JPH01103628A - Preparation of curable polymer - Google Patents

Abstract

PURPOSE:To prepare a curable polymer having excellent coatability even when the viscosity is low and the solid content is high, by reacting a diamino compd. with a specified silicon compd. CONSTITUTION:A curable polymer is prepd. by reacting a diamino compd. (e.g., 4,4'-diaminodiphenyl ether) (A) with a dicarboxylic acid anhydride contg. a silicon atom. having a hydrolyzable group (e.g., 3-trimethoxysilyl-1,2,5,6- tetrahydrophthalic anhydride) (B). It is possible to prepare a curable polymer having excellent coatability even when the viscosity is low and the solid content is high by this method. Therefore, when a coated film is prepd. by using this curable polymer, a coated film having excellent smoothness can be formed and the cured film obtd. by heat-treatment has a high glass transition temp., excellent crack resistance and excellent adhesiveness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a curable polymer.

[Conventional technology]

Conventionally, polyimide with excellent heat resistance has been known as a protective film material, an insulating film material, etc. in the field of electronic devices. When polyimide is used as these materials, a method is used in which a solution of polyamic acid, which is a precursor of polyimide, is applied to a substrate and heat treated to cause an imidization reaction to form polyimide. however,
The polyimide thus obtained has problems such as insufficient adhesion to the substrate when the substrate is made of silicon or glass.

Therefore, recently, a composition has been disclosed which is made by mixing a polyimide resin precursor, a silyl foundation, and tetrahydrophthalic anhydride, which can form a cured film with excellent adhesion to a substrate (Japanese Patent Laid-Open No. 61 -293258).

[Problem that the invention seeks to solve]

However, this composition has the problem of high viscosity and poor coating properties in forming a coating film.

On the other hand, it is possible to lower the viscosity by adding a solvent to improve coating properties, but in this case, the solid content concentration will drop to the bottom, making it difficult to flatten the surface after the coating film has hardened. A problem arises in that the condition deteriorates.

In addition, the cured film obtained from the polyimide resin precursor composition has a low glass transition temperature, making it difficult to use at high temperatures, and has insufficient hardness. Furthermore, there is a problem in that the solution of the composition becomes colored when cured by heat treatment.

The present invention has been made based on the above problems, and
The objective is to have low viscosity and excellent coating properties even at high solids concentrations, as well as high glass transition temperature curing with excellent transparency, adhesion to substrates, flattening properties, and hardness without coloring. An object of the present invention is to provide a method for producing a curable polymer capable of forming a film.

[Means for solving problems]

The present invention is characterized in that a curable polymer is produced by reacting a diamino compound with a silicon atom-containing dicarboxylic acid anhydride having a hydrolyzable group.

The present invention will be explained in detail below.

In the present invention, the diamino compound is dissolved or suspended in a solvent as required, and a silicon atom-containing dicarboxylic acid anhydride having the hydrolyzable group, that is, a specific silicon compound, is added thereto, and the diamino compound is reacted and cured. to obtain a polymer.

Examples of the diamino compound used in the present invention include para-phenylene diamine, meta-phenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4.4 '-Diamino diphenyl sulfone, 4.4'-diaminodiphenyl ether, 1.5-diaminonaphthalene, 3.3°-dimethyl-
4,4°-diaminobiphenyl, 3°4"-diaminobenzanilide, 3.4'-diaminodiphenyl ether, 3.3'-diaminobenzophenone, 3.4"-diaminobenzophenone, 4,4"-diaminobenzophenone, 1 .4-bis(4-aminophenoxy)benzene,
1.3-bis(4-aminophenoxy)benzene, 1.
3-bis(3-aminophenoxy)benzene, 9.9-
Bis(4-aminophenyl)-10-hydro-anthracene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2°.

5.5'-tetrachloro-4,4'-diaminobiphenyl, 2.2'-dichloro-4,4'-diamino-5,5
'-dimethoxybipheninope3,3'-dimethoxy-4
, 4°-diaminobiphenyl and other aromatic diamines, metaxylylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4. 4'-
Dimethyl hebutamethylene diamine, 1,4-diaminocyclohexane, inphorone diamine, tetrahydrodicyclopentadienyl diamine, hexahydro-4,7
- Aliphatic and alicyclic diamines such as methanoindanilene shimethylene diamine, tricyclo(6,2,1,O2.7]-landecylenedimethyldiamine, 1,4-bis<3-aminopropyl-dimethylsilyl)benzene can be mentioned.

Furthermore, diaminoolkalisiloxanes represented by CH, CH5, etc. can be mentioned.

Among these diamino compounds, preferable examples include aromatic diamines such as 4,4''-diaminophenyl ether and 4.4°-diaminodiphenylmethane, and the above-mentioned diaminoorganosiloxanes. It can be used alone or in combination of two or more kinds.

The diamino compound used in the present invention may be a modified product modified by reaction with a tetracarboxylic dianhydride. This modified product is obtained by preferably gradually adding a tetracarboxylic dianhydride to a diamino compound dissolved or suspended in a solvent described below and reacting the diamino compound.

Examples of the tetracarboxylic dianhydride that modifies the diamino compound include pyromellitic dianhydride, 3
, 3°, 4,4°-biphenyltetracarboxylic dianhydride, 2.2', 3.3°-biphenyltetracarboxylic dianhydride, 2.3.3', 4°-biphenyltetracarboxylic dianhydride Anhydride, 3,3°, 4.4'-ben7'phenotetracarboxylic dianhydride, 2.3.3°, 4”-
Benzophenone tetracarboxylic dianhydride, 2,2°.

3.3°-benzophenonetetracarboxylic dianhydride,
Bis(3,4-dicarboxyphenyl)-courtelanhydride, bis(3,4-dicarboxyphenyl)-sulfonic anhydride, 1.2.5.6-naphthalenetetracarboxylic dianhydride, 2.3, 6.7-Aromatic tetracarboxylic dianhydride such as naphthalenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1.2.3.4-
Cyclobutanetetracarboxylic dianhydride L 1.2,3
．． 4-Cyclopenkune tetracarboxylic dianhydride, '2
, 3.5- tricarboxycyclopentyl acetic dianhydride, 3.5.6-)! I carboxynorbornane-2
-acetic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexenedicarboxylic dianhydride, bicyclo(2,2,2]-oct-7-ene-tetracarboxylic dianhydride Mention may be made of aliphatic and cyclic tetracarboxylic dianhydrides such as.

Among these tetracarboxylic dianhydrides, pyromellitic dianhydride, 3,3", 4,4°-biphenyltetracarboxylic dianhydride, 2,2°, 3.3"-biphenyltetracarboxylic dianhydride, Acid dianhydride, 3,3°, 4.4'
-benzophenonetetracarboxylic dianhydride, 1.2
゜3.4-Cyclobutanetetracarboxylic dianhydride, 2
．． 3.5-)! 7-carpoxycyclopentyl acetic dianhydride and the like are preferred.

These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

In the present invention, when a tetracarboxylic dianhydride is used for modifying a diamino compound, the proportion of the tetracarboxylic dianhydride used is 0.00% per mole of the diamino compound.
It is preferably 5 moles or less. By using tetracarboxylic dianhydride, the molecular weight of the resulting curable polymer increases, and the film formability on the substrate is further improved.

However, if this usage ratio is excessive, the modified product cannot be converted into a diamino compound.

Further, the reaction temperature between the tetracarboxylic dianhydride and the diamino compound is preferably about 0 to 80°C, for example.

The specific silicon compound used in the present invention, that is, the silicon atom-containing dicarboxylic acid anhydride having a hydrolyzable group, is, for example, the following formula (I) to general formula I [I
).

- Formula (I) General formula (It) General formula (III) In the above formulas (1) to (III), R1 and R2 each represent a hydrogen atom, a methyl group, an ethyl group,
C1-5 aliphatic hydrocarbon groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, phenyl group, tolyl group, xylyl group, nitro Phenyl group, α-
A naphthyl group represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and XI, X2 and X'' are each a methoxy group,
represents an alkoxy group having 1 to 5 carbon atoms, such as an ethoxy group or a propoxy group, or a halogen atom, such as a fluorine atom, a chlorine atom, or a bromine atom; Y is a trivalent aliphatic hydrocarbon group having 2 to 20 carbon atoms; Represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

Specific examples of such specific silicon compounds include those represented by the following structural formula.

Among these specific silicon compounds, 3-trimethoxysilyl-1゜2.5.6-
Examples include titrahydrophthalic anhydride, 3-trimethoxysilyl phthalic anhydride, 3-methyldimethoxysilyl phthalic anhydride, 3-dimethylmethoxysilyl phthalic anhydride, and the like.

These specific silicon compounds can be used alone or in combination of two or more.

In the present invention, the specific silicon compound is preferably used in an amount of 1 to 3 moles per mole of the diamino compound. When the proportion used is less than 1 mole, the film-forming properties of the resulting curable polymer tend to deteriorate, while when the proportion used exceeds 3 moles, the storage stability of the obtained curable polymer deteriorates.

In the present invention, it is preferable to use a solvent during the reaction, and the solvent in this case is not particularly limited as long as it is inert to the reaction raw materials and reaction products, such as N-methyl-2-pyrrolidone. , dimethylformamide, dimethylacetamide, tetramethylurea, hexamethylphosphonamide, methylformamide, amide solvents such as N-acetyl-2-pyrrolidone, sulfur-containing solvents such as dimethylsulfoxide and dimethylsulfone, benzene, toluene, xylene, and durene. Aromatic hydrocarbon solvents such as dichloromethane, chloroform, tricrene, chlorobenzene, dichlorobenzene, etc., alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, calpitol, butyl carpitol ester solvents such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carpitol acetate, carpitol acetate, butyl carpitol acetate, and ether solvents such as tetrahydrofuran, diethyl ether, glyme, diglyme, and dioxane. be able to.

These solvents can be used alone or in combination of two or more.

In the present invention, when a solvent is used, the concentration of the reaction system is practically about 10 to 90% by weight.

In the present invention, it is preferable that the diamino compound, the specific silicon compound, and the solvent used as necessary be sufficiently dehydrated, for example, those having a moisture content of 50 ppm or less as determined by the Karl Fischer method. If the dehydration is insufficient, there is a risk that a specific silicon compound may be hydrolyzed in the reaction system.

In the present invention, the diamino compound and the specific silicon compound are preferably 80°C or lower, particularly preferably 0 to 6°C.
The reaction is carried out dropwise at a temperature of 0° C., usually for 0.5 to 10 hours.

In the present invention, a catalyst may be added as necessary. Examples of such catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, and organic acids such as para-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, and trichloroacetic acid, and the proportions used are as follows: usually,
It is about 0.01 to 1% by weight based on the specific silicon compound.

Note that these reactions are preferably performed under a nitrogen atmosphere.

When using the curable polymer produced as described above as a coating solution for film formation, the reaction product solution may be used as it is after removing impurities by appropriate means if necessary. Alternatively, the curable polymer may be separated from the reaction product liquid and then used by adding an appropriate solvent, for example, the solvent used in the production of the curable polymer.

The weight average molecular weight of the curable polymer produced according to the present invention in terms of polystyrene is usually 500 to 20,000, and its solution is characterized by low viscosity even at high concentrations. Therefore, a film-forming coating solution using the curable polymer produced according to the present invention can provide good coating properties even if the solid content concentration is high. The concentration of the curable polymer in the coating solution is usually 10 to 90% by weight,
Its viscosity is 50-10,000 cp (25°C).

The coating method for forming a coating film using the coating liquid includes:
There are no particular limitations, and methods such as roll coating, spin coating, screen coating, and dipping coating can be used.

The heat treatment temperature for drying and curing the obtained coating film is
Although it can be appropriately selected depending on the type of curable polymer, it is usually 100 to 300°C, preferably 150 to 250°C.
It is ℃. Note that the time required for curing after drying is usually
It takes about 10 minutes to 5 hours. In addition, in order to further accelerate the curing of the coating film, a curing catalyst such as ammonia, triethylamine, diethylamine, etc. may be added to the coating solution as necessary.
Pyridine, quinoline, isoquinoline, etc. may be added in a strained amount of 0.01 to 1 part by weight per 100 parts by weight of the curable polymer.

The curable polymer obtained by the method of the present invention may contain other polymers that are compatible with it, such as polyamide, polyimide, silicone resin, epoxy resin, acrylic resin,
It can also be used in combination with urethane resin or the like.

The curable polymer produced by the method of the present invention can be applied to substrates made of glass substrates, color filter substrates, silicon substrates, ceramic substrates, copper, aluminum, iron, etc.
For example, it is possible to coat the film up to a thickness of about 1 mm.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited to these Examples.

Example 1 After purging the inside of the flask with nitrogen gas, 500 g of dehydrated N-methyl-2-pyrrolidone and 100 g (0.5 mol) of 4,4''-diaminodiphenyl ether were charged, and 3-trimethoxysilyl-1 , 272 g (1 mol) of 2,5,6-titrahydrophthalic anhydride at a reaction temperature of 5 to
The reaction was carried out dropwise at 10° C. over a period of about 30 minutes. Thereafter, the temperature was raised to room temperature, and the reaction was further carried out for 2 hours to obtain a solution containing a curable polymer having a polystyrene equivalent weight average molecular weight of 3.000.

This curable polymer solution was filtered through a membrane filter with a pore size of 0.2 μm to obtain a coating solution. This is called coating liquid A. The viscosity of this coating liquid A was 160 cp (25° C.), and the solid content concentration was 40% by weight.

Example 2 In Example 1, 4,4°-diaminodiphenylmethane 9 was used instead of 4,4°-diaminodiphenyl ether.
A solution containing a curable polymer having a polystyrene equivalent weight average molecular weight of 3.000 was obtained by the same procedure except that 9 g (0.5 mol) was used. This curable polymer solution was filtered through a membrane filter with a pore size of 0.2 am to obtain a coating solution. This will be referred to as coating liquid B.

The viscosity of this coating liquid B was 140 cp (25° C.), and the solid content concentration was 37% by weight.

Example 3 In Example 1, 3-trimethoxysilyl-1,2,
236 g of 3-dimethylmethoxysilylphthalic anhydride (1
A solution containing a curable polymer having a polystyrene equivalent weight average molecular weight of 5.400 was obtained by the same procedure except that mol) was used. This curable polymer solution was filtered through a membrane filter with a pore size of 0.2 μm to obtain a coating solution. This will be referred to as coating liquid C. The viscosity of this coating liquid C was 176 cp (25°C
), and the solid content concentration was 38% by weight.

Example 4 After purging the inside of the flask with nitrogen gas, 500 g of dehydrated dimethylacetamide and 50 g (0.25 mol) of 4.4''-diaminodiphenyl ether were charged into the flask, and 3.3', 4.4° - 40.3 g (0,125 mol) of benzophenone tetracarboxylic dianhydride was gradually added dropwise over about 2 hours at a reaction temperature of 40 to 50°C to react.Then, the mixture was cooled to room temperature and stirred for an additional 2 hours. After that, 3-trimethoxysilyl phthalic anhydride 67
g (0.25 mol) was gradually added dropwise over about 30 minutes at a reaction temperature of 5 to 10°C to react. Thereafter, the temperature was raised to room temperature, and the reaction was further carried out for 2 hours to obtain a solution containing a curable polymer having a polystyrene equivalent weight average molecular weight of 15.000. This curable polymer solution was filtered through a membrane filter with a pore size of 0.2 μm to obtain a coating solution. This is used as the coating liquid. The viscosity of this coating liquid is 280 cp (25℃
), and the solid content concentration was 21% by weight.

Test Example 1 The following tests were conducted using each of the coating liquids A to D obtained in Examples 1 to 4 above as sample coating liquids.

[Cured film formation test 1] Each sample coating solution was spin-coated onto a flat glass substrate using a spin coater at a rotation speed of 1000 to 5000 rpm.
Then, heat treatment was performed at 200° C. for 1 hour to form cured films having the thickness shown in Table 1.

These cured films were evaluated for (1) hardness, (2) light transmittance, and (2) adhesion. The results are shown in Table 1. The evaluation method is as follows.

■Hardness Evaluation was performed by measuring pencil hardness.

(2) Light Transmittance Using a visible light absorption spectrometer, the transmittance of the cured coating film to visible light having a wavelength of 400 to 100 nm was measured and evaluated.

(2) Adhesion After the glass substrate provided with the cured film was immersed in boiling water at 100° C. for 1 hour, a cross-cut tape peeling test was conducted in accordance with the method specified in JIS-5400 for evaluation.

[Cured film formation test 2] Each sample coating solution was applied to a silicon substrate with a pattern of 1 μm unevenness formed on the surface using a spin coater at a rotation speed of 10.
A coating film was formed by spin coating at 00 to 5000 rpm, and then heat treated at 200° C. for 1 hour to form a cured film having the same film thickness (recessed portions) shown in Table 1 as in Cured Film Formation Test 1. Note that the space width in the uneven pattern is 10
0μ, and the line width is 100n.

These cured films were evaluated for (1) flattening properties and (2) crack resistance. The results are also shown in Table 1. The evaluation method is as follows.

(2) Flattenability The surface of the cured film was observed using a surface roughness meter and a scanning electron microscope (SEM), and the flattenability was evaluated by determining the flattening rate δ defined by the following formula.

Flattening rate δ = (1-a/b) x 100 (%) (In the formula, a represents the level difference on the surface of the cured film, and b represents the level difference in the uneven pattern.) ■Crack resistance The silicon substrate provided with the cured film was left in an atmosphere at 300° C. for 2 days, and evaluated based on whether or not cracks were generated in the cured film.

〔Effect of the invention〕

According to the method of the present invention, a curable polymer having low viscosity and excellent coating properties even at a high solid content concentration can be produced. Therefore, when forming a coating film using the curable polymer obtained by the method of the present invention, it is possible to form a coating film with excellent flattening properties, and the cured film obtained by heat treatment is made of glass. It has a high transition temperature, excellent crack resistance, and excellent adhesion.

In addition, since the hardness of the cured film is high, it is possible to form a film with excellent mechanical durability, and the light transmittance to visible light is high, so it can be advantageously used in applications that require high light transmittance. Can be done.

Therefore, the curable polymer obtained by the method of the present invention is
Passivation films for glass substrates, liquid crystal alignment films, surface protection films and planarization films for semiconductors, surface protection films and planarization films for color filters, multilayer wiring interlayer insulation films, gas separation films, etc. for electronic applications such as liquid crystal devices and semiconductor devices. It can be suitably used in various fields including the equipment field.

Claims (1)

[Claims] 1) A method for producing a curable polymer, which comprises reacting a diamino compound with a silicon atom-containing dicarboxylic acid anhydride having a hydrolyzable group.