JP2978990B2 - Method for producing polyamic acid solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyamic acid solution which is a precursor of a polyimide useful as a heat-resistant resin.

[0002]

2. Description of the Related Art When a polyamic acid is obtained by reacting a diamine and a tetracarboxylic anhydride, a method of charging a diamine and a tetracarboxylic anhydride in a reactor in advance and then adding a solvent is adopted. A phenomenon in which the viscosity partially increases due to rapid polymerization before homogeneous dissolution is observed. Further, there may be a problem that the amine component and the tetracarboxylic acid component form a complex, and in some cases, a solid block is partially formed and is not easily dissolved. Therefore, in order to obtain a uniform polyamic acid solution, a method in which a tetracarboxylic acid component is sequentially added to a solvent in which a conventional diamine component is dissolved and polymerization is performed, or a diamine component is dissolved in a solvent in which a tetracarboxylic acid component is dissolved. A method of polymerizing by successive addition is adopted.

[0003] Among them, generally, acid anhydrides generally used as tetracarboxylic acid components have low solubility, and tetracarboxylic acid anhydrides are generally used as amides which are aprotic polar solvents which are generally used. A method is known in which a complex is formed with a system compound and the resulting polyamic acid solution has a low increase in viscosity. Therefore, a method in which a tetracarboxylic acid component is sequentially added to a solvent in which a diamine component is dissolved to carry out polymerization is employed.

A polyamic acid having a high degree of polymerization which gives a polyimide having excellent physical properties can be obtained by using substantially equivalent amounts of a high-purity diamine component and a tetracarboxylic acid component, and is usually used as a tetracarboxylic acid component. Since the tetracarboxylic acid anhydride is gradually hydrolyzed by the moisture in the atmosphere, it is difficult to always maintain such conditions. Therefore, the equipment for producing polyamic acid
Various devices have been proposed to control the moisture in the polymerization medium and polymerization atmosphere.

[0005] In addition, since the viscosity of a solution in which both components are mixed as described above increases as the polymerization reaction proceeds, especially when a high-viscosity polyamic acid solution is produced, the added component is not used. A special device such as an addition device designed to link the addition speed with the reaction speed, and a special device such as installing a stirring device corresponding to high viscosity in the reactor are used.

However, when producing a high-viscosity polyamic acid solution containing low particles, the above-mentioned measures are not sufficient. That is, it is not easy to remove particles by filter treatment from the polyamic acid solution prepared by the above-described apparatus. Particularly, when the viscosity is 100 poise or more, the treatment usually remains untreated or is not limited to treatment with a filter having a coarse pore diameter. Did not get.

To solve this problem, Japanese Patent Application Laid-Open No. Sho 60-212428 discloses a method of controlling the charge ratio to separately prepare a relatively low-viscosity polyamine solution containing a diamine excess and a tetracarboxylic acid excess. A method of obtaining a high-viscosity solution by filtering and then mixing and reacting these two solutions in an equivalent ratio is disclosed, but the production method is rather complicated.

[0008]

Even with the above-described device, it takes a long time for the sequential addition and the dissolution reaction of the sequentially added components, it is not easy to withdraw from the reactor, In the production of many kinds, there are disadvantages such as complicated washing and drying of the reactor every time the kinds are changed. Accordingly, the present invention is to eliminate the non-versatility of the manufacturing apparatus, which involves the complexity of the conventional reaction operation and the use of special equipment when manufacturing polyamic acid solutions of various compositions, concentrations, and viscosities. In addition, the present invention provides a method for economically and efficiently producing a polyamic acid solution having extremely low particle content.

[0009]

SUMMARY OF THE INVENTION The present invention comprises a step of dissolving a diamine component comprising one or more diamines in a solvent; a step of dissolving a tetracarboxylic acid component comprising one or more tetracarboxylic acids in a solvent; A step of weighing each component solution so that the diamine component and the tetracarboxylic acid component are substantially equivalent, and dispensing the mixture into a product container, and allowing the mixture dispensed into the product container to react for a predetermined time to advance the polymerization reaction. step, Ri name than four steps, the diamine component and / or tetracarboxylic acids
Each solution of the components is a filtered solution.
Therefore, 0.3 contained in the polyamic acid solution in the product container
10000 particles / g varnish or less
A method for producing a polyamic acid solution, characterized in that
is there.

Here, the solvent in which each component is dissolved may be the same or different, and any solvent may be used as long as it does not substantially react with each component and can be dissolved at a high concentration. Irrelevant. Therefore, in the present production method, it is also possible to produce a polyamic acid solution comprising a gel-like polyamic acid, which was conventionally not easily produced. One or more solutions can be used as a solution containing a diamine component and a tetracarboxylic acid component, respectively. Also, by separately preparing a solvent and measuring and mixing to an arbitrary composition, a desired copolymer composition, concentration, and viscosity can be obtained. It is possible to obtain a polyamic acid solution of

In the present invention, the container used in the steps (1) and (2) is the same, and this container is used as a product container as it is. The material is not particularly limited, but a material that is stable to a solvent such as stainless steel, polyethylene, or polypropylene is preferable.

The steps (1) to (4) are usually carried out at room temperature in a dry atmosphere, but the step (3) can be carried out, if necessary, at a temperature of from -10 ° C to 100 ° C. In this step, if necessary, stirring by shaking may be performed.
It is not necessary. The reaction time depends on the reaction temperature and the composition and properties of the intended polyamic acid solution,
About 1 hour to 10 days is preferable.

As a measuring method, a method of measuring by weight or a method of measuring by volume can be applied. After the measurement, the mixture is poured into a small container and mixed, but after the measurement, it can be dispensed through a mixer. . Above all, a method of measuring each component solution by volume, for example, a method of feeding and dispensing liquid into a small container via a mixer for a certain period of time by a precision metering pump does not require a special device, and any composition is optional. This is a preferred method because it can be continuously produced in the amount of, and in addition, the washing of the device is unnecessary or easy.

The production method of the present invention is also characterized in that the content of particles can be extremely reduced by performing a filter treatment at the stage of the diamine component and / or tetracarboxylic acid component solution. In this case, the treatment by circulation filtration is excellent in that the particle removal efficiency is high, and the liquid passing through the filter can be directly metered and dispensed into a clean bottle, so that it is preferable to obtain a polyamic acid solution having a small particle content. Polyamic acid solutions having a low particle content are particularly important for electronic materials for forming fine patterns or for optical materials for which the presence of particles causes scattering loss. Its usefulness is high at a low particle content of 10,000 or less / g varnish.

The solvent used in the present invention includes amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, sulfones such as sulfolane, phenol, and the like. Cresols, phenols such as halogenated phenols, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and γ-butyrolactone, ethers such as tetrahydrofuran, dibutyl ether, dimethoxyethane, diethoxyethane, ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, acetic acid Ester such as ethyl, butyl acetate, ethyl cellosolve acetate, methyl cellosolve acetate, and aromatics such as xylene, toluene and chlorobenzene Mention may be made of the medium. Of these, ketone solvents are not preferred as solvents for diamine components, and sulfoxide and amide solvents are not preferred as solvents for tetracarboxylic acid components,
Naturally, it can be used as a solvent for the obtained polyamic acid.

The alcohols that can be added include aliphatic alcohols having 5 or less carbon atoms and alkoxy alcohols. Specific examples include methanol, ethanol, i-propanol, n-propanol, n-butanol and amyl. Examples include alcohol, methyl cellosolve, and ethyl cellosolve.

The diamine component used in the present invention is not particularly limited, and is selected from aromatic, aliphatic and alicyclic diamines and derivatives thereof. For example, the following general formula

[0018]

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(Wherein, R is an alkyl group or an alkoxy group having or not having a side chain having 1 to 20 carbon atoms, and a part or all thereof is F, Cl or Br, respectively)
Is a substituent which may be R bonded to each aromatic ring
May be the same or different. X is a single bond, -O
-, - CO -, - C (CH 3) 2 -, - C (CF 3) 2 -,
—S—, —SO— or —SO ₂ —, and the X bonding between the aromatic rings may be the same or different. n is 0 or an integer of 5 or less, and each aromatic ring may be the same or different. l is 0 or an integer of 10 or less. ), And particularly preferred specific examples are m-phenylenediamine, diaminotoluene,
5-diaminoxylene, diaminodulene, 2,5-diaminoanisole, 2,5-diaminoacetophenone,
2,5-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone,
2,5-diaminodiphenyl, benzidine, 1,1-bis (4-aminophenyl) ethane, 2,2- (4-aminophenyl) propane, 2,2- (4-aminophenyl) hexafluoropropane, 2, 2'-dimethyl-
4,4'-benzidine, 3,3 ', 5,5'-tetramethylbenzidine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'
-Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 4,
4'-oxydianiline, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 3,3'- Dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4 '
-Diaminodiphenylmethane, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene, 4,4'-bis (p-aminophenoxy) biphenyl, N, N-bis (4-aminophenyl) methylamine, N, N-bis (4-aminophenyl) amine, N,
N-bis (4-aminophenyl) -n-butylamine,
4,4′-diaminoazobenzene, 3,3′-diaminoazobenzene, m-xylylenediamine, p-xylylenediamine, 2,5-diaminohalogenobenzene, 2,
4-diaminopentafluorophenoxybenzene, diaminopolyfluoroalkoxybenzene, 3,3′-dichloro-4,4′-benzidine, octafluoro-4,
4′-benzidine, diaminonaphthalene, 1,3-bis (4-aminophenyl) hexafluoropropane,
4'-bis (4-aminophenoxy) diphenyl sulfone, 3,3'-dimethyl-4,4'-benzidine, dimethylbenzidine, 4,4'-diamino-1,4-terphenyl, 1,4-phenylenediamine , 2-methyl-
1,4-phenylenediamine (2,5-diaminotoluene) Examples thereof include phenylenediamine, diaminotoluene, diaminoxylene, and diaminodurene.

