JPS5849718A - Resin material resistant to hot water - Google Patents

Abstract

PURPOSE:The titled resin material, prepared by adding a catalyst capable of forming ethereal bonds between epoxy resin molecules and a three dimensional network structure to a resin composition of a specific thermoplastic resin and the epoxy resin, and curing the resultant mixture under heating, and having improved mechanical strength and heat resistance. CONSTITUTION:A cured resin material obtained by curing a resin composition prepared by adding a catalyst, e.g. a metallic salt of a dialkyldithiocarbamic acid, to a mixture obtained by mixing a thermoplastic resin selected from a polysulfone resin, polyether sulfone resin, polyphenylene sulfide resin or polytetrafluoroethylene resin with an epoxy resin, e.g. the bisphenol, alicyclic, glycidyl ester or novolak type, having two or more epoxy groups in the molecule, uniformly in the presence or absence of a solvent, e.g. water, under heating at about 40-380 deg.C for about 1-20hr. EFFECT:Resistant to hot water up to 350 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to hot water resistant resin materials. For more details,
The present invention relates to resin materials that can withstand hot water up to 650° without losing much of their mechanical strength. Thermoplastic resins such as polyethylene, polyethylene, polybutylene, and styrene are used as materials with excellent water resistance. Although it is known,
Due to their poor heat resistance, the temperature limit at which they can be used as water-resistant materials is about 80°a, and they cannot be used in hot water at higher temperatures.

As resin materials with improved hot water resistance, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, &911! Thermoplastic resins such as g7 fluorinated ethylene resin have been developed.

Although these thermoplastic resins have excellent heat resistance and can withstand fairly high temperature hot water, they have the disadvantage that their mechanical strength decreases when left in hot water.

The present invention has been made to overcome the above problems, and
The purpose of the present invention is to provide a resin material that can withstand hot water up to 55°C and 14°C without losing mechanical strength.

Generally, epoxy resin can be made into a cured resin with a three-dimensional network structure by heating with a curing agent such as 1! It is also widely used as a composite material based on carbon fiber. However, when these conventional cured epoxy resins are used in hot water, their intermolecular crosslinks are hydrolyzed, resulting in poor hot water resistance. For example, the crosslinked portion of a cured product obtained by curing an epoxy resin using an acid anhydride is an ester bond, which is hydrolyzed into carboxylic acid and alcohol in hot water.

The present inventors cured an epoxy resin using a cationic catalyst, an anionic catalyst, or a coordinating anionic thread catalyst medium, and at the same time added the above-mentioned thermoplastic resin having hot water resistance. It was discovered that it has excellent hot water resistance and hardly loses its mechanical strength even after being left in hot water, leading to the completion of the present invention.

That is, the present invention provides a resin composition obtained by mixing an epoxy resin and a thermoplastic resin selected from the group consisting of suisulfone resin, polyethersulfone resin, -polyphenylene sulfide resin, and l-tetraacid ethylene resin. The present invention relates to a hot water-resistant resin material obtained by adding a catalyst that can generate ether bonds between molecules of an epoxy resin and forming a six-dimensional network structure, and then curing the resin by heating.

The resin material of the present invention is first made of 10 to 70 parts (parts by weight, (same below) and 90 to 60 parts of epoxy resin are uniformly mixed in the presence or absence of a solvent, and then 0.5 to 4 parts of catalyst
The resin composition obtained by adding 0 parts of the resin composition and thoroughly mixing it can be heated at about 40 to 35,000 for about 1 to 20 hours.

Specific examples of hot water-resistant thermoplastic resins used in the present invention will be described below. D Examples of polysulfone resins include polymers represented by formula (I): and polymers represented by formula (I): The former is Bakelite. The product name is Polysulfone P-1700 (manufactured by FFL NCC, USA), and the latter is Astrelu'660.
(manufactured by 3M Corporation, USA) under the trade name.

The polyether sulfone resin is represented by the formula (1), and is commercially available, for example, under the trade name Victorex (a British company owned by Imperial P.K. Industries).

Polyphenylene sulfide resin is represented by the formula (l=), and commercially available products include, for example, Line (Philips, USA)! Liu A Company 11 [),? Steal (manufactured by Hodogaya Chemical Industry ■) etc. can be opened.

The polytetrafluoroethylene resin is represented by the formula (V), and commercially available products include, for example, Teftan (manufactured by DuPont, USA or Tamashiflo 12+Mikal).

When these resins are subjected to the above-mentioned curing reaction, they themselves do not take part in the reaction; after curing, they are incorporated into the cured resin having a 16-dimensional network structure formed by the reaction of the epoxy resin.

These hot water-resistant thermoplastic resins are used in an amount of about 10 to 70 parts in 100 parts of the resin composition. If more than 70 parts is used, the mechanical strength of the resin material after being discharged into hot water will not be sufficient, and if less than 10 parts, hot water resistance will hardly be observed. The epoxy resin used has two or more epoxy groups in its molecule, and bisphenol-type engineered mexyl resin is a typical example thereof. In the above formula (6), n6 is preferably up to about 15 in practical terms. These commercially available products include Epicote 8
28, Epicote 834 (all manufactured by Yuka Shell Chemical Co., Ltd.), DNR-552, nmR-33t (all manufactured by Dow Chemical Company, USA), Araldai) GY-250, Araldai) GY-6071 (all manufactured by Ciba Geigy Japan)
(manufactured by).

