TW201630980A - Polyimide precursor composition and method for producing insulating coating layer using same - Google Patents

Abstract

The present invention relates to a polyimide precursor composition for forming a polyimide insulating coating layer, the polyimide precursor composition comprising a specific polyamic acid and a specific phosphorus compound, wherein by performing a heat treatment under conditions where the maximum heating temperature is within a range from 300 to 500 DEG C, the polyamic acid can produce a polyimide film having a water vapor permeability coefficient that is greater than 1.0 g.mm/(m2*24h).

Description

Polyimine precursor composition and method for producing insulating coating using the same

The present invention relates to a polyimide composition precursor composition capable of efficiently producing a polyimide ink insulating coating layer having excellent heat resistance, and a method for producing an insulating coating layer using the composition.

Polyimine resins are known as resins which are excellent in heat resistance and have been widely used in various fields. For example, since it has high heat resistance and is excellent in low dielectric constant and mechanical properties, it can be used as an insulating layer of a wire having high characteristics. Patent Document 1 describes an insulated coated electric wire characterized in that a polyamine acid obtained by reacting biphenyltetracarboxylic dianhydride with 4,4'-diaminodiphenyl ether is provided on a core wire. The insulating layer is formed, and it is described that the polyimide-coated insulated electric wire has excellent resistance to thermal deterioration.

Polyimine may have crystallinity depending on the combination of the tetracarboxylic acid component and the diamine component, and as a result, it may limit the imidization of the polyamic acid which is a polyimide precursor. condition. For example, when 3,3',4,4'-biphenyltetracarboxylic dianhydride is used as the tetracarboxylic acid component, a crystalline polyimine resin is easily obtained, and the conditions of the imidization are particularly desirable. When the heat treatment is performed for a short time, the crystallization of the oxime is likely to cause local crystallization. Therefore, when the polyglycine which is obtained by using 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component is imidized to form a polyimine layer, it cannot be improved. Speed up and increase productivity.

Patent Document 2 describes a method for producing a polyimide coating layer, wherein the polyglycine obtained by using the 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component is used. A method in which a ruthenium is imidized to form a polyimide-based insulating coating layer, and this method can form a polyimide-based insulating coating layer without causing crystallization even if a rapid temperature rise is performed. Specifically, Patent Document 2 describes a method for producing an insulating coating layer, which is a method for producing a polyimide coating layer having a step of coating a substrate with a polyimide composition precursor and baking the substrate. The polyiminoimine precursor composition contains a polyglycine which is obtained by using 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, and is selected from the group consisting of imidazoles. And a basic compound in the group consisting of amine compounds, and in the baking step, heating the polyimide precursor composition for 10 to 180 seconds, and the average temperature rising rate from 100 ° C to 280 ° C is 5 ° C / Above s, the maximum heating temperature is 300~500 °C. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-61-273806 [Patent Document 2] International Publication No. 2014/142173

[Problem to be Solved by the Invention] An object of the present invention is to provide a method for producing a polyimide-based insulating coating layer which is a combination of a tetracarboxylic acid component and a diamine component which is a polyimine which is easy to provide crystallinity. Polylysine, in particular, polyglycine, which is obtained by using 3,3',4,4'-biphenyltetracarboxylic dianhydride as a tetracarboxylic acid component, is imidized to form a polyimine. The insulating coating layer forms a polyimide-based insulating coating layer without defects even if a rapid temperature rise is performed. In other words, the object of the present invention is to provide a polyimide composition precursor (polyamide) capable of forming an insulating coating layer of a polyimide resin having excellent heat resistance and mechanical properties in a short period of time without causing crystallization. An acid composition) and a method of producing an industrially advantageous insulating coating layer using the composition. [Means for solving the problem]

A polyimine precursor composition for forming a polyimide coating comprising a polyaminic acid, a solvent, and a phosphorus compound, characterized in that the polyamine contains 3,3'4,4'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the total content of the tetracarboxylic acid component is 50 to 100 mol%, a polyamic acid obtained from a diamine component containing 50 to 100 mol% of 4,4'-diaminodiphenyl ether; the phosphorus compound is selected from the group consisting of phosphates and phosphorus represented by the following formula (1) At least one of the group consisting of compounds; the polyglycolic acid is capable of being subjected to heat treatment at a maximum heating temperature of 300 to 500 ° C to produce a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24h) of the polyimide film;

【化1】 (wherein R ¹ is an alkylene group having 1 to 6 carbon atoms, and R ² is a phenyl group or a cyclohexyl group). 2. The polyimine imide precursor composition for forming a polyimide-based insulating coating layer according to Item 1, wherein the tetracarboxylic acid component contains 3,3',4,4'-biphenyltetracarboxylic acid Anhydride 50~95 mol%.

A method for producing an insulating coating layer, which is a method for producing a polyimide coating having a step of coating a substrate with a polyimide composition precursor and baking, characterized in that: The amine precursor composition contains polylysine, a solvent, and a phosphorus compound, and the polyamidene precursor composition contains polyglycolic acid containing 3,3',4,4'-biphenyltetracarboxylic acid. a dianhydride and a 2,3,3',4'-biphenyltetracarboxylic dianhydride having a total content of 50 to 100 mol% of a tetracarboxylic acid component and a 4,4'-diamino group a polyamic acid obtained from a diamine component having 50 to 100 mol% of a phenyl ether, the phosphorus compound being at least one selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following general formula (1). Moreover, the polylysine is capable of producing a polythenimine having a water vapor transmission coefficient of more than 1.0 g·mm/(m ² ‧24 h) by heat treatment at a maximum heating temperature of 300 to 500 ° C. In the baking step, the time of heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature rising rate of 100 ° C to 280 ° C is 5 ° C / s or more, the highest heating temperature Degree is 300~500 °C;

[Chemical 2] (wherein R ¹ is an alkylene group having 1 to 6 carbon atoms, and R ² is a phenyl group or a cyclohexyl group). 4. The method for producing an insulating coating layer according to Item 3, wherein the tetracarboxylic acid component contains 50 to 95 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride.

In addition, in the present specification, the polyimide coating layer, the polyimide layer, the polyimide film, and the polyimide film are mainly composed of polyimine, and include phosphorus. By. [Effects of the Invention]

According to the present invention, it is possible to provide a polyimide composition precursor composition which can form an insulating coating layer of a polyimide resin having excellent heat resistance and mechanical properties in a short period of time without causing crystallization. By using the polyimine precursor composition of the present invention, an insulating coating layer of a polyimide resin excellent in heat resistance and mechanical properties can be formed in a short time without causing crystallization. In addition, by using the polyimide intermediate precursor composition of the present invention, it is possible to form an insulating coating layer which is excellent in thermal strength at the time of high temperature and excellent in adhesion strength to a substrate and high in reliability. The polyimine precursor composition of the present invention and the method for producing the insulating coating layer of the present invention using the composition are particularly preferably used for the production of insulated wires, and can be efficiently produced with excellent heat resistance. Insulated coatings have no defects and high reliability of insulated wires.

The polyimine precursor composition of the present invention is characterized by using a specific polyaminic acid which provides a polyimine film having a specific water vapor transmission coefficient, and adding a specific phosphorus compound.

The polyamic acid used in the present invention can be a tetracarboxylic acid component (the tetracarboxylic acid component also contains a tetracarboxylic dianhydride in a solvent, for example, in water or an organic solvent, or in a mixed solvent of water and an organic solvent. ) is reacted with a diamine component to obtain. The polyamic acid is a tetracarboxylic acid component containing 50 to 100 mol% of biphenyltetracarboxylic dianhydride and a diamine component containing 50 to 100 mol% of 4,4'-diaminodiphenyl ether. Winner. The term "biphenyltetracarboxylic dianhydride" is a generic term for a majority of isomers, including 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyl. Tetracarboxylic dianhydride and 2,2',3,3'-biphenyltetracarboxylic dianhydride.

Moreover, the polyglycolic acid can be heated by setting the maximum heating temperature to 300 to 500 ° C, especially by heating from room temperature (25 ° C) to 400 ° C for 30 minutes and heating at 400 ° C. It was treated for 10 minutes to produce a polyimide film having a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24 h).

