TW201030057A - Phenolic hydroxyl group-containing polyimide resin and photosensitive resin composition using same - Google Patents

Abstract

Provided is a resin and a resin composition that are easily synthesized and patterned, and that sufficiently provide characteristics such as flame retardancy, heat resistance, mechanical characteristics, and flexibility. The resin is a phenolic hydroxyl group-containing polyimide resin obtained by condensation polymerization of (a) a tetrabasic acid dianhydride, (b) an aminophenol compound that has at least two amino groups and at least one phenolic hydroxyl group in a molecule, and (c) a diamino compound. In the phenolic hydroxyl group-containing polyimide resin, at least 5 mol% of tetrabasic acid dianhydride (a) is one or more alicyclic tetrabasic acid dianhydrides selected from the group comprising formula (1).

Description

201030057 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a positive-type photosensitive polyimide resin composition which can be developed in an aqueous solution. The polyimine resin composition is excellent in storage stability, and the cured product is excellent in flame retardancy and heat resistance and has sufficient flexibility even if it does not contain a flame retardant, an antimony compound, or a phosphorus compound. It is used as a solder mask for a thin package substrate, a cover film for a flexible printed wiring board, an interlayer insulating film for a multilayer printed wiring board, a semiconductor protective film, or the like. [Prior Art] In terms of high-precision, high-density, the use of photolithography is a part of the printed wiring board for the people's livelihood and the solder resist layer of most industrial printed wiring boards. After the exposure, a development process is carried out to form a pattern, and then a photocurable resin composition obtained by final curing by heat and/or light irradiation is used. In consideration of environmental problems, in the case of a developing solution, an alkaline developing type liquid solder mask using a dilute aqueous alkali solution is the mainstream of the developing solution. In particular, it is suitable for a ball grid array (baU gdd is used as a magic substrate, a solder mask of a flexible substrate, a cover film system, and a softness is required, and in terms of its material, the patent document) proposes a composition. A compound obtained by reacting a reaction product of a polyfunctional (tetra) epoxy resin having a soft structure with (meth)acrylic acid and a polybasic acid anhydride is used. On the other hand, 'polyimine has electrical properties, chemical resistance, etc. A variety of excellent electrical, electronic components, semiconductors, heat resistance, flame retardancy, softness, and different characteristics, and is widely used in the machine and its circuit parts, week 201030057 side machine. However, because of the polyimide resin It is hardly soluble in organic solvents. Therefore, it is applied to the substrate by using the precursor, ie, polylysine, and then drying the coating film, then performing exposure and development to pattern it. Then heating and dehydrating at about 35 ° C. (Patent Document 2). Patent Document 3 describes a block copolymerized polyamidene composition which is soluble in/treat, and describes that it can be developed in an aqueous alkali solution without performing a dehydration ring closure. Patent Document 1: Japanese Laid-Open Patent Publication No. 2 868 丨 〇 〇 专利 专利 专利 : : : : : : : 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明However, in the case of using a cured product of the solder resist cover composition disclosed in Patent Document 1, although excellent in photosensitivity, development can be carried out using a dilute aqueous alkali solution, and the chipping resistance of the surface is improved, but not only The flammability and the flexibility are insufficient, and it is impossible to follow the extreme bending. This is a problem. ❹ The photosensitive polyimide intermediate precursor composition disclosed in Patent Document 2 is excellent in physical properties after curing. The storage stability is low, and the shrinkage caused by the deflation in the closed loop occurs fiercely, which is the problem. The solvent-soluble block copolymerized polyimide composition disclosed in Patent Document No. 7F does not require dehydration. The closed loop, i~ cannot satisfy the developability, the resolution, the adhesion, the heat resistance, etc. The object of the present invention I & ^ „ provides a resin composition and a cured product thereof. The composition of the tree moon 可 可 庙 庙 . . . . . . . . . . . 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可The present inventors have solved the above problems in order to solve the above problems. That is, the present invention relates to: (1) a kind of aramid resin (4) containing a desired transuretic group, which has at least a tetrabasic acid anhydride (4). The co-condensation reaction of two amine groups with at least one amino group benzene (tetra) compound (b) and diamine compound (4) of the desired group is less than 5 mol% of the tetrabasic acid (4) One or more alicyclic tetrabasic dianhydrides selected from the group consisting of the following formula (1) are selected:

(2) The phenolic hydroxyl group-containing polyimine resin (A) according to the above (1), wherein the tetrabasic acid dianhydride (a) contains a tetrabasic acid other than the compound group represented by the formula (1) a dianhydride, and the tetrabasic acid dianhydride is selected from the group consisting of 3,3,4,4,-diphenylfluorene tetra-acid dianhydride, 3,3',4,4'-benzophenone tetrahydro acid One or more of the group consisting of anhydride, 3,3', 4,4,-biphenyltetracarboxylic dianhydride and 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride (3) The phenolic hydroxyl group-containing polyphthalocyanine 201030057 amine resin (A) as described in any one of the above (1) to (2) wherein the aminophenol compound (b) is selected from 3,3'-diamine 4--4,4,dihydroxydiphenylhydrazine, 3,3'-diamino-4,4,dihydroxydiphenyl ether, 3,3'-diamino-4 4,4,-dihydroxy Biphenyl, 3,3,-diamino-4,4,-dihydroxydibenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)decane, 2,2-dual ( 3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4.hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino group -4-hydroxyphenyl)propane and 9,9,_bis(3_amino-4.hydroxyphenyl)anthracene The phenolic hydroxyl group-containing polyimine resin (A) as described in any one of the above (1) to (3) wherein the diamine compound (the oxime is selected from 3, 4,_Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl sulfone, 4,4 • diaminodiphenyl sulfone, 4, 4 '_Diaminodiphenylmethane, anthracene, 4-diaminobenzene, 1'3-diaminobenzene, i,3^-(3-aminophenoxy)benzene, anthracene-...amine basic group One or more of the groups consisting of -1,3,3-trimethyl-1H•indole-5-amine and siiic〇ne diamine, (5) as in the above (1) to (4) The polyamidamine resin (A) having a heterogeneous group, wherein the hydroxyl equivalent is 200 to 5,000 g/eq., and (6) a positive photosensitive polyimide resin composition, The base material having the above-mentioned (1) a desired base group-containing polyanilin resin (4), a diazo-based positive-f-sensitizer (8), and an epoxy resin (6) or (7) as an optional component, which have the above-mentioned (6) A layer of a positive photosensitive polyimide film formed as described above. Advantageous Effects of Invention The polyimine resin containing the phenolic polyimine resin composition of the present invention is excellent in positive photosensitive stability, developability, and resolution, 7 201030057 and can reduce film loss during development. Further, it has excellent hardenability, solvent resistance, acid resistance, heat resistance, and flame retardancy, and has sufficient flexibility. Therefore, the resin composition of the present invention and the cured product thereof are widely used in a solder mask for a thin package substrate, a cover film for a flexible printed wiring board, an interlayer insulating film for a multilayer printed wiring board, and a semiconductor protective film. use. [Embodiment] The phenolic hydroxyl group-containing polyimine resin (A) of the present invention has a specific structure of tetrabasic acid dianhydride (a), has at least two amine groups in one molecule, and at least one phenolic hydroxyl group. The aminophenol compound (b) and the diamine compound (c) are reacted. The number of acid anhydride groups in the molecule of the tetrabasic acid dianhydride (a) used in the reaction and the number of moles of the tetrabasic acid dihepatic (a) are respectively defined as X and x, and the amine benzene is expected to be a compound (b) The number of amine groups in the molecule and the number of moles of the aminophenol compound (b) i are determined as Y and y ', respectively, when the number of moles of the diamine compound (c) is z, if Xx > Yy + 2z The end is an acid needle, and if xx < Yy + 2z, the end is an amine. In this case, the enthalpy of Xx/(Yy+2z) is preferably in the range of 0.5 to 2, more preferably in the range of 〇·7 to 1.5. More preferably, when the enthalpy is 0.8 or more and less than 1, it is preferably 0.9 or more and less than 1. In this case, both ends of the obtained polyfluorene imide are an amine group. When the enthalpy is less than 〇·5 or higher than 2, the raw material having a small molecular weight and unreacted remains, and various properties such as heat resistance and flexibility after curing cannot be obtained. Further, the aminophenol compound (b) is preferably added in such a manner that the phenolic base group amount of the phenolic hydroxyl group-containing polyimine resin obtained by the reaction is 200 to 5, 〇〇〇g/eq. . When it is less than 200 g/eq., the acidity becomes strong and film loss and peeling tend to occur upon development of the alkaline aqueous solution. When 201030057 is higher than 5,000g/eq., the alkali developability is greatly reduced. The phenolic hydroxyl group-containing polyimine resin (A) of the present invention is synthesized by a simple dehydration condensation reaction of an acid anhydride structure with an amine group. Therefore, the tetrabasic dianhydride (a) and the amine group necessary for synthesizing the phenolic transmissive polyacrylamide resin (A) having a desired terminal structure (an acid anhydride group or an amine group) and a hydroxyl equivalent amount are used. The amount of the benzene-promoting compound (b) and the diamine-based compound (c) can be easily changed from the respective molecular weights of (a) to (c) and the number of anhydride structures in one molecule, the number of amine groups, and the number of phenolic hydroxyl groups. Calculated. For example, for example, in the example i of the present invention, tetrabasic dianhydride (4) which is used as a raw material of the phenolic transmissive base resin (A), BPDA-H (hydrogenated 3, 3', 4) , 4'-biphenyltetracarboxylic dianhydride, molecular weight

306.31), an aminophenol compound having two amine groups and two phenolic hydroxyl groups in one molecule (b), ABPS (3,3,-diamino-4 4,4-dihydroxydiphenyl sulfone, molecularly placed 280.30) and a combination of a monoamine compound (c), APB-N (1,3-bis-(3-aminophenyloxy)benzene, molecular weight 292.34), when a polyphenol Q containing a phenolic hydroxyl group is desired When the terminal of the imide resin (A) is an amine, it may be used in an amount of 1 mol or more and 2 mol or less in total of ABPS and APB-N with respect to BPDA-H 1 mole. In this case, in order to make the phenolic hydroxyl equivalent of the phenolic hydroxyl group-containing polyimine resin (A) in the range of 200 to 5,000 g/eq., when, for example, ABPS and APB-N are used with respect to bPDA_h 1 When the total amount is 1 m, use ABPS of about 0.06 m or more (less than 1 m). When using ABPS and APB-N total 1.5 m with respect to BPDA-H 1 Mo, use ABPS about 7 m. Above (less than 1_5 moles), when using ABPS and APB-N total 2 mus relative to BPDA_h 1 Mo, use ABPS about 0.09 m or more (less than 2 m) 9 201030057 In the present invention, it is quaternary Acidic dianhydride (a) The hydrogenated 3,3',4,4'-biphenyltetracarboxylic dianhydride of the compound group represented by the formula (1) and the hydrogenated pyromellitic dianhydride and the general quaternary The hydride of the acid dianhydride is superior to the amine group. Therefore, the phenolic hydroxyl group-containing polyimine resin obtained by the co-condensation reaction has excellent solvent solubility and flexibility. In addition, when the diazo-based positive photosensitive agent (B) is used as the positive photosensitive polyimide, the solubility in the aqueous alkali solution during development is improved, so that the development time can be shortened, and the film which can suppress the positive type is the film. Loss. Further, since the transmittance of the ultraviolet ray used for the exposure is also excellent, the reaction efficiency of the sensitizer is high and the film thickness can be increased. Further, with the specific structure of the tetrabasic acid dianhydride (hydrogenated 3,3', 4,4'-biphenyltetracarboxylic dianhydride and/or hydrogenated tetraphenylene) in the tetrabasic acid dianhydride (a) The ratio of the acid dianhydride is lowered, and the above characteristics are also low. Therefore, the content of the tetrabasic acid dianhydride of the specific structure in the tetrabasic acid dianhydride (a) is usually 5 mol% or more, preferably 3 More than 5% of the molars are more than 7% of the molars of more than 7%, and more preferably ΒΓ ΟΖ Λ ν 又 又 ,, gasification of pyromellitic acid liver, in addition to the compound of formula (1): The isomer has a compound represented by the following formula (7), but the reaction proceeds, and the main chain (4) is reacted, and the reactivity is remarkably deteriorated, so that it is not suitable for use. Tea 201030057 Ο Ο

(2) In the present invention, the quaternary acid dianhydride (a) is contained in the quaternary acid dianhydride (a), and the phenolic hydroxyl group-containing polyimine resin (A) may be at least mol%, H〇) The alicyclic tetrabasic dianhydride is represented by at least 5 dianhydride. Specific examples of the alicyclic tetrabasic acid dianhydride may be used in combination with other quaternary acid "T and the other four gambling hexanic acid dianhydride may be mentioned: pyromellitic acid oxetane-double (partially three Acid liver), glycerol-bis(trimellitic acid liver) monoacetic acid vinegar, 1,2,3,4,-butane tetracarboxylic acid mono-, 'sucking-anhydride, 3,3,4,4 _ Pyromellitic dianhydride, 3,3,4,4-di-p-methyl, tetracarboxylic dianhydride, 3,3',4,4,biphenyltetracarboxylic acid-anhydride 3,3,4,4 diphenyl Ether ether tetracarboxylic dianhydride, 2,2-bis(3 4·dehydrated bis-phenyl)propane, 2,2-bis(3,4-disionylphenyl)hexa- 1 propyl, 5 -(2,5-dioxotetrahydro-3-furanyl)-3_methylcyclohexene], 2 dicarboxylic anhydride, 3a, 4,5,9b-tetrahydro-5-(tetrahydro-2, 5-Dioxo_3_吱n南基)_naphthalene, 2<] oxime 1,3-dione, hydrazine, hydrazine·cyclohexane tetracarboxylic dianhydride, bicyclo (22 octane·7-ene- 2,3,5,6-tetracarboxylic dianhydride and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, etc. Among them, solvent solubility, denseness to the substrate In terms of compatibility and photosensitivity, 3,3,4,4 _ diphenyl hard tetracarboxylic acid, 3,3,,4 4,·benzophenone tetracarboxylic dianhydride, 3,3 , 4,4, bis-tetracarboxylic acid bis-anhydride or 3,3,4,4-diphenyl ether tetracarboxylic dianhydride is preferred. It can be used together with the 11 201030057 he tetrabasic acid liver Use one type or a mixture of two or more types.

In the present invention, the aminophenol compound (b) for producing a phenolic hydroxyl group-containing polyimine resin is not particularly limited as long as it is a compound having at least two amine groups and at least one phenolic hydroxyl group in one molecule. The limitation is preferably, for example, a compound having two amine groups and two phenolic hydroxyl groups in one molecule. In the case of the amine-based compound (b) which can be used, 3,3,-diamino-4,4,4-dihydroxydiphenyl sulfone, 3,3'-diamino group _4,4,_ Dihydroxydiphenyl ether, 3,3,-diamino-4,4,-dihydroxybiphenyl, 3,3'-diamino-4,4,dihydroxydibenzophenone, 2,2- Bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3.amino-4-ylhydroxy)acetophenone, 2,2-bis(3-amino-4-hydroxybenzene Acetylene, 13_hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane and 99,_bis(3amino-4-hydroxyphenyl)anthracene, etc., preferably , 3'-diamino-4,4,dihydroxydiphenyl sulfone, 3,3-diamino-4,4,-dihydroxydibenzophenone, 2,2·bis (3·amino group _ 4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane or 9,9-bis(3-amino-4-hydroxyphenyl)芴 is preferred, with 3,3'-diaminopurine-4,4-diaminobenzophenone, 3,3'-diamino-4,4,-di-dibenzophenone or 1 More preferably, 3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane. These amino phenol compounds (b) may be used alone or in combination of two or more. In the present invention, the diamine-based compound (c) for producing the phenolic hydroxyl group-containing polyimine resin (A) is, in addition to the compound contained in the above aminophenol compound, in one molecule. Any compound having two amine groups may be used, and any of them may be used. Specific examples of the diamine-based compound (c) which can be used include m-phenylenediamine, p-phenylenediamine, m-toluenediamine, 4,4,-diaminodiphenyl ether, and 3,3'- Dimethyl-4,4'-diaminodiphenyl ether, 3,4·-diamine 12 201030057 bisdiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3' - Dimercapto-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl Thioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylfluorene Alkane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide , 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenylarylene, 3 , 3-diaminodiphenyl, 4,4'-diaminodiphenyl, 1,4-diamine-based, 1,3-diaminobenzene, 1,3-bis-(3- Aminophenoxy)benzene, 1(4-aminophenyl)-1,3,3-trimethyl-1Η-indol-5-amine, benzidine, 2,2'-di Benzyl aniline, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylene Amine, o-xylene diamine, 2, 2'-bis(3-aminophenoxyphenyl)propane, 2,2,-bis(4-aminophenoxyphenyl)propane, l,3 - bis(4-aminophenoxyphenyl)benzene, 1,3'-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)pyrene Burned, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5- Diethylphenyl) oxime, bis(4-amino-3-propylphenyl)methane, bis(4-amino-3,5-dipropylphenyl)methane, polystearyldiamine, Isoflurane diamine, hexamethylene diamine, trimethyl hexamethylene diamine, etc. 'but are not limited thereto. Among them, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether, which are excellent in adhesion to a substrate, developability, and flexibility, are preferred. , 3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl, 4,4-diaminodiphenyl fluorene, 1,4-diaminobenzene, 1,3-diamine Benzobenzene, 1,3-bis-(3-aminophenoxy)benzene, 1-(4-aminophenyl)_13 3_ 13 201030057 Trimethyl-1H-indole-5-amine, polyoxydiamine Or 2,2, dimethylbenzidine; more preferably 3,4'-diaminodiphenyl ether, 4,4,-diaminodiphenyl hydrazine, anthracene, 4-diaminobenzene, 1, 3-bis-(3-aminophenoxy)benzene or iota-(4-aminophenyl)-1,3,3-trimethyl-1H-indole-5-amine; especially preferably 3,4,- Diaminodiphenyl ether, or hydrazine, 3·bis-(3-aminophenyloxy)benzene. These diamine-based compounds (c) may be used alone or in combination of two or more. For the phenolic hydroxyl group-containing polyimine resin of the present invention, it is preferred

And a combination of tetrakisic acid dianhydride (a), the above preferred aminophenol compound (b) and the above preferred diamine compound (c), wherein the tetrabasic acid dianhydride (a) is selected a mixture of a tetrabasic acid monoanhydride of a compound of the compound group represented by the formula (1) and a tetravalent acid anhydride which is preferably used in combination with the above; more preferably a tetrabasic acid dianhydride (a), the above The combination of the preferred aminophenol compound 0) and the above-mentioned preferred diamine compound (c) is one or more selected from the group consisting of compounds represented by the formula (1). That is, more specific and tongue, especially the phenolic hydroxyl-containing polyimide tree

The cerium (A) is produced by the following method: tetrabasic acid dianhydride q) using one or more kinds of tetrabasic acids selected from the compound group represented by the formula (1): anhydride, and 3, 3' , 4,4'-diphenyl-tetracarboxylic dianhydride, 33, 44, _ two are ketone tetradecanoic acid, 3,3, ,M, _biphenyl tetra-retensive two closed ^ 3,3, a mixture of 4,4'-diphenyl ether tetracarboxylic dianhydride; an amino phenolated name (b) using 3,3,-diamino _4 4, - « * makeup 丞 4,4 hydroxydiphenyl sulfone , 3,3,-diamine side-4,4'-dihydroxydiphenyl ether, 3 3, _ _ , not 丞氓 U _ amino group _4,4, ·dihydroxybiphenyl

— 丞 one ketone, 2,2-bis(3-amino-4-hydroxyj-group)-methyl, 2,2-bis(3-amino-4_hydroxy-poor, ^

Ethyl, 2,2-bis(3-amine J 14 201030057 -4-hydroxyphenyl)propane, 1,3-hexafluoro·2,2-bis(3-amino-4-hydroxyl) Phenyl)propane and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene, preferably 3,3,-diamino-4,4'-dihydroxydiphenylhydrazine, 3 , 3' _diamino-4,4,-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, anthracene, 3_hexafluoro_2, 2_ Bis(3-amino-4-hydroxyphenyl)propane or 9,9'-bis(3-amino-4-hydroxyphenyl)anthracene, more preferably 3,3'-diamino-4,4 '-Dihydroxydiphenyl hydrazine, 3,3'-diamino-4,4'-dihydroxydiphenyl fluorenone or ι,3_hexafluoro-2,2_bis(3_amino-4_hydroxyl) Benzene)propane; diamine compound (c) using 3,4,-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl , 4,4'-diamino-benzophenone, 4,4-diaminodipyridyl, 1,4-diaminobenzene, 1,3-diaminobenzene, 1,3-double -(3-Aminophenoxy)benzene, iota-(4-aminophenyl)-indole, 33-trimethyl-1H-indole-5-amine, polyoxydiamine or 2,2,-di Mercaptobenzidine, preferably 3,4 - Aminodiphenyl ether, 4,4'-diaminodiphenyl hard, 1,4-diaminobenzene, 1,3-bis-(3-aminophenoxy)benzene or ι_(4-amine Phenyl)-1,3,3-trimethyl-1H-indole-5-amine, more preferably 3,4,-diaminodiphenyl Q ether or 1,3-bis-(3-amine Phenoxy group) is produced by benzene. The phenolic hydroxyl group-containing polyimide resin (A) of the present invention can make the tetrabasic acid (a) and the aminophenol compound in the presence of a catalyst formed by an equilibrium reaction between vinegar and a base. (b) and the diamine-based compound (c) are obtained by a co-condensation reaction. At this time, when a dehydrating agent such as toluene or xylene is used in combination, the reaction proceeds and is thus more efficient. By this manufacturing method, it is possible to easily manufacture a straight portion without causing a reaction of a phenolic thiol group with another reactive group (for example, an acid anhydride or an amine group) without protecting a functional group, that is, a phenolic hydroxyl group. A key-shaped aromatic polyimine copolymer. Although the block copolymer disclosed in Patent Document 15 201030057 3 may be used, the non-block copolymer is preferred from the viewpoint of ease of synthesis and the like. Therefore, in the present invention, the above-mentioned desired polyimine is usually synthesized by a reaction. In the reaction, the use ratio of the tetrabasic acid dianhydride (a) and the diamine component (the aminophenol compound (b) and the diamine compound (c)) is preferably in the above range. When it is desired to obtain a high molecular weight, it is preferred to use a theoretical excess or a slightly excess of 1 mol% or less, preferably 5 mol% or less. The phenolic hydroxyl group-containing polyimine resin of the present invention may be used in any type as long as it is synthesized in the above manner, and it is preferred that the diamine component is slightly excessive (the excess amount is about 〜1 to 5 mol%). The two ends obtained are amine-based polyimine resins. Further, the ratio of use of the 'amino phenol compound and the diamine compound (c) (mole ratio) is preferably relative to the amino phenol compound (b) 1 molar 'diamine compound Mo, more Good for 0.1~2.5 m. When used in this ratio, the proportion of each component in the polyamidene resin is determined by the ratio of use of the compound. The lactone to be used as the above catalyst is preferably T. valerolactone, and the base to be used as the catalyst is preferably pyridine or N-mercaptomorpholine. The solvent used in the synthesis of the phenolic hydroxyl group-containing polyimine resin (A) may be exemplified by: acetophenone, oxime acetone, decyl isopropanone, indolinone, decyl isobutyl ketone, decyl hexanone. Diethyl ketone, diisopropanone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, butyrolactone, diacetone alcohol, cyclohex-1-ene, dipropylene Ether, diisopropyl, dibutyl ether, tetrahydrofuran, tetrahydro "pyran, ethyl isoamyl ether, ethyl-tert-butyl ether, ethylbenzyl ether, cresol 16 201030057 methyl Ether, anisole, phenylethyl ether, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate Ester, cyclohexyl acetate, decyl cyclohexyl acetate, benzyl acetate, decyl acetate, ethyl acetate, decyl propionate, ethyl propionate, butyl propionate, propionate, Methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, decyl lactate, ethyl lactate, butyl lactate, ethyl isovalerate, isovalerate Ester, oxalic acid Ethyl vinegar, dibutyl oxalate, decyl benzoate, ethyl benzoate, propyl benzoate, decyl salicylate, N-methylpyrrolidone, N, N_: methyl formamide, hydrazine, hydrazine - It is not limited to these. These solvents may be used alone or in combination of two or more. The solvent at this time is preferably a solvent which dissolves the phenolic hydroxyl group-containing polyimine resin (Α) formed by the reaction, and is preferably a solvent such as r-butyrolactone, more preferably 4 ~5 member ring of cyclic ketone. Hereinafter, the method for producing the phenolic hydroxyl group-containing polyimine resin (A) will be more specifically described. First, a diamine component (amino benzene-promoting compound (b) and a diamine-based compound (c) is appropriately added to any of the above solvents in which a lactone and a base as a catalyst are mixed in an inert gas atmosphere such as nitrogen. And the tetrabasic acid dianhydride (a) and the dehydrating agent for removing the water formed in the reaction, if necessary, and then distilling off the water formed by the formation of the quinone ring while heating and stirring. The reaction is sufficiently carried out 'by this to obtain a solution of a phenolic hydroxyl group-containing polyimine resin (A). The dehydrating agent at this time is, for example, toluene, xylene or the like. The reaction temperature is usually preferably from 120 to 23 (TC. The reaction time is affected by the polymerization degree of the final polyimine and the reaction temperature. Usually, it is set according to the desired degree of polymerization of the polyene 17 201030057. Under the conditions (for example, the ratio of the use of the tetrabasic acid dianhydride (a) to the diamine component, the reaction temperature, etc.), when the viscosity increases as the reaction progresses, the reaction proceeds continuously until the maximum molecular weight is obtained. In a few minutes to about 20 hours, the obtained solution can be separated into a poor solvent such as decyl alcohol or hexane to separate the resulting polymer, and then purified by a precipitation method to remove by-products, thereby obtaining a high-purity phenol. The polyhydroxyimine resin (A) having a hydroxyl group. The number average molecular weight of the phenolic hydroxyl group-containing polyimine resin (A) of the present invention obtained in the above manner is preferably from about 5,000 to 50,000, more preferably from 8,000 to 30,000. The weight average molecular weight is preferably about 30,000 to 300,000, more preferably about 50,000 to 200,000, and the hydroxyl equivalent of the solid component is from 200 to 5,000 g/eq., preferably from 300 to 4,000 g/eq., more preferably 40. 0 to 2000 g/eq., more preferably 400 to 1000 g/eq·' is preferably 450 to 650 g/eq. Further, the number average molecular weight and the weight average molecular weight are converted by polyethylene obtained by colloidal filtration chromatography. The following is a description of the positive photosensitive polyimide resin composition of the present invention. The positive photosensitive polyimide resin composition of the present invention is a phenolic hydroxyl group containing the present invention. A composition of a polyimine resin (A) and a diazo-based positive photosensitive agent (B). A phenolic hydroxyl group-containing polyimine resin in a positive photosensitive polyimide resin composition of the present invention ( The content ratio of A) is usually 20 to 95% by weight, preferably 40 to 95% by weight, more preferably 50 to 95% by weight, based on 100% by weight of the solid content of the resin composition. More preferably, it is 60 to 90% by weight. 18 201030057 The diazo-based positive sensitizer used in the positive photosensitive polyimide resin composition of the present invention is a diazonium sulfonic acid compound (diazobenzene) The vinegar of the continuation of the compound) has an azo (dizid) group and is via light. The sensitizing agent which can be used for positive development can be used, and is not particularly limited, and examples thereof include Sb which is a sulfonic acid-substituted azo compound and a hydroxy compound, preferably a diazo sulfonic acid compound and a thiol compound. An ester of a compound (preferably a phenol compound), which may be diazonium sulfonate or diazonaphthoquinone sulfonate®, preferably diazonium. The ester of the acid acid can be exemplified by hydrazine, 2 azo alkaloids, 1,2-naphthoquinone-2-diazido-5-sulfonate, 1,2-naphthoquinone _ 2_Azo-4-sulfonate, 1,2-naphthoquinone-2-azo-5-sulfonate-o-cresol and hydrazine, 2_naphthoquinone-2_azo-5-sulfonate - p-phenolic esters and the like. The esterifying component (hydroxy compound) used as the above ester is preferably a phenol compound, and examples thereof include 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, and 2,3. ,4,4,-tetrahydroxybenzophenone, 2,2',3,4,4,pentahydroxydibenzophenone, phenol, l53_dihydroxybenzene, 1 3 φ trihydroxybenzene, bisphenol A , bisphenol F, bisphenol S, phenolic resin, methyl gallate, ethyl gallate and phenyl gallate. The amount of the diazo-based positive sensitizer (B) to be added is usually 5 to 30% by weight, preferably 1 to 2% by weight, based on the phenolic hydroxyl group-containing polyienimine resin (A). The positive photosensitive resin composition of the present invention may contain an epoxy resin (C) as an optional component. The epoxy resin (C) is added for the purpose of reacting with a phenolic hydroxyl group and a terminal acid or a terminal amine group in the phenolic hydroxyl group-containing polyimine resin (A) after alkaline development. That is, after the patterning, the epoxy resin (c), 19 201030057 is reacted with the above reactive substituent in the polyphenolimine resin of the phenolic hydroxyl group, and thus the crosslinking of the polyimine resin of the present invention The bonding density is increased, the resistance to the polar solvent is improved, and the adhesion to the substrate and the heat resistance are improved. The reaction temperature at this time is preferably 150 to 250 °C. The epoxy resin (C) is not particularly limited as long as it has two or more epoxy groups per molecule, but is preferably a cyclopentene, a biphenyl ring or a naphthalene from the viewpoints of mechanical strength, flame retardancy and the like. An epoxy resin having such an aromatic ring. Specific examples thereof include a phenolic epoxy resin, an epoxy resin containing xylylene ◎ skeleton, an epoxy resin containing a biphenyl skeleton, a bisphenol A epoxy resin, and a bisphenol F epoxy resin. Resin, triphenylmethane type epoxy resin and glyoxal type epoxy resin are preferably biphenyl-containing from the viewpoint of compatibility with a phenolic hydroxyl group-containing polyimine resin (A). Skeleton epoxy resin. The amount of the epoxy resin (C) added is relative to the total of the desired hydroxyl group of the phenolic hydroxyl group-containing polyimine resin (A) and the terminal acid anhydride group or terminal amine group, and the epoxy resin in the epoxy resin (C) The amount of the base is preferably in the range of 5 equivalents. Further, the amount of the phenolic hydroxyl group and the acid anhydride group or the amine group in the polyamidene resin (A) having a desired basis can be used for synthesizing the phenolic hydroxyl group-containing polyimine resin (A). The number of moles of the tetrabasic acid dianhydride (a), the aminophenol compound (b) and the diamine compound (c), the number of anhydride structures in one molecule, the number of amine groups, and the number of phenolic hydroxyl groups are calculated. . The weight ratio of the phenolic transmissive polyimine resin (A) to the epoxy resin (C) in the positive photosensitive polyimide resin composition of the present invention is dependent on the activity of the compound used The hydrogen equivalent and the epoxy equivalent vary, so it cannot be generalized. In general, the epoxy resin (c) is 100 parts by weight (solid content) relative to the phenolic hydroxyl group-containing polyphthalocyanine 20 201030057 amine resin (A). I5 to 2 parts by weight, preferably 20 to 100 parts by weight, more preferably 25 to 8 parts by weight, still more preferably 30 to 70 parts by weight. In the positive photosensitive polyimide resin composition of the present invention, a thermosetting catalyst may be added as needed to promote the thermosetting reaction of the phenolic hydroxyl group-containing polyimine resin (A) and the epoxy resin (C). Examples of the thermosetting catalyst include: 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Imidazoles such as phenyl_4-methyl-5-hydroxymethylimidazole, 2-(dimethylaminomethyl)benzene, 1,8-diaza-bicyclo(5,4,0) A metal compound such as a tertiary amine such as monoene-7 or a phosphine such as triphenylphosphine or tin octylate is preferable. The addition amount of the thermosetting catalyst 罝 is 0 to 10% by weight with respect to the epoxy resin (C). It is preferably (M to 7 wt%, more preferably 2 to 5 wt%). The positive photosensitive t-imine resin composition preferably contains a solvent which dissolves the polyimine (polyimine dissolved in an inert solvent) from the viewpoint of convenience in use. The solvent is exemplified as a synthesis. Preferably, the solvent used in the solvent is a polyimine-soluble solvent, more preferably a cyclic ketone having 4 to 5 member rings such as γ-butyrolactone. When the polyimide resin composition is a solvent-containing resin In the case of the solution, the content of the solid component relative to the entire resin solution is from 1 to 65 wt%, preferably from 20 to 50% by weight, more preferably from 25 to 50% by weight. The resin solution can be used to form the present invention. A film or layer composed of a positive photosensitive polyimide resin composition. For the formation of the film or the layer, the resin solution can be applied to a flat smooth substrate, and the coating film is usually used. It is formed by drying at a temperature of ll 〇 ° C, preferably 60 to 100 ° C. 21 201030057 The positive photosensitive polyimide resin composition of the present invention may also be added with a filler such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, oxidized indium, cerium oxide or clay, if necessary. A shaker such as Aerosil, a coloring agent such as Phthal〇Cyanine, phthalocyanine green, or titanium oxide, a polyfluorene oxide, a fluorine-based leveling agent, an antifoaming agent, etc. These systems are used in the present invention. The amount of 〇~5〇% by weight of the photosensitive polyimide composition (solid content). The positive photosensitive polyimide resin composition of this month may also be supported by a support film and a protective film. The dry film resist type formed by sandwiching the structure is used. The positive photosensitive polyimide resin composition (liquid or film) of the present invention is useful. It is used as an interlayer insulating material for electronic components, an optical waveguide for connecting optical components, a solder resist for printed circuit boards, a photoresist material such as a cover film, and the like as a filter or printing ink. , alignment film, sealant, coating , a coating agent, an adhesive, etc. The cured product of the positive-type photosensitive polyimide resin composition of the present month is used for electrical purposes such as a photoresist film or an interlayer insulating material for a build-up process. The specific use of the electronic component is, for example, a computer or a home appliance, a portable device, etc. The film thickness of the cured layer is 6 〇 "about the claw, preferably about 5 to 100 " m. The substrate of the cured product of the positive photosensitive polyimide resin composition can be obtained, for example, in the following manner. That is, when a liquid resin composition is used, a screen printing method or a spray roll can be used. By a coating method, an electrostatic coating method, a curtain coating method, or the like, the composition of the present invention is applied to a substrate by a film thickness of (9) after drying, and the coating film is usually 50 to 140 ° C. Preferably, it is 60 to 12 (Γ (: κ temperature is dried, thereby forming a coating film and then passing through a photomask formed with an exposure pattern, directly or indirectly with an intensity of usually 10 to 20 μm/cm 2 The coating film is irradiated with an active energy ray and then developed using the latter. The liquid is developed by, for example, spraying, shaking, brushing, scrubbing, or the like. Thereafter, ultraviolet rays are irradiated as needed, and heat treatment is performed at a temperature of usually 100 to 25 (rc, preferably 14 Å to 22 Å), thereby obtaining excellent flame retardancy and satisfying heat resistance. The substrate of the cured film of the polyi-imine resin composition having various properties such as solvent resistance, acid resistance, adhesion, and flexibility. Examples of the active energy ray include ultraviolet rays, visible rays, infrared rays, electron beams, radiation, and the like. It is especially preferable to use ultraviolet rays or electron wires for the purpose of use. The aqueous alkali solution used for the above development may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium cesium carbonate, potassium hydrogencarbonate, sodium phosphate or phosphorus. An aqueous solution of an inorganic alkali such as potassium acid or an organic alkali solution such as tetramethylammonium hydride, tetraethylammonium hydride, tetrabutylammonium hydride, monoethanolamine, diethanolamine or triethanolamine. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples. Example 1 After a nitrogen gas was passed through a 500 mL flask equipped with a stirring device, a reflux tube, a moisture trap, and a thermometer, it was filled therein. Solvents _butyrolactone 23 201030057 132.78g, as a catalyst for the lactone i.i9g and pyridine i.88g, as a tetrabasic dianhydride (4) BPDA-H (氲化3,3,,4,4 ,-biphenyltetracarboxylic dianhydride, manufactured by Iwatani Gas Co., Ltd., molecular weight 3〇6 31) 36 41 g, ABPS (3,3,-diamino-4,4, as the aminophenol compound (b) -Dihydroxydiphenyl hydrazine, manufactured by Nippon Kayaku Co., Ltd., molecular weight 28〇3〇) 16 58g, APB-N (1,3-bis-(3-aminophenoxy) as diamine compound (c) Benzene, manufactured by Mitsui Chemicals Co., Ltd., molecular weight: 292.34) 18.50 g, 28-66 g of toluene as a dehydrating agent, and stirred while removing water generated in the reaction at 180 ° C for 8 hours to obtain phenolic properties. a hydroxyl group-containing polyimine resin (33.6 wt% of a resin solution (this solution is designated as A_i). The obtained polyiminoimine resin has a hydroxyl equivalent (solid content) of 568 18 g/eq•, and the number average molecular weight in terms of styrene It is 22,100 and has a weight average molecular weight of 1〇9 〇〇〇. Example 2 附 with stirring device, return pipe, moisture trap and temperature After passing nitrogen gas through a 5 mL flask, 1 33.99 g of butyrolactone as a solvent, 71 g of r-valerolactone i as a catalyst, and 69 g of pyridine were used as tetradecanoic acid dianhydride (a). The pMDA_Hs (manufactured by hydrogenated pyromellitic dianhydride lava gas granules, molecular weight 224.17) 38.18 g, which is an aminophenol compound 卬) (ι, 3 hexafluoride) represented by the following formula (3) (3_Amino_4_Phenylphenyl)-propanone oxime Chemical Co., Ltd. Limited: system, molecular weight 366.26) 21.28g, as the diamine compound (4) 仏diaminobenzene (molecular weight H) 8.14) 12.69 g, as a dehydrating agent, a stupid 28 9^ and then - with 180. . "When the water formed in the reaction is removed, the mixture is stirred to obtain a 23 201030057 resin solution containing 33% by weight of the phenolic hydroxyl group-containing polyimine resin (this solution is obtained as A-2^). The hydroxyl equivalent (solid content) of the imine resin was 568.18 g/eq. The number average molecular weight in terms of stupid ethylene was 23,600 'the weight average molecular weight was 115, 〇〇〇.

(3) Example 3 After passing nitrogen gas through a 50 OmL flask equipped with a stirring device, a reflux tube, a moisture trap, and a thermometer, 132.40 g of 7-butyrolactone as a solvent was charged therein as a catalyst. Valerolactone i.〇3g and pyridine i.62g, DSDA as a tetrabasic acid dianhydride (a) (3,3,,4,4'-diphenylfluorene 1 tetra-retensive dianhydride, New Japan Physical and Chemical Co., Ltd. Company, molecular weight 358.28) 34.90g, BPDA-H (hydrogenated 3,3',4,4'-biphenyltetracarboxylic dianhydride rock valley gas company, molecular weight 306.3 1) 1.5 8g, as an aminophenol compound (b) ABFL (9,9'-bis(3-amino-4-hydroxyphenyl)anthracene, manufactured by Nippon Kayaku Co., Ltd., molecular weight 380.44) 24.73 g, as the diamine compound (c) 4,0-diaminodiphenyl hydrazine (molecular weight: 248.30), 10.09 g, toluene (28.57 g) as a dehydrating agent, and further stirred while removing water formed in the reaction at 180 ° C for 8 hours to obtain a phenolic property. Hydroxyl polyimide resin 33.8 wt% resin solution (this solution was designated as A-3). The resulting polyiminoimine tree 25 201030057 has a hydroxyl equivalent weight (solid content) of 520. 〇g/eq., a number average molecular weight of 19,800 in terms of styrene, and a weight average molecular weight of 97,2 〇 (^ Example 4 After a nitrogen gas was passed through a 500 mL flask equipped with a stirring device, a reflux tube, a water trap, and a thermometer, 132.85 g of the lactone was used as a solvent, and the catalyst was used as a catalyst. u bite i.93g, as quaternary acid dianhydride (a) BTDA (3,3 ',4,4,_dibenzophenone tetrahydro acid dianhydride, manufactured by Daicel Chemical Industry Co., Ltd., molecular weight 322 322.23 37.28g, PMDA-HS (manufactured by pyromellitic acid dihepatic acid, Iwatani Gass Co., Ltd., molecular weight 224.17) 1.3 7g, BAA as an aminophenol compound (b) (2,2-bis(3-amine) 4--4-phenylphenyl)propane, manufactured by Nippon Kayaku Co., Ltd., molecular weight 258.32) 16.68 g, TMDA (1-(4-aminophenyl)-l, as the diamine compound (c), 3,3-Trimethyl_ιΗ-茚_5_amine, manufactured by Nippon Pure Pharmaceutical Co., Ltd., molecular weight 266.38) 16 21g, toluene 28.68g as a dehydrating agent, and 18 (TC) The water formed in the reaction was removed while stirring for 8 hours to obtain a resin solution containing 33.6 wt% of a polyamidimine resin having a phenolic hydroxyl group (this solution was designated as A_4). The obtained polyimine resin The hydroxyl equivalent (solid content) was 52 〇g/eq, the number average molecular weight in terms of styrene was 26,200, and the weight average molecular weight was 122 Å. Example 5 was equipped with a stirring device, a reflux tube, and moisture trapping. After passing nitrogen gas through a 5 〇〇 mL flask of a thermometer and a thermometer, 133.21 g of butyrolactone as a solvent, i.37 g of valerol as a catalyst, and pyridine 2 oxime were added as a tetrabasic acid dianhydride ( a) BPDA-H (hydrogenation 3,3,,4,4, _ phenyl stearic acid hexahydrate 26 26 201030057 needle, manufactured by Iwatani Gas Co., Ltd., molecular weight 306 31) 41 96 g, as an aminophenol compound (b) ABPS (3,3,-diamino-4,4,-dihydroxydiphenyl, manufactured by Sakamoto Chemical Co., Ltd., molecular weight 280.30) 2.40 g, as a diamine compound (Hook 3 4, _ 〇Da (3,4,-diaminodiphenyl mystery, manufactured by JFE Chemical Co., Ltd., molecular weight 200.24) 2 7.3 6g, as The toluene was 28.76 g of toluene, and the mixture was stirred while removing water formed in the reaction at 180 ° C for 8 hours to obtain a resin solution containing 33.4% by weight of a polyaniline resin having a phenolic hydroxyl group. For a_5). The obtained polyiminoimine resin had a hydroxyl equivalent (solid content) of 39 〇〇g/eq, a number average molecular weight of 9,400 in terms of styrene, and a weight average molecular weight of 61,000. Comparative Example 1 After passing nitrogen gas through a 500 mL flask equipped with a stirring device, a reflux tube, a moisture trap, and a thermometer, '13.76 g of 7-butylic vinegar as a solvent was added thereto, and a lactone as a catalyst was added. I8g and η ratio i.87g, ODPA (3,3,4,4,-diphenyl ether tetra-hypo-dianhydride, manufactured by Manac, molecular weight 310_22) as 0-tetrabasic acid dianhydride (4) 36.64g ABPS (3,3'-diamino-4,4,-dihydroxydiphenyl sulfone, manufactured by Sakamoto Chemical Co., Ltd., molecular weight 280.30) as an aminophenyl compound (b), 16.59 g, as two APB-N (1,3-bis-(3-aminophenoxy)benzene, manufactured by Mitsui Chemicals, Inc., molecular weight: 292.34) of the amine compound (c), 18.27 g, and 28.66 g of toluene as a dehydrating agent. Further, while stirring the water formed in the reaction at 180 ° C for 8 hours, stirring was carried out to obtain a resin solution containing 33.6% by weight of a polyimine resin having a phenolic hydroxyl group (this solution was designated as R-1). The base equivalent (solid content) of the obtained polyimine resin 27 201030057 was 568.1 8 g/eq., and the average molecular weight in terms of styrene was 20,200, and the weight average molecular weight was 101,500. Examples 6 to 10 Resin solutions (Α-1), (Α-2), (Α-3) obtained in Examples 1, 2, 3, 4 and 5 as a phenolic hydroxyl group-containing polyimine resin. ), (Α-4)&(Α-5), DTEP-350 (2,3,4,4'-tetrahydroxybenzophenone 1,2-naphthalene) as a diazo-based positive sensitizer _2_Oto-5-acid acid S, daitochemix Co., Ltd.), NC-3000 as an epoxy resin (epoxy tree resin containing biphenyl skeleton, manufactured by Sakamoto Chemical Co., Ltd., The oxy equivalent weight is 28 〇g/eq., the softening point is 60 ° C), and the 2-phenyl-4,5-dihydroxymethyl p-m which is a hardening accelerator. The sitting (2PHZ) was mixed in the proportion shown in Table 1 (the unit is "parts by weight"; unless otherwise specified, parts by weight) to obtain a positive photosensitive polyimide resin composition of the present invention. Comparative Example 2 A resin solution (R-1) obtained in Comparative Example 1 as a comparative polyimide resin, DTEP-350 as a diazo-based positive sensitizer, and NC-3 as an epoxy resin. 〇〇 and 2PHZ as a hardening accelerator were mixed at a mixing ratio shown in Table 1 to obtain a positive photosensitive polyimide resin composition for comparison. 28 201030057 Table 1 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 2 A-1 10.00 A-2 10.00 A-3 10.00 A-4 10.00 A-5 10.00 R-1 10.00 Λ CA DTEP -350 0.50 0.50 0.50 0.50 0.50 NC-3000 1.32 1.32 1.32 1.32 1 *50 2PHZ 0.02 0.02 0.02 0.02 1 0.02 (I) Formation, development and hardening of a dried resin film on a printed circuit board and evaluation thereof Ο Using screen printing method The positive-type photosensitive polyimide resin composition was applied to a printing substrate so as to have a film thickness of 20 at the time of drying, and the coating film was dried in a hot air dryer of 100 C for 3 minutes to obtain a film thickness of 20 on the substrate. Dry resin film. The following evaluation test was carried out using this dried resin film. ❹ (1) tackiness The viscosity of the obtained dried resin film was evaluated by the method described later, and the evaluation results were not shown in Table 2. (2) Developability and resolution Next, a dry resin film in which a mask having an L/S=25 β m/25 /zm pattern is adhered to the substrate obtained above is used, and an ultraviolet exposure apparatus (ORC Manufacturing Co., Ltd.) is used. Co., Ltd., model hmw-680GW) irradiates ultraviolet light with an integrated light quantity of 1000mJ/cm2. After the irradiation, the mixture was subjected to pressure development with a 3% by weight aqueous sodium hydroxide solution for 120 seconds and 2. 〇kg/cm2, and then washed with water to remove the resin of the ultraviolet irradiation portion at 29 201030057. The developing method and the resolution of the transfer pattern of the obtained resin film after the evaluation were evaluated by the method described later, and the evaluation results are shown in Table 2. w (3) Adhesiveness, film reduction rate, solvent resistance, acid resistance, heat resistance PCT resistance and thermal shock resistance The resin film after development is heated in a hot air dryer of 180 c, and The obtained resin cured film was used, and the above-mentioned respective items were evaluated by the method described later, and the evaluation results are shown in Table 2. (II) Evaluation of warpage and bendability of the substrate on the polyimide film substrate In the above (1), in addition to changing the printed substrate to a polyimide film having a thickness of 25 " m, the same method as in the above (1) was used for the polymerization. A resin cured film was formed on the quinone imine film, and warpage (substrate warpage) and bendability of the obtained film were evaluated by the method described later, and the evaluation results are shown in Table 2. (III) Evaluation of flame retardancy of the resin cured film In the above (I), except that the printed substrate was changed to a PET film, a resin cured film was formed in the same manner as in the above (I), and only the substrate was formed from the film. Strip the resin cured film. The flame retardancy of the obtained resin cured film was evaluated by the method described later, and the evaluation results are shown in Table 2. The test methods and evaluation methods of the above (I) to (III) are as follows. (i) Adhesiveness The dried resin film applied to the printed circuit board was wiped with absorbent cotton, and the tackiness was evaluated by the following criteria. 〇...The absorbent cotton cannot be adhered to X. The cotton wool of the absorbent cotton is adhered to the film. 30 201030057 (ii) Developability The appearance of the resin film in development was visually observed, and the time until the resin composition of the exposed portion was completely removed was evaluated. (iii) Resolution The appearance of the transfer pattern of the resin film after development and water washing was observed under a microscope, and the resolution was evaluated by the following criteria. 〇...The unexposed part is not peeled off, and the linear pattern edge is reproduced ❾X...The unexposed part is peeled off, or the edge of the pattern is wavy (iv) Adhesiveness is made according to JIS K5400' Resin cured film on the substrate. After one checkerboard was placed, a peeling test using a cellophane tape was performed, and the adhesion was evaluated by the following criteria. Oh... no peeling. △... Although there is no peeling, the edge of the checkerboard is jagged. X.·· 1/100 or more peeling. 〇 (V) Coating film reduction rate The decrease rate of the thickness of the cured resin film after development and heating at 180 ° C for 60 minutes with respect to the thickness of the dried resin film on the printed substrate was evaluated. (vi) Solvent resistance The resin cured film on the printed substrate was immersed in N_fluorene at room temperature. More than 30 minutes of ketone. After the film was taken out and the appearance was confirmed to be abnormal, the peeling test by the cellophane tape was carried out, and the solvent resistance was evaluated by the following criteria. 〇...The surface is free of abnormalities and there is no swelling or peeling. △...The surface is rough, but there is no swelling or peeling. 31 201030057 X----With expansion or peeling. (vii) Acid resistance The resin cured film on the printed substrate was immersed in a 3.5% aqueous hydrochloric acid solution at room temperature for 30 minutes. After the film was taken out and the appearance was confirmed to be abnormal, the peeling test by the cellophane tape was performed, and the acid resistance was evaluated by the following criteria. 〇...The surface is free of abnormalities and there is no swelling or peeling. △...The surface is rough, but there is no swelling or peeling. X··.. has swelling or peeling. (viii) Heat resistance The resin cured film on the printed substrate was coated with a rosin-based flux & (The solder bath was subjected to a 10 second phantom dipping. After cooling to room temperature, the peeling test by the cellophane tape was performed, and the heat resistance was evaluated by the following criteria. 〇 The surface was free from abnormalities and there was no swelling or peeling. △...The surface is rough, but there is no expansion or peeling. X—Expansion or peeling. (ix) PCT resistance The resin cured film on the printed substrate is immersed in 丨2丨C, 2 atmospheres for 96 hours. After the removal was confirmed to have an abnormality in appearance, a peeling test using a paper-breaking tape was performed, and the resistance was evaluated by the following criteria. (PCT: Pressure Cooker Test) 〇·.. The surface was free from abnormalities and did not swell or peel. ································································································ The surface appearance was observed with a microscope, and the thermal shock resistance was evaluated on the basis of the following criteria: 〇...The surface was not cracked. X.·,. The surface was cracked. (xi) The substrate was warped to visually observe the resin cured film. Polyimine film The appearance was evaluated on the basis of the following criteria: ϋ ¥ 〇... No warpage was observed on the film. △... The film was slightly inferior to the film. X····The film was warped. Xii) Flexibility The bending property of the polyimide film having the cured resin film was observed, and the appearance was visually observed and the flexibility was evaluated by the following criteria. 〇.. No crack was observed in the cured film of the resin. The resin cured film is cracked. p (xiii) Flame retardancy The resin cured film peeled off from the PET film is cut into a short square of 丨 cin width, and then the movement near the burner is observed, and the flame retardancy is evaluated on the basis of the following criteria. 〇...Unburned, or quenched as soon as it leaves the burner. X··. Burns even if it leaves the burner for a period of time. 33 201030057 Table 2 Example 6 Example 7 Example 8 Example 9 Implementation Example 10 Comparative Example 2 Viscosity 〇0 〇〇〇〇 developability 1.2 minutes 1.1 minutes 1.5 minutes 1.5 minutes 1.8 minutes 2 minutes still unable to develop resolution 〇〇〇〇〇X adhesion 〇〇〇〇〇△ Coating film Reduction rate 9.2% 8.5% 10.5% 12.5% 12.5% 35.0% Resistant to dissolution Properties 〇〇〇〇Δ △ Acid resistance 〇〇〇〇0 〇 Thermal 〇〇〇〇0 Δ PCT resistance 热 Thermal shock 〇〇〇〇〇〇 substrate warpage 〇〇 Λ 〇 〇 Δ 弩 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 The patterning of the resin composition is easy to be excellent in adhesion to a substrate, flame retardancy, and heat resistance, and has sufficient flexibility. (Industrial use) The positive photosensitive property of the polyimine resin containing the phenolic hydroxyl group of the present invention. The polyimide polyimide resin composition is excellent in storage stability, developability, and resolution, and can reduce film during development. The wear and tear are excellent in adhesion, solvent resistance, acid resistance, heat resistance, and flame retardancy, and have sufficient flexibility. Therefore, the resin composition of the present invention and the cured product thereof are widely used in a solder mask for a thin package substrate, a cover film for a flexible printed wiring board, an interlayer insulating film for a multilayer printed wiring board, and a semiconductor protective film. . While the invention has been described in detail with reference to the specific embodiments of the present invention, it will be understood that various modifications and changes can be made without departing from the spirit and scope of the invention. Further, the present application is based on a patent application filed on Oct. 14, 2008 (Japanese Patent Application No. Hei. Further, all of the reference portions cited herein are used in their entirety. [Simple description of the diagram] None [Key component symbol description] None ❹

35

Claims (1)

201030057 VII. Patent application scope: 1. A phenolic hydroxyl group-containing polyimine resin (A) which is composed of tetrabasic acid dianhydride (a), having at least two amine groups in one molecule and at least one phenolic property. The hydroxy-based compound (b) and the mono-amino compound (c) are obtained by a co-condensation reaction, and 5 mol% or more of the tetrabasic acid dianhydride (a) is selected from the group consisting of the following formula (1) One or more alicyclic tetrabasic acid dianhydrides in the group: 2. For example, the phenolic hydroxyl group-containing polyamidiamine resin (A) in the scope of the patent application, wherein the tetrabasic acid dianhydride (a) contains a tetrabasic acid other than the compound represented by the formula An anhydride, and the tetrabasic acid dianhydride is selected from the group consisting of 3,3,,4,4,_ benzene sulfonate dianhydride, 3,3', 4,4, benzophenone tetracarboxylic dianhydride One or more of the group consisting of 3,3', 4, 4, _biphenyltetracarboxylic dianhydride and 3,3,4,4, diphenyl ether tetracarboxylic acid. 3. In the case of the sulphur-containing group of the first aspect of the patent application, the polyaminoimine tree (A), wherein the aminophenol compound (b) is selected from the group consisting of 3,3,-diamino- 4,4,-dihydroxydimethane, 3,3'-diamino-4,4,dihydroxydiphenyl ether, 3,3, 36 201030057 -diamino-4,4,_dihydroxy Biphenyl, 3,3,-diamino-4,4,-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2_bis (3) _Amino-4_hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4 One or more of the group consisting of -hydroxyphenyl)propane and 9,9,-bis(3amino-4-hydroxyphenyl)fluorene. 4. The phenolic hydroxyl group-containing polyimine resin (A) as claimed in claim 1 wherein the diamine compound (c) is selected from the group consisting of 3,4' diaminodiphenyl ether, 4 , 4 _-aminodiphenyl ether, 3,3, diaminodiphenyl, 4,4,-diaminodiphenyl hydrazine, 4,4, diadiaminodiphenylmethane, U4_ Diaminobenzene, 1,3-diaminobenzene, 1,3_bis-(3-aminophenoxy)benzene, 丨_(4aminophenyl)-1,3,3-trimethyl More than j of the group consisting of -1H-indole-5-amine and polyoxydiamine. 5. The phenolic hydroxyl group-containing polyimide resin (A) according to any one of claims 4 to 4, which has a hydroxyl equivalent of 2 〇〇 5 , 〇〇〇 g / eq. 6. A positive-type photosensitive polyimide resin composition, which comprises a polyaniline resin (A) and a diazo which are intended to be used in any of the first to fifth items of the range 1-5. A positive sensitizer (B) and an epoxy resin (4) as an optional component. 7. A substrate which is a layer of a positive photosensitive polyimide composition having a towel of the sixth aspect of the patent. Eight, schema: None 37