JPH08100103A - Liquid phenolic resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition excellent in heat resistance, workability and substrate wettability, and capable of being used as a raw material for molding materials, a binder for organic fibers, a compounding agent for rubbers, a binder for whetstones, a binder for inorganic fibers, a coating agent for electronic or electric parts, a resin for laminate boards, a binder for frictional materials, a binder for sliding members, etc., to give the products having excellent heat resistance and toughness. CONSTITUTION: This liquid phenolic resin composition is produced by dissolving a phenol resin and an aromatic hydrocarbon-modified maleimide resin compound in a single solvent or mixed solvents selected from N-methyl-2-pyridone, dimethylformamide, acetone, methylethylketone and dioxane. The aromatic hydrocarbon-modified maleimide resin compound is produced by reacting (A) an unsaturated bismaleimide compound derived from an aromatic diamine or polyamine and a dicarboxylic acid having an ethylene type carbon-carbon double bond or its reactive derivative with (B) an aromatic hydrocarbon-formaldehyde reaction product obtained by the reaction of an aromatic hydrocarbon with formaldehyde in the presence of an acid catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid phenol resin composition which is a binder used for obtaining a molded article having excellent heat resistance and which is excellent in heat resistance, workability and wettability with a substrate. It is a thing.

[0002]

2. Description of the Related Art As a method for improving the heat resistance of a phenol resin, boric acid having a phenolic hydroxyl group in the phenol resin,
Known methods include blocking with phosphoric acid and silicon compounds, introducing aromatic hydrocarbon groups such as aralkyl groups having high heat resistance in place of internuclear methylene, and adding various other heat resistant resins. ing. However, the block method and the introduction of an aromatic hydrocarbon group have a drawback that the heat resistance is improved but the curability as a phenol resin is impaired. On the other hand, in the blending method of various heat resistant resins,
Resins having higher heat resistance than phenolic resins generally have poor solvent solubility and poor compatibility in many cases, and there is a problem that it is difficult to mix or dilute as a uniform liquid resin.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventor intends to improve the heat resistance of a phenol resin without impairing the curability of the phenol resin by using a maleimide resin as a compounding agent for improving the heat resistance of the phenol resin. As a result of intensive research, we found that aromatic hydrocarbon-modified maleimide resin compounds are excellent as compounding agents, and by using a specific solvent, these aromatic hydrocarbon-modified maleimide resin compounds and phenol resins can be uniformly dissolved. That is, the present invention has been completed by further researching various findings.

[0004]

The present invention provides an unsaturated bisimide compound derived from an aromatic diamine or polyamine compound and a dicarboxylic acid having an ethylene-type carbon-carbon double bond, or a reactive derivative thereof. N-methyl, an aromatic hydrocarbon-modified maleimide resin compound and a phenol resin, which are obtained by reacting an aromatic hydrocarbon formaldehyde reaction product obtained by reacting an aromatic hydrocarbon with formaldehyde in the presence of an acid catalyst. -2-pyrrolidone,
The present invention relates to a liquid phenol resin composition characterized by being dissolved in a single or mixed solvent containing at least one of dimethylformamide, acetone, methylethylketone and dioxane.

The amount of the aromatic hydrocarbon-modified maleimide compound used as the heat resistance improving compounding agent in the present invention in the resin component is preferably 10% by weight or more and 70% by weight or less. Below this amount, the effect of improving the heat resistance is small. Moreover, even if it is more than this, the heat resistance hardly changes even if compounded. The resin content of the liquid resin is not limited within the range of less than 100% by weight.

The solvent for dissolving the aromatic hydrocarbon-modified maleimide resin compound and the phenol resin is N-methyl-2.
-Pyrrolidone, dimethylformamide, acetone, methylethylketone, a single or mixed solvent containing at least one or more selected from dioxane, N-methyl-2-pyrrolidone, dimethyl if any one is contained Solvents other than formamide, acetone, methyl ethyl ketone and dioxane can be used together.
When the aromatic hydrocarbon-modified maleimide resin compound and the phenol resin are dissolved in the solvent, they may be dissolved at the same time, or they may be mixed in advance and then dissolved. Alternatively,
A solvent and / or the other resin may be added during the process of synthesizing each resin.

In order to produce such an aromatic hydrocarbon-modified maleimide resin composition for improving heat resistance, for example,
Aromatic diamine or polyamine compound and aromatic hydrocarbon formaldehyde reaction product, that is, aromatic hydrocarbon formaldehyde resin, dimethylolated aromatic hydrocarbon, dimethoxymethylated aromatic hydrocarbon, dihalogenomethylated aromatic hydrocarbon, etc. To an aromatic hydrocarbon-modified polyamine by nucleophilic reaction in the presence of an acid catalyst, and further reacted with a dicarboxylic acid anhydride having an ethylene-type carbon-carbon double bond by an ordinary method to form an aromatic hydrocarbon-modified maleimide compound. It is obtained by doing.

The aromatic hydrocarbon compound for obtaining the aromatic hydrocarbon formaldehyde reaction product, which is a modifier for obtaining the above-mentioned aromatic hydrocarbon-modified maleimide resin compound, is
Lower alkylbenzene such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, mesitylene,
Chlorobenzene, dichlorobenzene, bromobenzene,
Dibromobenzene, chlorotoluene, chloroxylene,
Examples thereof include halogenated benzene such as bromoxylene and dibromoxylene, and halogenated lower alkylbenzene.

The aromatic diamine or polyamine used here includes metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane, 4.4'-diaminodiphenylmethane, 1,3,5-
Triaminobenzene, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) methylphosphine oxide, bis (3-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, Bis (4-aminophenyl) phenylamine, metaxylylenediamine, paraxylylenediamine, 1,1-bis (p-aminophenyl) phthalane, 6,
6'-diamino-2.2'-dipyridyl, 4,4'-diaminobenzophenone, 4,4'-diaminoazobenzene, bis (4-aminophenyl) phenylmethane, 1,1-bis
(4-aminophenyl) cyclohexane, 1,1-bis (4
-Amino-3-methylphenyl) cyclohexane, 2,5
-Bis (m-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-aminophenyl) -1,3,4-
Oxadiazole, 2,5-bis (m-aminophenyl)
Thiazolo (4,5-α) thiazole, 5,5′-di (m-aminophenyl)-(2,2 ′)-bis (1,3,4-oxadiazolyl) diphenyl sulfide, 4,4′-diaminodiphenyl Sulfone, 3,3′-diaminodiphenyl sulfone,
4,4′-diaminodiphenyl ether, 2,6-diaminopyridine, tris (4-aminophenyl) phosphine oxide, bis (4-aminophenyl) N-methylamine,
1,5-diaminonaphthalene, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,5-diamino-1,3,4-oxadiazole, 2,4-bis (β-amino-tert-butyl) toluene, bis (p- β-amino-tert-butylphenyl) ether, bis (p-β-methyl-α-aminophenyl) benzene, bis-p- (1,1-dimethyl-5-aminopentyl) benzene, 1-isopropyl-2, 4-m-phenyldiamine, 4,4'-bis (p-aminophenyl) -2,2 '
-Dithiazole, m-bis (4-p-aminophenyl-
2-thiazolyl) benzene, 2,2'-bis (m-aminophenyl) -5,5'-dibenzimidazole, 4,4'-dibenzanilide, 4,4'-diaminophenylbenzoate, N, N'-bis (4-Aminobenzyl) -p-phenylenediamine, 3,5-bis (m-aminophenyl) -4-
Phenyl-1,2,4-triazole and the like can be mentioned.

Further, the aromatic amine compound of the present invention includes triazine ring compounds such as melamine, cyclohexanecarboguanamine, acetoguanamine and benzoguanamine. Further, these may be used alone or as a mixture of two or more kinds.

As the diamine and polyamine compounds,
In addition to the above aromatic diamines or polyamines, aliphatic, cycloaliphatic, or heterodiamine or polyamine compounds can be used, and silicone compounds such as diaminodimethylsiloxane can also be used.

The aromatic hydrocarbon formaldehyde reaction product used here is a reaction product of an aromatic hydrocarbon and formaldehyde in the presence of an acid catalyst, which is then neutralized and washed, and the diarylmethanes are decompressed under reduced pressure. And those produced by removing other low-boiling fractions are preferable, and have an oxygen content of 8% or more and have no reactivity like diarylmethane.
It is preferable that there is no nuclear component as much as possible.

As the acid catalyst, organic acids such as oxalic acid, p-toluenesulfonic acid, xylenesulfonic acid and phenolsulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride,
Α, β-unsaturated dicarboxylic acid anhydrides such as citraconic anhydride, itaconic anhydride, pyrocinconic anhydride, dichloromaleic anhydride or one of these anhydrides and an acyclic, alicyclic or heterocyclic diene, for example, Examples thereof include Diels-Alder reaction products with cyclopentadiene and the like.

On the other hand, the phenol resin used in the present invention may be an ordinary phenol resin synthesized by the reaction of phenols and aldehydes, and a novolak type synthesized by an acid catalyst or a resol synthesized by an alkali catalyst. It may be a mold, or a modified phenolic resin modified with various modifiers such as cashew oil, aromatic hydrocarbon resin, melamine, oil, terpenes, epoxy resin, urea and rubber.

Examples of phenols include phenol, orthocresol, metacresol, paracresol, xylenol, paratertiary butylphenol, paracumylphenol, paraphenylphenol, bisphenol A, bisphenolmethane, bisphenolsulfone, bisphenol ether, resorcin, hydroquinone. Can be used. As the aldehyde, formaldehyde, acetaldehyde, butyraldehyde, benzaldehyde, acrolein or a mixture thereof, a substance which is a generation source of these aldehydes, or a solution of these aldehydes can be used.

As the acid catalyst, organic acids such as oxalic acid, maleic acid, formic acid, acetic acid, succinic acid, benzenesulfonic acid, benzenesulfonic acid chloride, p-toluenesulfonic acid, xylenesulfonic acid, or boric acid, phosphoric acid, hydrochloric acid, Inorganic acids such as sulfuric acid can be used. As the alkali catalyst, sodium hydroxide, potassium hydroxide, calcium hydroxide,
Alkali metal or alkaline earth metal hydroxides such as barium hydroxide, ammonia or amines can be used.

With respect to the aromatic hydrocarbon-modified maleimide resin compound-containing phenol resin composition obtained as described above, vinyl compounds, allyl compounds, epoxy resins, melamine resins, polyamides, polycarbonates,
It may be reacted or mixed with polysulfone, polyether sulfone, polyether ether ketone, polyphenylene oxide, polyphenylene sulfide, polyetherimide, organic silicone compound, organic fluorine compound and the like.

Further, as curing accelerators, for example, radical polymerization initiators such as azo compounds and organic peroxides, tertiary amines, quaternary ammonium salts, phosphonium compounds, imidazoles, boron trifluoride compounds, amine salts, etc. Ions may be added. If necessary, organic or inorganic additives and fillers other than these may be added. Also,
These components may be pulverized and mixed or melt-mixed in advance before being dissolved in the solvent and then dissolved in the solvent, or may be dissolved individually for each component.

[0019]

EXAMPLES The present invention will be described in detail below with reference to examples.
All "parts" and "%" described herein indicate "parts by weight" and "% by weight".

Production Example 1 3000 parts of 4,4'-diaminodiphenylmethane, xylene formaldehyde resin Nikanol G manufactured by Mitsubishi Gas Chemical Co., Inc.
(Oxygen content 15%) 300 parts was put in a flask equipped with a stirrer, a reflux condenser and a thermometer, and the internal temperature was heated to 110 ° C., and when 4,4′-diaminodiphenylmethane was completely dissolved, Add 40 parts of toluenesulfonic acid,
Further, the mixture was reacted for 2 hours while heating under reflux. Furthermore, the reaction was carried out for 2 hours under atmospheric pressure dehydration, and 1000 parts of methyl cellosolve was added while cooling to obtain 4250 parts of an aromatic polyamine solution. The viscosity of this product at 25 ° C is 200 cps.
The nonvolatile content measured by heating at 135 ° C for 1 hour is 72%.
Met.

Production Example 2 1925 parts of acetone was placed in the same reactor as in Production Example 1, 600 parts of maleic anhydride was added and completely dissolved, and then 40 ° C.
While maintaining the following, 825 parts of the aromatic polyamine solution obtained in Production Example 1 was added dropwise over 90 minutes, and after the completion of the addition, the temperature was kept for 1 hour. After that, 165 parts of triethylamine,
19.5 parts of nickel acetate tetrahydrate and 800 parts of acetic anhydride were further added, and the mixture was reacted at a reflux temperature for 2 hours. After completion of the reaction, the solvent was immediately distilled off under vacuum and warm water at 70 ° C
500 parts was added and stirred and mixed for 10 minutes. Then, the mixture was allowed to stand and the supernatant aqueous layer was removed. Further, 1500 parts of 90 ° C. warm water was added with stirring at the same temperature, and the mixture was stirred and mixed at 90 ° C. for 10 minutes and then allowed to stand to remove the supernatant aqueous layer. Then, after repeating this operation twice, methanol 500
After adding 10 parts of the mixture and stirring at 70 ° C. for 10 minutes, the supernatant was removed, and the internal temperature was raised to 120 ° C. while dehydrating and removing the solvent under reduced pressure. At this point, 4110 parts of dimethylformamide was added and dissolved to obtain 5480 parts of a liquid resin. The viscosity of this product at 25 ° C. was 3 cps, and the nonvolatile content after heating at 135 ° C. for 1 hour was 25%.

Production Example 3 1000 parts of cresol were added to a reactor similar to that in Production Example 1.
After charging 1200 parts of 7% formalin and 5 parts of sodium hydroxide, the temperature was gradually raised and the reflux reaction was carried out for 60 minutes after the temperature reached 100 ° C. Then 60 mmHg in the system
The temperature in the system was raised to 70 ° C. while dehydrating under vacuum. At this point, 1000 parts of methanol was added and dissolved to obtain 2400 parts of a liquid resin. This product had a viscosity of 150 cps at 25 ° C. and a nonvolatile content of 45% after being heated at 135 ° C. for 1 hour.

Example 1 Liquid resin 40 obtained in Production Example 2
Parts and 200 parts of the liquid resin obtained in Production Example 3 were mixed and diluted with dimethylformamide to obtain a uniform liquid phenol resin composition having a nonvolatile content of 25% by heating at 135 ° C. for 1 hour.

Example 2 Liquid resin 28 obtained in Production Example 2
0 parts and 67 parts of the liquid resin obtained in Production Example 3 were mixed and diluted with dimethylformamide to obtain a uniform liquid phenol resin composition having a nonvolatile content of 25% by heating at 135 ° C. for 1 hour.

Comparative Example 1 The liquid resin obtained in Production Example 3 was diluted with methanol to obtain a liquid phenol resin having a nonvolatile content of 25% by heating at 135 ° C. for 1 hour.

Comparative Example 2 1925 parts of acetone was placed in the same reactor as in Production Example 1, 600 parts of maleic anhydride was added and completely dissolved, and the aromatic polyamine obtained in Production Example 1 was maintained at 40 ° C. or lower. 825 parts of the solution was added dropwise over 90 minutes, and after completion of the addition, the temperature was maintained for 1 hour. Then, 165 parts of triethylamine and nickel acetate tetrahydrate 19.5
Then, 800 parts of acetic anhydride was added, and the mixture was reacted at reflux temperature for 2 hours. After completion of the reaction, the solvent was immediately distilled off under vacuum, 1500 parts of 70 ° C. warm water was added, and the mixture was stirred and mixed for 10 minutes. Then, the mixture was allowed to stand and the supernatant aqueous layer was removed.
Further, 1500 parts of 90 ° C. warm water was added with stirring at the same temperature, and the mixture was stirred and mixed at 90 ° C. for 10 minutes and then allowed to stand to remove the supernatant aqueous layer. Then, after repeating this operation twice, 500 parts of methanol was added, the mixture was stirred at 70 ° C. for 10 minutes, the supernatant was removed, and the internal temperature was raised to 120 ° C. while dehydrating and removing the solvent under reduced pressure. At this point, 390 parts of 4,4′-diaminodiphenylmethane was added, and the mixture was stirred and reacted at the same temperature for 20 minutes, and then dimethylformamide 52 was added.
80 parts was added and dissolved to obtain 7040 parts of a liquid resin. The viscosity of this product at 25 ° C. was 3 cps, and the nonvolatile content after heating at 135 ° C. for 1 hour was 25%.

Using the liquid resins obtained in the above Examples and Comparative Examples, a substrate was impregnated under the following drying and post-curing conditions to prepare test pieces, and heat resistance was evaluated. The results are shown in Table 1. Base material Filter paper (1 mm thick) Drying temperature 80 ° C, time 30 minutes Post-curing temperature 200 ° C, time 30 minutes

[0028]

[Table 1] Resin blending ratio = aromatic hydrocarbon modified maleimide resin / phenolic resin (weight ratio)

As is clear from Table 1, when the liquid resin formulations obtained in the examples are used, an impregnated processed product having little deterioration in tensile strength due to heat and excellent in heat resistance can be obtained.

[0030]

The phenol resin composition according to the present invention is
It has excellent heat resistance, workability, and wettability with base materials. For example, materials for molding materials, organic fiber binders, rubber compounding agents, whetstone binders,
Inorganic fiber binder, electronic / electrical component coating agent, resin for laminated board,
A product having excellent heat resistance and toughness can be obtained by using it as a binder for friction materials, a binder for sliding members, and the like.

Claims (2)

[Claims] 1. A single or a mixture comprising an aromatic hydrocarbon-modified maleimide resin compound and a phenol resin, and at least one selected from N-methyl-2-pyrrolidone, dimethylformamide, acetone, methyl ethyl ketone and dioxane. A liquid phenol resin composition characterized by being dissolved in a mixed solvent. 2. The aromatic hydrocarbon-modified maleimide resin compound is an aromatic diamine or polyamine compound (A).
And an aromatic hydrocarbon formaldehyde reaction product (B) obtained by reacting an aromatic hydrocarbon with formaldehyde in the presence of an acid catalyst, and a dicarboxylic acid having an ethylene-type carbon-carbon double bond or a derivative thereof. The liquid phenol resin composition according to claim 1, which is an aromatic hydrocarbon-modified maleimide resin compound formed by bonding with an unsaturated bisimide compound (C) derived from a reactive derivative.