The tetracarboxylic acid component used in the present invention contains 3,3',4,4'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the total content thereof It should be 50~100% by mole. In particular, from the viewpoint of heat resistance and mechanical properties, it is preferred to use 50 mol% or more of 3,3',4,4'-biphenyltetracarboxylic dianhydride. As described above, when 3,3',4,4'-biphenyltetracarboxylic dianhydride is usually used as the tetracarboxylic acid component, it is easy to cause localized if it is to be subjected to a short-time heat treatment for rapid temperature rise for hydrazylation. Crystallization; according to the present invention, even if a rapid temperature rise is performed, the polyimine layer can be formed without causing crystallization. The content of 3,3',4,4'-biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is more preferably from 50 to 95 mol%.

In the present invention, the 3,3',4,4'-biphenyltetracarboxylic dianhydride and the 2,3,3',4'-biphenyltetracarboxylic acid may be used in the range of 50 mol% or less. As the tetracarboxylic acid component, the 2,2',3,3'-biphenyltetracarboxylic dianhydride of the biphenyltetracarboxylic dianhydride other than the anhydride may be used in the range of 50 mol% or less. A tetracarboxylic acid component other than dianhydride (tetracarboxylic dianhydride). The tetracarboxylic dianhydride which can be used in combination with the biphenyltetracarboxylic dianhydride in the present invention is not particularly limited, but the aromatic carboxylic acid dianhydride and the alicyclic tetracarboxylic acid are considered in consideration of the properties of the obtained polyfluorene imide. A dianhydride is preferred. For example, preferred are: pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylphosphonium tetracarboxylic acid Di-anhydride, conjugated triphenyltetracarboxylic dianhydride, cross-linked triphenyltetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1,2,4,5- Cyclohexane tetracarboxylic dianhydride or the like. When a tetracarboxylic acid component other than biphenyltetracarboxylic dianhydride is used, among them, the characteristics of the obtained polyfluorene imide are used to use 4,4'-oxydiphthalic dianhydride or pyromellitic acid. The dianhydride is particularly good. The above tetracarboxylic dianhydride is not necessarily one type, and may be a mixture of a plurality of types.

The diamine component used in the present invention contains 50 to 100 mol% of 4,4'-diaminodiphenyl ether as described above, and further, another diamine may be used in the range of 50 mol% or less. The other diamine is not particularly limited and can be exemplified by 4,4'-diaminodiphenylmethane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, and 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, m-xylene Diamine, p-xylylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-methylenebis(2,6-xylyleneamine) An aromatic diamine such as α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, hexamethylenediamine, heptamethylenediamine, octamethylene Amine, nonamethylenediamine, decamethyldiamine, diaminopropyltetramethylene, 3-methylhexamethylenediamine, 2,11-diaminododecane, 1, An aliphatic diamine such as 12-diaminooctadecane. The diamines are not necessarily one type, and may be a mixture of plural kinds.

The polylysine used in the present invention must be heat-treated by setting the maximum heating temperature at 300 to 500 ° C, especially from room temperature (25 ° C) to 400 ° C and 400 ° C for 30 minutes. The heat treatment was carried out for 10 minutes to produce a polyimide film having a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24 h). In particular, it is preferred to produce a polyimide film having a water vapor transmission coefficient of more than 1.2 g ‧ mm / (m ² ‧ 24 h). When the water vapor transmission coefficient of the obtained polyimide film is smaller than this, in the production of the polyimide coating, it is easy to cause localization in the short-time heat treatment by rapid heating. Crystallization.

Here, the crystallization in the imidization process will be explained. During the imidization of the hydrazine, solvent evaporation occurs in parallel with the hydrazide reaction. When the temperature increase rate is large, the evaporation amount of the solvent is reduced with respect to the ruthenium iodide reaction, and the amount of residual solvent is relatively large. When the polyaminic acid is imidized and the quinone bond is formed, the solubility of the molecular chain in the solvent is reduced. Therefore, in a state where the amount of residual solvent is large, the molecular chain is easily crystallized and precipitated. On the other hand, when the rate of temperature rise is small, the amount of evaporation of the solvent increases with respect to the ruthenium imidization reaction, and the amount of residual solvent is small, so that crystallization is less likely to occur. Since the gas permeable polyimide resin can be obtained from the polyaminic acid used in the polyimide composition of the present invention, the solvent is easily evaporated, and the problem of crystallization is less likely to occur under conditions of a high temperature increase rate.

The polyaminic acid having a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24 h) obtained by heat-treating at a maximum heating temperature of 300 to 500 ° C, for example a tetracarboxylic acid component containing 3,3',4,4'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 4,4 A polyglycolic acid composed of a diamine component of '-diaminodiphenyl ether is preferred. At this time, the content of 3,3',4,4'-biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is preferably 95 to 50 mol%, 2, 3, 3', 4'-linked. The content of the benzenetetracarboxylic dianhydride is 5 to 50 mol%.

In the solvent, in order to inhibit the ruthenium iodide reaction at 100 ° C or lower, preferably at a lower temperature of 80 ° C or lower, about equimolar tetracarboxylic dianhydride is reacted with a diamine, whereby polylysine can be used. The polylysine used in the present invention is obtained in the form of a solution.

It is not limited, but usually the reaction temperature is from 25 ° C to 100 ° C, preferably from 40 ° C to 80 ° C, more preferably from 50 ° C to 80 ° C; and the reaction time is from about 0.1 to 24 hours, preferably from about 2 to 12 hours. . The reaction temperature and the reaction time are set within the above range, whereby a high molecular weight polyamine solution can be easily obtained with good production efficiency.

Further, the reaction can also be carried out under an air atmosphere, but it is usually carried out under a passive gas atmosphere, preferably under a nitrogen atmosphere.

The molar ratio of the tetracarboxylic dianhydride to the diamine is specifically about 0.90 to 1.10, preferably about 0.95 to 1.05.

The solvent used in the present invention may be any solvent as long as it can polymerize polylysine, and may be an aqueous solvent or an organic solvent. The solvent may be a mixture of two or more kinds, and a mixed solvent of two or more kinds of organic solvents or a mixed solvent of water and one or more organic solvents may be preferably used.

The organic solvent which can be used in the present invention is not particularly limited, and examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N- Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, trimethylamine hexamethylphosphate, 1,2 -dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxy) Ethoxy)ethyl]ether, 1,4-two Alkane, dimethyl hydrazine, dimethyl hydrazine, diphenyl ether, cyclobutyl hydrazine, diphenyl hydrazine, tetramethyl urea, anisole, m-cresol, phenol, γ-butyrolactone and the like.

Further, the solvent used for the reaction may be a solvent contained in the polyimide composition precursor composition of the present invention.

The polyamic acid used in the present invention is not limited, but the logarithmic viscosity measured at a temperature of 30 ° C and a concentration of 0.5 g / 100 mL is preferably 0.2 or more. When the logarithmic viscosity is lower than the above range, since the molecular weight of the polylysine is low, it is difficult to obtain a polyimine having a high degree of characteristics.

The polyimine precursor composition used in the present invention has a solid content concentration of polyamic acid which is not limited, and is preferably from 5% by mass to 50% by mass based on the total amount of the polyamic acid and the solvent. More preferably, it is 5 mass% to 45 mass%, more preferably 10 mass% to 45 mass%, still more preferably 15 mass% to 40 mass%. When the solid content concentration is less than 5% by mass, the workability at the time of use may be deteriorated; if it is more than 45% by mass, the solution becomes fluid-free.

Further, the viscosity of the solution of the polyimine precursor composition used in the present invention at 30 ° C is not limited, and is preferably 1,000 Pa sec or less, more preferably 0.5 to 500 Pa sec, and still more preferably 1 to 300 Pa ‧ Sec, especially when it is 2~200Pa‧sec, it is ideal for operation.

The polyimine precursor composition of the present invention contains polylysine and a solvent, and further contains a phosphorus compound. The addition of the phosphorus compound can suppress the thermal decomposition of the formed polyimide polyimide insulating coating layer at a high temperature and improve the adhesion strength to the substrate.

The phosphorus compound used in the present invention is preferably selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following chemical formula (1).

[化3] (wherein R ¹ is an alkylene group having 1 to 6 carbon atoms, and R ² is a phenyl group or a cyclohexyl group.)

R ^{1 of the} formula (1) is preferably an alkylene group having 1 to 4 carbon atoms.

Among the phosphorus compounds represented by the above chemical formula (1), bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, and 1,3-bis(diphenylphosphino) can be exemplified. Propane, 1,4-bis(diphenylphosphino)butane, and 1,4-bis(dicyclohexylphosphino)butane are particularly preferred.

The phosphate ester is derived from phosphoric acid and an alcohol, and the structure is not particularly limited. The phosphate ester used in the present invention may be any of a monoester, a diester or a triester, and is preferably derived from an aliphatic or aromatic alcohol having 1 to 18 carbon atoms. Further, the monoester and the diester may form a salt with an amine or the like.

The phosphate ester can be exemplified by trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and a phosphate compound represented by the following chemical formula (2) and salts thereof. The compound which forms a salt with the phosphate compound represented by the following chemical formula (2) can be exemplified by the amine represented by the following chemical formula (3).

【化4】 (wherein R ³ is a hydrogen atom or an alkyl group having 6 to 18 carbon atoms or a polyoxyalkylene group, and R ⁴ is an alkyl group having 6 to 18 carbon atoms or a polyoxyalkylene group.)

【化5】 (wherein R ⁵ , R ⁶ and R ⁷ are a hydrogen atom, a hydroxyethyl group or an alkyl group having 1 to 4 carbon atoms.)

Further, the phosphate ester used in the present invention can also be exemplified by the phosphate compound represented by the following chemical formula (4).

【化6】 (wherein R ⁸ is an organic group having 3 to 12 carbon atoms having a reactive functional group.)

R ⁸ of the formula (4) is a reactive functional group, specifically, an organic group having a carbon number of 3 to 12 having a carbon-carbon unsaturated bond, and R ⁸ is exemplified by an acrylonitrile group, a methacryl fluorenyl group, or a propylene group. Alkoxyethyl, methacryloxyethyl and the like.

The phosphate compound represented by the chemical formula (4), specifically, 2-(methacryloxy)ethyl phosphate and bis(2-(methacryloxy)ethyl phosphate) can be exemplified.

In addition, one type of these phosphorus compounds may be used, or two or more types may be used in combination. Further, other phosphorus compounds may be used in combination.

The amount of the phosphorus compound added to the polyimide precursor composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass based on the mass of the polyamic acid. If the concentration of the phosphorus compound in the polyimide precursor composition is too small, it is difficult to sufficiently obtain the effect of suppressing thermal decomposition in a temperature range of 400 ° C or higher. On the other hand, if the concentration of the phosphorus compound is too large, a large amount of phosphorus remains in the obtained polyimide-based insulating coating layer, which may cause a volatile component (dissipating gas), which is not preferable.

The phosphorus compound may be added before the preparation of the polyamic acid or may be added after the preparation. That is, after a tetracarboxylic acid component and a diamine component are reacted in a solvent to obtain a polyaminic acid solution, a phosphorus compound is added to the solution, whereby a polyphosphorimide precursor composition of the present invention containing a phosphorus-containing compound can be obtained. Things. Further, the present invention can be obtained by adding a tetracarboxylic acid component, a diamine component, and a phosphorus compound to a solvent, and reacting a tetracarboxylic acid component with a diamine component in a solvent in the presence of a phosphorus compound to obtain a phosphorus-containing compound. Polyimine precursor composition.

The polyimide precursor composition is removed by heat treatment and simultaneously subjected to hydrazide (dehydration ring closure), thereby forming a polyimine, but by using the polyimine precursor of the present invention as described above The material can be heated in a short time and baked at a high temperature to form a polyimide coating. Here, the temperature is raised in a short time and baked at a high temperature, for example, the time for heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature increase rate at 100 ° C to 280 ° C is 5 ° C / The temperature is raised above s, and the maximum heating temperature is 300 to 500 °C.

In the present invention, a polyamidene precursor composition containing a polyphthalic acid, a solvent, and a phosphorus compound as described above is applied to a substrate by a known method and heated (baked) to form a polyimide insulation. Covered layer. In the baking step, the time for heating the polyimide precursor composition (in the heating furnace, meaning the time in the heating furnace) can be set to 10 to 180 seconds, and the average of 100 ° C to 280 ° C is set. The heating rate is 5 ° C / s or more, and the maximum heating temperature is set to 300 to 500 ° C. The upper limit of the average temperature increase rate from 100 ° C to 280 ° C is not particularly limited, but is preferably, for example, 50 ° C / s or less.

In the present invention, the average temperature increase rate from 100 ° C to 300 ° C may be further set to 5 ° C / s or more (that is, from 100 ° C to 300 ° C for 40 seconds), or from 100 ° C to the highest heating temperature The average temperature increase rate (300 to 500 ° C) is set to 5 ° C / s or more. The average temperature increase rate to 100 ° C is also not particularly limited, and may be set to 5 ° C / s or more.

In the present invention, the average temperature increase rate from 100 ° C to 280 ° C is 5 ° C / s or more (that is, the temperature is raised from 100 ° C to 280 ° C within 36 seconds), and the temperature rise from room temperature to the maximum heating temperature is not The limitation can be increased by a certain heating rate, or the heating rate can be changed during the heating process, and the temperature can be raised in stages.

This heat treatment for hydrazine imidation can be carried out, for example, in an air atmosphere or in a passive gas atmosphere.

Further, the polyimine imide precursor composition of the present invention can be heat-treated under the conditions other than the above to form a polyimide conductive coating layer.

Further, the substrate is not particularly limited and may be appropriately selected depending on the intended use. Further, the thickness of the formed polyimide coating layer is not particularly limited, and may be appropriately selected depending on the application.

The polyimide coating layer obtained by the present invention is an insulating member (coating layer) having high voltage resistance, heat resistance, and moist heat resistance. Therefore, it is particularly suitable for use in electric, electronic parts, automotive, aerospace, etc., and can also be used in the field of HV motor coils or ultra-small motors. [Examples]

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples.

The measurement method of the characteristics used in the following examples is shown below. <Solid component concentration> The sample solution (having the mass of w ₁ ) was heated in a hot air dryer at 120 ° C for 10 minutes, heated at 250 ° C for 10 minutes, and then heated at 350 ° C for 30 minutes, and the mass after heat treatment was measured. (Let its quality be w ₂ ). The solid content concentration [% by mass] was calculated according to the following formula.

Solid content concentration [% by mass] = (w ₂ / w ₁ ) × 100 <solution viscosity (rotational viscosity)> Measurement was carried out at 30 ° C using an E-type viscometer manufactured by Tokimec Co., Ltd. <Observation of State of Insulating Coating Layer (Evaluation of Coating Film)> The obtained coating layer was visually observed. Those who were completely turbid were rated as good, and those with more than 10% of turbidity were rated as turbid. "Having turbidity" means that at least a portion of the polyimide resin is crystallized. <Measurement of Temperature Increase Rate> In the coating layer forming step, the measurement unit NR-TH08 manufactured by Keyence Co., Ltd. and the analysis software WAVE LOGGER were used to measure the time required for the sample temperature to change from 100 ° C to 280 ° C. <Water vapor transmission coefficient> The measurement was carried out at 40 ° C and a relative humidity of 90% in accordance with the method B of JIS K7129. <Amount of change in weight at the time of heating at 490 ° C (reduction amount)> A 25 μm-thick polyimide film was cut into a square of 10 cm × 10 cm, and the weight was measured. Then, it was heat-treated at 490 ° C for 30 minutes (0.5 hours) in an air atmosphere, and the weight loss of the film was measured. Similarly, the weight reduction of the film was further measured after heat treatment at 490 ° C for 60 minutes (1.5 hours); and then the weight reduction of the film was measured after heat treatment at 490 ° C for 60 minutes (2.5 hours). Further, the weight of the film before the heat treatment was 368 mg/100 cm ² . <Continuing Strength> A laminate composed of a polyimide layer and a copper foil was cut into a width of 10 mm, and a 90° peeling test was carried out under the conditions of a peeling speed of 50 mm/min, and the average value of the three samples was defined as the bonding strength.

The abbreviations of the compounds used in the following examples are explained. s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride ODA: 4,4'- Aminodiphenyl ether NMP: N-methyl-2-pyrrolidone DPPE: 1,2-bis(diphenylphosphino)ethane TEP: triethyl phosphate

[Example 1] In a glass reaction vessel having a 500 mL internal volume of a mixer, a nitrogen gas introduction, and a discharge tube, NMP (300 g) was added as a solvent, and ODA 60.08 g (0.3 mol) was added thereto, and the mixture was stirred at 50 ° C for 1 hour to dissolve. . To this solution, 70.61 g (0.24 mol) of s-BPDA, 17.65 g (0.06 mol) of a-BPDA, and 1.62 g (0.09 mol) of water were added, and the mixture was stirred at 50 ° C for 3 hours to obtain a solid concentration of 30.6 mass %. Polyimine precursor composition having a solution viscosity of 7.0 Pa ‧ s. In this polyimine precursor composition, 3.37 g of DPPE as a phosphorus compound (0.75 mass% with respect to the composition and 2.27 mass% with respect to the mass of the polyglycolic acid) was added to obtain a polyimide precursor composition. Things.

The polyimide precursor composition was applied onto a polyimide film having a thickness of 50 μm, placed on a SUS plate heated to 350 ° C and held for 1 minute to prepare an insulating coating layer (polyimine). Membrane). At this time, the temperature of the sample was raised from 100 ° C to 280 ° C for 12 seconds (temperature rising rate 15 ° C / s). The evaluation results of the state observation are shown in Table 1 for the obtained insulating coating layer.

Further, the polyimide precursor composition was applied onto a glass plate as a substrate, heated from room temperature to 400 ° C for 30 minutes, and heat-treated at 400 ° C for 10 minutes to obtain a polyimide having a thickness of 25 μm. Membrane. The obtained polyimide film (polyimine film) was peeled off from the substrate, and the water vapor transmission coefficient and the weight change amount at 490 ° C during heating were measured. The evaluation results are shown in Table 1.

Further, the obtained polyimide phase precursor composition was applied to a smooth surface of a copper foil (manufactured by Mitsui Mining & Mining Co., Ltd., 3EC-VLP) having a thickness of 18 μm so that the obtained polyimide layer having a thickness of 25 μm was time-consuming. The temperature was raised from room temperature to 400 ° C for 30 minutes, and heat treatment was performed at 400 ° C for 10 minutes to obtain a laminate. The adhesion strength between the polyimide layer and the copper foil was measured for the obtained laminate. The evaluation results are shown in Table 1.

[Example 2] Polyfluorene was prepared in the same manner as in Example 1 except that 6.74 g (1.5% by mass of the composition and 4.54% by mass based on the mass of the polyglycolic acid) of the DPPE was used as the phosphorus compound. The imine precursor composition is produced by producing an insulating coating layer on a polyimide film, producing a polyimide film, and manufacturing a laminate comprising a polyimide layer and a copper foil, and performing State observation and measurement of characteristics ‧ Evaluation. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Example 3] Using JPA-514 (manufactured by Seongbuk Chemical Industry, a mixture of 2-(methacryloxy)ethyl phosphate and bis(2-(methacryloxy)ethyl) phosphate) 3.37 g (Polyimide precursor composition was prepared in the same manner as in Example 1 except that the composition was 0.75% by mass based on the mass of the polyamic acid and 2.27 mass% based on the mass of the polyglycolic acid). Production of an insulating coating layer on a polyimide film, production of a polyimide film, and production of a laminate comprising a polyimide layer and a copper foil, and observation of the state and measurement of characteristics. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Example 4] Prepared in the same manner as in Example 1 except that 6.74 g (1.5% by mass based on the composition and 4.54% by mass based on the mass of the polyglycolic acid) of JPA-514 was used as the phosphorus compound. The polyimide composition precursor composition, the production of an insulating coating layer on a polyimide film, the production of a polyimide film, and the production of a laminate comprising a polyimide layer and a copper foil. The state observation and the measurement of the characteristics were evaluated. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Example 5] Polyfluorene was prepared in the same manner as in Example 1 except that 3.37 g of TEP (0.75 mass% based on the composition and 2.27 mass% based on the mass of the polyglycolic acid) was used as the phosphorus compound. The imine precursor composition is produced by producing an insulating coating layer on a polyimide film, producing a polyimide film, and manufacturing a laminate comprising a polyimide layer and a copper foil, and performing State observation and measurement of characteristics ‧ Evaluation. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Example 6] Polyfluorene was prepared in the same manner as in Example 1 except that 6.74 g of TEP (1.5 mass% based on the composition and 4.54 mass% based on the mass of the polyglycolic acid) was used as the phosphorus compound. The imine precursor composition is produced by producing an insulating coating layer on a polyimide film, producing a polyimide film, and manufacturing a laminate comprising a polyimide layer and a copper foil, and performing State observation and measurement of characteristics ‧ Evaluation. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Comparative Example 1] A polyimide composition precursor was prepared in the same manner as in Example 1 except that the phosphorus compound was not added, and the insulating coating layer was formed on the polyimide film, and the polyimide was coated. The production of a film and the production of a laminate comprising a polyimide layer and a copper foil, and observation of the state and measurement of characteristics were evaluated. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

[Comparative Example 2] Into a reaction vessel made of glass containing 500 mL of an internal volume of a stirrer, a nitrogen gas introduction, and a discharge tube, 396 g of NMP was added as a solvent, and ODA (40.05 g (0.2 mol) was added thereto, and the mixture was stirred at 50 ° C for 1 hour. Dissolved. To the solution, 58.84 g (0.2 mol) of s-BPDA was added, and the mixture was stirred at 50 ° C for 3 hours to obtain a polyimine precursor composition having a solid concentration of 18.5% by mass and a solution viscosity of 5.0 Pa s. In the polyimine precursor composition, a TEP of 4.50 g (1.0% by mass based on the composition and 4.55% by mass based on the mass of the polyglycolic acid) as a phosphorus compound was added to obtain a polyimide precursor composition. Things.

Using this polyimide intermediate precursor composition, in the same manner as in Example 1, the production of an insulating coating layer on a polyimide film, the production of a polyimide film, and a polyimide layer and a polyimide layer were used. The laminate of the copper foil was produced, and the state observation and the measurement of the characteristics were evaluated. Further, when the insulating coating layer was formed on the polyimide film, the temperature rising rate at 100 ° C to 280 ° C was 15 ° C / s. The results are shown in Table 1.

【Table 1】

no

Claims (4)

A polyimine precursor composition for forming a polyimide polyimide insulating coating layer, comprising a poly-proline, a solvent, and a phosphorus compound, wherein: the polyamine contains 3, 3', 4 4'-biphenyltetracarboxylic dianhydride and 2,3,3',4'-biphenyltetracarboxylic dianhydride, and the total content of the tetracarboxylic acid component and the content of 50 to 100 mol% a polyamic acid obtained from a diamine component of 4,4'-diaminodiphenyl ether of 50 to 100 mol%; the phosphorus compound is selected from the group consisting of a phosphate compound and a phosphorus compound represented by the following formula (1) At least one of the group; the polyglycolic acid can be heated by a maximum heating temperature of 300 to 500 ° C to produce a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24h) of the polyimide film; [Chemical 1] In the formula, R ¹ is an alkylene group having 1 to 6 carbon atoms, and R ² is a phenyl group or a cyclohexyl group. A polyimine precursor composition for forming a polyimide-based insulating coating layer according to the first aspect of the invention, wherein the tetracarboxylic acid component contains 3,3',4,4'-biphenyltetracarboxylic acid The dianhydride is 50~95 mol%. A method for producing an insulating coating layer, which is a method for producing a polyimide coating having a step of coating a substrate with a polyimide composition precursor and baking, characterized in that: the polyimide precursor The bulk composition contains polyamic acid, a solvent, and a phosphorus compound, and the polyamidene precursor composition contains polyglycine which contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. And a 2,3,3',4'-biphenyltetracarboxylic dianhydride having a total content of 50 to 100 mol% of a tetracarboxylic acid component and a 4,4'-diaminodiphenyl ether a polyamic acid obtained by a diamine component of 50 to 100 mol%, which is at least one selected from the group consisting of a phosphate ester and a phosphorus compound represented by the following general formula (1), and The polylysine is a polyimine film capable of producing a water vapor transmission coefficient of more than 1.0 g ‧ mm / (m ² ‧ 24 h) by heat treatment at a maximum heating temperature of 300 to 500 ° C In the baking step, the time of heating the polyimide precursor composition is 10 to 180 seconds, and the average temperature rising rate of 100 ° C to 280 ° C is 5 ° C / s or more, the highest heating temperature Of 300 ~ 500 ℃; [Chemical 2] In the formula, R ¹ is an alkylene group having 1 to 6 carbon atoms, and R ² is a phenyl group or a cyclohexyl group. The method for producing an insulating coating layer according to claim 3, wherein the tetracarboxylic acid component contains 50 to 95 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride.