JP2009280661A - Novel polyimide precursor composition, use thereof and production process thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide precursor solution that can be cured at a low temperature (250°C or lower) and has a low viscosity although it has a high concentration, to provide a process for producing the polyimide precursor solution, to provide a polyimide coating film that is produced from the polyimide precursor solution and has good physical properties, to provide a photosensitive resin composition and to provide a process for producing the photosensitive resin composition. <P>SOLUTION: A polyimide precursor composition characterized by containing an imidized dicarboxylic acid having a specific structure and a diamine having a specific structure and/or an isocyanate compound is used to solve the problem. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyimide precursor composition that can be cured at a low temperature of 250 ° C. or less and has excellent long-term storage stability, a method for producing the same, and a polyimide precursor solution, a polyimide coating film, and a photosensitive resin obtained from the polyimide precursor composition. The present invention relates to a composition and a method for producing the composition.

  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 is low, so the concentration of the solute cannot be adjusted to a high concentration. When forming a film, it was necessary to volatilize a large amount of the solvent, which was a problem of poor productivity. In the case of a polyimide resin precursor solution, it is necessary to imidize when it is formed into a coating film, and it is necessary to imidize at a temperature exceeding 300 ° C. When used as a protective agent or adhesive for molded products, there is a problem that the wiring material cannot withstand high temperatures, and a resin that can be cured at a low temperature (250 ° C. or lower) that does not cause deterioration of the wiring is required. ing.

  Regarding the technology of these polyimide resin solutions, a high-concentration and low-viscosity polyimide precursor solution in which tetracarboxylic acid or its diester acid derivative and diamine are dissolved has been proposed (for example, see Patent Documents 1 to 4).

  In addition, a high-concentration and low-viscosity polyimide precursor solution in which a carboxylic acid having an amide bond and a diamine are dissolved in the structure has been proposed (see, for example, Patent Documents 5 to 7).

Furthermore, the photosensitive resin composition or plasma etching resist using the terminal half esterified imide siloxane oligomer is proposed (for example, refer patent documents 8-11).
Japanese Patent Laid-Open No. 11-209609 JP-A-11-217502 JP 2000-319389 A JP 2000-319391 A JP 2001-31764 A JP 2001-163974 A Japanese Patent Application Laid-Open No. 2000-234023 JP 2000-212446 A JP 2001-89656 A JP 2001-125273 A JP 2001-215702 A

  As described in the above patent document, various methods have been proposed as a method for adjusting to a high concentration. However, the solution of a salt using tetracarboxylic acid or its diester acid derivative and diamine described in Patent Documents 1 to 4 has a very high imidization temperature and does not become a solution of a salt that can be cured at low temperature. Became clear. In addition, in the case of the polyamic acid solution having an amide bond described in Patent Documents 5 to 7, the amide bond is broken and the solution stability is poor, and particularly when the solution is prepared at a high concentration, the amount of change in the solution viscosity is large. It became clear that there is. On the other hand, when the terminal half esterified imide siloxane oligomer described in Patent Documents 8 to 11 is used, the temperature when the organic molecule is desorbed from the esterified product and imidized is high, and the alcohol-based desorbing material Is difficult to evaporate from the polyimide coating film, which may cause foaming and the like.

  In view of the above situation, an object of the present invention is to provide a polyimide precursor solution that can be cured at a low temperature (250 ° C. or lower) and has a low viscosity despite its high concentration, a method for producing the same, and good physical properties obtained therefrom. It is in providing the polyimide coating film which has, and the photosensitive resin composition and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a polyimide coating film having good physical properties by low-temperature curing from a composition containing an imidized dicarboxylic acid and a diamine and / or isocyanate compound. I found out that That is, the polyimide precursor composition containing the imidized dicarboxylic acid represented by the general formula (1) and the diamine and / or isocyanate compound represented by the general formula (2) has a high solute when prepared in a solution. Despite being dissolved at a concentration, it showed low viscosity, and obtained the knowledge that a high-strength polyimide coating film was obtained from this solution. Based on these findings, the present invention has been achieved. It is. The present invention can solve the above problems with a polyimide resin precursor composition having the following novel configuration.

That is, the present invention
At least the following general formula (1)

(Wherein R represents a tetravalent organic group, R ′ independently represents a divalent organic group, R ″ each independently represents a trivalent organic group, and 1 represents 1 Represents an integer of ~ 20.)
And an imidized dicarboxylic acid represented by the following general formula (2)

(In the formula, R ′ ″ represents a divalent organic group.)
It is a polyimide precursor composition characterized by including the diamine and / or isocyanate type compound shown by these.

  In the general formula (1), R represents the following general formula group (1)

It is preferably a tetravalent organic group selected more.

  In the general formula (1), R ′ represents the following general formula group (2)

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
It preferably contains at least a divalent organic group represented by

  In addition, R ′ ″ in the general formula (2) represents the following general formula group (3)

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
It is preferably a divalent organic group selected more.

  Another invention of the present invention is a polyimide precursor composition solution obtained by dissolving a polyimide precursor composition in a solute concentration of 40 to 90% by weight.

  Furthermore, another invention of the present invention is a polyimide coating film obtained from the polyimide precursor composition or the polyimide precursor composition solution.

  Furthermore, another invention of the present invention is a printed wiring board with a polyimide coating obtained by applying the polyimide precursor composition or the polyimide precursor composition solution to a printed wiring board and imidizing by heating.

  Furthermore, another invention of the present invention is a photosensitive resin composition comprising the polyimide precursor composition, at least a photosensitive resin, and a photopolymerization initiator.

  Furthermore, another invention of the present invention is the following general formula (3)

(In the formula, R represents a tetravalent organic group.)
A tetracarboxylic dianhydride shown in
The following general formula (4)

(In the formula, R ′ represents a divalent organic group.)
A diamine shown in
The step (1) of obtaining an amic acid by reacting at a ratio of 1.50 to 2.50 mol of the diamine shown in the general formula (4) with respect to 1 mol of tetracarboxylic dianhydride shown in the general formula (3), Imidize amic acid,
The following general formula (5)

(In the formula, R represents a tetravalent organic group, R ′ independently represents a divalent organic group, and l represents an integer of 1 to 20.)
And a step of obtaining a diamine in which the inside is imidized, and the following general formula (6)

(In the formula, R ″ represents a trivalent organic group.)
And the imidized diamine represented by the general formula (5),
A step (2) of obtaining an amic acid by reacting at a ratio of 0.20 to 0.80 mol of an imidized diamine represented by the general formula (5) with respect to 1 mol of the tricarboxylic acid anhydride represented by the general formula (6); Imidizing the amic acid, the inside is imidized, the terminal is a dicarboxylic acid, comprising the step of obtaining an imidized dicarboxylic acid,
Furthermore, the imidized dicarboxylic acid obtained in the step,
The following general formula (2)

(In the formula, R ′ ″ represents a divalent organic group.)
The diamine and / or isocyanate compound is converted into the general formula (5) used in the step (2) of obtaining the amic acid with respect to 1 mol of the imidized dicarboxylic acid. It is a manufacturing method of the polyimide precursor composition characterized by including the process of mixing in the ratio used as the total ratio united with the imidized diamine shown to be 0.70 mol-1.30 mol.

  The diamine represented by the general formula (4) is represented by the following general formula group (4).

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
It is preferable that at least the diamine shown by these is included.

  Another invention of the present invention includes a step of dissolving a polyimide precursor composition obtained by the above production method in an organic solvent so as to have a solute concentration of 40 to 90% by weight. It is a manufacturing method of a physical solution.

  Furthermore, another invention of the present invention is a method for producing a polyimide coating film, comprising a step of obtaining a polyimide coating film from the polyimide precursor composition obtained by the production method or the polyimide precursor composition solution. is there.

  Furthermore, another invention of the present invention includes a step of applying a polyimide precursor composition obtained by the production method or the polyimide precursor composition solution to a printed wiring board and heating to imidize. It is a manufacturing method of the printed wiring board with a polyimide coating film.

  Furthermore, another invention of the present invention includes a step of mixing a polyimide precursor composition obtained by the above production method, at least a photosensitive resin, and a photopolymerization initiator. It is a manufacturing method.

  When the polyimide precursor composition of the present invention is dissolved in an organic solvent, the solution has a low viscosity even though the solute is dissolved at a high concentration. And the polyimide coating film obtained from the polyimide precursor composition of this invention is excellent in the adhesiveness of a coating film, environmental test stability, chemical resistance, and flexibility, and has a favorable physical property. Therefore, the polyimide precursor composition of the present invention can be used as a protective film for various wiring boards, and has excellent effects. In addition, the photosensitive resin composition using the polyimide precursor composition of the present invention can be cured at a low temperature, and exhibits a variety of excellent properties when applied and molded on a wiring board. It is a thing. Moreover, according to the method for producing a polyimide precursor composition of the present invention, a polyimide precursor solution that dissolves at a high concentration and has a low viscosity can be easily produced. A polyimide coating film can be easily produced. Furthermore, according to the method for producing a photosensitive resin composition, a photosensitive resin composition having various excellent properties can be produced as a photosensitive resin composition.

  The present invention will be described in detail below. The polyimide precursor composition of the present invention has at least the following general formula (1)

(Wherein R represents a tetravalent organic group, R ′ independently represents a divalent organic group, R ″ each independently represents a trivalent organic group, and 1 represents 1 Represents an integer of ~ 20.)
An imidized dicarboxylic acid shown in
The following general formula (2)

(In the formula, R ′ ″ represents a divalent organic group.)
The polyimide precursor composition characterized by containing the diamine and / or isocyanate type compound shown to these. The polyimide precursor composition of the invention of the present application contains the structure of the above general formula (1), diamine and / or isocyanate compound, but each does not have a covalent bond. That is, the general polyimide precursor composition refers to a polymer in which, for example, tetracarboxylic dianhydride and diamine are partially covalently bonded by an amide bond, but the polyimide precursor composition of the present invention has the general formula (1 ), A compound in which the diamine and / or isocyanate compound does not have a covalent bond. Thus, by setting it as the polyimide precursor composition which does not have a covalent bond, it becomes possible to raise the density | concentration of the solution which melt | dissolved the said General formula (1), a diamine, and / or an isocyanate type compound, and the change of the viscosity of a solution ( (Molecular weight change) can hardly occur.

<Imidized dicarboxylic acid>
The imidized dicarboxylic acid is represented by the following general formula (1)

(Wherein R represents a tetravalent organic group, R ′ independently represents a divalent organic group, R ″ each independently represents a trivalent organic group, and 1 represents 1 Represents an integer of ~ 20.)
As shown in the above, it is a dicarboxylic acid having a structure in which at least four imide bonds are included in the structural formula and both ends are carboxylic acids. In addition, the imidized dicarboxylic acid of the present invention is preferable as the molecular weight is shorter because the solubility in an organic solvent is improved. For example, a polymer called an oligomer having a relatively low molecular weight is preferable. Although it is imidized by setting it as such a dicarboxylic acid structure, the solubility to an organic solvent can be improved. Moreover, since the bond in the structure is not an amide bond but an imide bond, the storage stability is excellent. Therefore, when the polyimide precursor composition solution is prepared, deterioration of the solution viscosity with time can be prevented, and a change in viscosity can be suppressed.

  Especially, it is preferable that R in General formula (1) has a structure chosen from the following general formula group (1).

In particular, by using the structure of the above general formula group (1), the solubility of the imidized dicarboxylic acid in the organic solvent is increased, and the concentration can be increased when a solution of the polyimide precursor is prepared. It is preferable because it is possible.

  Furthermore, R ′ in the general formula (1) preferably has at least a divalent organic group selected from the following general formula group (2).

  In order to obtain the structure of the general formula (1), the following general formula (3)

(In the formula, R represents a tetravalent organic group.)
And tetracarboxylic dianhydride shown in the following general formula (4)

(In the formula, R ′ represents a divalent organic group.)
Is reacted with the diamine shown in the following general formula (5):

(In the formula, R represents a tetravalent organic group, R ′ independently represents a divalent organic group, and l represents an integer of 1 to 20.)
Is obtained, and the following general formula (6)

(In the formula, R ″ represents a trivalent organic group.)
It can be obtained by reacting the tricarboxylic acid anhydride shown in FIG.

  More specifically, as the tetracarboxylic dianhydride represented by the general formula (3), 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′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic anhydride Preferably used, particularly preferably 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride 3,3 ′, 4,4′-oxydiphthalic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride It is preferable to improve the solubility of the polyimide precursor and improve the chemical resistance of the polyimide resin. Among these, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is preferably used for improving solubility and improving film properties.

  More specifically, the diamine represented by the general formula (4) preferably has a structure containing at least a divalent organic group selected from the following general formula group (2) as the structure of R ′.

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)

  By giving the structural skeleton, flexibility can be imparted to the polyimide resin coating when the polyimide resin is molded, and the imidization temperature when molding into the polyimide resin can be lowered. By using this structural skeleton together, it is possible to lower the imidization temperature of the polyimide resin to 250 ° C. or lower.

  A particularly preferred R ′ structure is the following general formula group (5).

(Wherein, _{R 1} and _{R 2} each independently represents an alkyl group or an aromatic group, of 1 to 12 carbon atoms, m is 1 to 40 integer, n is an integer of 1-20. m represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)

Use of the above structure is preferable because flexibility can be imparted to the polyimide coating, the imidization temperature can be lowered, the solute concentration can be adjusted to a high concentration, and the adhesion to the substrate is improved.

  In order to introduce the above structure into the structural skeleton, a long-chain diamine represented by the following general formula group (4) is used.

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)

  Especially, when the adhesiveness with a base material is considered especially, it is preferable that it is the following general formula group (6) in the said structure.

(Wherein, o and p each independently represent an integer of 1 to 30; R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group; m represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)

In particular, the structure of silicon diamine used in the present invention is preferably a structure in which R ₁ and R ₂ are a methyl group, an ethyl group, and a phenyl group, m is 1 to 40, and n is 2 or more. With such a structure, the solute concentration can be dissolved at a high concentration.
R ₃ is a heptamethylene group, a hexamethylene group, a pentamethylene group, a tetramethylene group, or a trimethylene group, and o and p are each independently a structure having an integer of 1 to 30.

  Such a structure is preferable because flexibility can be imparted to the polyimide resin and adhesion with the substrate is improved.

  In addition, it is also possible to use together the diamine shown by General formula (7) in manufacture of the imidized dicarboxylic acid as needed.

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

  More specifically, the diamine represented by the general formula (7) has a structure containing at least a divalent organic group selected from the following general formula group (7) as the structure of R ′ ″ ″.

  The combined amount is 1 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less when the diamine mole number of the general formula (4) is 1. This is preferable because it increases the solubility of the imidized dicarboxylic acid of the general formula (1) in an organic solvent and the imidization temperature at the time of imidization can be imidized at a low temperature.

  More specific examples of the tricarboxylic acid anhydride represented by the general formula (6) include trimellitic acid anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Among them, it is preferable to use trimellitic anhydride for improving the solubility and improving the properties of the film.

<Method for producing imidized dicarboxylic acid>
Various methods are mentioned as a manufacturing method of the said imidized dicarboxylic acid.

  Method 1: In a solution in which a tetracarboxylic dianhydride represented by the above general formula (3) is dispersed or dissolved in an organic solvent, a diamine represented by the general formula (4) or a general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (7). At this time, the total amount of diamine added is 1.50 to 2.50 moles per mole of tetracarboxylic dianhydride. After the reaction between the tetracarboxylic dianhydride and the diamine is completed, the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to perform imidization. In this way, a diamine solution in which the inside represented by the general formula (5) is imidized is obtained. Next, a tricarboxylic acid anhydride represented by the general formula (6) is added to the obtained imidized diamine solution and reacted to prepare a polyamic acid solution. At this time, the amount of imidized diamine added is 0.20 to 0.80 mole per mole of tricarboxylic anhydride. After the reaction between the tricarboxylic acid anhydride and the imidized diamine is completed, the resulting polyamic acid solution is heated to 100 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower to perform imidization. In this way, a partially imidized dicarboxylic acid can be obtained. In addition, it is preferable to use the solvent which can be heated to the glass transition temperature or more of the polyimide resin as the solvent used in this method, and it is particularly preferable to use a solvent which can be heated to a temperature higher by 30 ° C. than the glass transition temperature. It is preferable.

  Method 2: In a solution in which the tetracarboxylic dianhydride represented by the above general formula (3) is dispersed or dissolved in an organic solvent, the diamine represented by the general formula (4) or the general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (7). At this time, the total amount of diamine added is 1.50 to 2.50 moles per mole of tetracarboxylic dianhydride. Next, an imidization catalyst (preferably tertiary amines such as pyridine, picoline, isoquinoline, trimethylamine, triethylamine, and tributylamine are used) and a dehydrating agent (such as acetic anhydride) are added to the polyamic acid solution. The imidization is carried out by heating at a temperature of from ℃. In this way, a diamine solution in which the inside represented by the general formula (5) is imidized is obtained. Next, a tricarboxylic acid anhydride represented by the general formula (6) is added to the obtained imidized diamine solution and reacted to prepare a polyamic acid solution. At this time, the amount of imidized diamine added is 0.20 to 0.80 mole per mole of tricarboxylic anhydride. After the reaction between the tricarboxylic acid anhydride and the imidized diamine is completed, an imidization catalyst and a dehydrating agent are added to the polyamic acid solution and heated to 60 ° C. or higher and 180 ° C. or lower to perform imidization. It is possible to obtain an imidized dicarboxylic acid by adding water to the imidized solution or by adding the imidized solution to water to precipitate it in a solid state, followed by filtration and drying. it can.

  Method 3: In a solution in which the tetracarboxylic dianhydride represented by the above general formula (3) is dispersed or dissolved in an organic solvent, the diamine represented by the general formula (4) or the general formula (4) A polyamic acid solution is prepared by adding and reacting both diamines of general formula (7). At this time, the total amount of diamine added is 1.50 to 2.50 moles per mole of tetracarboxylic dianhydride. The polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or more and 250 ° C. or less, and imidation is performed by drawing a vacuum while heating and drying. In this way, a diamine solution in which the inside represented by the general formula (5) is imidized is obtained. Next, a tricarboxylic acid anhydride represented by the general formula (6) is added to the obtained imidized diamine solution and reacted to prepare a polyamic acid solution. At this time, the amount of imidized diamine added is 0.20 to 0.80 mole per mole of tricarboxylic anhydride. After the reaction between the tricarboxylic acid anhydride and the imidized diamine is completed, the polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or more and 250 ° C. or less and imidized by pulling a vacuum while performing heating and drying. To obtain an imidized dicarboxylic acid.

  The above method is preferably used, but regardless of the above method, any method can be used as long as a carboxyl group is present at both ends and an imidized dicarboxylic acid having an imidized center can be obtained. there is no problem.

  Tetracarboxylic dianhydride shown in the general formula (3) and diane shown in the general formula (4) or the general formula (4) and the general formula for obtaining a diamine in which the inside shown in the general formula (5) is imidized. (7) The reaction with both diamines is preferably 1.50 to 2.50 mol of diamine with respect to 1 mol of tetracarboxylic dianhydride, more preferably 1 diamine with respect to 1 mol of tetracarboxylic dianhydride. .80 to 2.20 moles. Further, a tricarboxylic acid anhydride represented by the general formula (6) for obtaining a dicarboxylic acid having an imidized inside represented by the general formula (1) and a diamine having an imidized inside represented by the general formula (5) The reaction is preferably 0.20 to 0.80 mol of a diamine having an imidized interior represented by the general formula (5) with respect to 1 mol of a tricarboxylic acid anhydride, and more preferably with respect to 1 mol of a tricarboxylic acid anhydride. The inside of the diamine formed by imidation in the general formula (5) is 0.40 to 0.60 mol. By controlling in such a range, the molecular weight of the imidized dicarboxylic acid represented by the general formula (1) can be kept low, and an imidized dicarboxylic acid having high solubility in an organic solvent can be obtained efficiently. .

  Examples of the solvent used for polymerization in the present invention include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N-dimethylacetamide. , Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated Phenolic solvents such as phenol and catechol, or hexamethylphosphoramide, γ-butyrolactone, methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyether) ether), methyl triglyme ( 1,2-bis 2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ) Ether), symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, 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 Reacted monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, acetates such as 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. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination.

  Furthermore, the polyimide precursor composition of this invention may contain the tricarboxylic acid shown by following General formula (8).

(Wherein R ″ represents a trivalent organic group, provided that R ″ does not include an imide ring.)

  The tricarboxylic acid is prepared by previously preparing the tricarboxylic acid represented by the general formula (8) and adding it during the preparation of the polyimide precursor solution, or partially imidized by the general formula (1). During the preparation of the dicarboxylic acid solution, the tricarboxylic acid represented by the general formula (8) can be simultaneously prepared by adding an excess of tricarboxylic acid anhydride. That is, in the production process of the general formula (1), the diamine amount of the imidized diamine represented by the general formula (5) is 0.5 with respect to 1 mol of the tricarboxylic acid anhydride represented by the general formula (6). When the reaction is carried out at a molar ratio or less, the tricarboxylic acid represented by the above general formula (8) coexists in the finally obtained imidized dicarboxylic acid. However, depending on the reaction process, it may occur even when an amount of 0.5 mol or more is added.

  Specific examples of the tricarboxylic acid represented by the general formula (8) include trimellitic acid and naphthalene-1,2,4-tricarboxylic acid.

  In particular, trimellitic acid is preferably used to lower the solution viscosity and lower the final imidization temperature.

<Diamine>
The diamine represented by the following general formula (2) that can be suitably used in the present invention is:

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

R ′ ″ in the formula is preferably a divalent organic group selected from the following general formula group (3).

  More specifically, 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) sulfoxide, bis (3 -Aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'- Diaminobenzophenone, 3,3'-diaminodiphenyl Tan, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-amino Phenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfide, 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-aminophenoxy) Phenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-aminophenoxy) 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-aminophenoxyphenyl)] [ 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-amino Phenoxyphenyl)]-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, poly Tetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene 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, 2,2-bis [3-amino-4- Ruboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 2,2-bis [4- Amino-3-carboxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino- 2,2′-dicarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxydiphenyl sulfone, 4,4′-diamino- 2,2′-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2,4-diaminophenol, 2, -Diaminophenols such as diaminophenol and 3,5-diaminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4 ' -Hydroxybiphenyl compounds such as diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenyl, 3,3'-diamino-4,4'- Dihydroxydiphenylmethanes such as 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-hydroxyphenyl] propane, etc. Bis [hydroxyphenyl] propanes, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane and the like Hydroxyphenyl] hexafluoropropanes, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′- Hydroxydiphenyl ethers such as dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2 Dihydroxydiphenyl, such as' -dihydroxydiphenylsulfone Sulfones, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide Dihydroxydiphenyl sulfides such as 3,3′-diamino-4,4′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-2,2 ′ Dihydroxydiphenyl sulfoxides such as dihydroxydiphenyl sulfoxide, bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 4,4 ′ -Bis (4-amino-3-hydroxyphenoxy ) Bis (hydroxyphenoxy) biphenyl compounds such as biphenyl, bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, 4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4 Examples thereof include bis (hydroxyphenoxy) biphenyl compounds such as' -bis (4-amino-3-hydroxyphenoxy) biphenyl.

  In particular, in order to improve the heat resistance of a polyimide resin film produced using the obtained polyimide precursor composition, the glass transition temperature of the substance is preferably 50 ° C. or higher. Such raw materials include p-phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4 ′. -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3 -Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] 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, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, , 3-bis (4-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, polytetramethylene oxide-di-P-amino Benzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate) G), 3,5-diaminobenzoic acid, [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, and 2,2-bis [3-amino-4-carboxyphenyl] propane are preferably used.

  It is preferable to use the diamine because high heat resistance can be imparted to the cured film obtained when the polyimide precursor composition is cured.

  In the production of the polyimide precursor composition of the present invention, the addition amount of the diamine represented by the general formula (2) is the general formula (1) with respect to 1 mol of the tricarboxylic acid anhydride used in the production method of the general formula (1). The total ratio of diamines present in the final polyimide precursor composition that is the amount of imidized diamine shown in 5) and the amount of diamine shown in general formula (2) is 0.70 mol to 1.30 mol, The amount is more preferably 0.80 to 1.10 mol, and particularly preferably 0.90 to 1.10. When the addition ratio of the diamine represented by the general formula (2) is controlled within the above range, it is preferable because imidization reaction proceeds easily and a high molecular weight polyimide resin is easily obtained. The temperature at which the diamine represented by the general formula (2) is added is not limited as long as imidization does not proceed, and mixing at 100 ° C. or lower, more preferably 80 ° C. or lower is preferable.

<Isocyanate compounds>
The isocyanate compound used in the present invention is a compound having two or more isocyanate groups.

  Examples of such isocyanate compounds include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Diisocyanates such as alicyclic diisocyanates such as isophorone diisocyanate and norbornene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate. In particular, the isocyanate compounds suitably used in the present invention are aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and tetramethylxylene diisocyanate.

  It is preferable to use the isocyanate compound because high heat resistance can be imparted to the cured film obtained when the polyimide precursor composition is cured.

  Moreover, in this invention, the blocked isocyanate compound etc. which stabilized the said isocyanate type compound with the blocking agent can be used. The blocked isocyanate compound is a compound that is inactive at room temperature, and is heated to dissociate a blocking agent such as oximes, diketones, phenols, caprolactams, and regenerate isocyanate groups. Product names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T, 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, Million Over preparative MS-50 and the like. In particular, the blocked isocyanate compound suitably used in the present invention is a block isocyanate compound such as a hexamethylene diisocyanate type isocyanurate type, biuret type, adduct type, etc. in which the dissociation temperature of the blocking agent is 160 ° C. or less, hydrogenated diphenylmethane diisocyanate type, water It is an additive xylylene diisocyanate block isocyanate compound.

  It is preferable to use the above-mentioned blocked isocyanate compound because the cured film obtained when the polyimide precursor composition is cured can be provided with high adhesion to the substrate.

  In addition, these isocyanate compounds may be used alone or in combination of two or more.

  In the production of the polyimide precursor composition of the present invention, the addition amount of the diamine and / or isocyanate compound shown in the general formula (2) is 1 mol of the tricarboxylic acid anhydride used in the production method of the general formula (1). In contrast, the amount of imidized diamine represented by general formula (5) and the total amount of diamine and / or isocyanate compound present in the final polyimide precursor composition having the diamine amount represented by general formula (2). The amount is such that the ratio is 0.70 to 1.30 mol, more preferably 0.80 to 1.10 mol, and particularly preferably 0.90 to 1.10. When the addition ratio of the diamine and / or isocyanate compound is controlled within the above range, when imidation is performed by heating, the imidization reaction easily proceeds, and a high molecular weight polyimide resin is easily obtained, which is preferable. The temperature at which the diamine and / or isocyanate compound is added is not limited as long as imidization does not proceed. Mixing is preferably performed at 100 ° C. or lower, more preferably 80 ° C. or lower.

<Preparation method of polyimide precursor composition solution>
It describes about the preparation method of the polyimide precursor composition solution of this invention. When preparing a polyimide precursor composition solution in a solution obtained by synthesizing an imidized dicarboxylic acid, the solution is used as it is, and a diamine and / or an isocyanate compound is added to the solution to obtain a polyimide precursor composition. It is preferable to obtain a solution, and the polyimide precursor composition once separated as a solid is preferably diluted with a solvent.
As the solvent to be used, it is preferable to use one or a mixture of two or more of the solvents described as the solvent used in the polymerization.

  In preparing the polyimide precursor solution, the solute concentration is preferably 40 to 90% by weight as the concentration of the polyimide precursor composition solution, and particularly preferably 45 to 85% by weight.

  The solute concentration of the present invention is a value calculated from the following calculation formula 1.

  Solute concentration (%) = solute weight / (solute weight + solvent weight) × 100 Equation 1

  The solute weight and solvent weight in the formula are raw material weights other than the solvent dissolved in the organic solvent. For example, a certain amount (A gram) of the resin solution is taken out and heated to a temperature at which the solvent can be volatilized or left. The weight (B gram) of the solid content is measured, the weight of the solid content (B gram) is the solute weight, and the value calculated by the following calculation formula 2 is the solvent weight.

  Solvent weight = AB Formula 2

  As described above, the solution concentration in which the polyimide precursor composition in the present invention is dissolved is preferably 40 to 90% by weight, more preferably 45 to 85% by weight. When making a molded body using the polyimide resin composition by making such a range, the solvent removal amount is reduced, the handleability is improved, and the coating film thickness when being molded into a film body is dried. The amount of change in film thickness is reduced, and formability is significantly improved. Moreover, since the viscosity of a polyimide precursor composition solution can be controlled in the optimal range, it is preferable. For example, when a polyimide precursor composition solution is applied and dried to produce a film-shaped molded body, it depends on the coating method, but is usually preferably 6000 poise or less at 23 ° C., more preferably 5000 poise or less. . If the viscosity exceeds 6000 poise, coating may be difficult. In the present invention, it is possible to freely control from high viscosity to low viscosity by adjusting the concentration.

  Furthermore, in the polyimide precursor solution of the present invention, other known materials such as organic silanes, pigments, conductive carbon black and fillers such as metal particles, abrasives, dielectrics, lubricants, etc. may be used as necessary. Additives can be added as long as the effects of the present invention are not impaired. In addition, other polymers and solvents such as water-insoluble ethers, alcohols, ketones, esters, halogenated hydrocarbons, hydrocarbons and the like can be added as long as the effects of the present invention are not impaired.

  In order to obtain a polyimide coating film, a polyimide precursor composition solution is obtained by a known method such as a conventionally known spin coating method, spray coating method, screen printing method, dipping method, curtain coating method, dip coating method, or die coating method. It is obtained by imidation after coating on the material, drying at a temperature of 250 ° C. or less to remove the solvent.

  The polyimide precursor composition of the present invention has a low temperature required for imidization and can be cured at 250 ° C. or lower. In addition, when apply | coating on the printed wiring board which can be hardened at low temperature, since the copper foil which is a conductor does not oxidatively degrade, it is preferable. A particularly preferable curing temperature is preferably 200 ° C. or lower, and the polyimide precursor composition of the present invention also supports curing at a low temperature of 200 ° C. or lower.

<Photosensitive resin composition>
A photosensitive resin composition is mentioned as an example of utilization of the polyimide precursor composition of this invention. Hereinafter, the photosensitive resin composition will be described in detail. In addition, it cannot be overemphasized that it is restricted to this as an example of utilization of the polyimide precursor composition of this invention. The composition of the photosensitive resin composition is as follows. That is, a photosensitive resin composition comprising the polyimide precursor composition, at least a photosensitive resin, and a photopolymerization initiator. In addition, about the polyimide precursor composition used for the photosensitive resin composition, if it is the said polyimide precursor composition, it can be used without specifically limiting. Of the polyimide precursor composition, for the imidized dicarboxylic acid, a terminal dicarboxylic acid siloxane imide oligomer obtained using silicon diamine (siloxane diamine) is preferably used, but is not limited thereto. .

  Each constituent material will be described.

<Photosensitive resin>
The photosensitive resin in the present invention is a monomer, oligomer, or polymer resin that is polymerized by radicals, acids, bases, protons, amines, etc. generated by light or heat. More preferred is a resin having at least one unsaturated double bond. Furthermore, the unsaturated double bond is an acryl group (CH ₂ ═CH— group), a methacryloyl group (CH ₂ ═C (CH ₃ ) — group) or a vinyl group (—CH═CH— group). It is preferable. Although the photosensitive resin used suitably by this invention below is illustrated below, what kind of resin may be used if it is resin which has at least one said unsaturated double bond.

  For example, bisphenol F EO modified (n = 2-50) diacrylate, bisphenol A EO modified (n = 2-50) diacrylate, bisphenol S EO modified (n = 2-50) 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-hexanediol diacrylate, neopentyl glycol diacrylate, Ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate Tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylol Propane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, Allyl 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-bi [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- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (acryloxy-polyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane trimethacrylate, Tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenol Xylethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1, 4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol dia Chryrate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl-1,5-pentane Diol diacrylate, ethoxylated totimethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, Ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triac Liloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, allobarbital, 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′-isopropylidene diphenol diacrylate, etc. Although preferable, it is not limited to these. 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 a product having an EO repeating unit in the range of 2 to 50, the solubility 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 addition to the above examples, for example, 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri, tetraacrylate, etc. Those having a hydroxyl group or a carbonyl group in the molecular structure skeleton 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.

<Photopolymerization initiator>
As the photopolymerization initiator, those having any structure can be used as long as they generate radicals, acids, bases, protons, amines and the like upon irradiation with light. For example, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 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, benzyldimethylket -Ru, benzyldiethylketa- 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) -phenyl] -2-hydroxy-2-methyl 1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morphol Linophenyl) -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-cyclopentadien-1-yl) -bis (2 , 6-Difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanonedione, 1- [4- (phenyl) Ruthio)-, 2- (O-benzoyloxime)], iododium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-), ethyl-4-dimethyl Aminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxyome) Etc. The photopolymerization initiator is preferably selected as appropriate, and one or more types are preferably mixed and used.

  In the present invention, the component ratio of the polyimide precursor composition, the photosensitive resin, and the photopolymerization initiator in the photosensitive resin composition is 10 parts by weight with respect to 100 parts by weight of the solid content of the polyimide precursor composition. It is preferable that ˜200 parts by weight and the photopolymerization initiator are blended so as to be 0.1 to 50 parts by weight.

  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 is less than the above range, the heat resistance of the cured film after photo-curing the photosensitive resin is lowered and the contrast when exposed and developed tends to be difficult. 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.

  When the photopolymerization initiator is less than the above range, the curing reaction of the photosensitive resin during light irradiation hardly occurs, and curing may be insufficient. 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.

<Thermosetting resin>
The photosensitive resin composition of the present invention is excellent in heat resistance after curing (solder heat resistance, etc.), chemical resistance (alkali solution resistance, acid resistance, solvent resistance, etc.), moisture resistance environment stability, and heat resistance environment stability. In order to make a resin composition, it is preferable to mix a thermosetting resin.

  Thermosetting resins used in the photosensitive resin composition of the present invention include epoxy resins, bismaleimide resins, bisallyl nadiimide resins, acrylic resins, methacrylic resins, hydrosilyl cured resins, allyl cured resins, unsaturated polyester resins, etc. Thermosetting resin: Use of a side chain reactive group type thermosetting polymer having a reactive group such as an allyl group, a vinyl group, an alkoxysilyl group, or a hydrosilyl group at the side chain or terminal of the polymer chain. it can. The thermosetting component may be used alone or in combination of two or more.

  Among these, it is preferable to use an epoxy resin. By containing an epoxy resin component, heat resistance (solder heat resistance, etc.) and chemical resistance (alkali solution resistance, acid resistance, solvent resistance, etc.) for a cured resin obtained by curing a thermosetting resin composition ), Humidity resistance environment stability and heat resistance environment stability can be imparted, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  Any epoxy resin may be used as long as it contains at least two epoxy groups in the molecule. For example, 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, water-added bisphenol A type epoxy resin, ethylene oxide adduct bisphenol A type epoxy resin, Propylene oxide adduct bisphenol A type epoxy resin, novolak type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, polyglycol type epoxy resin, cyclic aliphatic epoxy resin, Cyclopentadiene type epoxy resin, dicyclopentadiene type epoxy resin, cresol novolac type epoxy resin, glycidyl a Emission type epoxy resins, naphthalene type epoxy resins, urethane modified epoxy resins, rubber-modified epoxy resins, and epoxy resins 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., Epicoat 152, 154 manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku ( 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.

  The amount of the thermosetting resin used in the present invention is 0.5 to 100 parts by weight with respect to 100 parts by weight of the solid content of the polyimide precursor resistant composition, the photosensitive resin, and the photopolymerization initiator. It is preferable to mix. More preferably, it is 1.0-50 weight part, Most preferably, it is 1.0-10 weight part. 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. Moreover, since a softness | flexibility can be provided to hardened | cured material after the photosensitive resin composition hardens | cures by controlling a compounding ratio to the said range, it is preferable.

  Furthermore, the epoxy resin used in the photosensitive resin composition of the present invention can be used in combination with an epoxy compound having only one epoxy group in one molecule, in addition to the above epoxy resin. For example, there are n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether and the like. In addition, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate are exemplified.

  The photosensitive resin composition of the present invention includes a compound having a phenolic hydroxyl group, a compound having an amine group, a compound having a carboxylic acid, a compound having a mercapto group, an isocyanate as a curing agent for the thermosetting resin. A compound having a group can also be used. For example, phenol novolac type phenol resin, cresol novolac type phenol resin, phenol resin such as naphthalene type phenol resin, amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazole compounds, Lewis acid, and Bronsted acid salts, polymercaptan compounds, isocyanates and blocked isocyanate compounds, and the like can be used in combination.

  In addition, the curing accelerator for the thermosetting resin is not particularly limited. For example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine, and tetraethanolamine Borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl; Imidazoles such as imidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; Methyl imidazoline, 2-ethyl ester Imidazolines such as dazoline, 2-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 Examples include azine-based imidazoles such as-[2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine. When an amino group is contained in the urethane resin, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6- [ It is preferable to use imidazoles such as 2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine.

<Other ingredients>
Various additives such as a flame retardant, an antifoaming agent, a coupling agent, a filler, an adhesion aid, a leveling agent, and a polymerization inhibitor can be added to the photosensitive resin composition of the present invention as necessary. . As the filler, a fine inorganic filler such as silica, mica, talc, barium sulfate, wollastonite, calcium carbonate, or a fine organic polymer filler may be contained. It is preferable to select the content appropriately.

<Photosensitive resin composition solution>
The photosensitive resin composition of the present invention is preferably used as a photosensitive resin composition solution dissolved in an organic solvent from the viewpoint of handling. The photosensitive resin composition of the present invention is highly soluble in various organic solvents, such as sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ) Ether), Methyl Trigura (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldigig Symmetric glycol diethers such as lime (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, 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)) Acetates such as 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 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 Methyl 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. In addition, it can be set as the photosensitive resin composition solution using hexane, acetone, toluene, xylene, etc. of low boiling point as needed.

  Among these, symmetric glycol diethers are particularly preferable because the solubility of the photosensitive resin composition is high.

  In the photosensitive resin composition solution of the present invention, the organic solvent is preferably blended in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition.

  It is preferable to use a photosensitive resin composition solution within this range because the film reduction rate after drying becomes small.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention is obtained by uniformly mixing various raw materials blended in the photosensitive resin composition. As a method of uniformly mixing, 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.

<Usage method of photosensitive resin composition>
The pattern can be formed as follows, either directly with the photosensitive resin composition of the present invention or after preparing the photosensitive resin composition solution. First, the photosensitive resin composition 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. Drying of the coating film (preferably thickness: 5 to 100 μm, particularly 10 to 100 μm) is performed at 120 ° C. or less, preferably 40 to 100 ° C. 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 velocity of the developing device and the temperature of the etching solution, it is preferable to find optimal apparatus 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.

  Next, a cured film rich in heat resistance can be obtained by imidizing dicarboxylic acid and diamine imidized by heat treatment. Although a cured film is determined in consideration of wiring thickness etc., it is preferable that thickness is about 2-50 micrometers. In this case, it is desired that the final curing temperature can be imidized by heating at a low temperature for the purpose of preventing the 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 190 ° C. or lower. If the final heating temperature is high, the wiring is oxidatively deteriorated, which is not preferable.

  A pattern comprising a cured film formed from the photosensitive resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and particularly excellent in flexibility. For example, the insulating film of the present invention 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. Therefore, the insulating film of the present invention 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.

  Thus, the polyimide precursor composition of the present invention is excellent in low-temperature processability, and the printed wiring board (including a flexible printed wiring board) made of a resin such as a polyimide resin, an epoxy resin, or an aramid resin as a base material, for example. It can preferably be used as a wiring coating protective agent for protecting the surface of the substrate as a base material, a wiring coating protective agent for electric wires and cables, a heat resistant interlayer adhesive when laminating a flexible printed wiring board, and the like. In particular, since it has excellent electrical insulation reliability, it is used as a wiring coating protective agent for printed wiring boards.

  As a method of coating the surface of such a printed wiring board, it can apply | coat by using the method similar to the manufacturing method of said coating film.

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

Example 1
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 189 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 256 g (0.308 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solute concentration of this solution was 70% by weight, and the viscosity of the solution was 280 poise at 23 ° C.

  In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 280 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored at room temperature for a long time.

(Preparation of coating film on polyimide film)
Using the above-mentioned polyimide precursor composition solution, using a Baker type applicator, it was cast and applied to a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) so that the final dry thickness was 25 μm, and 120 ° C. After drying for 60 minutes, imidization was performed by heating at 160 ° C. for 90 minutes in a nitrogen atmosphere.

(Adhesiveness of coating film)
The adhesive strength of this polyimide 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.

(Stability of environmental resistance test of film)
If the imidization of the polyimide film is not sufficient, the stability in the environmental test apparatus is lowered. Therefore, the stability in the environmental test apparatus was measured.
The environmental test apparatus was judged by the state of the coating film on the polyimide film after the 85 ° C./85% RH 1000 hour test using a constant temperature and high humidity device manufactured by ESPEC CORP. Model: PR-1K.
Yes, polyimide resin does not change
△, where the polyimide resin is partly dissolved
The polyimide resin was completely dissolved.

(chemical resistance)
The chemical resistance of the polyimide film surface was evaluated. The evaluation method evaluated by observing the state of the film surface, after immersing a film on the evaluation conditions of the following evaluation items 1-3.
Evaluation item 1: After dipping in 25 ° C. isopropanol 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 dipping in a 2N sodium hydroxide solution at 25 ° C., it was washed with pure water and air-dried.
Yes, polyimide resin does not change
△, where the polyimide resin is partly dissolved
A sample in which the polyimide resin was completely dissolved was taken as x.

(Flexibility evaluation)
A polyimide resin solution is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) so that the final film thickness is 25 μm, and dried at 120 ° C. for 60 minutes and at 160 ° C. for 90 minutes to obtain a polyimide film laminate. Got. This polyimide film laminate was cut into 30 mm × 10 mm strips, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○ that there is no crack in the cured film,
△ that there are some cracks in the cured film,
The case where there was a crack in the cured film was rated as x.
The evaluation results are shown in Table 1.

(Example 2)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 181 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 256 g (0.308 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, this solution was cooled to room temperature, and 26.8 g (0.154 mol) of tolylene diisocyanate (a mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate) was added at room temperature. Were mixed uniformly for 1 hour to obtain a polyimide precursor composition solution. The solution had a solute concentration of 70% by weight and a solution viscosity of 260 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 260 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored for a long time at room temperature.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

(Example 3)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 276 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-9409S, molecular weight 1492, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are a methyl group or a phenyl group, n = 3, and m = 9 to 12. ) (460 g (0.308 mol)) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solute concentration of this solution was 70% by weight, and the viscosity of the solution was 120 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 120 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored at room temperature for a long time.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

Example 4
55.0 g (0.154 mol) of 4,4′-diphenylsulfonetetracarboxylic dianhydride was dispersed in 178 g of 1,2-bis (2-methoxyethoxy) ethane and kept at 80 ° C. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 256 g (0.308 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solution had a solute concentration of 70% by weight and a solution viscosity of 300 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 300 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored for a long time at room temperature.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

(Example 5)
47.8 g (0.154 mol) of 4,4′-oxydiphthalic dianhydride was dispersed in 175 g of 1,2-bis (2-methoxyethoxy) ethane and kept at 80 ° C. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 256 g (0.308 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solution had a solute concentration of 70% by weight and a solution viscosity of 250 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 250 poise at 23 ° C., and it became clear that it could be stored at room temperature for a long time without any change in viscosity.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

(Example 6)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 235 g of 1,2-bis (2-methoxyethoxy) ethane, and 80 Kept at ℃. This is polycarbonate diol bis (4-aminobenzoate) (a diamine represented by the following general formula (10),

In the formula, R ₃ is a hexamethylene group, R ₄ is a pentamethylene group, o, p = 1 to 20, 363 g (0.308 mol) of molecular weight 1180) is charged, and uniform stirring is performed for 30 minutes. It was. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solution had a solute concentration of 70% by weight and a solution viscosity of 180 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 180 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored for a long time at room temperature.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

(Example 7)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 173 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 205 g (0.246 mol), and 15.2 g (0.062 mol) of 3,3′-diaminodiphenylsulfone was further added, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. Next, the solution was cooled to room temperature, charged with 45.1 g (0.154 mol) of 1,3-bis (3-aminophenoxy) benzene, and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor composition solution. It was. The solution had a solute concentration of 70% by weight and a solution viscosity of 320 poise at 23 ° C.

In order to confirm the storage stability of the polyimide precursor composition solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 320 poise at 23 ° C., and it became clear that it could be stored at room temperature for a long time without any change in viscosity.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
2.73 g (23.5 mmol) of hexamethylenediamine was dissolved in 24.0 g of dimethylacetamide, and 3.78 g (11.75 mmol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added thereto. Gradually added over a minute to obtain an oligomer with polyamide linkages. After stirring uniformly for 1 hour, 3.02 g (9.40 mmol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid was added and stirring was continued for 1 hour to obtain a viscous solution (solute concentration) 28% by weight). When the viscosity of this solution was measured, it was 3100 poise.

In order to confirm the storage stability of the solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 300 poise at 23 ° C., the viscosity change was large, and there was a problem in storage stability.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 2.

(Comparative Example 2)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 183 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. 128 g (0.154 mol) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature and 49.3 g (1.54 mol) of methanol was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 3 hours. Thus, an imide solution in which the terminal carboxylic acid was half-esterified was obtained. Next, the solution was cooled to room temperature, charged with 99.7 g (0.230 mol) of bis [4- (3-aminophenoxy) phenyl] sulfone, and stirred uniformly at room temperature for 1 hour to obtain a polyimide precursor composition solution. Obtained. The solute concentration of this solution was 70% by weight, and the viscosity of the solution was 120 poise at 23 ° C.

In order to confirm the storage stability of the solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 120 poise at 23 ° C., and it was revealed that the viscosity was not changed and could be stored at room temperature for a long time.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 2.

  It became clear that the stability of the environmental resistance test was poor and the solvent resistance and alkali resistance were poor.

(Comparative Example 3)
8.22 g (41.1 mmol) of 4,4′-diaminodiphenyl ether was dissolved in 55.0 g of N, N-dimethylacetamide and stirred at room temperature. To this was added 11.9 g (54.8 mmol) of pyromellitic dianhydride, and the mixture was stirred at room temperature for 2 hours. 1.32 g (41.1 mmol) of methanol and 0.066 g of dimethylaminoethanol were added, and the mixture was heated and stirred on a 70 ° C. hot water bath for 2 hours. After cooling to room temperature, 2.74 g (13.7 mmol) of 4,4′-diaminodiphenyl ether was added, and stirring was further continued for 1 hour to obtain a uniform solution. The viscosity of this solution was 18 poise at 23 ° C.

In order to confirm the storage stability of the solution, it was left for 1 month in a room kept at 20 ° C. and sealed with a 10 ml screw tube, and the viscosity after 1 month was measured. The viscosity at that time was 50 poise at 23 ° C., and it became clear that there was a problem in storage stability at room temperature.
Furthermore, the characteristic of the cured film obtained from a polyimide precursor composition was performed by the same method as Example 1. The evaluation results are shown in Table 2.

(Comparative Example 4)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 183 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. 128 g (0.154 mol) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. After cooling to room temperature, 27.7 g (1.54 mol) of water was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 3 hours. A solution in which the imidized tetracarboxylic acid was dissolved was obtained.

  The solution obtained by dissolving the imidized tetracarboxylic acid containing no diamine was evaluated in the same manner as in Example 1. The results are listed in Table 2.

(Comparative Example 5)
Disperse 7.00 g (32.1 mmol) of pyromellitic dianhydride in 31.3 g of 1,2-bis (2-methoxyethoxy) ethane, add 2.31 g of water, and stir at 80 ° C. for 10 hours. As a result, a pyromellitic acid solution was obtained. To this solution, 6.43 g (32.1 mmol) of 4,4-diaminodiphenyl ether was added to prepare a solution.

  Although this solution was tried to form a film by the same evaluation method as in Example 1, it was solidified on the surface of the polyimide film and did not become a film.

(Comparative Example 6)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 183 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. 128 g (0.154 mol) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. After cooling to room temperature, without adding water, 99.7 g (0.230 mol) of bis [4- (3-aminophenoxy) phenyl] sulfone was added and stirred uniformly for 1 hour at room temperature to obtain a polyimide precursor. A composition solution was obtained. The solution had a solute concentration of 70% by weight, and the viscosity of the solution became a high-viscosity elastic body at 10000 poise at 23 ° C. Even when this solution was diluted to a solute concentration of 20% by weight, it became a very viscous solution of 6000 poise at 23 ° C., and the physical property value could not be evaluated.

(Synthesis Example 1)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 189 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 256 g (0.308 mol) and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. The solution had a solute concentration of 66% by weight and a solution viscosity of 210 poise at 23 ° C. This terminal carboxylic acid solution was a stable solution with almost no change in viscosity even when left at room temperature for 1 month. This synthesized compound is abbreviated as Compound A.

(Synthesis Example 2)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 276 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name X-22-9409S, molecular weight 1492, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are a methyl group or a phenyl group, n = 3, and m = 9 to 12. ) (460 g (0.308 mol)) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. The solution had a solute concentration of 66% by weight and a solution viscosity of 120 poise at 23 ° C. This terminal carboxylic acid solution was a stable solution with almost no change in viscosity even when left at room temperature for 1 month. This synthesized compound is abbreviated as Compound B.

(Synthesis Example 3)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 235 g of 1,2-bis (2-methoxyethoxy) ethane, and 80 Kept at ℃. This is polycarbonate diol bis (4-aminobenzoate) (a diamine represented by the following general formula (10),

In the formula, R ₃ is a hexamethylene group, R ₄ is a pentamethylene group, o, p = 1 to 20, 363 g (0.308 mol) of molecular weight 1180) is charged, and uniform stirring is performed for 30 minutes. It was. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. The solute concentration of this solution was 66% by weight, and the viscosity of the solution was 150 poise at 23 ° C. This terminal carboxylic acid solution was a stable solution with almost no change in viscosity even when left at room temperature for 1 month. This synthesized compound is abbreviated as Compound C.

(Synthesis Example 4)
80.2 g (0.154 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 173 g of 1,2-bis (2-methoxyethoxy) ethane, 80 Kept at ℃. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. ) Was added in an amount of 205 g (0.246 mol), and 15.2 g (0.062 mol) of 3,3′-diaminodiphenylsulfone was further added, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. Thus, an imidized diamine solution was obtained. Next, this solution was cooled to room temperature, and 59.2 g (0.308 mol) of trimellitic anhydride was added thereto, followed by uniform stirring for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. A solution in which the imidized dicarboxylic acid (terminal carboxylic acid siloxane imide oligomer) was dissolved was obtained. The solute concentration of this solution was 66% by weight, and the viscosity of the solution was 280 poise at 23 ° C. The terminal carboxylic acid solution was a stable solution with little change in viscosity even when it was allowed to stand at room temperature for 1 month. This synthesized compound is abbreviated as Compound D.

(Synthesis Example 5)
200 g (0.384 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is dispersed in 183 g of 1,2-bis (2-methoxyethoxy) ethane and heated to 80 ° C. Kept. Silicon diamine (siloxane diamine) (trade name: KF8010, molecular weight 830, silicon diamine of the following general formula (9),

In the formula, R ₁ and R ₂ are methyl groups, n = 3, and m = 6 to 11. 128 g (0.154 mol) was added and stirred uniformly for 30 minutes. Next, the mixture was heated to 140 ° C. and stirred for 1 hour to complete the reaction, and then heated to 180 ° C. and heated to reflux for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature and 49.3 g (1.54 mol) of methanol was added. After stirring uniformly for 30 minutes, the mixture was heated to 80 ° C. and refluxed for 3 hours. Thus, an imide solution in which the terminal carboxylic acid was half-esterified was obtained. The solute concentration of this solution was 66% by weight, and the viscosity of the solution was 140 poise at 23 ° C. The terminal carboxylic acid solution was a stable solution with little change in viscosity even when it was allowed to stand at room temperature for 1 month. This synthesized compound is abbreviated as Compound E.

(Examples 8 to 11)
The terminal tetracarboxylic acid obtained in Synthesis Examples 1 to 4 (represented as (A) component in Table 3), diamine and / or isocyanate compound (represented as (B) component in Table 3), and photosensitivity. A resin (represented as component (C) in Table 3), a photopolymerization initiator (represented as component (D) in Table 3), and an organic solvent were added to prepare a photosensitive resin composition solution. Table 3 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 a solvent in the table, is the total amount of solvent including the solvent and the like contained in the photosensitive resin composition solution.

The photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.
The evaluation results are shown in Table 4.

(Preparation of coating film on polyimide film)
The above photosensitive resin composition solution is cast and coated on a 75 μm polyimide film (manufactured by Kaneka Co., Ltd .: trade name 75 NPI) using a Baker type applicator to an area of 100 mm × 100 mm so that the final dry thickness is 25 μm. And dried at 80 ° C. for 20 minutes. Ten sheets of this dry film were prepared. Nine sheets have a negative photomask with a completely transparent area of 50 mm × 50 mm, and one sheet has a negative photomask with a line width / space width = 100 μm / 100 μm (30 mm length × 100 μm width). A photomask with 10 lines left) was placed and exposed to UV light at 300 mJ / cm ² in a nitrogen atmosphere. This photosensitive film was subjected to spray development for 30 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 thoroughly washed with pure water, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

(Photosensitivity evaluation)
The evaluation of the photosensitivity 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).
◯: Clear line width / space width = 100/100 μm photosensitive pattern is drawn on the polyimide film surface, no line shaking occurs due to peeling of the line part, and there is no residual residue in the space part thing.
Δ: A clear photosensitive pattern having a line width / space width = 100/100 μm is drawn, and the line portion is shaken due to peeling, but there is no undissolved residue in the space portion.
X: A clear line width / space width = 100/100 μm photosensitive pattern was not drawn, the line portion was peeled off, and a dissolution residue was generated in the space portion.

(Coating film adhesion)
The adhesive strength of the cured film of the photosensitive resin composition 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%.

(Solvent resistance)
The solvent resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in isopropanol at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality in the coating film.
X: Abnormality occurs in the coating film.

(Acid resistance)
The acid resistance of the cured film of the photosensitive resin composition obtained in the above item (Preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was immersed in a 2N hydrochloric acid solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: The coating film has no abnormality (whitening or peeling).
X: Abnormality (whitening or peeling) occurs in the coating film.

(Alkali resistance)
The alkali resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in a 2N sodium hydroxide solution at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality (whitening or peeling) in the coating film.
X: Abnormality (whitening or peeling) occurs in the coating film.

(Flexibility)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). The cured film laminated film was cut into a 30 mm × 10 mm strip, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(Moisture resistance)
A comb-shaped pattern of line width / space width = 100 μm / 100 μm on a flexible copper-clad laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and polyimide adhesive is used to bond copper foil) After being prepared and immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, the surface of the copper foil was treated by washing with pure water. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the production method of the cured film on a 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 6 or more in 500 hours after the start of the test, and no occurrence of migration or dendrite.
X: Migration, dendrite, etc. occurred in 500 hours after the start of the test.

Example 12
Example 8 except that 5 parts by weight of an epoxy resin (Epicron N-665, which is a cresol novolac type polyfunctional epoxy resin) was added to 100 parts by weight of the solid content of the photosensitive resin composition of Example 8 above. The evaluation was performed in the same manner as above. Further, as a solder heat resistance test, evaluation was performed by the following evaluation method. The evaluation results are shown in Table 4.

(Solder heat resistance)
The photosensitive resin composition solution is 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 is 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask having a completely transparent area of 50 mm × 50 mm was placed and exposed to UV light at 300 mJ / cm ² in a nitrogen atmosphere. This photosensitive film was subjected to spray development for 30 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 the development, it was washed purely and sufficiently, and then dried by heating in an oven at 170 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

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%.

(Example 13)
Example 8 except that 5 parts by weight of an epoxy resin (Epicron N-665, which is a cresol novolac type polyfunctional epoxy resin) was added to 100 parts by weight of the solid content of the photosensitive resin composition of Example 9 above. The evaluation was performed in the same manner as above. Furthermore, as a solder heat resistance test, evaluation was performed by the same evaluation method as in Example 12. The evaluation results are shown in Table 4.

(Comparative Example 7)
A photosensitive resin composition solution was prepared in the same manner as in Example 8 except that the half-esterified compound obtained in Synthesis Example 5 was used, and evaluation was performed in the same manner as in Example 8. The evaluation results are shown in Table 4. The imidization did not proceed sufficiently, and the moisture resistance insulation was very poor.

* 1 Mixture of 80% tolylene-2,4-diisocyanate and 20% tolylene-2,6-diisocyanate * 2 Product name M-5710 (2-hydroxy-3-phenoxypropyl acrylate) manufactured by Toa Gosei Co., Ltd.
* 3 Bisphenol A EO-modified diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 1684
* 4 Photopolymerization initiator manufactured by Ciba Specialty Chemicals

Claims (14)

At least the following general formula (1)

(Wherein R represents a tetravalent organic group, R ′ independently represents a divalent organic group, R ″ each independently represents a trivalent organic group, and 1 represents 1 Represents an integer of ~ 20.)
And an imidized dicarboxylic acid represented by the following general formula (2)

(In the formula, R ′ ″ represents a divalent organic group.)
The polyimide precursor composition characterized by including the diamine and / or isocyanate type compound shown by these. R in the general formula (1) represents the following general formula group (1)

The polyimide precursor composition according to claim 1, wherein the polyimide precursor composition is a tetravalent organic group. R ′ in the general formula (1) represents the following general formula group (2)

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
The polyimide precursor composition according to claim 1, comprising at least a divalent organic group represented by the formula: R ′ ″ in the general formula (2) represents the following general formula group (3)

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
The polyimide precursor composition according to any one of claims 1 to 3, wherein the polyimide precursor composition is a divalent organic group selected from the above.   The polyimide precursor composition solution obtained by melt | dissolving the polyimide precursor composition of any one of Claims 1-4 in the solute concentration of 40 to 90 weight%.   The polyimide coating film obtained from the polyimide precursor composition of any one of Claims 1-4, or the polyimide precursor composition solution of Claim 5.   A polyimide coating obtained by applying the polyimide precursor composition according to any one of claims 1 to 4 or the polyimide precursor composition solution according to claim 5 to a printed wiring board and imidizing by heating. Printed wiring board with film.   A photosensitive resin composition comprising the polyimide precursor composition according to claim 1, at least a photosensitive resin, and a photopolymerization initiator. The following general formula (3)

(In the formula, R represents a tetravalent organic group.)
A tetracarboxylic dianhydride shown in
The following general formula (4)

(In the formula, R ′ represents a divalent organic group.)
A diamine shown in
The step (1) of obtaining an amic acid by reacting at a ratio of 1.50 to 2.50 mol of the diamine shown in the general formula (4) with respect to 1 mol of tetracarboxylic dianhydride shown in the general formula (3), Imidize amic acid,
The following general formula (5)

(In the formula, R represents a tetravalent organic group, R ′ independently represents a divalent organic group, and l represents an integer of 1 to 20.)
And a step of obtaining a diamine in which the inside is imidized, and the following general formula (6)

(In the formula, R ″ represents a trivalent organic group.)
And the imidized diamine represented by the general formula (5),
A step (2) of obtaining an amic acid by reacting at a ratio of 0.20 to 0.80 mol of an imidized diamine represented by the general formula (5) with respect to 1 mol of the tricarboxylic acid anhydride represented by the general formula (6); Imidizing the amic acid, the inside is imidized, the terminal is a dicarboxylic acid, comprising the step of obtaining an imidized dicarboxylic acid,
Furthermore, the imidized dicarboxylic acid obtained in the step,
The following general formula (2)

(In the formula, R ′ ″ represents a divalent organic group.)
The diamine and / or isocyanate compound is converted into the general formula (5) used in the step (2) of obtaining the amic acid with respect to 1 mol of the imidized dicarboxylic acid. The manufacturing method of the polyimide precursor composition characterized by including the process of mixing in the ratio used as the total ratio united with the imidized diamine shown to be 0.70 mol-1.30 mol. The diamine represented by the general formula (4) is represented by the following general formula group (4).

(In the formula, o, p and q each independently represent an integer of ₁ to 30. R ₁ and R ₂ each independently represents an alkyl group having 1 to 12 carbon atoms or an aromatic group. M represents an integer of 1 to 40, and n represents an integer of 1 to 20. R ₃ and R ₄ are each independently an alkyl group having 1 to 12 carbon atoms.)
The manufacturing method of the polyimide precursor composition of Claim 9 characterized by including the diamine shown by these.   A method for producing a polyimide precursor composition solution comprising a step of dissolving the polyimide precursor composition obtained in claim 9 or 10 in an organic solvent so as to have a solute concentration of 40 to 90% by weight.   The manufacturing method of a polyimide coating film characterized by including the process of obtaining a polyimide coating film from the polyimide precursor composition obtained by Claim 9 or 10, or the polyimide precursor composition solution obtained by Claim 11.   A polyimide precursor comprising a step of applying a polyimide precursor composition obtained in claim 9 or 10 or a polyimide precursor composition solution obtained in claim 11 to a printed wiring board and heating to imidize. A method for producing a printed wiring board with a coating film.   The manufacturing method of the photosensitive resin composition characterized by including the process of mixing the polyimide precursor composition obtained by Claim 9 or 10, at least photosensitive resin, and a photoinitiator.