JPH10330479A - Hydrophilic polyamidic acid resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin suitable as a polymer component for alkali developing type photosensitive resin compositions used for production of printed circuit board, etc., by introducing a polyoxyalkylene skeleton into a base polymer. SOLUTION: This resin has a repeating unit represented by formula I [R<1> is a 6-30C quadrivalent tetracarboxylic acid residue; R<2> is a 1-10C alkylene; (n) is 2-500] and has 10,000 to 200,000 weight-average molecular weight. Furthermore, the objective resin is obtained by reacting a diamine containing a polyoxyalkylenediamine represented by formula II as an essential component and 2,2-bis[4-(4-aminophenoxy)phenyl]propane with a tetracarboxylic anhydride represented by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hydrophilic polyamic acid resin and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, for a protective film or a cover coat of a printed wiring board or the like, a photosensitive heat-resistant material having excellent heat resistance, flexibility and flame retardancy has been strongly desired in order to improve reliability. Conventionally, as a base polymer of these photosensitive heat-resistant materials, for example, a phenoxy resin, a high-molecular-weight epoxy resin, a polyamide resin, a polyimide resin, and the like described in US Pat. No. 4,638,038 have been used. Developers that can use photosensitive heat-resistant materials using any of the resins are mostly solvent-based or water-based, which is a mixture of a solvent and an aqueous alkaline solution. As the developer, an inorganic alkali aqueous solution that does not use a solvent, particularly an inorganic alkali aqueous solution, is most preferably used from the viewpoint of cost and environmental hygiene. In order to perform development with a developer composed of an alkaline aqueous solution, it is necessary that the base polymer itself has a high carboxyl group concentration and the base polymer itself has excellent hydrophilicity. However,
In the case of the above-mentioned addition type or condensation type resin, the hydrophilicity of the base polymer itself is insufficient, and it is possible to develop the photosensitive heat-resistant material with an aqueous alkali solution, that is, to provide alkali developability. It was extremely difficult.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a method for increasing the hydrophilicity of a base polymer itself, by introducing a polyoxyalkylene skeleton into the base polymer, thereby improving the alkali developing property used in the production of printed wiring boards and the like. It is an object of the present invention to provide a hydrophilic polyamic acid resin soluble in an aqueous alkali solution, which is suitable as a polymer component of a photosensitive resin composition of the type, and a suitable production method thereof.

[0004]

That is, the present invention provides a hydrophilic polyamic acid resin having a repeating unit represented by the following general formula [I] and having a weight average molecular weight of 10,000 to 200,000. Is what you do.

[0005]

Embedded image (In the formula, R ¹ is a tetravalent tetracarboxylic acid residue having 6 to 30 carbon atoms, R ² is each independently an alkylene group having 1 to 10 carbon atoms, and n is a number of 2 to 500.) The present invention also relates to (A) a diamine containing a polyoxyalkylenediamine represented by the following general formula [II] as an essential component:

[0006]

Embedded image (In the formula, R ² independently represents an alkylene group having 1 to 10 carbon atoms, and n is a number of 2 to 500.) (B) Tetracarboxylic dianhydride represented by the following general formula [III]

[0007]

Embedded image (Wherein, R ¹ is a tetravalent tetracarboxylic acid residue having 6 to 30 carbon atoms). A process for producing a hydrophilic polyamic acid resin, comprising:

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrophilic polyamic acid resin of the present invention comprises (A) a diamine containing a polyalkylenediamine represented by the above general formula [II] as an essential reaction component and (B) a diamine containing the above-mentioned general formula [III] And generally reacting them in a single step.

The polyoxyalkylenediamine represented by the general formula [II] of the component (A) used in the present invention is not particularly limited as long as it is represented by the general formula [II]. Huntsman Corporation Jeffamine D series [polyoxypropylenediamine: Jeffamine D-230, D-400, D
-2000, D-4000], Jeffamine ED series [polyoxyethylene propylene diamine: Jeffamine ED-600, ED-900, ED-200
3], Jeffamine EDR series [Polyoxyethylenediamine: Jeffamine EDR-148, EDR
-192], bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropyl) ethane, 1,3-bis- (3-aminopropyl) manufactured by Koei Chemical Industry Co., Ltd.
-2,2-dimethylpropane, α, ω- (3-aminopropyl) -polyethylene glycol and the like.
These polyoxyalkylene diamines are used alone or in combination of two or more.

The average molecular weight of the polyoxyalkylenediamine is preferably from 200 to 10,000, more preferably from 500 to
5000 is more preferable, and 1000 to 3000 is particularly preferable. If the average molecular weight is less than 200, the hydrophilicity and flexibility of the obtained hydrophilic polyamic acid resin tend to decrease. If the average molecular weight exceeds 10,000, the obtained hydrophilic polyamic acid resin (the hydrophilic polyamic acid resin is heated). The heat resistance of the polyimide resin converted by the treatment tends to decrease. Here, the average molecular weight is a value converted from an amine value.

The tetracarboxylic dianhydride represented by the general formula [III] of the component (B) used in the present invention is not particularly limited as long as it is one represented by the above general formula. Meric acid dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3 ', 4,4'-
Tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3',
4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (2,3- or 3,4-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (2,3- or 3,4
-Dicarboxyphenyl) propane dianhydride, 2,2-
Bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3
3,3-hexafluoro-2,2-bis [4- (2,3
-Or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,3-bis (3,4, -dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, butane Tetracarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-2: 3:
Compounds such as 5: 6-tetracarboxylic dianhydride and ethylene glycol bisanhydrotrimellitate are exemplified. These tetracarboxylic dianhydrides are used alone or in combination of two or more.

The diamine of the component (A) may contain a diamine having no polyoxyalkylene skeleton in addition to the polyoxyalkylenediamine contained as an essential component. The diamine having no polyoxyalkylene skeleton is not particularly limited. For example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-
(3,4'-, 3,3 ', 2,4' or 2,2 '-) diaminodiphenylmethane, 4,4'-(3,4'-,
3,3'-, 2,4'- or 2,2 '-) diaminodiphenyl ether, 4,4'-(3,4 '-, 3,3'
-, 2,4'- or 2,2 '-) diaminodiphenylsulfone, 4,4'-(3,4'-, 3,3'-, 2,
4'- or 2,2 '-) diaminodiphenyl sulfide, 4,4'-benzophenonediamine, 3,3'-benzophenonediamine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4, Compounds such as 4'-diaminobenzanilide are exemplified. These diamines having no polyoxyalkylene skeleton are used alone or in combination of two or more.

When a diamine having no polyalkylene skeleton is used in combination as a part of the diamine of the component (A), the compounding amount of the polyalkylene diamine is based on the total amount of the polyalkylene diamine and the diamine having no polyalkylene skeleton. 10 to 100% by weight, preferably 20 to 90% by weight, more preferably 30 to 80% by weight, and 40 to 7% by weight.
0% by weight is particularly preferred. If the compounding amount is less than 10% by weight, the hydrophilicity of the resulting hydrophilic polyamic acid resin decreases, and when this is used as the polymer component of the photosensitive resin composition, the alkali developability of the photosensitive resin composition is reduced. It tends to decrease, and the flexibility of the obtained hydrophilic polyamic acid resin (a polyimide resin obtained by converting the hydrophilic polyamic acid resin by heat treatment) tends to decrease, and the obtained polyamic acid resin is hardly imidized. , Low-temperature curability.

Reaction equivalent ratio of component (A) to component (B) [amino group of component (A) / acid anhydride group of component (B)]
Is preferably 0.9 to 1.1, and 0.95 to 1.1.
1.05 is more preferred, and 1.0 is particularly preferred. When the reaction equivalent ratio is less than 0.9 or more than 1.1, the weight average molecular weight of the obtained hydrophilic polyamic acid resin is low, and the obtained hydrophilic polyamic acid resin (when the hydrophilic polyamic acid resin is heated). The flexibility of the polyimide resin converted by the treatment tends to decrease. Here, the weight average molecular weight of the hydrophilic polyamic acid resin is 0.3 mol / l of lithium bromide monohydrate and phosphoric acid as a buffer, respectively.
Calculated as a polystyrene equivalent value from a calibration curve prepared using polystyrene as a standard substance, using an equal volume mixed eluent of N, N-dimethylformamide and tetrahydrofuran prepared so as to have a concentration of 0.6 mol / l. Is used.

The reaction between the components (A) and (B) is carried out in an organic solvent. The organic solvent is not particularly limited, for example, lactones such as γ-butyrolactone, γ-caprolactone, ethylene carbonate, carbonates such as propylene carbonate, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and n-butyl acetate; glymes such as diglyme, triglyme and tetraglyme; hydrocarbons such as toluene, xylene and cyclohexane; N-methyl-2- Amides such as pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, ureas such as N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea and tetramethylurea, and sulfones such as sulfolane Among them, lactones are preferred as the main component, because they are excellent in low-temperature drying property when a dried film is obtained from a solution of a hydrophilic polyamic acid resin.

The amount of the organic solvent used depends on the amount of the component (A) and the amount of the component (B).
30 to 2000 parts by weight, preferably 50 to 1000 parts by weight, more preferably 100 to 100 parts by weight of the total amount of the components,
70 to 400 parts by weight are particularly preferred. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, and the reaction system tends to become non-uniform or highly viscous. If the amount of the organic solvent used exceeds 2000 parts by weight, the reaction is completed Tends to be difficult. These organic solvents are used alone or in combination of two or more.

The reaction temperature is preferably -50 to 130 ° C,
0-80 degreeC is more preferable, and 20-60 degreeC is especially preferable. When the reaction temperature is lower than −50 ° C., the reaction does not easily proceed, and the reaction tends to be difficult to complete.
When the temperature exceeds ℃, the produced hydrophilic polyamic acid resin further undergoes a secondary reaction (dehydration imidation reaction accompanied by disappearance of a carboxyl group) to be easily converted to a polyimide resin having no carboxyl group, and this is converted into a photosensitive resin composition. When used as a polymer component of the above, the alkali developability of the photosensitive resin composition tends to decrease.

In the production of the polyamic acid resin of the present invention, a reaction catalyst is used if necessary. The reaction catalyst is not particularly limited, and for example, triethylamine, triethylenediamine, N, N-dimethylaniline, N, N
N-diethylaniline, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo [5,4,0] undecene Tertiary amines such as -7, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-
2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-
Imidazoles such as 4,5-dihydroxymethylimidazole and 1-azine-2-methylimidazole; organic tin compounds such as dibutyltin dilaurate and 1,3-diacetoxytetrabutyldistannoxane; tetraethylammonium bromide; tetrabromide Quaternary ammonium salts such as butylammonium, benzyltriethylammonium chloride, trioctylmethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium iodide, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium acetate, and tetraphenylphosphochloride Quaternary phosphonium salt compounds such as chromium, triphenylmethylphosphonium chloride and tetramethylphosphonium bromide; 3-methyl-1-phenyl-2 Organic phosphorus compounds such as phosphorene-1-oxide, alkali metal salts of organic acids such as sodium benzoate and potassium benzoate, inorganic salts such as zinc chloride, iron chloride, lithium chloride and lithium bromide, octacarbonyl dicobalt (cobalt carbonyl) ) And the like. These reaction catalysts can be used alone or in combination of two or more.

The hydrophilic polyamic acid resin obtained by the above-described production method is a polyamic acid resin having a repeating unit represented by the above general formula [I], and is a solder resist for a printed wiring board and a photosensitive coverlay. It can be widely used as a polymer component of an alkali-developable photosensitive resin composition for various uses such as a film, a color filter material for liquid crystal, and a heat-resistant material for electronic parts, and is industrially extremely useful.

[0020]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited thereto.

Example 30.00 g (0.015 mol) of polyoxypropylenediamine (Jeffamine D-2000 manufactured by Huntsman Corporation, average molecular weight 2000) was placed in a flask equipped with a stirrer, thermometer, cooling tube and nitrogen gas inlet tube. ,
14.37 g (0.035 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,
17.90 g (0.050 mol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 145.3 g of γ-butyrolactone were charged, and the temperature was raised to 60 ° C. while stirring and passing nitrogen gas. After keeping it at the same temperature for 0.5 hour, it was cooled to room temperature. The measured acid value of the solid content of the obtained solution of the hydrophilic polyamic acid resin was 92 KOH mg / g (theoretical acid value: 90 KOH mg / g), and the weight average molecular weight was 5 KOH.
It was 8,000. A dried film of the hydrophilic polyamic acid resin (thickness: about 50 μm) obtained by heating and drying the solution of the hydrophilic polyamic acid resin at 100 ° C. for 10 minutes has an acid value of 7 measured.
It was 2 KOH mg / g (calculated imidation ratio: 20%) and was soluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution). The polyimide film obtained by heating the dried film obtained by heating and drying at 100 ° C. for 10 minutes and further heating at 150 ° C. for 45 minutes has an actually measured acid value of 4K.
OH mg / g (calculated value of imidation ratio: 96%), and it was insoluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution).

Comparative Example Polyoxypropylenediamine (Jeffamine D-2000 manufactured by Huntsman Corporation, average molecular weight: 20)
00) without using 20,53 g (0.050 g) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane.
Mol) was used in the same manner as in Example. The solid content of the solution of the obtained polyamic acid resin is 147K.
OH mg / g (theoretical acid value: 146 KOH mg / g). From this polyamic acid resin solution at 100 ° C., 10
The dried polyamic acid resin film (thickness: about 50 μm) obtained by heating and drying for 1 minute had an actually measured acid value of 132 KOH mg / g (calculated imidation ratio of 10%) and an alkali aqueous solution (1% by weight).
In aqueous sodium carbonate solution).

As described above, the hydrophilic polyamic acid resin obtained by the present invention is generally soluble in a 1% by weight aqueous solution of sodium carbonate used as an alkali developing solution. It turns out that it is suitable as a polymer component of the composition.

[0024]

According to the present invention, by introducing a polyoxyalkylene skeleton into a polyamic acid resin, the hydrophilicity of the polyamic acid resin itself can be increased, and this polyamic acid resin is soluble in an alkaline aqueous solution. Therefore, it is suitably used as a base polymer component of an alkali-developable heat-resistant photosensitive resin composition used for manufacturing a printed wiring board and the like.

Claims (4)

[Claims] 1. A compound having a repeating unit represented by the following general formula [I] and having a weight average molecular weight of 10,000 to 200,0.
00 hydrophilic polyamic acid resin. Embedded image (In the formula, R ¹ is a tetravalent tetracarboxylic acid residue having 6 to 30 carbon atoms, R ² is each independently an alkylene group having 1 to 10 carbon atoms, and n is a number of 2 to 500.) 2. The hydrophilic polyamic acid resin according to claim 1, wherein R ¹ is a 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid residue and R ² is a propylene group. 3. A diamine containing, as an essential component, a polyoxyalkylene diamine represented by the following general formula [II]: (In the formula, R ² independently represents an alkylene group having 1 to 10 carbon atoms, and n is a number of 2 to 500.) (B) Tetracarboxylic dianhydride represented by the following general formula [III] Embedded image (Wherein, R ¹ is a tetravalent tetracarboxylic acid residue having 6 to 30 carbon atoms). 4. The method for producing a hydrophilic polyamic acid resin according to claim 3, wherein the diamine is a diamine containing polyoxypropylenediamine and 2,2-bis [4- (4-aminophenoxy) phenyl] propane.