TWI595023B - Polyamic acid composition, cured film and electronic parts - Google Patents

Description

Polylysine composition, cured film, and electronic parts

The present invention relates to a composition having a high refractive index which can be used for forming an insulating material in an electronic component and which can also be applied to a printing blanket having a low surface energy, obtained from the composition. An insulating film (protective film) and an electronic component having the insulating film.

In the case of forming an insulating film (protective film) for the above use, a composition in which a polymer is dissolved in an organic solvent is used, and a film is formed on a substrate to be a substrate by various coating methods. However, according to an electronic device, there is a case where a substrate on which a cured film is formed has a low surface energy. In this case, when the conventional composition is used, there is a problem that the composition is repelled and coating failure occurs due to coating by spin coating, slit coating, or printing. On the other hand, in order to reduce the cost of the electronic device manufacturing process, the microfabrication step (photolithography step) is simplified, and for this reason, it is attempted to directly pattern by a printing method. There are various methods, for example, in the case of the reverse offset printing method, a composition is applied to the entire surface of the anthrone-based coating layer by a slit coater or the like, and the coating layer is patterned with irregularities on the surface in advance. a glass plate (cliche) on which the unwanted portion is transferred, and then the group remaining on the coating The resultant is transferred onto a substrate to be patterned. In the coating material at this time, an anthrone-based material having a low surface free energy is used. Therefore, when the conventional composition is directly applied, the composition is coated on the coating layer to cause repulsion, and there is no possibility. Printing problems.

On the other hand, there are also applications exposed to high temperatures (300 ° C ~ 400 ° C) in the formation process of the components. In this application, a material having high heat resistance such as photosensitive polyimide is used. However, the polyethylenimine or the polyglycine which is a precursor thereof has low solubility in the above organic solvent, and it is necessary to use N-methylpyrrolidone or γ-butyrolactone to have a high risk to the human body. Solvent, in addition, requires a photolithography step.

Patent Document 1 discloses a technique for performing reverse offset printing on an organic semiconductor ink. The coating property to the coating layer can be imparted by adding a fluorine-based surfactant. However, when a fluorine-based surfactant is added to a polyamic acid composition, it can be applied to a coating layer, and it is difficult to satisfy good coating uniformity and to not erode all properties such as a coating layer.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication 2010/113931

An object of the present invention is to provide an organic solvent which can be applied to a substrate having a low surface energy and which has high heat resistance and which does not use N-methylpyrrolidone or γ-butyrolactone to be harmful to the human body. Further, it is possible to perform offset printing, reverse offset printing of a polyamic acid composition, and an electronic component having the cured film.

The present inventors conducted active research to solve the above problems, and as a result, found that a compound having a dimethyloxantane structure has low surface free energy. Further, it has been found to have a polylysine which is soluble in a skeleton in an organic solvent other than N-methylpyrrolidone or γ-butyrolactone which is often used for dissolving polyimine. Further, an organic solvent having a hydroxyl group is found as an organic solvent having an effect of not eroding the coating for printing and not increasing the surface free energy of the composition, thereby completing a composition capable of solving the above problems.

The present invention includes the following constitutions.

[1] A polyaminic acid composition for use in offset printing or reverse offset printing comprising: a diamine represented by the formula (1) (a1) and a diamine represented by the formula (2) ( A2), and polyglycine (A) obtained by polycondensation of acid dianhydride (a3); and organic solvent (B) having a hydroxyl group:

In the formula (1), R ¹ is an alkylene group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 150;

In the formula (2), X, Y ¹ and Y ² are each independently a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -, m and n. They are independently 0 or 1 respectively.

[2] The polyaminic acid composition according to [1], wherein the diamine (a2) is at least one selected from the group consisting of compounds represented by formula (a2-1) to formula (a2-5):

[3] The polyaminic acid composition according to [1] or [2] wherein the acid dianhydride (a3) is selected from the compounds represented by the formula (a3-1) and the formula (a3-2) At least one of the following:

[4] The polyaminic acid composition according to any one of [1] to [3] wherein the organic solvent (B) contains at least one organic solvent having a boiling point of 110 ° C or higher.

[5] The poly-proline composition according to any one of [1] to [4] wherein the organic solvent (B) comprises at least one selected from the group consisting of diacetone alcohol and acetic acid-2. -hydroxyethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Tripropylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether.

[6] A cured film obtained by using the polyaminic acid composition according to any one of [1] to [5].

[7] An electronic component having the cured film according to [6].

The cured film or the insulating film (pattern-like) cured film formed by using the polyacrylic acid composition for printing of the present invention is excellent in printability, and is excellent in heat resistance and adhesion to a substrate. As a result, the display quality of the display element using the cured film or the like using the polyamino acid composition for printing of the present invention is improved.

1. The polylysine composition of the present invention

The polyaminic acid composition of the present invention comprises a polycondensation of a diamine (a1) represented by the formula (1), a diamine (a2) represented by the formula (2), and an acid dianhydride (a3). Polylysine (A); and an organic solvent (B) having a hydroxyl group.

R ¹ is an alkylene group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 150.

In the formula (2), X, Y ¹ and Y ² are each independently a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -, m and n. They are independently 0 or 1 respectively.

Further, in the present specification, tetracarboxylic dianhydride is referred to as "acid dianhydride".

Further, the polyaminic acid composition of the present invention may contain other components than the above insofar as the effects of the present invention are not impaired.

The polyglycine composition of the present invention is preferably 100 parts by weight relative to the polyamic acid (A) from the viewpoint of improving the coatability of the cured film obtained from the poly-proline composition of the present invention. Instead, 100 parts by weight to 100,000 parts by weight of the organic solvent (B) is used.

Further, other polymers than the polyamine acid (A) may be mixed as long as the range of the effects of the present invention is not impaired.

1-1. Polyglycine (A)

The mixing ratio of the diamine to the acid dianhydride in the synthesis of the above polyamic acid (A) is 1:1 (mole ratio), wherein the mixing ratio (mol ratio) of the diamine is: the diamine (a1) is 0.1~0.99, diamine (a2) is 0.1~0.99.

1-1-1. Diamine (a1)

In the present invention, the diamine (a1) represented by the following formula (1) is used as a raw material for obtaining the polymer (A).

In the present invention, among the diamines represented by the formula (1), R ¹ is preferably an alkylene group having 1 to 5 carbon atoms, R ² is a methyl group, and n is an integer of 1 to 150.

More preferably, R ¹ is a propyl group, R ² is a methyl group, and n is an integer of 1 to 100. Further, particularly preferably, R ¹ is a stretching propyl group, R ² is a methyl group, and n is 1~. An integer compound of 30.

1-1-2. Diamine (a2)

In the present invention, the diamine (a2) represented by the formula (2) is used as a raw material for obtaining the polyamic acid (A).

In the formula (2), X, Y ¹ and Y ² are each independently a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -, m and n. They are independently 0 or 1 respectively.

Here, in the case of m=0 and n=0, the compound represented by the formula (2) preferably has X as -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF). ₃ ) ₂ -, and Y ¹ and Y ² are each a single bond compound.

In the case of m=1 and n=0, the compound represented by the formula (2) preferably has X as -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) _{2 .} -, Y ¹ is a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -, and Y ² is a single bond compound.

In the case where m=0 and n=1, the compound represented by the formula (2) preferably has X as -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) _{2 .} -, Y ¹ is a single bond, and Y ² is a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -.

In the case of m=1 and n=1, the compound represented by the formula (2) preferably has X as -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) _{2 .} -, and Y ¹ and Y ² are each independently a compound of a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -.

Further, in the formula (2), when X is a single bond, at least one of Y ¹ and Y ² is preferably -O-, -SO ₂ -, -C(Me) ₂ -, or -C( CF ₃ ) ₂ -.

In order to obtain solubility in the organic solvent (B) having a hydroxyl group, a diamine of a specific structure having a low molecular symmetry is used as the diamine (a2). Here, the term "low molecular symmetry" means a compound having a large flexibility of a molecule. When such a diamine (a2) is used, the solubility of the organic solvent (B) having a hydroxyl group can be obtained by reducing the linearity of the polyamic acid. A preferred diamine (a2) is a diamine of the formula (2) having an ether bond in the structure or a benzene ring having an amine group bonded to a position other than 4,4'-. It can be synthesized and dissolved in an organic solvent (B) having a hydroxyl group by using a diamine having a flexible ether bond or a bond having an amine group whose bond position is not para (4, 4'-). Polylysine. Specific examples of the diamine (a2) include 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, and 3,3'-diaminodiphenylanthracene. 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(aminophenoxy)phenyl] Propane, 2,2-bis[4-(aminophenoxy)phenyl]hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]indole, 1,4-bis(4- Aminophenoxy)butane, 1,5-bis(4-aminophenoxyl) Pentane, and 3,3'-diamino-1,3-diphenylpropane.

The diamine (a2) is preferably a formula (a2-1) (4,4'-diaminodiphenyl ether), a formula (a2-2) (3,3'-diaminodiphenylanthracene), Formula (a2-3) (1,3-bis(4-aminophenoxy)benzene), formula (a2-4) (2,2-bis[4-(aminophenoxy)phenyl]propane And a compound represented by the formula (a2-5) (bis[4-(3-aminophenoxy)phenyl]indole).

The diamine (a2) is particularly preferably a compound represented by the formula (a2-2), the formula (a2-3), the formula (a2-4), and the formula (a2-5).

However, the diamine (a2) of the present invention is not limited to the above compounds.

1-1-3. Acid dianhydride (a3)

In the present invention, acid dianhydride (a3) is used as a raw material for obtaining polyamic acid (A). When the diamine (a2) to be combined is a compound represented by the formula (a2-2) to the formula (a2-5), the synthesized polylysine has high solubility in a solvent having a hydroxyl group, and thus the acid The dianhydride (a3) is not particularly limited, and in the case where the combined diamine (a2) is other than the compound represented by the formula (a2-2) to the formula (a2-5), the synthesized polyetheramine acid exists. The solubility in a solvent having a hydroxyl group is not so high, and therefore the acid dianhydride (a3) is more preferably a compound having an ether bond.

Specific examples of the acid dianhydride are: pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, 3,3'-4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 3,3'-4,4'-biphenyl-perfluoropropane tetracarboxylic dianhydride, 3,3'-4,4'-diphenyl Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride.

Among these compounds, a compound represented by the formula (a3-1) (pyromellitic anhydride) or a compound represented by (a3-2) (4,4'-oxydiphthalic anhydride) is particularly preferred.

However, the acid dianhydride (a3) of the present invention is not limited to the above compounds.

1-1-4. Method for producing polylysine (A)

The polyaminic acid (A) is polycondensed by the diamine (a1) represented by the above formula (1), the diamine (a2) represented by the formula (2), and the acid dianhydride (a3). obtain. The method for producing the polyamic acid (A) is not particularly limited, and it can be produced by mixing the above diamine and an acid dianhydride in an organic solvent (B) having a hydroxyl group at room temperature.

The reaction temperature is not particularly limited, but is usually in the range of 10 ° C to 40 ° C. The reaction time is also not particularly limited, but is usually in the range of 1 hour to 48 hours. In this case, heating may be performed at about 50 ° C to 100 ° C for about 1 hour to 48 hours after the polymerization.

The solvent used in the above polycondensation reaction uses an organic solvent (B) having a hydroxyl group. Specific examples are described in items 1-2. The solvent to be used may be one of the solvents, or a mixture of two or more of the solvents.

If the weight average molecular weight determined by gel permeation chromatography (GPC) analysis of polyacrylic acid (A) is in the range of 500 to 100,000, film formation is carried out. Good sex, so it is better. Further, when the weight average molecular weight is in the range of 1,500 to 100,000, the substrate adhesion is good, and therefore it is more preferable.

The weight average molecular weight of polylysine (A) can be determined by GPC analysis. The measurement conditions are as follows: for example, standard polystyrene is polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by VARIAN Co., Ltd.), and the column is PLgel MIXED-D (VARIAN). Company system Made) and using N,N-dimethylformamide as the mobile phase.

1-2. Organic solvent having a hydroxyl group (B)

The organic solvent (B) having a hydroxyl group used in the present invention is preferably a compound having a boiling point of from 110 ° C to 300 ° C.

Specific examples of preferred solvents include diacetone alcohol, 2-hydroxyethyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and ethylene. Alcohol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, And dipropylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more.

The solvent (B) contained in the poly-proline composition of the present invention is selected from the group consisting of diacetone alcohol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and triethylene glycol. At least one of the monomethyl ethers is more preferable in terms of improving the uniformity of coating of the polyaminic acid composition and safety to the human body. On the other hand, from the viewpoint of printability, it is preferred to contain a solvent (B) having a boiling point of 180° C. or higher of 3% by weight to 90% by weight based on the total amount of the solvent (B). More preferably, it is 5% by weight to 50% by weight, particularly preferably 10% by weight to 30% by weight.

The solvent (B) is used as a solvent in the production of polyglycolic acid (A), and is used as a diluent solvent in the preparation of a polyamic acid composition. From the viewpoint of printability, it is preferred to use a solvent (B) having a boiling point of 180 ° C or higher.

The solvent contained in the polyaminic acid composition of the present invention can be used without damaging the present invention. The solvent other than the solvent (B) is further included in the range of the effect of the poly-proline composition. It is preferred to contain 3% by weight to 100% by weight of the solvent (B) with respect to the total amount of the solvent. More preferably, it is 5% by weight to 100% by weight, and particularly preferably 30% by weight to 100% by weight.

Further, in the poly-proline composition of the present invention, it is preferred to use polyglycine (A) as a solid component with respect to the total amount of polyamic acid (A) and an organic solvent (B) having a hydroxyl group. The preparation is carried out in a manner of from 0.1% by weight to 50% by weight.

1-3. Other ingredients

In the poly-proline composition of the present invention, various additives may be added in order to improve coating uniformity and adhesion. The additives are mainly anionic, cationic, nonionic, fluorine- or quinone-based surfactants, adhesion improvers such as decane coupling agents, crosslinking agents, and antioxidants.

1-3-1. Surfactant

In the polyphthalic acid composition of the present invention, a surfactant may be added in order to improve coating uniformity. Examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all of which are trade names; Kyoei Chemical Industry Co., Ltd.), BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346 (all of which are trade names; BYK-Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS , KF-50-100CS (all of which are trade names; Shin-Etsu Chemical Industry Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S-611 (all of which are trade names; AGC Seimi Chemicals (AGC Seimi) Chemical), Ftergent 222F, Ftergent 251, FTX-218 (all of which are trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all of which are trade names; Mitsubishi Materials Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-475, Megafac F-556, Megafac R-30 (all of the above are trade names; DIC Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluorine Alkyl sulfonate, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octane Phenyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether , polyoxyethylene lauryl ester, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan lauryl ester, dehydrated sorbus Alcohol palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan lauryl ester, polyoxyethylene sorbitan palmitate , polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, or alkyl diphenyl ether disulfonate, etc. . It is preferred to use at least one selected from the group of surfactants for the surfactant.

Among the surfactants, if selected from a fluoroalkylbenzenesulfonate, a fluoroalkylcarboxylate, a fluoroalkyl polyoxyethylene ether, a fluoroalkyl ammonium iodide, a fluoroalkyl betaine, a fluoroalkyl group Sulfonate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium a salt, or a fluorine-based surfactant such as a fluoroalkylaminosulfonate or Surflon S-611, or at least one of a lanthanoid additive such as BYK306, BYK342, BYK346, KP-341, KP-358, or KP-368 Further, since the coating uniformity of the thermosetting composition is improved, it is preferable.

Further, the content of the surfactant in the present invention is preferably from 0.01% by weight to 5% by weight based on the total amount of the polyamic acid composition. If it is this range, the effect of this invention will not be impaired, and coating uniformity can be improved.

1-3-2. Adhesion improver

The polyaminic acid composition of the present invention may further contain an adhesion improving agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate. From the above viewpoints, the content of the adhesion improving agent is preferably from 0.01% by weight to 10% by weight based on the total amount of the polyamic acid composition. If it is this range, the effect of this invention will not be impaired, and adhesiveness can be improved.

As such an adhesion improving agent, for example, a decane-based, aluminum-based or titanate-based coupling agent can be used, and specific examples thereof include 3-glycidoxypropyldimethylethoxy decane and 3-glycidyloxy group. a decane coupling agent such as propylmethyldiethoxysilane or 3-glycidoxypropyltrimethoxydecane, an aluminum coupling agent such as acetoxy aluminum diisopropylate, or tetraisopropyl A titanate coupling agent such as bis(dioctylphosphite) titanate.

Among these compounds, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving adhesion.

1-3-3. Crosslinking agent

The polyaminic acid composition of the present invention may contain a crosslinking agent from the viewpoint of further improving chemical resistance, film in-plane uniformity, flexibility, flexibility, and elasticity. Further, the crosslinking agent may be a thermal crosslinking agent crosslinked by heat, or may be a photocrosslinking agent crosslinked by light irradiation. The content of the crosslinking agent is preferably from 0.01% by weight to 30% by weight based on the total amount of the polyamic acid composition. If it is this range, the effect of this invention will not be impaired, and characteristics, such as the said chemical resistance, can be improved.

Examples of such a thermal crosslinking agent include: jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P, jER1004, jER1256, YX8000 (trade name; Mitsubishi Chemical Corporation), Araldite CY177, Araldite CY184 (trade name; Huntsman Japan Co., Ltd., Celloxide 2021P, EHPE-3150 (trade name; Daicel Chemical Industry Co., Ltd.), Tecmoa VG3101L (trade name; Printec Co., Ltd.), Nikalac MW-30HM , Nikalac MW-100LM, Nikalac MW-270, Nikalac MW-280, Nikalac MW-290, Nikalac MW-390, Nikalac MW-750LM, (trade name; Sanwa Chemical Co., Ltd.).

Further, examples of such a photocrosslinking agent include: 4,4'-diazidostilbene 2,2'-disodium sulfonate, 4 , 4'-diazidebenzylideneacetone-2,2'-disulfonic acid disodium salt, 1,3-bis(4'-azido-2'-sulfobenzylidene)butanone disodium salt , 2,6-bis(4'-azido-2'-sulfobenzylidene)cyclohexanone disodium salt, 2,6-bis(4'-azido-2'-sulfobenzylidene) -4-methylcyclohexanone disodium salt, 2,5-bis(4'-azido-2'-sulfobenzylidene)cyclopentanone disodium salt, 4,4'-diazide Acetone-2,2'-disodium sulfonate, 2,6-bis(4'-azido-2'-sulfoylidene)cyclohexanone disodium salt, 2,5-double (4' - Azide-2'-sulfoyocamphenyl)cyclopentanone disodium salt.

1-3-4. Antioxidants

An antioxidant such as a hindered phenol type, a hindered amine type, a phosphorus type or a sulfur type compound may be added to the polyamic acid composition of the present invention. Among them, from the viewpoint of weather resistance, a hindered phenol system is preferred. Specific examples include Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Irganox 245FF , Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Irganox 565DD, Irganox 295 (trade name; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO -60, ADK STAB AO-70, and ADK STAB AO-80 (trade name; ADEKA Co., Ltd.). More preferably, it is AO-60.

The content of the antioxidant is preferably from 0.01 part by weight to 10 parts by weight per 100 parts by weight of the polyamic acid (A).

1-4. Preservation of polylysine composition

When the polyglycine composition of the present invention is stored at a temperature of from -30 ° C to 0 ° C, the composition has a good stability with time. If the storage temperature is -20 ° C to 0 ° C, there is no precipitate, so it is more preferable.

1-5. Use of polylysine composition

The polyphthalic acid composition of the present invention is most suitable for forming an insulating film or a high refractive index film. The term "insulating film" as used herein means, for example, in order to make a wiring layer arranged in a layer shape. A film (interlayer insulating film) or the like provided on the edge.

A method of forming a cured film on a substrate having a low surface energy using the composition of the present invention is as follows.

First, the polylysine composition of the present invention is applied to a substrate having a low surface energy by a known method such as spin coating, roll coating, or slit coating. Examples of the substrate include a substrate coated with an anthrone-based material or a fluorine-based material, or a coating layer for printing fluorenone.

For example, in the case of a substrate coated with an anthrone-based material, the poly-proline composition is applied onto the substrate, and then treated at 80 ° C to 120 ° C for 1 minute to 5 minutes using a hot plate or an oven. The solvent is evaporated and dried.

The dried film is thermally cured at 150 ° C to 350 ° C for 10 minutes to 60 minutes in an oven. A cured film was obtained in the above manner.

On the other hand, in the case of reverse offset printing, the polyaminic acid composition is applied onto the fluorenone coating layer by slit coating, and the waiting time is set in order to dry the solvent to a predetermined level (waiting) Time). Then, the coating layer was pressed on a glass electroforming plate having a concave-convex pattern formed on the surface thereof, and an unnecessary portion was transferred onto the electroforming plate to be removed. Further, the patterned cured film remaining on the coating layer is transferred onto a glass substrate or the like.

The patterned cured film obtained in the above manner is treated in a hot plate or an oven at 80 ° C to 120 ° C for about 1 minute to 5 minutes, and the solvent is evaporated and dried.

The dried film is processed in an oven at 150 ° C ~ 350 ° C for 10 minutes. ~60 minutes or so and heat hardened. A patterned cured film was obtained in the above manner.

The (pattern-like) cured film formed in the above manner may also be formed by forming a transparent electrode on the cured film and patterning it by etching to form a film subjected to alignment treatment. Since the cured film has high sputtering resistance, even if a transparent electrode is formed, wrinkles do not occur on the insulating film, and a high-quality transparent electrode can be formed.

The above (pattern-like) cured film is used for a display element using a liquid crystal or the like. For example, a liquid crystal display element is formed by bonding an element substrate on which a patterned cured film is provided on a substrate, a color filter substrate as a counter substrate, and then heat-treating by using a sealant. The liquid crystal is injected between the opposing substrates, and the injection port is sealed to be produced.

Alternatively, the liquid crystal may be dispersed on the element substrate, and then the element substrate may be stacked to seal the liquid crystal so that the liquid crystal does not leak. The display element may be a display element produced as described above.

A cured film having excellent heat resistance and transparency formed of the polyaminic acid composition of the present invention in the above manner can be used for a liquid crystal display element. In addition, the liquid crystal used in the liquid crystal display device of the present invention, that is, the liquid crystal compound and the liquid crystal composition are not particularly limited, and any liquid crystal compound and liquid crystal composition can be used.

The polyaminic acid composition of the preferred embodiment of the present invention has, for example, high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, and adhesion to a substrate which are generally required for a cured film. And so on. As a result, it is possible to improve the use of a cured film or the like using the polyaminic acid composition of the preferred embodiment of the present invention. Display quality of products such as components.

Further, the polyglycine composition of the preferred embodiment of the present invention is excellent in solvent resistance, acid resistance, alkali resistance, heat resistance, and transparency, and a transparent film using the thermosetting composition, a display element, and the like. Even if it is immersed, contacted, heat-treated, or the like in a solvent, an acid, an alkali solution or the like in a subsequent step after the formation of the transparent film, it is difficult to cause surface roughness on the film.

[Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited to the examples.

[Synthesis Example 1] Synthesis of Polylysine (A1)

A thermometer was placed in a four-necked flask equipped with a stirrer, and propylene glycol monomethyl ether (PGME) as a polymerization solvent and Silaplane FM-3311 as a diamine (a1) were added under the following weight (trade name, JNC Co., Ltd.) 4,4'-diaminodiphenyl ether as diamine (a2), 4,4'-oxydiphthalic anhydride (manac) as acid dianhydride (a3) The product was stirred at 25 ° C for 6 hours to obtain a polyglycine solution having a solid content of 20% by weight.

Further, the above ratio is a total amount of diamines: the total amount of the acid dianhydrides (a3) is 1:1 (mole ratio), and the solvent (PGME) is mixed to have a solid content of 20 Adjust by weight %. The "total amount of diamine" means the total amount of the diamine (a1), the diamine (a2), and the diamine other than the formula (a2).

A portion of the solution was collected and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polyaminic acid (A1) had a weight average molecular weight of 38,300.

[Synthesis Example 2 to Synthesis Example 10] Synthesis of Polymer (A2) to Polymer (A10)

Polymerization was carried out in the same manner as in Synthesis Example 1 at an input ratio shown in Table 1, to obtain a polyglycine solution having a solid content of 20% by weight. Further, a part of the solution was collected, and GPC analysis (polystyrene standard) of polyamic acid (A2) to polyaminic acid (A10) was carried out. The results are shown in the table.

[Comparative Synthesis Example 1 to Comparative Synthesis Example 4] Synthesis of Polymer (C1) to Polymer (C4)

Polymerization was carried out in the same manner as in Synthesis Example 1 at an input ratio as described in the following table. However, neither the polymer (C1) nor the polymer (C2) has solubility in the organic solvent (B), and the polymerization liquid precipitates in a cloudy manner. For the polymer (C3) and the polymer (C4), a transparent polyamic acid solution having a solid content of 20% by weight was obtained, and GPC analysis was performed. The results are shown in Table 1.

The product name of Table 1 is abbreviated as follows.

(diamine (a1))

FM3311: bis(aminopropyl)polydimethyloxane

(Silaplane FM3311 (trade name, JNC (share)), Mn~1000)

FM3321: bis(aminopropyl)polydimethyloxane

(Silaplane FM3321 (trade name, JNC), Mn~5000)

(diamine (a2))

DPE: 4,4'-diaminodiphenyl ether

m-DDS: 3,3'-diaminodiphenylanthracene

TPE-R: 1,3-bis(4-aminophenoxy)benzene

BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

BAPS-M: 4,4'-bis(3-aminophenoxy)diphenylanthracene

(diamine other than diamine (a2))

PPD: 1,4-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

(acid dianhydride (a3))

ODPA: 4,4'-oxydiphthalic anhydride

PMDA: pyromellitic anhydride

(Organic solvent (B))

PGME: propylene glycol monomethyl ether

[Example 1]

[Manufacture of polylysine composition]

The diethylene glycol monomethyl ether as a diluent solvent, the polymer (A1) obtained in Synthesis Example 1, and the surfactant Surfl S-611 (manufactured by AGC Seimi Chemical Co., Ltd.) were mixed and dissolved to obtain a solid. 10% by weight of the composition Proline composition. The amount of the surfactant added was 500 ppm with respect to the total amount of the composition.

[Example 2 to Example 15, Comparative Example 1 to Comparative Example 4] Production of Polylysine Composition

Example 2 to Example 11 In the same manner as in Example 1, according to Table 2, each component was mixed and dissolved to obtain a polyglycine composition having a solid content of 10% by weight. In addition, when the solvent for dilution is two or more types, it is used by mixing in the ratio (weight ratio) shown in the table. In Comparative Example 1 to Comparative Example 4, in the same manner as in Example 1, each component was mixed and dissolved according to Table 2, and a polyamine composition having a solid content of 10% was obtained. In Comparative Example 1 and Comparative Example 2, the polyamic acid solution obtained in Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was compared with a white turbid precipitate, and thus the polyglycine composition was also cloudy, and a uniform film could not be obtained even after coating. Therefore, it cannot be evaluated as a composition.

The product names of Table 2 are abbreviated as follows.

(Organic solvent for dilution (B))

ECa: diethylene glycol monoethyl ether

MCa: diethylene glycol monomethyl ether

DAA: Diacetone alcohol

TEGME: Triethylene glycol monomethyl ether

(surfactant)

S-611: Fluorine surfactant manufactured by AGC Qingmei Chemical Co., Ltd.

[Method for evaluating polylysine composition]

1) Substrate coating properties

The applicability to a substrate having a low surface energy was confirmed based on the coatability of the fluorenone coating layer for reverse offset printing. The polyaminic acid composition was coated on the coating layer by a bar coater to visually confirm the presence or absence of repulsion. In the case of rejection, it was evaluated as ×, and in the case of uniform coating, it was evaluated as ○.

2) Formation of cured film and measurement of film thickness after calcination

The thermosetting composition was spin-coated on a glass substrate at 500 rpm for 10 seconds, and dried on a hot plate at 100 ° C for 2 minutes. The substrate was baked in an oven at 230 ° C for 30 minutes to form a transparent film having a film thickness of 1.0 μm ± 0.1 μm. The average value of the measurement of the three parts was made into the film thickness using the stylus type film thickness meter P-15 manufactured by KLA-Tencor Japan Co., Ltd.

3) Coating uniformity

The thermosetting composition was spin-coated on a glass substrate on which chromium was deposited, and dried on a hot plate at 100 ° C for 2 minutes. Then, the substrate was baked in an oven at 230 ° C for 30 minutes to form a transparent film having a film thickness of 3.0 μm ± 0.2 μm. The surface of the substrate after the calcination was visually confirmed, and the case where blurring and unevenness were confirmed was evaluated as ×, and the case where blurring or unevenness was not confirmed was evaluated as ○.

4) Heat resistance

The glass substrate on which the cured film obtained in the above 2) was formed was additionally baked in an oven at 300 ° C for 30 minutes, and from the post-baking to the residual film rate after the additional baking. The lower the drop, the better it can be judged to be good. The rate of change in film thickness was calculated according to the following formula.

(additional film thickness after baking / film thickness after post-baking) × 100 (%)

5) Pattern transferability

The ketone coating layer coated with the polyaminic acid composition by a bar coater in 1) is pressed against a glass substrate (electroformed plate) having a concave-convex structure formed on the surface thereof, and is electroformed. The cured film of the portion where the convex portion is in contact is removed, and then the coating is pressed on the flat glass substrate, whereby the pattern printability evaluation of the cured film is performed. The case where the pattern was clearly transferred was evaluated as ○, and the case where the pattern was not transferred at all was evaluated as ×.

The results obtained by the above evaluation methods for the thermosetting compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 4 are shown in Table 3.

[Industrial availability]

The thermosetting composition of the present invention can be used, for example, to form an insulating material in an electronic component. More specifically, it can be used, for example, to form a passivation film, a buffer coating film, an interlayer insulating film, or a planarization film in a semiconductor device. Alternatively, it can be used for an interlayer insulating film in a liquid crystal display element or a protective film for a color filter. Alternatively, it can be used to form an insulating film or the like of an organic EL element.

Claims (7)

A polyaminic acid composition for use in offset printing or reverse offset printing, comprising: a diamine (a1) represented by the formula (1), a diamine (a2) represented by the formula (2), And a polyphthalic acid (A) obtained by polycondensation of an acid dianhydride (a3); and an organic solvent consisting only of an organic solvent (B) having a hydroxyl group: In the formula (1), R ¹ is an alkylene group having 1 to 5 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 150; In the formula (2), X, Y ¹ and Y ² are each independently a single bond, -O-, -SO ₂ -, -C(Me) ₂ -, or -C(CF ₃ ) ₂ -, m and n. They are independently 0 or 1 respectively. The polyaminic acid composition according to claim 1, wherein the diamine (a2) is at least one selected from the group consisting of compounds represented by formula (a2-1) to formula (a2-5): The polyaminic acid composition according to the first aspect of the invention, wherein the acid dianhydride (a3) is at least one selected from the group consisting of compounds represented by formula (a3-1) and formula (a3-2). : The polyaminic acid composition according to claim 1, wherein the organic solvent (B) comprises at least one organic solvent having a boiling point of 110 ° C or higher. The polyphthalic acid composition according to any one of the preceding claims, wherein the organic solvent (B) comprises at least one selected from the group consisting of diacetone alcohol and acetic acid-2. -hydroxyethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Tripropylene glycol, 1,3-butanediol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and dipropylene glycol monomethyl ether. A cured film obtained by using the polyaminic acid composition according to any one of claims 1 to 5. An electronic component having a cured film as described in claim 6 of the patent application.