JP2011116848A - Novel polyimide precursor composition and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide precursor solution which can be hardened at low temperature (≤200°C) and is excellent in long-term storage stability, to provide a photosensitive resin composition which is obtained from the solution and can preferably be used as an insulating material for electric/electronic use, to provide a photosensitive resin film, to provide a thermosetting resin composition, to provide a polyimide insulating film, and to provide a printed circuit board with an insulating film. <P>SOLUTION: The polyimide precursor composition solution includes a polyimide precursor having a partially-imidized urethane bond containing at least elemental phosphorus. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is curable at low temperature, has excellent long-term storage stability, is excellent in flame retardancy, can suppress bleed out of flame retardant components, and is suitable as an insulating material for electrical and electronic applications. The polyimide precursor and thermosetting resin composition that can be used, and can be cured at low temperature, have excellent long-term storage stability, and also have excellent flame retardancy, and can suppress bleed-out of flame retardant components. A photosensitive resin composition that can be developed with an alkaline aqueous solution, which can be suitably used as an insulating material for electrical and electronic applications, a resin film obtained therefrom, a cured film, an insulating film, and a printed wiring board with an insulating film It is about.

  Polyimide resins are used for electrical and electronic applications because of their excellent heat resistance, electrical insulation and chemical resistance, and excellent mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, surface protective materials such as flexible circuit boards and integrated circuits, base resin, and fine circuit interlayer insulating films and protective films. . In particular, when used as a coating material, a protective material obtained by bonding a molded body such as a polyimide film with an adhesive or a liquid polyimide resin solution has been used.

  There are roughly two types of polyimide resin solutions. One type is a polyamic acid solution which is a polyimide resin precursor, and the other type is a polyimide resin solution soluble in an organic solvent. However, since these polyamic acid solutions and polyimide solutions are high molecular weight polymer solutions, the molecular weight is large and the solubility in the solvent is low, so the concentration of the solute cannot be adjusted to a high concentration. For example, when forming a coating film, it is necessary to volatilize a large amount of solvent, which is a problem of poor productivity. Also, in the case of a polyamic acid solution, which is a polyimide resin precursor solution, the amide bond in the structure is likely to be decomposed, so the stability of the solution is poor, especially when the solution is prepared at a high concentration. There is a problem that the amount of change is large, and a polyimide resin precursor solution having high solution storage stability is required. In addition, it is necessary to imidize when it is formed into a coating film, and it is necessary to imidize at a temperature that exceeds 300 ° C. For example, it is used as a protective agent for flexible substrates, adhesives for molded articles, etc. In such a case, there is a problem that the wiring material cannot withstand high temperatures, and a resin that can be cured at a low temperature (200 ° C. or less) that does not cause deterioration of the wiring is required.

  Regarding the technology of these polyimide resin solutions, a copolymer consisting of a polyimide precursor (polyamic acid) having a specific structure and a polyimide with good solution storage stability, that is, a poly (amic acid-imide) copolymer has been proposed. (See Patent Document 1).

  In addition, a polyamic acid having a specific structure that can be cured at a low temperature of 200 ° C. or lower has been proposed (see Patent Document 2).

  In addition, a polyamideimide having a specific functional group containing a phosphorus element and an organosiloxane structure, which has good flame retardancy, has been proposed (see Patent Document 3).

  Also proposed is a photosensitive resin composition containing a photopolymerizable unsaturated compound including a urethane compound having an ethylenically unsaturated bond, which is excellent in flexibility, photocurability, insulation and flame retardancy and can be alkali-developed. (For example, refer to Patent Document 4).

JP 2005-336243 A JP 2008-308553 A JP 2005-264054 A JP 2000-241969 A

  In the said patent document, the various method which solves the subject of a polyimide resin solution is proposed. However, a copolymer composed of a polyimide precursor (polyamic acid) having a specific structure and a polyimide described in Patent Document 1, that is, a poly (amide acid-imide) copolymer is an imide in a part of the polyamide acid structure. Although it has excellent solution storage stability by introducing a structured structure, it is difficult to control the molecular weight and to reduce the concentration and viscosity of the resulting solution, and it is also difficult to cure at a low temperature of 200 ° C. or lower. There is. Since the polyamic acid having a specific structure described in Patent Document 2 has an aliphatic long-chain flexible skeleton in the molecule, the polymer has a low glass transition temperature and can be cured at a low temperature of 200 ° C. or lower. There is a problem that the solution storage stability is poor and the amount of change in the solution viscosity is large. The polyamideimide having a specific functional group containing a phosphorus element and an organosiloxane structure described in Patent Document 3 has a siloxane skeleton in the molecule, and impurities contained in the siloxane diamine as a raw material are removed from the cured film. There is a problem of bleeding out and inducing semiconductor malfunction. At the same time, when a cured film formed from a resin composition containing a siloxane skeleton is used as a circuit board material, there is a problem that the wettability of the surface of the cured film is poor and the adhesion to various sealants is poor.

  When the cured film formed from the photosensitive resin composition described in Patent Document 4 is used as a surface protective film for a flexible circuit board, it is formed from a photosensitive resin composition containing a polyimide resin or a polyimide precursor. Compared to the case of using a cured film, the electrical insulation reliability and heat resistance under high temperature and high humidity are poor. In addition, a condensed phosphate ester-based additive flame retardant is added for the purpose of imparting flame retardancy, and the hydrolysis of this flame retardant causes a significant decrease in electrical insulation reliability. There were problems such as bleeding out of the condensed phosphate ester type flame retardant and elution into an organic solvent or a gold plating bath.

  As a result of intensive studies to solve the above problems, the present inventors have at least a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, which can be cured at a low temperature. It has been found that a cured polyimide film having good physical properties can be obtained from the precursor. That is, a polyimide precursor solution containing a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond has a solution storage stability at room temperature when prepared in solution. Although it was good and the solute was dissolved at a high concentration, it showed low viscosity, and from this solution, we obtained knowledge that a cured polyimide film with good physical properties was obtained. Based on the above, the present invention has been achieved. The present invention can solve the above problems with a polyimide precursor having the following novel structure.

  That is, the present invention relates to a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond.

  The polyimide precursor preferably further has a phosphorus element content in the molecular structure of 0.1 to 5.0% by weight.

  Moreover, in the polyimide precursor concerning this invention, it is preferable that the said polyimide precursor contains a polycarbonate frame | skeleton further.

  In addition, the polyimide precursor according to the present invention comprises at least (a) a diol compound represented by the following general formula (1) and (b) a diisocyanate compound represented by the following general formula (2). A terminal isocyanate compound is synthesized by reaction, and then (c) a tetracarboxylic dianhydride represented by the following general formula (3) is reacted to synthesize a terminal acid anhydride urethane imide oligomer. It is preferable to obtain the diamine represented by the formula (4) by addition reaction.

(In the formula, R represents a divalent organic group.)

(In the formula, X represents a divalent organic group.)

(In the formula, Y represents a tetravalent organic group.)

(In the formula, Z represents a divalent organic group).

  Moreover, in the polyimide precursor concerning this invention, it is preferable that the said (a) diol compound contains the polycarbonate diol shown by following General formula (5) at least.

(In the formula, a plurality of R _{1 's} each independently represents a divalent organic group, and m is an integer of 1 to 20).

  Moreover, in the polyimide precursor concerning this invention, it is preferable that the said (d) diamine contains a phosphorus element at least.

  Moreover, in the polyimide precursor concerning this invention, it is preferable that the said polyimide precursor contains a carboxyl group further in a side chain.

  Moreover, the photosensitive resin composition concerning this invention is partially imidated which has a phosphorus element in (A) molecular structure of any one of Claims 1-7, and has a urethane bond. A polyimide precursor, (B) a photosensitive resin, and (C) a photopolymerization initiator.

  In addition, the photosensitive resin composition according to the present invention includes (A) a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, (B) a photosensitive resin, and ( C) The photopolymerization initiator is (B) photosensitive to (B) 100 parts by weight of the solid content of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond. It is preferable that 10 to 200 parts by weight of the resin and (C) the photopolymerization initiator be blended to be 0.1 to 50 parts by weight.

  Moreover, it is preferable that the photosensitive resin composition concerning this invention contains (D) thermosetting resin further.

  Further, the photosensitive resin composition according to the present invention was partially imidized in that the blending ratio of the (D) thermosetting resin had (A) a phosphorus element in the molecular structure and a urethane bond. It is preferable that 0.5 to 100 parts by weight of the polyimide precursor, (B) the photosensitive resin, and (C) 100 parts by weight of the total photopolymerization initiator are mixed.

  Moreover, it is preferable that the thermosetting resin composition concerning this invention contains the said polyimide precursor and (D) thermosetting resin.

  Further, the thermosetting resin composition according to the present invention is partially imidized in that the blending ratio of the (D) thermosetting resin has (A) a phosphorus element in the molecular structure and a urethane bond. It is preferable to mix | blend so that it may become 0.5-100 weight part with respect to 100 weight part of solid content of the polyimide precursor.

  Moreover, the polyimide precursor composition solution concerning this invention is obtained by melt | dissolving the said polyimide precursor, the said photosensitive resin composition, or the said thermosetting resin composition in the organic solvent.

  Moreover, the resin film concerning this invention is obtained by apply | coating the said polyimide precursor composition solution to a base-material surface, and drying.

  The insulating film according to the present invention is obtained by curing the resin film.

  Moreover, the printed wiring board concerning this invention coat | covers the said insulating film on a printed wiring board.

  When the polyimide precursor of the present invention is dissolved in an organic solvent, the solution has a low viscosity and good solution storage stability at room temperature even though the solute is dissolved at a high concentration. And the polyimide cured film obtained from the polyimide precursor of the present invention is excellent in flame retardancy, can suppress the bleed out of the flame retardant component, and further has adhesiveness of coating film, environmental test stability, chemical resistance It has excellent physical properties, flexibility and wettability of the coating film, and good physical properties. Therefore, the polyimide precursor of the present invention can be used for protective films of various circuit boards and exhibits excellent effects. In addition, the photosensitive resin composition and the thermosetting resin composition using the polyimide precursor of the present invention can be cured at low temperature, and exhibit various excellent properties when applied and molded on a wiring board. To do.

Schematic diagram measuring the amount of warping of the film

  Hereinafter, regarding the present invention, (I) a polyimide precursor, (II) a photosensitive resin composition, (III) a thermosetting resin composition, (IV) a polyimide precursor composition solution, and (V) a polyimide precursor composition. It explains in detail in order of usage.

(I) Polyimide precursor The polyimide precursor of the present invention is a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, and at least a phosphorus element in the molecular structure. The polyimide precursor has a polyamic acid structure and a urethane structure, and the imide ring is partially closed, and the number average molecular weight is 1000 or more in terms of polyethylene glycol. With such a structure, it is possible to increase the concentration of the solution when dissolved in a solvent, and it is difficult to cause a change with time in viscosity (molecular weight change) of the solution when stored at room temperature. It becomes possible. Moreover, it is preferable that the phosphorus element in molecular structure contains 0.1 to 5.0 weight%. The flame retardance of a polyimide precursor is more effectively acquired as content of a phosphorus element is 0.1 weight% or more. Further, when the content of the phosphorus element is 5.0% by weight or less, a sufficient proportion of urethane bonds in the molecular structure can be secured, and excellent flexibility can be obtained.

  More specifically, in the present invention, the partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is represented by the following general formula (6).

(In the formula, R and X each independently represent a divalent organic group, and m represents an integer of 1 or more.)
It has at least one repeating unit having a urethane bond represented by the following general formula (7)

(In the formula, each R ² independently represents a divalent organic group, each Y independently represents a tetravalent organic group, and n represents an integer of 1 or more.)
And an imide bond represented by the following general formula (8)

(In the formula, each Z independently represents a divalent organic group, each Y independently represents a tetravalent organic group, and p represents an integer of 1 or more.)
It is a compound which has a polyamic acid structure shown by these.

  The number average molecular weight of the partially imidized polyimide precursor having a phosphorus element in the molecular structure of the present invention and having a urethane bond is preferably 1,000 or more and 1,000,000 in terms of polyethylene glycol. 000 or less, more preferably 1,000 or more and 100,000 or less, and particularly preferably 1,000 or more and 50,000 or less. By controlling the reaction to a number average molecular weight within the above range, the concentration of the solution when dissolved in a solvent can be increased, and the viscosity of the solution can be kept low, which is preferable.

  In addition, the partially imidized polyimide precursor having a phosphorus element in the molecular structure of the present invention and having a urethane bond has a flexible urethane bond in the structure. It is possible to proceed the reaction at a low temperature of 200 ° C. or lower. Moreover, the cured film formed using this is excellent in the softness | flexibility and the wettability of the cured film surface, and adhesiveness with various sealing agents is favorable.

  The partially imidized polyimide precursor having a phosphorus element in the molecular structure of the present invention and having a urethane bond preferably contains a polycarbonate skeleton in the structure. By adopting such a structure, it becomes possible to further improve the heat resistance, flexibility, water resistance, chemical resistance, and electrical insulation reliability under high temperature and high humidity of the obtained cured film.

  The partially imidized polyimide precursor having a phosphorus element in the molecular structure used in the present invention and having a urethane bond is not particularly limited as long as it has the above structure. More preferably, at least (a) the following general formula (1)

(In the formula, R represents a divalent organic group.)
(B) the following general formula (2)

(In the formula, X represents a divalent organic group.)
The terminal isocyanate compound is synthesized by reacting with the diisocyanate compound represented by formula (3), and then (c) the following general formula (3)

(In the formula, Y represents a tetravalent organic group.)
The terminal acid anhydride urethane imide oligomer is synthesized by reacting the tetracarboxylic dianhydride represented by the following general formula (4).

(In the formula, Z represents a divalent organic group.)
It is obtained by reacting a diamine compound represented by

<(A) Diol compound>
The (a) diol compound used in the present invention is a branched or straight-chain compound having two hydroxyl groups in the molecule, represented by the following general formula (1).

(Wherein R represents a divalent organic group).

  (A) The diol compound is not particularly limited as long as it has the above structure. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neo Pentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decane Diols, alkylene diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, dimethylolpropionic acid (2,2-bis (hydroxymethyl) propionic acid), dimethylolbutanoic acid (2,2-bis ( Hydroxymethyl) butanoic acid), 2,3-dihydroxybenzoic acid, 2 Carboxyl group-containing diols such as 4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, polyoxyalkylene diols such as random copolymers of tetramethylene glycol and neopentyl glycol, polyester diols obtained by reacting polyhydric alcohols with polybasic acids, polycarbonate diols having a carbonate skeleton, γ -Polycaprolactone diol obtained by ring-opening addition reaction of lactones such as butyl lactone, ε-caprolactone, δ-valerolactone, bisphenol A, ethylene oxide adduct of bisphenol A, bisphenol Examples include a propylene oxide adduct of Nord A, hydrogenated bisphenol A, an ethylene oxide adduct of hydrogenated bisphenol A, a propylene oxide adduct of hydrogenated bisphenol A, and these can be used alone or in combination of two or more. .

  (A) As a diol compound, following General formula (5)

(In the formula, plural R _{1 s} each independently represent a divalent organic group, and m is an integer of 1 to 20.)
It is particularly preferable to use a polycarbonate diol represented by This is preferable in that the heat resistance, flexibility, water resistance, chemical resistance, and electrical insulation reliability under high temperature and high humidity of the obtained cured film can be further improved.

  More specifically, examples of the polycarbonate diol include trade names PCDL T-4671, T-4672, T-4691, T-4692, T-5650J, T-5651, T-5651 manufactured by Asahi Kasei Chemicals Corporation. , T-6001, T-6002, Daicel Chemical Industries, Ltd. Product Name Plaxel CD CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL, Kuraray Co., Ltd. product name Kuraray Polyol C-1015N , C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, Nippon Polyurethane Industry Co., Ltd., trade names NIPPOLAN 981, 980R, 982R These can be used alone or in combinations of two or more. The number average molecular weight of the polycarbonate diol is preferably 500 to 5000, more preferably 750 to 2500 in terms of polystyrene. When the number average molecular weight of the polycarbonate diol is within the above range, it is preferable in that the chemical resistance and flexibility of the obtained cured film can be improved. When the number average molecular weight is less than 500, the flexibility of the resulting cured film may be reduced. When the number average molecular weight is 5000 or more, the partial imide has a phosphorus element in the molecular structure and has a urethane bond. The solvent solubility of the converted polyimide precursor may decrease.

  More preferably, by combining the polycarbonate diol and the carboxyl group-containing diol, a carboxyl group is also added to the side chain of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond. Can be introduced. As a result, the branch point of the main chain of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond is increased, the crystallinity is lowered, and the phosphorus structure is included in the molecular structure. And it is preferable at the point which can improve the solvent solubility of the partially imidized polyimide precursor which has a urethane bond.

<(B) Diisocyanate compound>
The (b) diisocyanate compound used in the present invention is a compound having two isocyanate groups in the molecule, represented by the following general formula (2).

(Wherein X represents a divalent organic group).

  Examples of the (b) diisocyanate compound include diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- Or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2 ' -Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, Diphenylmethane-3,3'-diiso Anate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2 , 6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate Compounds, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc., hexamethylene diisocyanate Sulfonate, trimethyl hexamethylene diisocyanate, aliphatic diisocyanate compounds and the like such as lysine diisocyanate, and these may be used alone or in combinations of two or more. Use of these is preferable for increasing the heat resistance of the resulting cured film. Moreover, you may use what was stabilized with the blocking agent required in order to avoid a change over time. Such blocking agents include alcohol, phenol, oxime and the like, but are not particularly limited.

  (B) As the diisocyanate compound, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate It is particularly preferable to use norbornene diisocyanate. Thereby, it is preferable at the point which can improve the heat resistance of the cured film obtained, and water resistance further.

  In order to improve the developability of the photosensitive resin composition, (b) tolylene-2,6-diisocyanate, tolylene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate are suitable as the diisocyanate compound. Used for.

<Method for synthesizing terminal isocyanate compound>
The method for synthesizing a terminal isocyanate compound obtained by reacting (a) a diol compound and (b) a diisocyanate compound used in the present invention is the ratio of the number of hydroxyl groups to the number of isocyanate groups. Is reacted in a solvent-free or organic solvent such that isocyanate group / hydroxyl group = 1 or more and 2.10 or less, more preferably 1.10 or more and 2.10 or less, and further preferably 1.90 or more and 2.10 or less. Can be obtained.

  When two or more types of (a) diol compounds are used, the reaction with (b) diisocyanate compound may be carried out after mixing two or more types of (a) diol compounds. You may react a compound and (b) diisocyanate compound separately. Moreover, after reacting (a) diol compound and (b) diisocyanate compound, the obtained terminal isocyanate compound is further reacted with another (a) diol compound, and this is further reacted with (b) diisocyanate compound. May be. The same applies when two or more types of (b) diisocyanate compounds are used. In this way, a desired terminal isocyanate compound can be produced.

  The reaction temperature between (a) and (b) is preferably 40 to 160 ° C, more preferably 60 to 150 ° C. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The above reaction can be carried out in the absence of a solvent. However, in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system. For example, examples of the organic solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N , N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2 Examples include pyrrolidone solvents such as -pyrrolidone, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  Furthermore, for example, methyl monoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (Bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2 Symmetric glycol diethers such as -butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Cetate (aka carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether Acetates such as acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n Propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethyl ether also ethylene glycol. Of these, symmetrical glycol diethers are preferably used because side reactions are unlikely to occur.

  The amount of solvent used in the reaction is desirably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. The solute weight concentration in the reaction solution is more preferably 10 wt% or more and 80 wt% or less. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.

  Moreover, the terminal isocyanate compound obtained by the said reaction can also block the isocyanate group of the resin terminal after completion | finish of synthesis | combination with blocking agents, such as alcohol, lactams, and oximes.

<Terminal acid anhydride urethane imide oligomer>
The terminal acid anhydride urethane imide oligomer used in the present invention can be obtained by reacting the terminal isocyanate compound obtained as described above with tetracarboxylic dianhydride. At this time, the blending amount of the terminal isocyanate compound and the tetracarboxylic dianhydride is preferably such that the ratio of the number of isocyanate groups to the number of acid dianhydride groups is acid dianhydride group / isocyanate group = 2.10 or less, It is more preferably 1.10 or more and 2.10 or less, and further preferably 1.90 or more and 2.10 or less. Moreover, the solvent used at the time of the synthesis | combination of the said terminal isocyanate compound may be used for reaction of a terminal isocyanate compound and tetracarboxylic dianhydride as it is, and also said solvent can be added in addition.

<Tetracarboxylic dianhydride>
In the present invention, tetracarboxylic dianhydrides used for the synthesis of partially imidized polyimide precursors having a phosphorus element in the molecular structure and a urethane bond include, for example, 3,3 ′, 4, 4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) ) Phenyl] propane dianhydride, 2,2-bis (4-hydroxyphenyl) propane dibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride, 3,3', 4,4'- Diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 5- (2,5 -Dioxotetrahydro 3-furanyl) methyl-3-cyclohexene-1,2-tetracarboxylic dianhydride, such as dicarboxylic acid anhydride can be used.

  More preferably, the tetracarboxylic dianhydride used for the synthesis of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is 2,2-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride is there. The cured film obtained by improving the solubility of the partially imidized polyimide precursor having a phosphorus element in the molecular structure obtained by using these and having a urethane bond in an organic solvent. It is preferable for improving the chemical resistance.

  The tetracarboxylic dianhydride is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride or 5- (2,5-dioxotetrahydro-3-furanyl). It is more preferable to use -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride from the viewpoint of compatibility with other materials in the photosensitive resin composition.

  The amount of the tetracarboxylic dianhydride used in the present invention is as follows when the amount of the polyol (more specifically, the diol compound) used in the production of the terminal isocyanate compound is 1 mol. When used in a proportion of 50 mol or more and 4.00 mol or less, a partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is preferably flexible. A preferable use range is to use it in a proportion of 1.70 mol or more and 3.00 mol or less. This is preferable because tetracarboxylic dianhydride that does not contribute to the reaction can be reduced.

<Method for producing terminal acid anhydride urethane imide oligomer>
Various methods can be used as the reaction method of the terminal isocyanate compound and tetracarboxylic dianhydride in the method for producing a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond. . The typical method is illustrated below. However, any method may be used as long as tetracarboxylic dianhydride is arranged at the terminal.

  Method 1: A terminal isocyanate compound is gradually added to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. The reaction temperature at this time is 100 ° C. or higher and 300 ° C. or lower, more preferably 140 ° C. or higher and 250 ° C. or lower. It is preferred that the reaction occurs and imidization proceeds at the same time when the terminal isocyanate compound is added by heating to such a temperature. However, after the terminal isocyanate compound and tetracarboxylic dianhydride are completely dissolved at a low temperature, a method of imidizing by heating to a high temperature may be used.

  Method 2: A terminal isocyanate compound is gradually added and dissolved in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. Imidization can be carried out by drawing a vacuum while heating and drying a uniformly dissolved solution heated to 100 ° C. or higher and 250 ° C. or lower.

<Method of synthesizing a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond>
A terminal acid anhydride urethaneimide oligomer obtainable by the above method is reacted with a diamino compound to obtain a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond. be able to.

  The diamino compound used in the present invention is a compound having two or more amino groups. Preferably, the following general formula (4)

(In the formula, Z represents a divalent organic group.)
Is an aromatic diamine.

  More specific examples of the diamino compound include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3 -Aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) ) Sulphoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone 3,3′-diaminobenzophenone, , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, 3,4′-diaminodiphenylether, bis [4 -(3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfi Bis [4- (aminophenoxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4 , 4'-diaminobenzanilide, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [4- (4-Aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-a Nophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl) ] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-amino) Phenoxyphenyl)] [4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4-aminophenoxyphenyl)] [4 -(3-Ami Phenoxyphenyl)]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4 -Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl Bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4- Aminophenoxy) phenyl] ether, polytetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethyl) Ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis ( 4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4 ′ -Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino- 3-carboxy) phenyl] methane, [bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, , 2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoro Propane, 2,2-bis [4-amino-3-carboxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-di Carboxydiphenyl ether, 4,4′-diamino-2,2′-dicarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxy Diphenylsulfone, 4,4′-diamino-2,2′-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2, Diaminophenols such as 4-diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3 ′ Hydroxybiphenyl compounds such as -dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenyl, 3,3' Dihydroxydiphenylmethanes such as -diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2- Bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3- Bis [hydroxyphenyl] propanes such as droxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexa Bis [hyhydroxyphenyl] hexafluoropropanes such as fluoropropane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′- Hydroxydiphenyl ethers such as diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4 '-Diamino-2,2'-dihydroxydiphenylsulfur Dihydroxydiphenyl sulphones such as 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2, Dihydroxydiphenyl sulfides such as 2′-dihydroxydiphenyl sulfide, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′- Dihydroxydiphenyl sulfoxides such as diamino-2,2′-dihydroxydiphenyl sulfoxide, and bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane 4,4′-bis (4- Bis [(hydroxyphenoxy) biphenyl compounds such as mino-3-hydroxyphenoxy) biphenyl, bis [(hydroxyphenoxy) such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone Phenyl] sulfone compound, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxy Bis (hydroxyphenoxy) biphenyl compounds such as phenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl. These can be used alone or in combination of two or more.

  More preferably, the diamino compound used for the synthesis of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is m-phenylenediamine or bis (3-aminophenyl) sulfone. Bis (4-aminophenyl) sulfone, 3,3′-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] methane, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) ) Aromatic diamines such as benzene and 1,3-bis (4-aminophenoxy) benzene. Since the heat resistance of the cured film obtained by using said aromatic diamine improves, it is desirable.

<Method of introducing phosphorus element into polyimide precursor>
The method for introducing the phosphorus element into the polyimide precursor of the present invention is not particularly limited, but for example, it may be introduced by using a diol compound, diisocyanate compound, tetracarboxylic dianhydride, diamino compound or the like having a phosphorus element. I can do it. These can be used alone or in combination of two or more. The diol compound, diisocyanate compound, tetracarboxylic dianhydride, and diamino compound having the phosphorus element are represented by, for example, a diol compound having a phosphorus element represented by the following general formula (9) or the following general formula (10). It is possible to increase diamino compounds having phosphorus element. Moreover, the phosphorus compound which has reactive groups, such as thermosetting groups, such as a hydroxyl group, an epoxy group, a carboxyl group, an amino group, an isocyanate group, photosensitive groups, such as a vinyl group and (meth) acryloyl group, said description A diol compound, a diisocyanate compound, a tetracarboxylic dianhydride, or a compound bonded to a side chain of a diamino compound can also be used. Among these, a diamino compound having a phosphorus element is preferable because it has good reactivity and can be easily incorporated into the skeleton of the polyimide precursor.

  Moreover, it is preferable that the phosphorus element in molecular structure contains 0.1 to 5.0 weight%. The flame retardance of a polyimide precursor is more effectively acquired as content of a phosphorus element is 0.1 weight% or more. Further, when the content of the phosphorus element is 5.0% by weight or less, a sufficient proportion of urethane bonds in the molecular structure can be secured, and excellent flexibility can be obtained.

  The phosphorus element content in the molecular structure is calculated from the amount of phosphorus element contained in the raw material used for the synthesis of a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond, for example. It is possible. Further, for example, it is possible to perform measurement by ICP emission spectroscopic analysis after performing pressure acid decomposition with a microwave decomposition apparatus.

(II) Photosensitive resin composition As an example of utilization of the polyimide precursor of the present invention, a photosensitive resin composition can be mentioned. Accordingly, the present invention includes a photosensitive resin composition using the polyimide precursor. Hereinafter, the photosensitive resin composition concerning this invention is explained in full detail. Needless to say, examples of the use of the polyimide precursor of the present invention are not limited thereto.

  The photosensitive resin composition of the present invention comprises at least (A) a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, (B) a photosensitive resin, and (C ) Photopolymerization initiator may be contained.

  In the photosensitive resin composition of the present invention, (A) a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond is obtained using polycarbonate diol. A partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond is more preferably used, but is not limited thereto.

  The photosensitive resin composition of the present invention comprises (A) a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, (B) a photosensitive resin, In addition to C) a photopolymerization initiator, (D) a thermosetting resin may be further contained.

  Here, although the present inventors discovered that the photosensitive resin composition of this invention was excellent in various characteristics, it estimates that this may be based on the following reasons.

  In other words, the polyimide obtained by heating a partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond has an imide skeleton and a urethane bond in the molecule, and therefore is derived from the imide skeleton. Excellent heat resistance, electrical insulation reliability, chemical resistance and flexibility derived from urethane bonds. In addition, a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond has a carboxyl group derived from polyamic acid, and therefore becomes soluble in a developer typified by a dilute alkaline aqueous solution. Fine processing is possible by exposure and development. Among them, polyimide obtained by heating a partially imidized polyimide precursor having a phosphorus element in a molecular structure obtained by using a polycarbonate diol and having a urethane bond has flexibility and low hygroscopicity. Excellent.

  In addition, since the molecular skeleton does not contain a siloxane skeleton, the resulting cured film surface has good wettability, not only very good adhesion to various members, but also derived from the siloxane component from the cured film Therefore, when a cured film is used as an insulating film of a printed wiring board, the semiconductor does not malfunction.

  (A) Since the partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is as described in (I) above, the description thereof is omitted here. , (B) photosensitive resin, (C) photopolymerization initiator, (D) thermosetting resin, other components, and a mixing method of (A) to (C) or (A) to (D). To do.

<(B) Photosensitive resin>
The photosensitive resin (B) in the present invention is a resin in which a chemical bond is formed by a photopolymerization initiator. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. Furthermore, the unsaturated double bond is an acryl group (CH ₂ ═CH— group), a methacryloyl group (CH═C (CH ₃ ) — group) or a vinyl group (—CH═CH— group). Is preferred.

  Examples of the photosensitive resin (B) include bisphenol F EO modified (n = 2 to 50) diacrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, and bisphenol S EO modified (n = 2 to 50). Diacrylate, bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) dimethacrylate, 1,6-hexane Diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethyl Propane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipenta Erythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2- Hide Xylpropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (Methacryloxyethoxy ) Phenyl] propane, 2,2-bis [4- (methacryloxy diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryl Roxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene group Cole acrylate, nonylphenoxy polyethylene glycol acrylate, nonyl phenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol di Methacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, Tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl -1,5-pentanediol diacrylate, ethoxylated tomethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylation Pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl ali Ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, arborbital, diallylamine, diallyldimethylsilane, diallyl Disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropyl Redene diphenol diacrylate and the like are preferable, but are not limited thereto. In particular, the repeating unit of EO (ethylene oxide) contained in one molecule of diacrylate or methacrylate is preferably in the range of 2-50, more preferably 2-40. By using an EO repeating unit in the range of 2 to 50, the solubility of the photosensitive resin composition in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. Furthermore, it is difficult for stress to remain in the cured film obtained by curing the photosensitive resin composition. For example, among the printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented. Features such as being able to be suppressed.

  In particular, it is particularly preferable to use the EO-modified diacrylate or dimethacrylate together with an acrylic resin having 3 or more acrylic groups or methacrylic groups in order to improve developability. For example, ethoxylated isocyanuric acid EO-modified triacrylate, Ethoxylated isocyanuric acid EO modified trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tri Acrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethyl Propanetetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 2,2,2-trisacryloyloxymethyl ethyl succinic acid, 2,2, 2-trisacryloyloxymethylethylphthalic acid, propoxylated ditrimethylolpropane tetraacrylate, propoxylated dipentaerythritol hexaacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, Caprolactone-modified ditrimethylolpropane tetraacrylate, the following general formula (11)

(Wherein a + b = 6 and n = 12.), A compound represented by the following general formula (12)

(Wherein a + b = 4 and n = 4), a compound represented by the following formula (13)

A compound represented by the following general formula (14)

(Where m = 1, a = 2, b = 4, or m = 1, a = 3, b = 3, or m = 1, a = 6, b = 0, or m = 2, a = 6 B = 0.)
A compound represented by the following general formula (15)

(Wherein a + b + c = 3.6), a compound represented by the following formula (16)

A compound represented by the following general formula (17):

(Where m · a = 3, a + b = 3, where “m · a” is the product of m and a)
An acrylic resin such as a compound represented by the formula is preferably used.

  In addition, hydroxyl groups in the molecular structure skeleton such as 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri and tetraacrylate, Those having a carbonyl group are also preferably used.

  In addition, any photosensitive resin such as an epoxy-modified acrylic (methacrylic) resin, a urethane-modified acrylic (methacrylic) resin, or a polyester-modified acrylic (methacrylic) resin may be used.

  In addition, although it is also possible to use 1 type as a photosensitive resin, using 2 or more types together is preferable when improving the heat resistance of the cured film after photocuring.

<(C) Photopolymerization initiator>
The (C) photopolymerization initiator in the present invention is a compound that is activated by energy such as UV and starts and accelerates the reaction of the photosensitive resin. Examples of the (C) photopolymerization initiator include Mihilaz ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, and 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1- Hydroxycyclohexyl phenyl ketone, diacetylbenzyl, benzyldimethyl Ketal, benzyldiethylketal, 2 (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4, 6-bis (trichloromethyl) -S-triazine, 2 (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidochalcone, di (tetraalkylammonium) -4,4′-diazidostilbene-2,2′-disulfonate, 2,2-dimethoxy-1,2-diphenylethane-1-one 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)- Enyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butane-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, bis (n5-2,4-cyclopentadiene -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2- Kutanonedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], iododium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1 -), Ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 -(O-acetyloxyome) etc. are mentioned. The photopolymerization initiator is desirably selected as appropriate, and it is desirable to use a mixture of one or more.

  In the photosensitive resin composition of the present invention, the component (A), the component (B) and the component (C) are 10 to 200 parts by weight of the component (B) with respect to 100 parts by weight of the solid content of the component (A). (C) It is preferable to mix | blend a component so that it may become 0.1-50 weight part.

  The blending ratio is preferable because various properties (such as electrical insulation reliability) of the cured product and insulating film finally obtained are improved.

  When the photosensitive resin of the component (B) is less than the above range, the heat resistance of the cured film after photocuring the photosensitive resin composition is lowered, and the contrast when exposed and developed is difficult to be applied. Therefore, it may not be preferable. Moreover, when too much, the photosensitive resin composition is coated on the substrate and the solvent is dried to increase the stickiness of the coating film, resulting in decreased productivity and increased crosslinking density. If it is too much, the cured film becomes brittle and easily cracked, which may not be preferable. For this reason, it is possible to set the resolution at the time of exposure / development to an optimal range by setting the value within the above range.

  (C) When there are few photoinitiators than the said range, the hardening reaction of the acrylic resin at the time of light irradiation hardly occurs, and hardening may become inadequate in many cases. Moreover, when there is too much, adjustment of light irradiation amount becomes difficult and may be in an overexposure state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<(D) Thermosetting resin>
As the thermosetting resin used in the photosensitive resin composition of the present invention, epoxy resin, isocyanate resin, block isocyanate resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured Thermosetting resins such as resins and unsaturated polyester resins; side chain reactive group type thermosetting having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of the polymer chain Can be used. The said thermosetting component, ie, (D) thermosetting resin, should just be used 1 type or in combination of 2 or more types.

  (D) As a thermosetting resin, it is more preferable to use an epoxy resin and a block isocyanate resin among these. By containing these components, heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  The epoxy resin contains at least two epoxy groups in the molecule, and is bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin. , Hydrogenated bisphenol A type epoxy resin, ethylene oxide adduct bisphenol A type epoxy resin, propylene oxide adduct bisphenol A type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, Alkylphenol novolac type epoxy resin, polyglycol type epoxy resin, cycloaliphatic epoxy resin, cyclopentadiene type epoxy resin, dicyclopentadi Emission type epoxy resin, cresol novolak type epoxy resins, glycidyl amine type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber-modified epoxy resin, an epoxy resin such as epoxy-modified polysiloxane. These epoxy resins may be used alone or in combination of two or more at any ratio.

  Examples of the epoxy resin include, for example, the product name Epicron HP-4700 of the naphthalene type tetrafunctional epoxy resin manufactured by Dainippon Ink Chemical Co., Ltd., the product name Epicron HP-7200 of the cyclopentadiene type epoxy resin, and the product of the phenol novolac type epoxy resin. The name Epicron N-740, Epicron EXA-7240, which is a high heat resistance epoxy resin, Epicron N-660, N-665, N-670, N-680, N-655-, which is a cresol novolac type polyfunctional epoxy resin EXP, trade name of phenol novolac type epoxy resin Epicron N-740, trade name of tetraphenylethane type epoxy resin, Epicron ETePE, trade name of triphenylmethane type epoxy resin, Epicron ETrPM, trade name of Japan Epoxy Resin Co., Ltd. Bisphenol A type epoxy resin such as Tote Kasei Co., Ltd., bisphenol F type epoxy resin such as YDF-170 manufactured by Toto Kasei Co., Ltd. Phenol novolac type epoxy resin such as trade name EPPN-201 manufactured by Dow Chemical Co., Ltd., and trade name EOCN-125S, 103S, 104S manufactured by Nippon Kayaku Co., Ltd. Novolac type epoxy resin, trade name Epon 1031S manufactured by Japan Epoxy Resins Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade names Denacol EX-611, EX-614 manufactured by Nagase Chemical Co., Ltd. EX-614B, EX-622, EX-512, EX-521, EX 421, EX-411, EX-321 and other polyfunctional epoxy resins, Japan Epoxy Resin Co., Ltd. trade name Epicoat 604, Toto Kasei Co., Ltd. trade name YH434, Mitsubishi Gas Chemical Co., Ltd. trade name TETRAD-X, TERRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, etc. Amine type epoxy resin, Ciba Specialty Chemicals Co., Ltd. Heterocycle-containing epoxy resins such as the name Araldite PT810, and alicyclic epoxy resins such as ERL4234, 4299, 4221, and 4206 manufactured by UCC, and the like can be used alone or in combination of two or more.

  In addition to the epoxy resin, an epoxy compound having only one epoxy group in one molecule, for example, n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether and the like may be used. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used in combination.

  Among these epoxy resins, an epoxy resin having two or more epoxy groups in one molecule is particularly preferable from the viewpoint of improving the heat resistance, solvent resistance, chemical resistance and moisture resistance of the photosensitive resin composition.

  The blocked isocyanate resin is a compound that is inactive at room temperature and is heated to dissociate blocking agents such as oximes, diketones, phenols, caprolactams, etc., and regenerate isocyanate groups. Product names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T manufactured by Asahi Kasei Chemicals Co., Ltd. Trade names Takenate B-830, Takenate B- 815N, Takenate B-846N, Takenate B-882N, trade names Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2515, Millionone manufactured by Nippon Polyurethane Industry Co., Ltd. Preparative MS-50 and the like. Particularly, the blocked isocyanate resin suitably used in the present invention is a block isocyanate compound such as hexamethylene diisocyanate type isocyanurate type, biuret type, adduct type, etc. whose dissociation temperature of the blocking agent is 160 ° C. or less, hydrogenated diphenylmethane diisocyanate type, This is an additive xylylene diisocyanate block isocyanate resin.

  It is preferable to use the above-mentioned blocked isocyanate resin because high adhesiveness with a base material can be imparted to the cured film obtained when the photosensitive resin composition is cured.

  These blocked isocyanate resins can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, examples of the thermosetting resin curing agent include phenol resins such as phenol novolac type phenol resins, cresol novolac type phenol resins, and naphthalene type phenol resins, amino resins, and urea resins. Melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acids, Bronsted acid salts, polymercaptan compounds and the like can be used in combination.

  The amount of the thermosetting resin used in the photosensitive resin composition of the present invention is (A) a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond, and (B) photosensitive. It is preferable to mix | blend so that it may become 0.5-100 weight part with respect to 100 weight part of solid content which totaled the photosensitive resin and (C) photoinitiator. Particularly preferred is 1.0 to 50 parts by weight. It is preferable to add it in the above range since the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition can be improved.

  When the thermosetting resin of component (D) is less than the above range, the effect of adding is difficult to obtain, and when too much, the photosensitive resin composition is applied on the substrate. Further, since the stickiness of the coating film obtained by drying the solvent increases, the productivity decreases, and when the crosslinking density becomes too high, the cured film becomes brittle and easily cracked, which is not preferable.

  Moreover, in the photosensitive resin composition of this invention, you may use a hardening accelerator with a thermosetting resin. Such curing accelerators are not particularly limited, but include, for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine, and tetraethanolamine; 1,8-diaza -Borate compounds such as bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl Imidazoles such as imidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2-ethyl Imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ And azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine. Of these, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6- [2′-undecylimidazolyl- ( It is more preferable to use imidazoles such as 1 ′)]-ethyl-s-triazine.

<Other ingredients>
Various additives such as a filler, an adhesion assistant, an antifoaming agent, a leveling agent, a colorant, and a polymerization inhibitor can be further added to the photosensitive resin composition of the present invention as necessary. As the filler, fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate, and fine organic polymer fillers may be contained. Moreover, as said antifoamer, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said leveling agent, a silicon type compound, an acryl-type compound, etc. can be contained, for example. Moreover, as said coloring agent, a phthalocyanine type compound, an azo type compound, carbon black, a titanium oxide etc. can be contained, for example. Moreover, as said adhesion assistant (it is also called adhesiveness imparting agent), a silane coupling agent, a triazole type compound, a tetrazole type compound, a triazine type compound, etc. can be contained. Moreover, as said polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, etc. can be contained, for example. In addition, the photosensitive resin composition of the present invention is excellent in flame retardancy because it contains a partially imidized polyimide precursor having at least (A) a phosphorus element in a molecular structure and a urethane bond. However, a flame retardant may be added to obtain a more flame retardant effect. As the flame retardant, for example, a phosphate ester compound, a halogen-containing compound, a metal hydroxide, an organic phosphorus compound, or the like can be contained. The above various additives can be used alone or in combination of two or more. Moreover, it is desirable to select each content suitably.

<The mixing method of (A)-(C) or (A)-(D)>
The photosensitive resin composition of the present invention is obtained by uniformly mixing the above components (A) to (C) or (A) to (D) and the other components as necessary. A method for uniformly mixing the above components is not particularly limited, and may be mixed using a general kneading apparatus such as a three roll or bead mill apparatus. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

(III) Thermosetting resin composition As another example of utilization of the polyimide precursor of this invention, a thermosetting resin composition can be mentioned. Therefore, the present invention includes a thermosetting resin composition using the polyimide precursor. Needless to say, examples of the use of the polyimide precursor of the present invention are not limited thereto.

  The thermosetting resin composition of the present invention comprises at least (A) a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, and (D) a thermosetting resin. It should just contain.

  In the thermosetting resin composition, (A) a partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond is obtained by using polycarbonate diol. A partially imidized polyimide precursor having a phosphorus element in the structure and a urethane bond is more preferably used, but is not limited thereto.

  The thermosetting resin composition of the present invention comprises (A) a partially imidized polyimide precursor having a phosphorus element in a molecular structure and a urethane bond, and (D) a thermosetting resin. In addition to the above, it may further contain other components.

  Since the component (A) is as described in the above (I), the description is omitted here. Moreover, about (D) thermosetting resin and another component, what was illustrated by said (II) can be used suitably.

  In the thermosetting resin composition of the present invention, the (A) component and the (D) component are 0.5 to 100 parts by weight of the (D) component with respect to 100 parts by weight of the solid content of the (A) component. It is preferable that they are blended as described above.

  The blending ratio is preferable because various properties (such as electrical insulation reliability) of the cured product and insulating film finally obtained are improved.

  (D) When there are more thermosetting resins than the said range, the hardening reaction of a polyimide precursor may be inhibited and sufficient mechanical strength may not be obtained. Moreover, when less than the said range, the effect by adding is hard to be acquired. Therefore, in order to advance the curing reaction efficiently, it is preferable to prepare within the above range.

<Mixing method of (A) and (D)>
The thermosetting resin composition of the present invention is obtained by uniformly mixing the above components (A) and (D) and other components as necessary. As a method of uniformly mixing the above components, for example, a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

(IV) Polyimide precursor composition solution Also, a polyimide precursor composition solution obtained by dissolving a polyimide precursor, a photosensitive resin composition, or a thermosetting resin composition according to the present invention in an organic solvent is also described in this application. Included in the invention. The polyimide precursor, the photosensitive resin composition, and the thermosetting resin composition are highly soluble in various organic solvents. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N- Formamide solvents such as dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and the like Pyrrolidone solvents, phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methyl monoglyme (1,2-dimethoxy) Ethane), methyl diglyme (bis ( 2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1 , 2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyl diglyme (bis (2-butoxyethyl) ether) and the like, γ-butyrolactone and N-methyl -2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate) 2- (2-butoxyethoxy) ethyl acetate), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol di Acetates such as acetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, di- Propylene glycol n-butyl ether, tripyrene glycol n-propyl ether, propylene glycol Lumpur phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, can be used diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent of ethers such as ethylene glycol monoethyl ether. In addition, as said solvent, low boiling point hexane, acetone, toluene, xylene etc. can be used together as needed.

  Among these, symmetric glycol diethers are particularly preferable because the polyimide precursor, the photosensitive resin composition, and the thermosetting resin composition have high solubility.

  In the polyimide precursor solution obtained by dissolving the polyimide precursor of the present invention in an organic solvent, the organic solvent is blended in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the solid content of the component (A). It is preferable.

  The polyimide precursor composition solution obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent comprises (A) component, (B) component, (C) component, and (D) component as required. It is preferable that the organic solvent is blended in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the total solid content.

  The polyimide precursor composition solution obtained by dissolving the thermosetting resin composition of the present invention in an organic solvent has an organic solvent with respect to 100 parts by weight of the total solid content of the component (A) and the component (D). It is preferable that 10 to 200 parts by weight is blended.

  By making the polyimide precursor composition solution within this range, the film reduction rate after drying becomes small, and the viscosity and viscosity of the polyimide precursor composition solution should be adjusted within the appropriate range for coating such as screen printing. This is desirable.

  When the organic solvent is less than the above range, the viscosity of the polyimide precursor composition solution becomes very high, coating becomes difficult, and foam entrainment during coating and leveling properties may be inferior. Moreover, when more than the said range, the viscosity of a polyimide precursor composition solution will become very low, application | coating will become difficult and the circuit coverage may be inferior.

(V) Method of using polyimide precursor composition The polyimide precursor, photosensitive resin composition, or thermosetting resin composition of the present invention was used directly, or the polyimide precursor composition solution was prepared. Later, a cured film or pattern can be formed as follows. First, the polyimide precursor, the photosensitive resin composition, or the thermosetting resin composition is applied to a substrate. Alternatively, the polyimide precursor composition solution is applied to a substrate and dried to remove the organic solvent. The substrate can be applied by screen printing, curtain roll, river roll, spray coating, spin coating using a spinner, or the like. The coating film (preferably having a thickness of 5 to 100 μm, particularly 10 to 100 μm) is dried at 120 ° C. or less, preferably 40 to 100 ° C.

  In the case of the photosensitive resin composition, after drying, a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams. Next, the relief pattern can be obtained by washing out the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.

  As the developer, an alkaline aqueous solution is preferably used. This developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, or N-methyl-2-pyrrolidone. Examples of the alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, specifically sodium hydroxide. , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium Hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, trii Such as propylamine can be mentioned, the aqueous solution is a compound other than this as long as it exhibits basicity can also be naturally used. The concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. Is preferably used.

  The relief pattern formed by the development process is rinsed to remove unnecessary residues. Examples of the rinsing liquid include water and acidic aqueous solutions.

  A film obtained by applying the polyimide precursor or thermosetting resin composition or the polyimide precursor composition solution containing these to a substrate and drying it, or a photosensitive resin composition or the same. Next, a heat treatment is performed on the relief pattern obtained by applying the polyimide precursor composition solution containing the solution to a substrate and performing exposure and development. A heat-treated cured film having high heat resistance can be obtained by imidizing a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond by performing heat treatment. The thickness of the cured film is determined in consideration of the wiring thickness and the like, but is preferably about 2 to 50 μm. It is desired that the final curing temperature at this time can be imidized by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate.

  The imidization temperature applied at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 180 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not desirable.

  The cured film formed from the polyimide precursor, photosensitive resin composition, or thermosetting resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and particularly excellent in flexibility.

  In addition, for example, the insulating film obtained from the photosensitive resin composition preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, particularly a resolution of about 10 to 1000 μm. For this reason, the insulating film obtained from the photosensitive resin composition is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.

  Further, for example, the insulating film of the thermosetting resin composition preferably has a thickness of about 2 to 50 μm and has good electrical insulation reliability, moisture resistance, and flexibility. For this reason, the insulating film obtained from a thermosetting resin composition is particularly suitable as an insulating material for flexible substrates that require high flexibility. Furthermore, it is used for various thermosetting type wiring coating protective agents, heat resistant adhesives, electric wire / cable insulation coatings, and the like.

  In addition, this invention can provide the same insulating material, even if it uses the resin film obtained by apply | coating the said polyimide precursor composition solution to the base-material surface, and drying.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[Synthesis Example 1]
<Synthesis of a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond>
In a separable flask pressurized with nitrogen, methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) (95 g) was charged as a polymerization solvent, and 20.7 g (norbornene diisocyanate) was added thereto. 0.1004 mol) was added and heated to 80 ° C. to dissolve. To this solution, 50.0 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd .: trade name PCDL T5652, polycarbonate diol represented by the following general formula (18), average molecular weight 2000), dimethylolbutane A solution of 7.4 g (0.050 mol) of acid (2,2-bis (hydroxymethyl) butanoic acid) in methyltriglyme (50.0 g) was added over 1 hour.

(In the formula, q, r and s are integers of 1 or more).

  This solution was heated and stirred at 80 ° C. for 5 hours. After completion of the reaction, 3,22 '(4,0') benzophenone tetracarboxylic dianhydride (BTDA) 32.22 g (0.100 mol) and methyltriglyme (52.0 g) were added to the above reaction solution. did. After the addition, the mixture was heated to 200 ° C. and reacted for 3 hours. The terminal acid anhydride urethane imide oligomer solution was obtained by performing the said reaction. After completion of the reaction, the reaction solution was cooled to about 5 ° C. with ice.

  To this solution, 26.72 g (0.075 mol) of a diamino compound containing a phosphorus element represented by the following general formula (10) was added and stirred at 5 ° C. for 4 hours. Thus, a partially imidized polyimide precursor having a phosphorus element and a urethane bond was obtained (weight average molecular weight 80,000, number average molecular weight 30,000). The solute concentration of this solution was 40%, and the viscosity of the solution was 750 poise at 23 ° C. Moreover, content of the phosphorus element in a polyimide precursor was 1.7 weight%.

Example 1
In order to confirm the storage stability of the polyimide precursor solution obtained in Synthesis Example 1, the polyimide precursor solution was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube. And the viscosity after one month was measured. The evaluation results are shown in Table 1.
○ when the viscosity change after 1 month is within 10%
Δ when the viscosity change after 1 month is 10 to 30%
The case where the viscosity change after one month was 30% or more was evaluated as x.

<Preparation of cured film on polyimide film>
The polyimide precursor solution obtained in Synthesis Example 1 was cast and applied to a polyimide film having a film thickness of 75 μm (manufactured by Kaneka Corporation: trade name: 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. And it dried at 80 degreeC for 20 minutes, and formed the resin film of this invention on the polyimide film used as a base. The obtained resin film was imidized by heating at 160 ° C. for 90 minutes in an air atmosphere to obtain a cured film, and a polyimide film laminate in which the cured film was formed on the base polyimide film was obtained.

<Evaluation of cured film>
The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 1.

(I) Adhesiveness of cured film The adhesive strength of the obtained cured film was evaluated by a cross-cut tape method according to JIS K5400.
○ The one that does not peel off by the cross-cut tape method
△, if more than half of the cells remain
The case where the residual amount of the squares was less than half was marked with x.

(Ii) Environmental Test Stability of Cured Film If imidization of the cured film is not sufficient, the stability in the environmental test apparatus is lowered. Therefore, the stability of the cured film in an environmental test apparatus was measured. As an environmental test apparatus, it was judged in the state of the cured film formed on the polyimide film after a 85 degreeC / 85% RH 1000 hour test using the constant temperature humidifier model made from ESPEC Corporation.
○ that the polyimide resin of the cured film does not change
△, in which the polyimide resin of the cured film is partially dissolved
The cured film polyimide resin was completely dissolved.

(Iii) Chemical resistance The chemical resistance of the cured film surface was evaluated. The evaluation method was evaluated by observing the state of the cured film surface after immersing the polyimide film laminate under the evaluation conditions of the following evaluation items 1 to 3.
Evaluation item 1: After dipping in isopropanol at 25 ° C. for 10 minutes, it was air-dried.
Evaluation item 2: After immersing in a 2N hydrochloric acid solution at 25 ° C. for 10 minutes, it was washed with pure water and air-dried.
Evaluation item 3: After being immersed in a 2N sodium hydroxide solution at 25 ° C. for 10 minutes, it was washed with pure water and air-dried.
○ that the polyimide resin of the cured film does not change
△, in which the polyimide resin of the cured film is partially dissolved
The cured film polyimide resin was completely dissolved.

(Vi) Flexibility evaluation The polyimide precursor solution was applied to the surface of a 25 μm-thick polyimide film (Akane 25NPI manufactured by Kaneka Corporation) so that the final film thickness was 25 μm, dried at 80 ° C. for 20 minutes, and 160 ° C. For 90 minutes to obtain a polyimide film laminate. The obtained polyimide film laminate was cut into 30 mm × 10 mm strips and bent 10 times at 180 ° at 15 mm to visually check for cracks in the coating film.
○: The cured film has no cracks Δ: The cured film has some cracks x: The cured film has cracks

(V) Wettability The wettability of the cured film prepared in the above <Preparation of cured film on polyimide film> was measured according to JIS K6768 measurement method.

[Synthesis Example 2]
<Synthesis of a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond>
In a separable flask pressurized with nitrogen, methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) (66.5 g) was charged as a polymerization solvent, and norbornene diisocyanate was added to 10. 3 g (0.050 mol) was charged and dissolved by heating to 80 ° C. To this solution, 50.0 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Corporation: trade name PCDL T5652, polycarbonate diol represented by the following general formula (18), average molecular weight 2000) and methyltriglyme A solution dissolved in (50.0 g) was added over 1 hour.

(In the formula, q, r and s are integers of 1 or more).

  This solution was heated and stirred at 80 ° C. for 5 hours. After completion of the reaction, 31.02 g (0.100 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) and methyltriglyme (52.0 g) were added to the above reaction solution. . After the addition, the mixture was heated to 200 ° C. and reacted for 3 hours. The terminal acid anhydride urethane imide oligomer solution was obtained by performing the said reaction. After completion of the reaction, the reaction solution was cooled to about 5 ° C. with ice.

  To this solution, 26.72 g (0.075 mol) of a diamino compound containing a phosphorus element represented by the following general formula (10) was added and stirred at 5 ° C. for 4 hours. Thus, a partially imidized polyimide precursor having a phosphorus element and a urethane bond was obtained (weight average molecular weight 90,000, number average molecular weight 35,000). The solute concentration of this solution was 40%, and the viscosity of the solution was 800 poise at 23 ° C. Moreover, content of the phosphorus element in a polyimide precursor was 2.0 weight%.

(Example 2)
In order to confirm the storage stability of the polyimide precursor composition solution obtained in Synthesis Example 2, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  Further, the cured film obtained from the polyimide precursor obtained in Synthesis Example 2 was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
In a well-dried three-neck flask with a stirrer, 22 mmol (7.045 g) of 2,2′-bis (trifluoromethyl) benzidine was dissolved in 28 mL of m-cresol containing 1 mL of γ-picoline at 60 ° C. 10 mmol (1.961 g) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride powder that had been vacuum-dried for 12 hours was gradually added at 60 ° C. over 10 to 15 minutes with stirring. The reaction solution was heated to 120 ° C. in a nitrogen atmosphere and stirred for 1 hour to obtain a uniform solution. The mixture was further refluxed at 190 ° C. for 2 hours to form a white precipitate. The reaction solution was dropped into a large amount of a mixed solvent of diethyl ether / hexane, and the precipitate was filtered off and dried in vacuo at 60 ° C. for 12 hours to obtain a white powder. Next, 20 mmol (6.405 g) of 2,2′-bis (trifluoromethyl) benzidine and 10 mmol (8.005 g) of the obtained white powder were placed in a well-closed sealed reaction vessel with a stirrer, and molecular sieves 4A. And then dissolved in 87 mL of N, N-dimethylacetamide sufficiently dehydrated at 1, then 30 mmol (5.883 g) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride powder, which had been vacuum-dried at 120 ° C. for 12 hours, was gradually added. Added to. The mixture was stirred at room temperature for 24 hours to obtain a transparent, uniform and viscous polyimide precursor solution (weight average molecular weight 120,000, number average molecular weight 40,000). The solute concentration of this solution was 19%, and the viscosity of the solution was 600 poise at 23 ° C.

<Evaluation of storage stability of polyimide precursor solution>
In order to confirm the storage stability of the obtained polyimide precursor solution, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  Furthermore, evaluation of the cured film obtained from the obtained polyimide precursor was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  As shown in Table 1, the cured film obtained in Comparative Example 1 has poor environmental stability stability and poor alkali resistance because the imidization reaction does not proceed sufficiently when heated at 160 ° C. for 90 minutes. Became clear.

(Comparative Example 2)
450 g of dehydrated and purified N-methylolpyrrolidone NMP was placed in a four-necked flask equipped with a dry nitrogen gas inlet tube, a thermometer, and a stirrer, and stirred vigorously for 10 minutes while flowing nitrogen gas. Next, 81.1 g (0.332 mol) of Jeffamine D230 (average molecular weight 243.9) manufactured by Huntsman was added and stirred until uniform. Further, 100.0 g (0.322 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride (ODPA, molecular weight 310.2) was kept in powder form while the system was cooled to 5 ° C. in an ice water bath. It was added little by little. Thereafter, stirring was continued for 12 hours. During this time, the flask was kept at 5 ° C. Thus, a polyimide precursor was obtained (weight average molecular weight 80,000, number average molecular weight 25,000). The solute concentration of this solution was 28.5%, and the viscosity of the solution was 800 poise at 23 ° C.

<Evaluation of storage stability of polyimide precursor solution>
In order to confirm the storage stability of the obtained polyimide precursor solution, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  Furthermore, evaluation of the cured film obtained from the obtained polyimide precursor was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 3)
Reactive silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) as a siloxane diamine was added to a 2.5-liter water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer. ) 215.0 g (0.25 mol), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 102.5 g (0.25 mol) as an aromatic diamine, trimellitic anhydride (TMA) ) 201.6 g (1.05 mol) and 519 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. After completion of the stirring, 200 mL of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised to 160 ° C. and refluxed for 2 hours. When it is confirmed that water has accumulated in the moisture determination receiver about 18 mL or more and water is no longer being distilled, the distillate in the moisture determination receiver is removed, and the temperature is further increased to 190 ° C. Toluene in the reaction solution was removed. Thereafter, the solution was lowered to room temperature to obtain a solution containing a diimide dicarboxylic acid mixture. In parallel with this, in another 5 L separable flask equipped with a 25 mL water quantitative receiver with a cock connected to a reflux condenser, a thermometer and a stirrer, NMP 1363 mL, HCA-HQ as a phosphorus-containing compound (manufactured by Sanko Co., Ltd., Phosphorus-containing product represented by the above chemical formula (2) 1944 g (0.6 mol) and 4,4′-diphenylmethane diisocyanate (MDI) 300 g (1.2 mol) were added as a diisocyanate compound and reacted at 60 ° C. for 2 hours. I let you. In this 5 L separable flask, the whole amount of the solution containing the above-mentioned diimide dicarboxylic acid mixture was added, and the temperature was raised to 160 ° C. and reacted for 2 hours. After the reaction, the solution was cooled to room temperature to obtain an NMP solution of polyamideimide having a phosphorus atom in the molecule. The content of polyamideimide in the obtained solution was 35% by weight, and the content of phosphorus atoms in the polyamideimide was 1.9% by weight.

<Evaluation of storage stability of polyimide precursor solution>
In order to confirm the storage stability of the obtained polyamideimide, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

  Further, the cured film obtained from the polyamideimide obtained above was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Synthesis Example 3]
<Synthesis of a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond>
In a separable flask pressurized with nitrogen, methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) (21.26 g) was charged as a solvent for polymerization. 54 g (0.085 mol) was charged and dissolved by heating to 80 ° C. To this solution, 41.56 g (0.021 mol) of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd .: trade name PCDL T5652, polycarbonate diol represented by the following general formula (18), average molecular weight 2000) and dimethylolbutane A solution of 6.3 g (0.043 mol) of acid (2,2-bis (hydroxymethyl) butanoic acid) in methyltriglyme (25.87 g) was added over 1 hour.

(In the formula, q, r and s are integers of 1 or more).

  This solution was heated and stirred at 80 ° C. for 5 hours. After completion of the reaction, 32.22 g (0.085 mol) of ODPA was added to the above reaction solution. After the addition, the mixture was heated to 200 ° C. and reacted for 3 hours. The terminal acid anhydride urethane imide oligomer solution was obtained by performing the said reaction. After completion of the reaction, the reaction solution was cooled to about 5 ° C. with ice.

  To this solution, 12.88 g (0.036 mol) of a diamino compound containing a phosphorus element represented by the following general formula (10) was added and stirred at 5 ° C. for 4 hours. Thus, a partially imidized polyimide precursor having a phosphorus element and a urethane bond was obtained (weight average molecular weight 20,000, number average molecular weight 15,000). The solute concentration of this solution was 44%, and the viscosity of the solution was 500 poise at 23 ° C. Moreover, content of the phosphorus element in a polyimide precursor was 1.0 weight%.

(Examples 3 to 5)
<Preparation of photosensitive resin composition>
(A) Partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond, (B) photosensitive resin, (C) photopolymerization start A photosensitive resin composition was prepared by adding an agent, (D) a thermosetting resin, other components, and an organic solvent. Table 2 shows the blending amount of each constituent raw material in the resin solid content and the type of raw material. In addition, 1,2-bis (2-methoxyethoxy) ethane which is an organic solvent in the table is the total amount of solvent including the amount used in Synthesis Examples 1 to 3, the amount used at the time of preparation, and the like. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

<1> Product name NK ester A-9300 (ethoxylated isocyanuric acid triacrylate) manufactured by Nakamura Chemical Co., Ltd.
<2> Nakamura Chemical Co., Ltd. Product name NK ester BPE-1300 (bisphenol A EO-modified diacrylate) Molecular weight: 1684
<3> Product name of photopolymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd. <4> Product name of cresol novolac type polyfunctional epoxy resin manufactured by Dainippon Ink Co., Ltd. <5> Product name of silica particles manufactured by Nippon Aerosil Co., Ltd. .

<Preparation of coating film on polyimide film>
The above photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask with a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and irradiated with ultraviolet rays with an integrated exposure amount of 300 mJ / cm ² to be exposed. Subsequently, spray development was performed for 60 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After development, the film was sufficiently washed with pure water, and then cured by heating in an oven at 160 ° C. for 90 minutes to prepare a cured film of the photosensitive resin composition.

<Evaluation of cured film>
The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 3.

(I) Photosensitivity evaluation The photosensitivity evaluation of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item <Preparation of coating film on polyimide film>.
◯: A clear photosensitive pattern with a line width / space width = 100/100 μm is drawn on the polyimide film surface, the line does not shake due to the peeling of the line portion, and there is no residual residue in the space portion. thing.
Δ: A clear line width / space width = 100/100 μm photosensitive pattern is drawn on the polyimide film surface, and the line portion is shaken due to peeling, but there is no undissolved residue in the space portion. thing.
×: A clear line width / space width = 100/100 μm photosensitive pattern was not drawn on the surface of the polyimide film, the line portion was peeled off, and a dissolution residue was generated in the space portion.

(Ii) Adhesiveness of cured film The adhesive strength of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Iii) Solvent resistance The solvent resistance of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried to observe the state of the film surface.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Iv) Flexibility A cured film laminated film of a photosensitive resin composition on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Was made. The cured film laminated film was cut into a 30 mm × 10 mm strip, bent at 180 ° 10 times at 180 °, and visually checked for cracks in the coating film.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(V) Insulation reliability Line width / space width = 100 μm on flexible copper-clad laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Co., Ltd., and copper foil is bonded with polyimide adhesive) A / 100 μm comb-shaped pattern was prepared, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the above-mentioned <Preparation of the coating film on a polyimide film> method, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
○: A resistance value of 10 8 or more in 1000 hours after the start of the test, and no occurrence of migration or dendrite.
X: Migration, dendrite, etc. occurred in 1000 hours after the start of the test.

(Vi) Wettability The wettability of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated according to JIS K6768.

(Vii) Solder heat resistance A cured film of a photosensitive resin composition is laminated on the surface of a 75 μm-thick polyimide film (Apical 75NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A film was prepared.

The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Viii) Warpage A cured film laminated film of a photosensitive resin composition is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Produced.

  The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less.

(Ix) Flame retardancy In accordance with the flame retardancy test standard UL94 for plastic materials, a flame retardancy test was performed as follows. A cured film laminated film of a photosensitive resin composition was prepared on both sides of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Cut out the sample prepared above into dimensions: 50 mm width x 200 mm length x 75 μm thickness (including the thickness of the polyimide film), put a marked line in the 125 mm part, round it into a cylinder with a diameter of about 13 mm, and above the marked line PI tape was affixed so that there was no gap in the overlapping part (75 mm location) and the upper part, and 20 flame retardant test tubes were prepared. Of these, 10 were treated at (1) 23 ° C./50% relative humidity / 48 hours, and the remaining 10 were treated at (2) 70 ° C. for 168 hours and then cooled in a desiccator containing anhydrous calcium chloride for 4 hours or more. The upper part of these samples is clamped and fixed vertically, and a burner flame is brought close to the lower part of the sample for 10 seconds to ignite. After 10 seconds, remove the burner flame and measure how many seconds after the flame or burning of the sample has disappeared.
○: For each condition ((1), (2)), the flame and combustion stopped within 5 seconds on average (average of 10) after the flame of the burner was moved away from the sample, and self-extinguishment within 10 seconds at maximum What you did.
×: Even one sample does not extinguish within 10 seconds, or the flame rises to the clamp at the top of the sample and burns.

(X) Bleed-out The test piece after the above insulation reliability test was observed to observe a minute bulge on the surface of the test piece, a bulge on the copper wiring, a seepage of oily substances, and the like.
○: Swelled on the surface of the test piece and the copper wiring in 1000 hours after starting the test, and no abnormality such as oozing out was observed. ×: Swelled on the surface of the test piece and the copper wiring in 1000 hours after the test started Any abnormalities such as

(Comparative Example 4)
The polyamideimide obtained in Comparative Example 3, (B) photosensitive resin, (C) photopolymerization initiator, (D) thermosetting resin, other components, and an organic solvent were added to obtain a photosensitive resin composition. Produced. Table 2 shows the blending amount of each constituent raw material in the resin solid content and the type of raw material. The mixed solution was completely defoamed with a defoaming apparatus, and the physical properties of this composition were evaluated in the same manner as in Examples 3 to 5. The results are listed in Table 3.

(Comparative Example 5)
After introducing air into a reaction vessel equipped with a stirrer, thermometer, cooling tube and air introduction tube, 196.8 g of polycarbonate diol (manufactured by Daicel Chemical Industries, Plaxel CD205PL, average molecular weight 500), dimethylolbutanoic acid (Mitsubishi) Chemical Co., Ltd.) 58.3 g, Diethylene glycol (Nisso Maruzen Chemical Co., Ltd.) 37.6 g, 1,4-cyclohexanedimethanol monoacrylate (Mitsubishi Chemical Corporation) 148.1 g, p-methoxyphenol (Wako Pure Chemical Industries, Ltd.) 0.55 g, dibutyltin laurate (Tokyo Fine Chemicals Co., Ltd., L101) 0.55 g and methyl ethyl ketone (Tonen Kagaku Co., Ltd.) 110.2 g were charged under an air stream. The temperature was raised to 65 ° C. with stirring. 305.9 g of trimethylhexamethylene diisocyanate (manufactured by Huls Japan Co., Ltd., VESTANAT TMDI) was charged into the dropping vessel and uniformly dropped into the reaction vessel over 3 hours while maintaining the temperature at 65 ± 3 ° C. After completion of the dropping, the dropping container was washed with 76.5 g of methyl ethyl ketone, and the washing liquid was directly put into the reaction container. The mixture was further kept warm for 2 hours with stirring, and then heated to 75 ° C. Thereafter, stirring and heating were continued at 75 ± 3 ° C. until the isocyanate peak in the infrared absorption spectrum disappeared. The isocyanate peak disappeared in about 6 to 8 hours. After confirming the disappearance of this peak, the temperature was lowered to 60 ° C., 9.3 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.4 g of methyl ethyl ketone was added to obtain a transparent resin solution. This resin had a solid content of 75.6%, an acid value of 22.2 mg KOH / g, and a viscosity of 1,810 cP. 62.5 g of the obtained resin solution (solid content 50 g), 2,2′-bis (4-methacryloxypentaethoxyphenyl) propane 30 g, (methacrylic acid, methyl methacrylate and butyl acrylate in a weight ratio of 22:71 : A copolymer having a weight average molecular weight of 80,000 and an acid value of 143 mgKOH / g copolymerized at a ratio of 7 was dissolved in methyl cellosolve / toluene (6/4, weight ratio) to a solid content of 40% by weight. 162.5 g (solid content 65 g), benzophenone 3.5 g, N, N′-tetraethyl-4,4′-diaminobenzophenone 0.1 g, hexamethylene-based isocyanurate type isocyanate compound is reacted with methyl ethyl ketone oxime. 20 g of a 75 wt% methyl ethyl ketone solution of the blocked isocyanate compound obtained 15g), CR747 (condensed phosphoric acid ester-based additive-type flame retardant) 40 g, and stirred for 1 hour at room temperature in acetone 85 g, to obtain a photosensitive resin composition. The physical properties of this composition were evaluated in the same manner as in Examples 3-5. The results are listed in Table 3.

(Examples 6 to 8)
<Preparation of thermosetting resin composition>
(A) Partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond obtained in Synthesis Examples 1 to 3, (D) thermosetting resin, other components, and An organic solvent was added to prepare a thermosetting resin composition. Table 4 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. In addition, 1,2-bis (2-methoxyethoxy) ethane which is an organic solvent in the table is the total amount of solvent including the amount used in Synthesis Examples 1 to 3, the amount used at the time of preparation, and the like. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device. The results are listed in Table 5.

<6> Product name of cresol novolac type polyfunctional epoxy resin manufactured by Dainippon Ink Co., Ltd. <7> Product name of silica particles manufactured by Nippon Aerosil Co., Ltd.

<Preparation of coating film on polyimide film>
The thermosetting resin composition is cast and coated on a 75 μm polyimide film (manufactured by Kaneka Co., Ltd .: trade name: 75 NPI) on a 100 mm × 100 mm area using a Baker type applicator so that the final dry thickness is 25 μm. Then, after drying at 80 ° C. for 20 minutes, it was cured by heating in an oven at 160 ° C. for 90 minutes to produce a cured film of the thermosetting resin composition.

<Evaluation of cured film>
The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 5.

(Ii) Adhesiveness of cured film The adhesive strength of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Iii) Solvent resistance The solvent resistance of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried to observe the state of the film surface.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Iv) Flexibility A cured film laminate of a thermosetting resin composition on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A film was prepared. The cured film laminated film was cut into a 30 mm × 10 mm strip, bent at 180 ° 10 times at 180 °, and visually checked for cracks in the coating film.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(V) Insulation reliability Line width / space width = 100 μm on flexible copper-clad laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Co., Ltd., and copper foil is bonded with polyimide adhesive) A / 100 μm comb-shaped pattern was prepared, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Thereafter, a cured film of a thermosetting resin composition was prepared on the comb pattern by the same method as the above <Preparation of coating film on polyimide film>, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
○: A resistance value of 10 8 or more in 1000 hours after the start of the test, and no occurrence of migration or dendrite.
X: Migration, dendrite, etc. occurred in 1000 hours after the start of the test.

(Vi) Wettability The wettability of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated according to JIS K6768.

(Vii) Solder heat resistance A cured film of a thermosetting resin composition on the surface of a 75 μm-thick polyimide film (Apical 75NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A laminated film was produced.
The coated film was floated so that the surface coated with the cured film of the thermosetting resin composition was in contact with the solder bath completely dissolved at 260 ° C. and pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Viii) Warpage A cured film laminated film of a thermosetting resin composition on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Was made.
The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less.

(Ix) Flame retardancy In accordance with the flame retardancy test standard UL94 for plastic materials, a flame retardancy test was performed as follows. A cured film laminated film of a thermosetting resin composition was prepared on both sides of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Cut out the sample prepared above into dimensions: 50 mm width x 200 mm length x 75 μm thickness (including the thickness of the polyimide film), put a marked line in the 125 mm part, round it into a cylinder with a diameter of about 13 mm, and above the marked line PI tape was affixed so that there was no gap in the overlapping part (75 mm location) and the upper part, and 20 flame retardant test tubes were prepared. Of these, 10 were treated at (1) 23 ° C./50% relative humidity / 48 hours, and the remaining 10 were treated at (2) 70 ° C. for 168 hours and then cooled in a desiccator containing anhydrous calcium chloride for 4 hours or more. The upper part of these samples is clamped and fixed vertically, and a burner flame is brought close to the lower part of the sample for 10 seconds to ignite. After 10 seconds, remove the burner flame and measure how many seconds after the flame or burning of the sample has disappeared.
○: For each condition ((1), (2)), the flame and combustion stopped within 5 seconds on average (average of 10) after the flame of the burner was moved away from the sample, and self-extinguishment within 10 seconds at maximum What you did.
×: Even one sample does not extinguish within 10 seconds, or the flame rises to the clamp at the top of the sample and burns.

(Comparative Examples 6-8)
Thermosetting resin compositions were prepared by adding the polyimide precursors obtained in Comparative Examples 1 to 3, or polyamideimide, (D) thermosetting resin, other components, and an organic solvent. Table 4 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. The mixed solution was subjected to the same evaluation as in Examples 6 to 8 by completely defoaming bubbles in the solution with a defoaming apparatus. The results are listed in Table 5.

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (17)

  A partially imidized polyimide precursor having a phosphorus element in its molecular structure and a urethane bond.   2. The polyimide precursor according to claim 1, wherein the phosphorus element content in the molecular structure is 0.1 to 5.0% by weight.   The polyimide precursor according to claim 1 or 2, wherein the polyimide precursor further contains a polycarbonate skeleton. The polyimide precursor reacts at least (a) a diol compound represented by the following general formula (1) and (b) a diisocyanate compound represented by the following general formula (2) to synthesize a terminal isocyanate compound, (C) A tetracarboxylic dianhydride represented by the following general formula (3) is reacted to synthesize a terminal acid anhydride urethane imide oligomer, and (d) an addition reaction of a diamine represented by the following general formula (4) The polyimide precursor according to claim 1, wherein the polyimide precursor is obtained.
(In the formula, R represents a divalent organic group.)
(In the formula, X represents a divalent organic group.)
(In the formula, Y represents a tetravalent organic group.)
(In the formula, Z represents a divalent organic group.) The polyimide precursor according to claim 4, wherein the (a) diol compound contains at least a polycarbonate diol represented by the following general formula (5).
(In the formula, plural R _{1 s} each independently represent a divalent organic group, and m is an integer of 1 to 20.)   6. The polyimide precursor according to claim 4, wherein the (d) diamine contains at least a phosphorus element.   The polyimide precursor according to any one of claims 1 to 6, wherein the polyimide precursor further contains a carboxyl group in a side chain.   A partially imidized polyimide precursor having at least (A) a phosphorus element in the molecular structure and having a urethane bond in any one of claims 1 to 7, and (B) a photosensitive resin, (C) The photoinitiator contains, The photosensitive resin composition characterized by the above-mentioned.   (A) Partially imidized polyimide precursor having a phosphorus element in the molecular structure and having a urethane bond, (B) photosensitive resin, and (C) a photopolymerization initiator in the photosensitive resin composition (A) The photosensitive resin has 10 to 200 weight parts per 100 weight parts of the solid content of the partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond. The photosensitive resin composition according to claim 8, wherein the photopolymerization initiator (C) is blended in an amount of 0.1 to 50 parts by weight.   Furthermore, (D) thermosetting resin is contained, The photosensitive resin composition of Claim 8 or 9 characterized by the above-mentioned.   The blending ratio of the (D) thermosetting resin is (A) a partially imidized polyimide precursor having a phosphorus element in the molecular structure and a urethane bond, (B) a photosensitive resin, and ( C) The photosensitive resin composition according to claim 10, which is blended in an amount of 0.5 to 100 parts by weight with respect to 100 parts by weight of the solid content of the total photopolymerization initiator.   A partially imidized polyimide precursor having at least (A) a phosphorus element in the molecular structure and having a urethane bond in (1) a thermosetting resin according to any one of claims 1 to 7 And a thermosetting resin composition.   The blending ratio of the (D) thermosetting resin is (A) having a phosphorus element in the molecular structure and having a urethane bond, and 100 parts by weight of the solid content of the partially imidized polyimide precursor. The thermosetting resin composition according to claim 12, wherein the thermosetting resin composition is blended so as to be 0.5 to 100 parts by weight.   The polyimide precursor according to any one of claims 1 to 7, the photosensitive resin composition according to any one of claims 8 to 11, or the thermosetting resin composition according to claim 12 or 13. A polyimide precursor composition solution obtained by dissolving in an organic solvent.   The resin film obtained by apply | coating the polyimide precursor composition solution of Claim 14 to the base-material surface, and drying.   An insulating film obtained by curing the resin film according to claim 15.   The printed wiring board with an insulating film which coat | covered the insulating film of Claim 16 on the printed wiring board.