Among them, diamines and derivatives thereof having an electron-withdrawing substituent bonded thereto, which have a high solubility in a solvent and allow a polymerization reaction to proceed slowly, are preferred. Particularly, a fluorine-, polyfluorinated alkyl or polyfluorinated alkoxyl group is substituted. Aromatic diamine having as a group is preferable, and specifically, a general formula

[0021]

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(Wherein R has a side chain having 1 to 20 carbon atoms)
An alkyl group or an alkoxy group having or not having
And part or all of them are F, Cl or Br, respectively.
Is a substituent which may be R bonded to each aromatic ring
May be the same or different. However, -NH_Twoof
At least one aromatic ring attached has at least one
Fluo having or not having a side chain having 1 to 20 carbon atoms
A loalkyl or fluoroalkoxy group is bonded.
You. X is a single bond, -O-, -CO-, -C (CH _Three)
_Two-, -C (CF_Three)_Two-, -S-, -SO- or -S
O_TwoAnd X bonding between the aromatic rings is the same.
But it may be different. n is 0 or an integer of 5 or less
May be the same or different for each aromatic ring.
No. l is 0 or an integer of 10 or less. )
Yes, specifically, 2-trifluoromethyl-1,4-
Phenylenediamine, 5-trifluoromethyl-1,3
-Phenylenediamine (3,5-diaminobenzotrif
Rulide), diaminobenzotrifluoride, 2-pen
Tafluoroethyl-1,4-phenylenediamine, 2-
Nanofluorobutyl-1,4-phenylenediamine, 5
-Pentafluoroethyl-1,3-phenylenediamine
, 5-Nanofluorobutyl-1,3-phenylenediamine
Min, 6-nanofluorobutyl-1,3-phenylene
Amine, diaminoperfluoroalkylbenzene, 5-
(3,3,2,2-tetrafluoropropyloxy)-
1,3-phenylenediamine, 2- (4,4,4,3,
2,2-hexafluorobutyloxy) -1,4-fe
Nilendiamine, 5- (4,4,4,3,2,2-hex
Safluorobutyloxy) -1,3-phenylenediamine
6- (4,4,4,3,2,2-hexafluorobu
Tyloxy) -1,3-phenylenediamine, 5-
(4,4,4,3,3,2,2-heptafluorobutyl
Oxy) -1,3-phenylenediamine, 6- (4,
4,4,3,3,2,2-heptafluorobutyloxy
B) -1,3-phenylenediamine, diaminopolyfur
Oroalkoxybenzene, 2,4-diaminopentaful
Orophenoxybenzene, 2,2-bis (4-aminophen
Enyl) hexafluoropropane, 2,2-bis (amido)
Nophenyl) hexafluoropropane, 2,2'-bis
(Trifluoromethyl) -4,4'-benzidine, 3,
3'-bis (trifluoromethyl) -4,4'-benzyl
Gin, bis (trifluoromethyl) benzidine, bis
(Perfluoroalkyl) benzidine, 2,2'-bis
(Trifluoromethyl) -4,4'-diaminodiphenyl
Ether, 3,3'-bis (trifluoromethyl)-
4,4'-diaminodiphenyl ether, bis (trif
(Fluoromethyl) diaminodiphenyl ether, 1,4-
Bis (4-amino-2-trifluoromethylphenoxy)
B) benzene, 4,4'-bis (4-amino-2-tri
Fluoromethylphenoxy) biphenyl, 2,2-bis
(4- (4-amino-2-trifluoromethylphenoxy)
Phenyl) propane, 2,2-bis (4- (4-a
Mino-2-trifluoromethylphenoxy) phenyl)
Hexafluoropropane, 2,2-bis (4- (amino
Perfluoroalkylphenoxy) phenyl) hexaf
Fluoropropane, 1,3-bis (2- (4-amino-2
-Trifluoromethylphenoxy) hexafluoro-2
-Propyl) benzene, 1,4-bis (2- (4-amido)
No-2-trifluoromethylphenoxy) hexafluoro
(2-2-propyl) benzene and the like.

The tetracarboxylic acid component is not particularly limited, and aromatic tetracarboxylic anhydride or alicyclic tetracarboxylic anhydride can be suitably used.

[0024]

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Wherein Y is two —COOH groups, —CO
Cl group, an -COBr group, -COOR group, -CONH ₂ group, or one of -CO-O-CO- group. R is an alkyl group or an alkoxy group having or not having a side chain having 1 to 20 carbon atoms, and a part or the whole thereof is a substituent which may be F, Cl or Br.
R bonded to each aromatic ring may be the same or different. X is a single bond, -O -, - CO -, - C (CH 3)
_{2 -, - C (CF 3} ) 2 -, - S -, - SO- or -S
X which is O ₂ — and bonds between the aromatic rings may be the same or different. n is 0 or an integer of 5 or less, and each aromatic ring may be the same or different. l is 0 or an integer of 10 or less. ), Specifically, pyromellitic acid, trifluoromethylpyromellitic acid, bis (trifluoromethyl) pyromellitic acid, perfluoroalkylpyromellitic acid, bis (perfluoroalkyl) pyromellitic Acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid,
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, tetracarboxydiphenyl ether, tetracarboxynaphthalene, tetracarboxydiphenylsulfone, terphenyltetracarboxylic acid,
2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (4- (3,4-dicarboxyphenyloxyphenyl)) propane, 2,2-bis (4- (3,
4-dicarboxyphenoxyphenyl)) hexafluoropropane, 1,4-bis (3,4-dicarboxyphenoxy) benzene, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl and the like, and acid derivatives thereof Can be exemplified.

Incidentally, a reaction product of an aromatic tetracarboxylic anhydride or an alicyclic tetracarboxylic anhydride with less than 0.5 equivalent of water, alcohol or diamine can also be used as the tetracarboxylic acid component. Here, the reaction product with water or alcohol is particularly useful for adjusting the degree of polymerization and viscosity in a highly concentrated solution, and the reaction product with less than 0.5 equivalent of diamine and the reaction product with water or alcohol. Is useful for dissolving the tetracarboxylic acid component in a state of high concentration and low viscosity. In this case, the reaction product solution with 0.5 equivalent or more of diamine is
It is not preferable because the increase in the viscosity of the solution deteriorates the quantitativeness of pumping.

Further, in order to adjust the degree of polymerization and viscosity at a predetermined concentration, in addition to using the reaction product of tetracarboxylic anhydride and water or alcohol as the tetracarboxylic acid component, water or alcohol is separately added and prepared. A method of adding and mixing the obtained solvent to the subdivision container, a method of adjusting by a cooking process, and the like can be applied.

Further, in addition to the diamines and tetracarboxylic acids exemplified above, it is also useful to add and copolymerize further other components. Such materials include diaminopolysiloxanes, diaminosilanes, tetracarboxypolysiloxanes, and tetracarboxysilanes in order to increase the adhesive strength of the polyimide film to the substrate.

[0029]

The present invention will be described in more detail with reference to the following examples. Solutions containing diamine or tetracarboxylic acid components
Preparation of liquid 2,2-bistrifluoromethylbenzidine (ABL-
21) A solution in which 800.0 g is dissolved in 1200 g of γ-butyrolactone (solution A, 1.249 mol / kg) and a solution in which 120.0 g of pyromellitic dianhydride (PMDA) is dissolved in 1880 g of γ-butyrolactone (solution B, 0.2751
mol / kg), a solution of 220.0 g of hexafluoroisopropylidenephthalic dianhydride (6FDA) dissolved in 1780 g of γ-butyrolactone (solution C, 0.4952 mol / k
g), 150.0 g (0.4684 mol) of ABL-
21, 200.0 g (0.9169 mol) of PMD
A, 10.00 g (0.0403 mol) of bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and 9.00 g (0.09 mol)
99 mol) of ethyl cellosolve was mixed with 660 g of γ-butyrolactone and treated at 70 ° C. for 1 hour (D)
Liquid, 0.4750 mol / kg tetracarboxylic acid component), 25
0.0 (0.7807 mol) of ABL-21, 10 g
(0.0402 mol) of a solution prepared by dissolving 1,3-bis (3-aminopropyl) tetramethyldisiloxane in 440 g of γ-butyrolactone (solution E, 1.173 mol / kg)
Diamine component) and γ-butyrolactone (Solution F) were prepared as a diluting medium.

In order to eliminate the influence of the density change due to the temperature, each of the liquids A, B, C, D, E, and F was used in the temperature chamber, and the relationship between the set flow rate and the set time of the precision metering pump and the supply amount was clarified. The quantitativeness was confirmed.

Example 1 The precision metering pump was set at 15.0 seconds at a flow rate of 60.0 mmol / min for each component of solution A and solution B,
The mixture was poured into a 100 ml polyethylene bottle under a dry nitrogen atmosphere through a mixer and sealed. The same operation was repeated for 10 bottles, and the viscosity was measured 24 hours later. The viscosity was 100 poise (22 ° C. or less), there was no variation, and the solid content was 12.1% by weight.

Example 2 In the same manner as in Example 1 except that no mixer was used, each of the five bottles was filled with the solution A and the solution B, and then the bottles were shaken for 5 seconds. When the viscosity was measured after 24 hours,
No variation was observed at 100 poise in each case.

Comparative Example 1 In a dry nitrogen atmosphere, 5.00 g of ABL-21 and 3.4056 g of PMDA were precisely weighed in a 100 ml glass separable flask, and 61.64 g of γ-butyrolactone was added thereto. With stirring. The solid concentration was 12.0 wt%, and the viscosity was measured 24 hours later to be 130 poise.

Example 3 A precision metering pump was used.
For the solution B, the tetracarboxylic acid component was reduced to 15.0 seconds at a flow rate of 54.0 mmol / min, and for the liquid C, the tetracarboxylic acid component was reduced to 6 mmol / min. The flow rate was set to 15.0 seconds, and the mixture was poured into a bottle under a dry nitrogen atmosphere via a mixer and sealed. The same operation was repeated for five bottles, and the viscosity was measured 24 hours later. In all cases, the viscosity was 70 poise, there was no variation, and the solid content was analyzed to be 12.7 wt%.
Met.

Example 4 A precision metering pump was set up for each component of solution D and solution E
The flow rate was set to 15.0 seconds at a flow rate of 0.0 mmol / min, and 15.0 seconds at a flow rate of 0 ml / min, 30.0 ml / min, and 60.0 ml / min for the solution F. D, E, F
Using a 0.1 μm pore diameter Teflon membrane filter for each liquid, after circulating through a pump overnight, the outlet liquid of the filter processing was led to a precision metering pump,
According to the settings, the bottle was sealed in a clean bottle under a dry nitrogen atmosphere, and shaken for 15 seconds. After 48 hours, the viscosity was measured and found to be 1700 poise (solids concentration, 35.
6 wt%), 260 poise (29.9 wt%), 4
8 poise (same as above, 25.8 wt%), and the number of particles of 0.3 μm or more in each polyamic acid solution is as follows:
The varnishes were 800, 700, and 300 / g varnish.

[0036]

According to the method of the present invention, as described in detail in the Examples, even when a simple apparatus is used, even when the preparation is repeated, the variation in the components and the viscosity among the products is not affected. It is possible to produce a stable quality polyamic acid and to easily obtain a polyamic acid having a high viscosity and a low particle content.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Junmichi Maruta 2805 Imafukunakadai, Kawagoe-shi, Saitama Tokyo Central Research Laboratory (56) References JP-A-62-156132 (JP, A) JP-A Sho 61-181832 (JP, A)

Claims (3)

(57) [Claims] 1. A step of dissolving a diamine component comprising one or more diamines in a solvent; a step of dissolving a tetracarboxylic acid component comprising one or more tetracarboxylic acids in a solvent; carboxylic acid component is metered such that substantially equivalent, Ri name from step, the fourth step to advance the polymerization reaction by causing dispensed process the product container, the mixture was dispensed into the product container for a predetermined time reaction , Diamine component and / or tetra
Each solution of the carboxylic acid component is filtered
Solution contained in the polyamic acid solution in the product container
10000 particles / 0.3μm or more
preparation of the polyamic acid solution, wherein less der Rukoto g varnish. 2. The method for producing a polyamic acid solution according to claim 1, wherein the diamine component contains a fluorine-containing aromatic diamine having a fluorine, polyfluorinated alkyl or polyfluorinated alkoxyl group as a substituent. Law. 3. A reaction product obtained by reacting an aromatic tetracarboxylic anhydride and / or an alicyclic tetracarboxylic anhydride with less than 0.5 equivalents of water, alcohol or diamine. The method for producing a polyamic acid solution according to claim 1, wherein: