can be used individually or in combination of two or more types.

[0040] Tetracarboxylic acid dianhydrides are preferable to contain an alicyclic structure because they exhibit excellent phase separation properties with block (B) described later, as well as good dielectric properties. Specifically, examples include 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 7-methyl-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 7-tert-butyl-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, and 7-tert-bitoxy-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride. Among these, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride are more preferred in terms of improved phase separation and dielectric properties.

[0041] Block (A) can be manufactured by various known methods. The manufacturing methods for the case where block (A) is a polyamic acid block derived from a dimer structure having repeating units of the structure shown in general formula (6), and the case where block (A) is a polyimide block derived from a dimer structure having repeating units of the structure shown in general formula (5), are described below, respectively.

[0042] If block (A) is a polyamic acid block derived from a dimer structure, one method for synthesizing polyamic acid is to react a tetracarboxylic dianhydride with a diamine. More specifically, it can be produced by dissolving monomers containing a tetracarboxylic dianhydride and a diamine in a solvent and polymerizing them at a relatively low temperature of about 10 to 80°C.

[0043] The reaction between tetracarboxylic dianhydride and diamine can be carried out by known methods in an aprotic polar solvent. Examples of aprotic polar solvents include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), methyl diglyme, cyclohexanone, and 1,4-dioxane. One type of aprotic polar solvent may be used, or two or more types may be mixed. In this case, it is also acceptable to use a nonpolar solvent that is compatible with the above aprotic polar solvent in the mixture; for example, aromatic hydrocarbons such as toluene, xylene, mesitylene, and solvent naphtha are commonly used. The proportion of the nonpolar solvent in the mixed solvent is preferably 30% by mass or less. This is because if the nonpolar solvent is 30% by mass or more, the dissolving power of the solvent increases, making it difficult for polyamic acid to precipitate. The reaction between tetracarboxylic dianhydride and the diamine component is preferably carried out by dissolving the well-dried diamine component in the aforementioned reaction solvent obtained by dehydration and purification, and then adding the well-dried tetracarboxylic dianhydride to this solution.

[0044] The reaction between the tetracarboxylic dianhydride and the diamine may be either a random reaction or a blocked reaction. The reactants may be, for example, a mixture of homoreactants obtained by reacting each diamine component separately, or the reactants may be further recombined if necessary. For example, an acid-terminated oligomer prepared in excess of polycarboxylic dianhydride may be mixed with an amine-terminated oligomer prepared in excess of diamine and then reacted together.

[0045] If block (A) is a polyimide block derived from a dimer structure, one method for synthesizing polyimide is to cyclize a polyamic acid or polyamic acid ester resin, which is a polyimide precursor, by thermal or chemical imidation to convert it into an imide group. Alternatively, the step of converting to polyamic acid can be omitted, and it can be obtained by a one-step reaction in which polymerization and imidation are carried out in an organic solvent at a relatively high temperature, for example, around 130°C to 250°C.

[0046] Thermal imidation can be carried out at temperatures of approximately 200-400°C, while chemical imidation can be performed in the presence of an organic base such as pyridine or triethylamine, and acetic anhydride. The temperature can be selected from any range of -20-200°C. Note that when chemical imidation cyclizes polyamic acid or polyamic acid ester resin, which are polyimide precursors, to convert them into imide groups, if the reaction temperature is below 50°C, some of the polyimide precursor will remain in an open ring state without being imidized.

[0047] Block (A), obtained by thermal or chemical imidization of polyamic acid, can also be used in its polymerization solution form in the multi-block formation process with block (B) described later. Alternatively, a poor solvent such as methanol or ethanol can be added to precipitate the resin, which can then be isolated and recovered as a powder and used in the multi-block formation process with block (B) described later.

[0048] The block (A) represented by general formula (5) or general formula (6) according to the present invention preferably has a weight-average molecular weight of 1,000 to 100,000, and a glass transition temperature (Tg) of 20°C to 100°C, and more preferably 20°C to 60°C.

[0049] <Block (B)> Block (B) is a polyamic acid block represented by the following general formula (7) or a polyimide block represented by the general formula (8). [ka] [ka] (In the formula, X1 is a tetravalent tetracarboxylic acid residue, independently of each repeating unit, and X2 is a divalent organic group, independently of each repeating unit. X1 and the imide bond may or may not be bonded to each other to form two imide rings. n is a positive integer.)

[0050] As described above, X1 in general formula (7) or (8) is a tetravalent tetracarboxylic acid residue, each repeating unit having an independent structure. The tetracarboxylic acids used in polymerization to obtain X1 are not particularly limited. Aromatic tetracarboxylic acids containing an aromatic group, aliphatic tetracarboxylic acids containing an aliphatic group, and tetracarboxylic acids containing both an aromatic and aliphatic group are preferably used as tetracarboxylic acids. An aliphatic group is a hydrocarbon group that is linear, branched, cyclic (alicyclic structure), or a combination thereof. The aliphatic group may contain an unsaturated bond. The aliphatic group may also contain heteroatoms such as nitrogen, oxygen, sulfur, selenium, fluorine, chlorine, and bromine. Tetracarboxylic acids may be used alone or in combination of two or more. The above examples of monomers may have substituents as appropriate. Examples of substituents include alkyl groups, halogen atoms, nitro groups, cyano groups, etc.

[0051] Examples of tetracarboxylic dianhydrides used in the present invention include 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid dianhydride, and 2,2-bi (3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic acid dianhydride, 1,4-phenylenebis(trimellitic acid monoester) dianhydride, 1,2,3,4-benzenetetra Carboxylic acid anhydrides, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenic acid dianhydride, 9,9'-bis(3,4-dicarboxyphenoxy)fluorenic acid dianhydride, 1',2'-dianhydride; 4,4'-[4,4'-(propane-2,2-diyl)diphenoxy]diphthalic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4- Tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo[2.2.Examples include octane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 7-methyl-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 7-tert-butyl-4-(2,5-dioxotetrahydrodioxo3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, and 7-tert-bitoxy-4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride. Tetracarboxylic acid dianhydrides are not limited to those described above and can be used individually or in combination of two or more types.

[0052] Tetracarboxylic acid dianhydrides are preferably those containing an aromatic structure. Tetracarboxylic acid dianhydrides containing an aromatic structure have a high glass transition temperature, excellent heat resistance, and low linear expansion, resulting in excellent crack resistance. Specifically, examples include 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic acid dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, pyromellitic acid dianhydride, 1,4-phenylenebis(trimellitic acid monoester) dianhydride, 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenic acid dianhydride, and the like. Among these, 1,4-phenylenebis(trimellitic acid monoester) dianhydride and 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenic acid dianhydride are more preferred in terms of high heat resistance, high glass transition temperature, and low linear expansion.

[0053] In general formula (7) or (8), X2 is a divalent diamine residue, as described above, which may have an independent structure for each repeating unit. The diamine monomer of X2 preferably includes aromatic diamines that do not have a phenolic hydroxyl group and diamines that have a phenolic hydroxyl group. Specifically, these include aliphatic groups (which may have substituents, which may include unsaturated bonds, which may be linear hydrocarbon structures and / or alicyclic hydrocarbon structures), aromatic rings, and diamine compounds that are any combination thereof. Aromatic diamine compounds may be used in combination, as exemplified below. Aromatic diamines that can also be copolymerized with other diamines include, for example, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2'-bis(trifluoromethyl)benzidine, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3, 3,3-Hexafluoropropane, m-Phenylenediamine, o-Phenylenediamine, p-Phenylenediamine, m-Aminobenzylamine, p-Aminobenzylamine, 3,3'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl ether, 4,4'-Diaminodiphenyl ether, 3,3'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfoxide, 3,4'-Diaminodiphenyl sulfoxide, 4,4'-Diaminodiphenyl sulfoxide, 3,3'-Diaminodiphenyl sulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4 -(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1, 1,1,3,3,3-Hexafluoropropane, 1,4-Bis(3-aminophenoxy)benzene, 1,3-Bis(3-aminophenoxy)benzene, 1,4-Bis(4-aminophenoxy)benzene, 4,4'-Bis(4-aminophenoxy)biphenyl, Bis[4-(4-aminophenoxy)phenyl]ketone, Bis[4-(4-aminophenoxy)phenyl]sulfide, Bis[4-(4-aminophenoxy)phenyl]sulfoxide, Bis[4-(4-aminophenoxy)phenyl]sulfone, Bis[4-(3-aminophenoxy)phenyl]A Tel, bis[4-(4-aminophenoxy)phenyl] ether, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 4,4'-bis(3-aminophenoxy)benzoyl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis[3-(3 -aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl]sulfoxide, 4,4'-bis[3-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,[α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3 -Bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α,α-dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone Phenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxyben Zoyl)benzene, 1,4-bis(3-amino-4-phenoxybenzoyl)benzene, 1,3-bis(4-amino-5-phenoxybenzoyl)benzene, 1,4-bis(4-amino-5-phenoxybenzoyl)benzene, 1,3-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,4-bis(3-amino-4-biphenoxybenzoyl)benzene, 1,3-bis(4-amino-5-biphenoxybenzoyl)benzene, 1,4-bis(4-amino-5-biphenoxybenzoyl)benzene, 2,6-bis[4-(4-amino-α,Examples include α-dimethylbenzyl)phenoxy]benzonitrile, aromatic diamines having a benzoxazole structure, and aromatic diamines in which some or all of the hydrogen atoms on the aromatic ring are substituted with halogen atoms, C1-C3 alkyl or alkoxy groups, cyano groups, or C1-C3 halogenated alkyl or halogenated alkoxy groups in which some or all of the hydrogen atoms of the alkyl or alkoxy group are substituted with halogen atoms. These aromatic diamines can be used individually or in combination of two or more types. From the viewpoint of dielectric properties, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and 2,2'-bis(trifluoromethyl)benzidine are preferred.

[0054] The diamine monomer of X2 has phenolic hydroxyl groups, which allows for control of its alkali solubility through interaction with the photosensitive compound, as described later. Specifically, the strong interaction between the photosensitive compound and the hydroxyl groups in the resin containing phenolic hydroxyl groups prevents the resin containing phenolic hydroxyl groups from ionizing and dissolving into the alkaline aqueous developer. The resin containing phenolic hydroxyl groups itself is insoluble in the alkaline developer, but when irradiated with light, the photosensitive compound photodegrades and changes to indenecarboxylic acid, making it soluble in the alkaline developer. On the other hand, the base resin containing nophenolic hydroxyl groups has hydroxyl groups and is soluble in the alkaline developer; therefore, once the interaction with the photosensitive compound is eliminated, it becomes soluble in the alkaline developer, and the entire resist system dissolves in the alkaline developer. What is important here is the difference in solubility of the resist film before and after exposure; by creating this difference in solubility contrast, high resolution can be imparted.

[0055] Preferred examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, 2,2'-ditrifluoromethyl-5,5'-dihydroxyl-4,4'-diaminobiphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine. Furthermore, substituents may be introduced at any position in these compounds.

[0056] Another method for controlling alkaline solubility is to use a diamine containing a carboxylic acid. Preferred examples of diamines having a carboxylic acid include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 5,5'-methylenebis(2-aminobenzoic acid), 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid. Furthermore, substituents may be introduced at any position in these compounds.

[0057] Other diamines include, for example, aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine, and metaxylenediamine; and alicyclic diamines such as isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, and piperazine.

[0058] Block (B) can be manufactured by various known methods. The manufacturing methods for the cases where block (B) is a polyamic acid block having repeating units of the structure shown in general formula (7), and where block (A) is a polyimide block derived from a dimer structure having repeating units of the structure shown in general formula (8), are described below.

[0059] If block (B) is a polyamic acid block, polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. More specifically, it can be produced by dissolving monomers consisting of a tetracarboxylic dianhydride and a diamine in a suitable solvent and polymerizing them at a relatively low temperature of about 10 to 80°C.

[0060] The reaction between tetracarboxylic dianhydride and diamine can be carried out by known methods in an aprotic polar solvent. Examples of aprotic polar solvents include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), methyl diglyme, cyclohexanone, and 1,4-dioxane. One type of aprotic polar solvent may be used, or two or more types may be mixed. In this case, it is also acceptable to use a nonpolar solvent that is compatible with the above aprotic polar solvent in the mixture; for example, aromatic hydrocarbons such as toluene, xylene, mesitylene, and solvent naphtha are commonly used. The proportion of the nonpolar solvent in the mixed solvent is preferably 30% by mass or less. This is because if the nonpolar solvent is 30% by mass or more, the dissolving power of the solvent increases, making it difficult for polyamic acid to precipitate. The reaction between tetracarboxylic dianhydride and the diamine component is preferably carried out by dissolving the well-dried diamine component in the aforementioned reaction solvent obtained by dehydration and purification, and then adding the well-dried tetracarboxylic dianhydride to this solution.

[0061] The reaction between the tetracarboxylic dianhydride and the diamine may be either a random reaction or a blocked reaction. The reactants may be, for example, a mixture of homoreactants obtained by reacting each diamine component separately, or the reactants may be further recombined if necessary. For example, an acid-terminated oligomer prepared in excess of polycarboxylic dianhydride may be mixed with an amine-terminated oligomer prepared in excess of diamine and then reacted together.

[0062] On the other hand, if block (B) is a polyimide block, a method for producing polyimide includes cyclizing a polyimide precursor, such as polyamic acid or a polyamic acid ester resin, by thermal or chemical imidation to convert it into imide groups. Alternatively, the step of producing polyamic acid can be omitted, and it can be obtained by a one-step reaction in which polymerization and imidation are carried out in an organic solvent at a relatively high temperature, for example, around 130°C to 250°C.

[0063] Thermal imidation can be carried out at temperatures of approximately 200-400°C, while chemical imidation can be performed in the presence of an organic base such as pyridine or triethylamine, and acetic anhydride. The temperature can be selected from any range of -20-200°C. Note that when chemical imidation cyclizes polyamic acid or polyamic acid ester resin, which are polyimide precursors, to convert them into imide groups, if the reaction temperature is below 50°C, some of the polyimide precursor will remain in an open ring state without being imidized.

[0064] The block (B) represented by the general formula (7) or (8) according to the present invention preferably has a weight-average molecular weight of 1,000 to 100,000, and a glass transition temperature (Tg) of 150°C to 400°C, and more preferably 150°C to 350°C.

[0065] (Manufacturing of block polymers) The method for producing block polymers according to the present invention will be described. The following is a specific example of a manufacturing method, but it is not intended to be limited to this method.

[0066] For example, a block (A) with repeating unit m is synthesized so that the terminal end is an amine, and a block (B) with repeating unit n is synthesized so that the terminal end is an acid anhydride. Then, by mixing the polyimide block (A) and block (B) derived from the dimer structure and polymerizing them, a block polymer with repeating unit l can be obtained. Alternatively, the terminal end of block (A) may be an acid anhydride and the terminal end of block (B) may be an amine.

[0067] Furthermore, by synthesizing the block (A) portion of repeating unit m and then adding the acid anhydride and diamine constituting block (B) and polymerizing them, a block (B) of repeating unit n can be obtained, and finally a block polymer of repeating unit l can be obtained. Alternatively, the polymer may be synthesized from block (B) and block (A) may be synthesized later.

[0068] The block polymer having any of the structural units represented by the general formulas (1) to (4) according to the present invention preferably has a weight-average molecular weight of 20,000 to 200,000.

[0069] The glass transition temperature of the block polymer of the present invention can be controlled by the monomers used in block (A) and block (B), respectively. Furthermore, when a coating film is formed, this type of block polymer forms a phase-separated structure. The presence of a low-glass transition temperature portion (soft) and a high-glass transition temperature portion (hard) in each of the separated layers allows for both interfacial adhesion and cohesive force. This is also applied in the present invention; for example, by lowering the glass transition temperature of block (A) and raising the glass transition temperature of block (B), it is possible to form a phase-separated structure in which the soft portion composed of block (A) and the hard portion composed of block (B) are separated. For the reasons stated above, in the present invention, it is preferable that the glass transition temperature (TgA) of block (A) is 100°C or lower. Furthermore, in the present invention, it is preferable that the glass transition temperature (TgB) of block (B) is higher than the glass transition temperature (TgA) of block (A). That is, in the block polymer, it is preferable that block (B) is the hard segment and block (A) is the soft segment. It is believed that the hard segment of block (B) undergoes physical crosslinking, and the soft segment of block (A), which does not participate in physical crosslinking, crosslinks, thereby exhibiting elastomer functionality and having a positive effect on crack resistance. Specifically, it is preferable that the difference in glass transition temperatures ((TgB)-(TgA)) between block (B) and block (A) is 100°C or more. More preferably, it is 150°C or more. A difference of 100°C or more between TgB and TgA is preferable because it facilitates the formation of a phase separation structure, thereby achieving both interfacial adhesion and cohesive force. Furthermore, the difference in glass transition temperatures between block (B) and block (A) ((TgB)-(TgA)) is preferably 350°C or less.

[0070] The lower limit of the light transmittance of the block polymer of the present invention with respect to the exposure wavelength (365 nm) is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. The upper limit of the above light transmittance is not particularly limited, but may be less than 100% or 90% or less. This allows the photosensitive agent in the photosensitive resin composition to effectively absorb light of the exposure wavelength, thereby increasing the reactivity of the photosensitive compound.

[0071] ≪Photosensitive resin composition≫ The photosensitive resin composition according to this embodiment (hereinafter also referred to as "this composition") comprises the block polymer of the present invention and a photosensitive compound (C), and may further optionally contain a curable compound (D) and / or an inorganic filler (E).

[0072] It is preferable that the resin composition, excluding volatile components, contains 50% to less than 100% by mass of block polymer in 100% by mass. More preferably, it contains 60 to 95% by mass. By including 50% to less than 100% by mass of block polymer in the resin composition, low dielectric properties and stress relaxation properties can be imparted.

[0073] <Photosensitive compound (C)> A photosensitive compound is a substance that, when a photosensitive resin film formed by coating a photosensitive resin composition onto a substrate is irradiated with light, reacts to light and has the function of creating a difference in solubility in the developer between the irradiated and unirradiated areas. It is also called a photosensitive agent. Examples of photosensitive compound (C) used in the present invention include known photosensitive agents used in positive-type photosensitive resin compositions. As photosensitive compound (C), compounds having a quinone diazide group are preferred because they exhibit excellent photosensitivity. The photosensitive compound (C) according to the present invention preferably contains at least one compound represented by the following general formulas (9) to (12). [ka] [ka] [ka] [ka] In the general formulas (9) to (12) above, D is chemical formula (13) or hydrogen, and p is a positive integer. [ka]

[0074] The amount of photosensitive compound (C) is preferably 10 to 40 parts by mass, and more preferably 12 to 27 parts by mass, per 100 parts by mass of block polymer. When the amount of photosensitive compound (C) is in the range of 10 to 40 parts by mass, the block polymer in the unexposed areas becomes insoluble in the alkaline developer due to electrostatic interaction with the aforementioned block polymer, and in the exposed areas, the solubility in the alkaline developer is improved because the photosensitive compound represented by the general formulas (9) to (12) generates indenecarboxylic acid. As a result, the solubility of the unexposed and exposed areas becomes appropriately contrasted, and the resolution of the pattern is improved.

[0075] <Curable compound (D)> The curable compound (D) is not particularly limited as long as it is a compound that hardens upon reaction with phenol and carboxylic acid. Examples include epoxy compounds and oxazoline compounds.

[0076] From the viewpoint of heat resistance, it is preferable that the epoxy equivalent of the curable compound (D) is 140 g / eq or more and less than 500 g / eq.

[0077] In this composition, excluding fillers and solvents, it is preferable to use 1 to 30% by mass of the curable compound (D), and more preferably 1 to 10% by mass. Within this range, it is possible to improve crack resistance after heat cycle testing while maintaining low dielectric properties.

[0078] In this application, an epoxy compound is defined as a compound having two or more epoxy groups in its molecule. It is preferable to use an active ester compound in combination with the epoxy compound. An active ester compound is a compound having one or more ester groups that react with epoxy groups in one molecule, thereby curing the epoxy resin. Examples of commercially available active ester compounds include DIC's "HPC-8000-65T," "EXB9416-70BK," and "EXB8100-65T."

[0079] By using an activated ester compound, an ester group is generated through the reaction between the epoxy compound and the activated ester compound. Therefore, the polarity can be reduced compared to when using a phenol-based curing agent. As a result, dielectric properties can be enhanced more effectively.

[0080] Specific examples of epoxy compounds include glycyl ether type epoxy resins; glycylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, or tetraglycidylmetaxylylenediamine, sorbitol polyglycidyl ether; glycidyl ester type epoxy resins such as diglycidyl phthalate, diglycidyl hexahydrophthalate, or diglycidyltetrahydrophthalate; cyclic aliphatic (alicyclic) epoxy resins such as epoxycyclohexylmethyl-epoxycyclohexanecarboxylate or bis(epoxycyclohexyl)adipate; and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AD ​​type epoxy resins. Examples of other epoxy resins include cresol novolac type epoxy resins, phenol novolac type epoxy resins, α-naphthol novolac type epoxy resins, bisphenol A type novolac type epoxy resins, dicyclopentadiene type epoxy resins, tetrabrom bisphenol A type epoxy resins, and brominated phenol novolac type epoxy resins.

[0081] <Inorganic filler (E)> The resin composition of the present invention may further optionally contain an inorganic filler (E). The type of inorganic filler (E) is not particularly limited. By using an inorganic filler (E), crack resistance after heat cycle testing is improved.

[0082] Specific examples of inorganic fillers (E) include alumina, aluminum hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, magnesium sulfate, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, calcium oxide, magnesium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, calcium silicate, beryllia, calcium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, and titanium white. Examples of fillers include metal compounds such as zinc borate and aluminum borate; talc; clay; mica; metal oxides and metal nitrides such as glass fibers, kaolin, hydrotalcite, wollastonite, xonotlite, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, and sepiolite; hydrated metal compounds; silica-based fillers such as molten crushed silica, molten spherical silica, crystalline silica, amorphous silica, secondary aggregated silica, fine silica powder, hollow silica, and porous silica; and nitride-based and carbon-based fillers such as silicon carbide, silicon nitride, titanium carbide, and diamond. Among these, alumina, aluminum oxide, aluminum nitride, and boron nitride are more preferred, with alumina and boron nitride being particularly preferred from the viewpoint of effectively enhancing crack resistance.

[0083] <Hardening agent> A curing aid may be added to promote the crosslinking reaction of radically reactive non-conjugated carbon-carbon unsaturated bonds. Examples of curing aids include radical polymerization initiators and catalysts. Suitable examples of catalysts include imidazole-based, amine-based, and phosphorus-based catalysts.

[0084] The catalyst can be any known compound. Examples include imidazole-based curing agents such as 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6-(2'-undecylimidazolyl)-ethyl-s-triazine, and 2,4-diamino-6-[2'-ethyl-4-methylimidazolyl-(1')]-ethyl-s-triazine; amine-based curing aids such as aliphatic, alicyclic, or aromatic amines and modified polyamines; phosphorus-based curing aids such as phosphate esters such as triphenylphosphine and triphenylphospite; and metal salts or metal complexes such as cobalt, zinc, copper, iron, nickel, manganese, and tin.

[0085] The amount of radical polymerization initiator added is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 8 parts by mass, per 100 parts by mass of the block polymer. Within this range, the reaction proceeds well without inhibiting the curing reaction.

[0086] When using a catalyst as a curing aid, the amount it is added is not limited, but from the viewpoint of obtaining a high glass transition temperature, it is preferable to add 0.01 to 2 parts by mass of the catalyst relative to the total amount of the block polymer and curable compound (D), and more preferably 0.1 to 1 part by mass. When using two or more curing accelerators in combination, it is preferable that their total amounts satisfy the above ratio.

[0087] <Other ingredients> Furthermore, without departing from the spirit of this disclosure, the photosensitive resin composition may include other components. For example, a curable compound that does not fall under the category of block polymer may be used. Alternatively, any thermoplastic resin may be used.

[0088] Other components include heat stabilizers, dyes, pigments (e.g., carbon black), polymerization inhibitors, defoamers, leveling agents, ion capture agents, humectants, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, and electromagnetic shielding agents.

[0089] This composition may be solvent-free or contain a solvent. Examples of solvents include toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, n-hexane, cyclohexane, cyclohexanone, and mixtures thereof.

[0090] The photosensitive resin composition of the present invention may contain other alkali-soluble resins in addition to the block polymer of the present invention. Specifically, examples include alkali-soluble polybenzoxazole, acrylic polymer copolymerized with acrylic acid, novolac resin, and siloxane resin. Such resins dissolve in aqueous solutions of alkalis such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, and sodium carbonate. By including these alkali-soluble resins, it is possible to impart the properties of each alkali-soluble resin while maintaining the adhesion and excellent sensitivity of the cured film.

[0091] The viscosity of the photosensitive resin composition of the present invention at 25°C is preferably 2 to 5000 mPa·s. By adjusting the solid content concentration so that the viscosity is 2 mPa·s or higher, it becomes easy to obtain the desired film thickness. On the other hand, if the viscosity is 5000 mPa·s or lower, it becomes easy to obtain a coating film with high uniformity. A positive-type photosensitive resin composition having such viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.

[0092] Next, a method for forming a heat-resistant resin pattern using the photosensitive resin composition of the present invention will be described.

[0093] The photosensitive resin composition of the present invention is applied to a substrate. While silicon wafers, ceramics, and gallium arsenide are used as substrates, the invention is not limited to these. Application methods include rotary coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the application method, the solid content concentration of the composition, viscosity, etc., but is typically applied to achieve a dry film thickness of 0.1 to 150 μm.

[0094] To improve the adhesion between a substrate such as a silicon wafer and a photosensitive resin composition, the substrate can be pre-treated with the aforementioned silane coupling agent. For example, a solution prepared by dissolving 0.5 to 20% by mass of the silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate is used for surface treatment by spin coating, immersion, spray coating, or steam treatment. In some cases, heat treatment at 50°C to 300°C is then performed to promote the reaction between the substrate and the silane coupling agent.

[0095] Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably carried out using an oven, hot plate, infrared, etc., at a temperature of 50°C to 150°C for 1 minute to several hours.

[0096] Next, the photosensitive resin composition coating is exposed by irradiating it with a chemical beam through a mask having a desired pattern. Chemical beams that can be used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp.

[0097] To form a pattern on a heat-resistant resin, the exposed areas are removed using a developer after exposure. Preferred developers include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these alkaline aqueous solutions, either individually or in combination. After development, rinsing with water is preferable. Here too, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.

[0098] After development, a temperature of 100°C to 200°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment can be performed by selecting a temperature and gradually increasing it, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, heat treatment can be performed at 130°C and 200°C for 30 minutes each. In this invention, a curing temperature of 150°C to 250°C is preferred, but since this invention provides a cured film with particularly excellent low-temperature curability, a temperature of 150°C to 200°C is more preferred.

[0099] Furthermore, by incorporating an inorganic filler, such as a thermally conductive filler, into the cured product of this composition, it can be applied to a wide range of applications requiring heat dissipation. For example, by utilizing the moldability of the resin composition, it can be suitably used as a heat dissipation component of a desired shape. In particular, it is useful as a heat dissipation adhesive or heat dissipation sheet for electronic devices (smartphones, tablet terminals, etc.) where fans or heat sinks cannot be installed in order to achieve lightness, thinness, and miniaturization, and for battery casing materials. In addition, the cured product of this composition is suitable as an adhesive layer between a heating element and a heat sink, or as a heat spreader. It can also be applied as a heat dissipation layer covering one or more electronic components mounted on a substrate. [Examples]

[0100] The present invention will be described in more detail below with reference to examples and comparative examples. In the examples and comparative examples, parts and % refer to parts by mass and mass%, respectively, unless otherwise specified, and RH refers to relative humidity.

[0101] <Method for measuring weight-average molecular weight (Mw)> Mw was measured using the GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation. GPC is a liquid chromatography method that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in their molecular size. In this invention, the measurement was performed using two "LF-604" columns (Showa Denko K.K.: rapid analysis GPC column: 6mm ID × 150mm size) connected in series, under conditions of a flow rate of 0.6 ml / min and a column temperature of 40°C, and the weight-average molecular weight (Mw) was determined in terms of polystyrene equivalent.

[0102] <Measurement of glass transition temperature (Tg)> The obtained adhesive sheets were measured using a Shimadzu Corporation "Differential Scanning Calorimeter DSC-60PLUS" under the conditions of a starting temperature of 25°C, an ending temperature of 250°C, and a heating rate of 10.0°C / min. Using 10 mg of the sample, the sheet was rapidly cooled to the starting temperature after the first heating cycle, and the peak value measured in the second cycle under the same conditions was used for the measurement. Two Tg values ​​were observed, originating from block (A) and block (B). TgA represents the glass transition temperature originating from block (A), and TgB represents the glass transition temperature originating from block (B). The same measurement was performed only on the polyimide block (A) with a dimer structure to confirm the Tg of the polyimide block (A) with a dimer structure. Of the two Tg values ​​of the block polymer, the one with the same temperature as the Tg of the polyimide block (A) with a dimer structure was determined to be TgA.

[0103] The abbreviations for the compounds used in the examples are as follows: DDA: Product name: Priamin 1075 (manufactured by Croda Japan Co., Ltd.) MMCH:4,4'-Methylenebis(2-methylcyclohexylamine) (manufactured by Tokyo Chemical Industry Co., Ltd.) BAPP: 2,2-Bis[4-(4-aminophenoxy)phenyl)propane (manufactured by Seika Co., Ltd.) JEFFAMINE D-400: Polyoxypropylenediamine (manufactured by Huntsman) KF-8010: α,ω-bis(3-aminopropyl)poly(dimethylsiloxane) (manufactured by Shin-Etsu Chemical Co., Ltd.) MCTC: 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) BISDA: 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (manufactured by SABIC) TAHQ: 1,4-phenylenebis(trimellitic acid monoester) dianhydride (manufactured by Manac Co., Ltd.) DABPAF: Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Seika Co., Ltd.) TFMB: 2,2'-Bis(trifluoromethyl)benzidine (manufactured by Manac Corporation) HFBAPP: 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (manufactured by Seika Co., Ltd.) MBAA: 5,5'-Methylenebis(2-aminobenzoic acid) (Manufactured by Seika Co., Ltd.)

[0104] (Synthesis Example 1) Synthesis of polyimide block (A-1) derived from dimer structure In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 240 parts of N-methyl-2-pyrrolidone (hereinafter NMP) and 36.8 parts of MCTC were charged, and the mixture was heated to 100°C while stirring under a nitrogen atmosphere. 63.2 parts of DDA were added dropwise over 1 hour, and the mixture was then heated to 140°C for 14 hours to carry out the dehydration reaction. The mixture was further heated to 180°C to remove the solvent, yielding a block (A-1) with a weight-average molecular weight of 12,500. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0105] (Synthesis Examples 2-9) Synthesis of polyimide blocks (A-2)-(A-9) derived from dimer structures Polyimide blocks (A-2) to (A-9) derived from dimer structures were obtained by the same method as in Synthesis Example 1, except that the monomers listed in Table 1 were used. The Mw and Tg of the obtained polyimide blocks are shown in Table 1.

[0106] (Synthesis Example 10) Synthesis of polyamic acid block (A-10) derived from dimer structure In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 240 parts of N-methyl-2-pyrrolidone (hereinafter NMP) and 36.8 parts of MCTC were charged, and the mixture was heated to 70°C while stirring under a nitrogen atmosphere. 63.2 parts of DDA were added dropwise over 1 hour, and stirring was continued for 14 hours to obtain a block (A-10) with a weight-average molecular weight of 10,500. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0107] (Synthesis Examples 11, 12) Synthesis of polyimide blocks (A-11) and (A-12) derived from dimer structures Polyimide blocks (A-11) and (A-12) derived from dimer structures were obtained by the same method as in Synthesis Example 1, except that the monomers listed in Table 2 were used. The Mw and Tg of the obtained polyimide blocks are shown in Table 2.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Example 1] Synthesis of block polymer (AB-1) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 47.6 parts of dimer-structured polyimide block (A-1), 30.4 parts of TAHQ, 22.0 parts of TFMB, and 160 parts of NMP were charged and stirred at room temperature under a nitrogen stream for 7 hours. A block polymer (AB-1) with a weight-average molecular weight of 68,700 was obtained. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0111] [Example 2] Synthesis of block polymer (AB-2) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 12.6 parts of dimer-structured polyimide block (A-2), 49.5 parts of TAHQ, 37.9 parts of DABPAF, 160 parts of NMP, and 40 parts of toluene were charged. The mixture was heated to 170°C under a nitrogen atmosphere and stirred at 170°C for 4 hours. After that, a solvent was added as appropriate to obtain a block polymer (AB-2) with a weight-average molecular weight of 75,400. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0112] [Example 4] Synthesis of block polymer (AB-4) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 47.4 parts of dimer-structured polyimide block (A-2), 31.5 parts of TAHQ, 11.3 parts of DABPAF, 160 parts of NMP, and 40 parts of toluene were charged. The mixture was heated to 170°C under a nitrogen stream and stirred at 170°C for 4 hours. After cooling to room temperature, 9.8 parts of TFMB were added, and the mixture was stirred at room temperature under a nitrogen stream for 7 hours. Subsequently, a solvent was added as appropriate to obtain a block polymer (AB-4) with a weight-average molecular weight of 65,200. The amount of solvent was then adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0113] [Example 6] Synthesis of block polymer (AB-6) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 64.6 parts of dimer-structured polyimide block (A-3), 11.5 parts of TAHQ, 23.9 parts of HFBAPP, and 160 parts of NMP were charged and stirred at room temperature under a nitrogen stream for 7 hours. After that, a solvent was added as appropriate to obtain a block polymer (AB-6) with a weight-average molecular weight of 20,100. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%. In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 47.6 parts of dimer-structured polyimide block (A-1), 30.4 parts of TAHQ, 22.0 parts of TFMB, and 160 parts of NMP were charged and stirred at room temperature under a nitrogen stream for 7 hours. A block polymer (AB-1) with a weight-average molecular weight of 68,700 was obtained. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0114] [Example 5] Synthesis of block polymer (AB-5) (AB-5) was obtained in the same manner as in Example 4, except that the amount of polyimide block (A-2) derived from the dimer structure, and the amounts of TAHQ and TFMB were changed as shown in Table 3.

[0115] [Examples 7, 14] Synthesis of block polymers (AB-7) and (AB-14) (AB-7) and (AB-14) were obtained in the same manner as in Example 6, except that the type and amount of polyimide blocks derived from the dimer structure, as well as the amounts of TAHQ and HFBAPP, were changed as shown in Table 3.

[0116] [Examples 3, 8-13] Synthesis of block polymers (AB-3), (AB-7), (AB-8), (AB-9), (AB-10), (AB-11), (AB-12), (AB-13) Except for changing the type and amount of polyimide block (A) derived from the dimer structure, and the amounts of TAHQ and DABPAF as shown in Table 3, (AB-3), (AB-8), (AB-9), (AB-10), (AB-11), (AB-12), and (AB-13) were obtained in the same manner as in Example 2.

[0117] [Example 32] Synthesis of block polymer (AB-15) (AB-15) was obtained in the same manner as in Example 1, except that the type of polyimide block derived from the dimer structure was changed as shown in Table 4.

[0118] [Examples 33, 34] Synthesis of block polymers (AB-16) and (AB-17) (AB-16) and (AB-17) were obtained in the same manner as in Example 4, except that the type of polyimide block derived from the dimer structure was changed as shown in Table 4.

[0119] [Example 35] Synthesis of block polymer (AB-18) (AB-18) was obtained in the same manner as in Example 2, except that the type of polyimide block derived from the dimer structure was changed, and DABPAF was replaced with MBAA.

[0120] [Example 36] Synthesis of block polymer (AB-19) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 30.3 parts TAHQ, 21.7 parts DABPAF, 160 parts NMP, and 40 parts toluene were charged. The mixture was heated to 170°C under a nitrogen stream and stirred at 170°C for 4 hours. After cooling to room temperature, 47.4 parts of polyamic acid block (A-10) derived from a dimer structure were added, and the mixture was stirred at room temperature under a nitrogen stream for 7 hours. Subsequently, a solvent was added as appropriate to obtain a block polymer (AB-19) with a weight-average molecular weight of 67,400. After adjusting the amount of solvent as appropriate, a resin varnish with a resin solids content of 50% was obtained.

[0121] [Comparative Example 1] Synthesis of Aromatic Polyimide (B-1) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 58.3 parts TAHQ, 30.3 parts DABPAF, 160 parts NMP, and 40 parts toluene were charged. The mixture was heated to 170°C under a nitrogen stream and stirred at 170°C for 4 hours. After cooling to room temperature, 11.4 parts TFMB were added, and the mixture was stirred at room temperature under a nitrogen stream for 7 hours. Subsequently, an aromatic polyimide (B-1) with a weight-average molecular weight of 75,100 was obtained by adding a solvent as appropriate. After adjusting the amount of solvent as appropriate, a resin varnish with a resin solids content of 50% was obtained.

[0122] [Comparative Example 2] Synthesis of dimer structure-derived polyimide (A-13) In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank, and nitrogen gas inlet, 17.1 parts TAHQ, 22.9 parts MCTC, 35.3 parts HFBAPP, 24.7 parts DDA, 160 parts NMP, and 40 parts toluene were charged and stirred at room temperature under a nitrogen stream for 7 hours. After that, solvents were added as appropriate to obtain a polyimide (A-13) derived from a dimer structure with a weight-average molecular weight of 54,100. Subsequently, the amount of solvent was adjusted as appropriate to obtain a resin varnish with a resin solids content of 50%.

[0123] <Manufacturing of films for physical property measurement> The AB-1 to AB-14, AB-15 to AB-18, B-1, and A-9 prepared as described above were uniformly coated onto a 50 μm thick heavy release film (polyethylene terephthalate (PET) film coated with a heavy release agent) using a doctor blade so that the thickness after drying was 50 μm, and then dried at 120°C for 2 minutes. After that, the dried coated material was peeled off the heavy release film and heated at 200°C for 1 hour and then at 250°C for 1 hour. After that, it was cooled to room temperature to obtain a film for physical property measurement.

[0124] The following physical properties were measured using the obtained physical property measurement film. The results are shown in Tables 3 and 4.

[0125] (Measurement of light transmittance at 365nm) For measuring the light transmittance at 365 nm, for example, a visible-ultraviolet spectrophotometer can be used. Alternatively, for measuring the light transmittance, a 10 μm thick photosensitive resin film can be used, formed by preparing a varnish-like photosensitive resin composition coating and pre-baking the coating at 120°C for 2 minutes.

[0126] [Table 3]

[0127] [Table 4]

[0128] [Example 15] A positive-type photosensitive composition was prepared by placing 100 parts of block polymer (AB-1), 10 parts of compound (C-1) represented by the general formula (9) above as photosensitive compound (C) (product name: naphthoquinone diazide sulfonate ester 3, manufactured by Daito Chemix Co., Ltd.), and 3 parts of EOCN104S (novolac-type epoxy resin, epoxy equivalent 355-375 g / eq, manufactured by Nippon Kayaku Co., Ltd.) (D-1) as curable compound (D), adding 280 parts of γ-butyrolactone and mixing.

[0129] [Examples 16-28] A photosensitive resin composition was prepared in the same manner as in Example 15, except that the type of block polymer was changed as shown in Table 5.

[0130] [Comparative Examples 3 and 4] A photosensitive resin composition was prepared in the same manner as in Example 15, except that the resins shown in Table 5 were used instead of the block polymer.

[0131] [Examples 37-41] A photosensitive resin composition was prepared in the same manner as in Example 15, except that the type of block polymer was changed as shown in Table 6.

[0132] [Example 29] A positive-type photosensitive composition was prepared by charging 100 parts of block polymer (AB-4), 10 parts of compound (C-2) represented by the general formula (10) above as photosensitive compound (C) (product name: naphthoquinone diazide sulfonic acid ester 1, manufactured by Daito Chemix Co., Ltd.), and 3 parts of EOCN104S(D-1) as curable compound (D) into a light-shielding container, and dissolving the mixture with 280 parts of γ-butyrolactone.

[0133] [Example 30] A positive-type photosensitive composition was prepared by placing 100 parts of block polymer (AB-4), 10 parts of compound (C-1) represented by the general formula (9) as photosensitive compound (C), and 3 parts of Rikaresin BEO-60E (bisphenol A type epoxy resin, epoxy equivalent 220 g / eq, manufactured by Shin Nippon Rika Co., Ltd.) (D-2) as curable compound (D), adding 280 parts of γ-butyrolactone and mixing.

[0134] [Example 31] A positive-type photosensitive composition was prepared by placing 100 parts of block polymer (AB-4), 10 parts of compound (C-1) represented by the general formula (9) as the photosensitive compound (C), 3 parts of EOCN104S(D-1) as the curable compound (D), and 250 parts of AO-509 (manufactured by Admatex, alumina) as the inorganic filler (E) into a light-shielding container, adding 280 parts of γ-butyrolactone, and mixing.

[0135] [Comparative Example 5] A photosensitive resin composition was prepared in the same manner as in Example 31, except that an aromatic polyimide (B-1) was used instead of a block polymer.

[0136] (resolution) A photosensitive resin composition was applied to a 200 mm diameter silicon wafer substrate using a spin coater to a thickness of 0.80 μm after drying, and the substrate was dried at 100°C for 1 minute to obtain a coated substrate. Next, exposure was performed at a wavelength of 365 nm and 2000 J / m² using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon). Exposure was performed through a photomask with a square aperture. The exposed film was paddle developed for 1 minute with TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tama Chemical Industry Co., Ltd.). After paddle development, the film was rinsed with pure water using a spin shower for 20 seconds and then spin-dried. The planar dimensions of pixels formed by apertures were observed using a scanning electron microscope (Hitachi High-Tech Corporation "S-3000N"), and the diameter of the bottom of vias with apertures of 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and 50 μm in the photomask were measured. The smallest possible aperture size was defined as the resolution. A: Resolution less than 10 μm. This is a very good result. B: Resolution between 10 μm and 20 μm. Good results. C: Resolution between 20 μm and 30 μm. This is a reasonably good result. D: Resolution of 30μ or higher: This presents practical problems.

[0137] (Crack resistance (stress relaxation)) A glass cloth substrate epoxy resin copper-clad laminate was prepared as the inner layer circuit board, with circuit patterns formed on it where L / S = 25 μm / 25 μm, and copper thicknesses of 25 μm and 50 μm, respectively. On both sides of this laminate, resin sheets of each example, prepared by the above method, were vacuum-heated and pressed at 200°C, 3.0 MPa, and for 2 hours. Finally, copper foil was placed on the outermost layers on both sides to obtain an evaluation printed circuit board. The evaluation printed circuit boards were then placed in a thermal shock device ("TSE-11-A," manufactured by ESPEC), and alternating exposure was performed a predetermined number of times under the conditions of high-temperature exposure: 125°C for 15 minutes and low-temperature exposure: -50°C for 15 minutes. The evaluation printed circuit boards were cut, and the exposed cross-sections were observed for the presence or absence of cracks using a scanning electron microscope (SEM) at a magnification of 5000x. The presence or absence of cracks was observed every 100 heat cycle tests. A crack is defined as a fissure with a size of 0.1 μm or larger. The evaluation criteria are as follows. A: No cracks occurred after 3000 heat cycle tests. This is an extremely good result. B: Does not meet the above criteria A. No cracks occur after 1000 heat cycle tests. This is a very good result. C: Does not satisfy conditions A and B above. No cracks occur after 200 heat cycle tests. This is a good result. D: Does not meet the above criteria A-C. No cracks occur after 100 heat cycle tests. This is a reasonably good result. E: Cracks were observed after 100 heat cycle tests. This poses a practical problem.

[0138] <Measurement of relative permittivity (Dk) and dielectric loss tangent (Df)> A photosensitive resin composition was uniformly coated onto a 50 μm thick heavy release film (a polyethylene terephthalate (PET) film coated with a heavy release agent) using a doctor blade to achieve a dry thickness of 50 μm, and then dried at 120°C for 2 minutes. The dried coated material was then peeled off the heavy release film and heated at 200°C for 1 hour and then at 250°C for 1 hour. After cooling to room temperature, a film for physical property measurement was obtained. The photosensitive resin composition film for physical property measurement was stored for 24 hours or more in an atmosphere of 23°C and 50% RH. The release film was then removed, and the relative permittivity (Dk) and dielectric loss tangent (Df) at a measurement frequency of 10 GHz were determined using a dielectric constant measuring device manufactured by AET Co., Ltd., by the cavity resonator method under the same temperature and humidity conditions. The evaluation criteria are as follows. Relative permittivity (Dk) A: Less than 2.9. This is an extremely good result. B: 2.9 or higher, less than 3.0. This is a very good result. C: 3.0 or higher, less than 3.1. This is a good result. D: 3.1 or higher and less than 3.3. This is a reasonably good result. E: 3.3 or higher. This presents practical problems. Dielectric loss tangent (Df) A: Less than 0.004. This is an extremely good result. B: 0.004 or higher and less than 0.006. This is a very good result. C: 0.006 or higher and less than 0.009. This is a good result. D: 0.010 or higher and less than 0.015. This is a reasonably good result. E: 0.015 or higher. This poses a practical problem.

[0139] [Table 5]

[0140] [Table 6]

Claims

1. A block polymer having any of the structural units shown in the following general formulas (1) to (4), 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (X in the formula １ , X ３ Each repeating unit is independently a tetravalent tetracarboxylic acid residue, and X ２ , X ４ (Each repeating unit is independently a divalent diamine residue, and n, m, and l are positive integers.) The above X ４ This is residue X derived from dimer amine and / or dimer isocyanate. ４ A block polymer characterized by having d.

2. For all diamine residues in the block polymer, residue X is derived from dimer amine and / or dimer isocyanate. ４ The block polymer according to claim 1, characterized in that it contains d in an amount of 1% by mass or more and less than 50% by mass.

3. The block polymer according to claim 1, characterized in that the glass transition temperature of the polyimide block (A) derived from the dimer structure represented by the following general formula (5) or general formula (6) that constitutes the block polymer is 100°C or less. 【Transformation 5】 【Transformation 6】 (In the formula, X ３ is, independently for each repeating unit, a tetravalent tetracarboxylic acid residue, and X ４ is, independently for each repeating unit, a divalent organic group, and the X ３ and the imide bond are bonded to each other to form two imide rings. m is a positive integer.)

4. Having general formula (5) or (6), and general formula (7) or (8), The block polymer according to claim 1, characterized in that it satisfies the following formula. (TgB)-(TgA)≧100℃ TgA: Glass transition temperature of a polyimide block (A) derived from a dimer structure represented by the following general formula (5) or a polyamic acid block (A) derived from a dimer structure represented by the general formula (6) that constitutes a block polymer. TgB: Glass transition temperature of block (B), which consists of a polyamic acid block represented by the following general formula (7) or a polyimide block represented by the general formula (8) that constitutes the block polymer. 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 (X in the formula １ , X ３ Each repeating unit is independently a tetravalent tetracarboxylic acid residue, and X ２ , X ４ (Each repeating unit is independently a divalent diamine residue, and n and m are positive integers.)

5. In general formulas (1) to (4), X ２ The block polymer according to claim 1, characterized in that it comprises a diamine residue having a phenolic hydroxyl group and an aromatic diamine residue not having a phenolic hydroxyl group.

6. In general formulas (1) to (4), X ３ The block polymer according to claim 1, characterized in that is a tetravalent tetracarboxylic acid residue having an alicyclic structure.

7. A photosensitive resin composition comprising the block polymer described in any one of claims 1 to 6 and a photosensitive compound (C), characterized in that the block polymer is contained in 50% by mass or more and less than 100% by mass of 100% by mass of the resin composition excluding volatile components.

8. The photosensitive resin composition according to claim 7, characterized in that the photosensitive compound (C) comprises at least one compound represented by the following general formulas (9) to (12): 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 In the general formulas (9) to (12) above, D is chemical formula (13) or hydrogen, and p is a positive integer. 【Chemistry 15】

9. The photosensitive resin composition according to claim 7, further containing a curable compound (D).

10. The photosensitive resin composition according to claim 7, further containing an inorganic filler (E).

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