Other epoxy resins include alicyclic epoxy resins such as Ninox 221 (manufactured by Nippon Co., Ltd., USA), Araldite AY-182 (manufactured by Nippon Ciba Geigy), and Ebicor) 190 (manufactured by Yuka Shell Chemical Co., Ltd.). made)
Glycidyl ester type epoxy resin represented by Araldai) IPNIt3a (manufactured by Nippon Ciba Geigy)
and novolac type epoxy resins such as DIN4S8 (manufactured by Dow Chemical Co., USA).

Catalysts that can be used in the present invention include dialkyldithiocarbaturonic acid metal salts, metal carboxylates, imidazole compounds, triethanolamine titanate-triphenylbore F complex, boron trifluoride amine complex, trimethoxybotetraxin, anhydrous Examples include boric acid. When these catalysts are added to epoxy resins and cured, they form ether bonds between the epoxy resins that are difficult to hydrolyze.

Specific examples of dialkyldithiocarbamate metal salts include diethyldithiocarbamate zinc salt, dibutyldithiocarbamate magnesium salt, dinutyldithiocarbamate iron salt, and dibenzyldithiocarbamate tin salt. For example, when diethyldithiocarbamic acid zinc salt is used, it is thought to coordinate to the epoxy ring as shown in the following formula to open the epoxy ring and induce opening polymerization.

/ / Specific examples of metal carboxylates include lead palmitate, zinc caprylate, iron caproate, tin laurate, and manganese caprate. For example, lead palmitate is thought to attack the epoxy ring to open the epoxy ring as shown in the following formula, causing opening polymerization.

In addition, when an acid anhydride is added to a metal carboxylate as a reaction accelerator, for example, the curing of an epoxy resin by zinc caprylate and hexahydrophthalic anhydride is coordinated as shown in the following formula, and the ether bond is It is thought that this causes the formation of

＼ Specifically, the blood imidazole compound is 2-methyl-
Imidazole, 2-ethyl-isedazole, 2-ethyl-4-imidazole, 2-phenyl-tdazole, 1-
Examples include cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole. Further, these imidazole compounds modified with dicyancyanide can also be used in the present invention. For example, 2-ethyl-4
-Methyl-imidazole is thought to attack the epoxy ring as shown in the following formula and induce opening polymerization.

H3 Specific examples of amine complexes of boron trifluoride include ethylamine, n-butylamine, benzylamine, or imidazole and boron trifluoride complexes. For example, the monoethylamine complex of boron trifluoride is as follows. It is thought that it coordinates to the epoxy ring as shown in the formula, opens the epoxy ring, and causes opening polymerization.

It is believed that the triethanolamine titanate-triphenylporate complex coordinates to the epoxy ring as shown in the following formula to open the epoxy ring and cause opening polymerization.

It is believed that the epoxy ring is opened according to the reaction formula of trimethoxyboroxine to induce opening polymerization.

When commonly used curing agents such as primary amines and acid anhydrides are used in the present invention, they are unable to impart sufficient hot water resistance to the resulting cured resin materials. Although there is still no sufficient theoretical basis for the reason, it is probably because addition-reaction cured products made from primary amines and ester bond-containing cured products made from acid anhydrides are hydrolyzed by hot water. .

An appropriate solvent may be used in the above-mentioned curing reaction, if necessary. These solvents are not particularly limited and include water,
methanol, ethanol, n-butanol, acetone,
Methyl ethyl naton, benzene 1) Select and use solvents such as toluene and xylene as appropriate. Further, during the curing reaction, suitable additives such as glass fiber, mica powder, silica powder, etc. can be appropriately added to improve the heat resistance and mechanical strength of the cured resin material.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

Example 1 40 parts of polysulfone tree JlP-1700 (manufactured by SNC, USA) were mixed with 60 parts of dioxane and 60 parts of toluene.
The mixture was added to a mixed solvent consisting of 100% and dissolved at 45°0 with stirring. Next, 60 parts of novolak type epoxy resin Araldite MPM11!8 was added as an epoxy resin,
The mixture was dissolved at 45°O with stirring. Furthermore, 6 parts of diethyldithiocarbamic acid zinc salt was added as a catalyst and mixed uniformly. The resulting mixture was heated at 100°O for 2 hours, 1
5 hours at 50°o, 180'(lt'2 hours, 260°
The resin material was cured by heating at 0 for 1 hour to obtain a cured resin material.

The obtained resin material and it was ao in an autoclave.
25° after 600 hours immersion in hot water at o'a
The tensile strength at 0 was measured according to the method of ASTM-→668. As a result, the initial value is 800 kyaw
", and the value after immersion was 720 kg 10 n."

Examples 2 to 6 Cured resin materials were obtained by carrying out experiments in the same manner as in Example 1, except that the catalyst and heat curing conditions were changed to those shown in Table 1.

The obtained resin material and it was placed in hot water at 60,000 °C.
Table 1 shows the tensile strength at 25'O after immersion for 00 hours.

Comparative Example 1 In place of the diethyldithiocarbamic acid zinc salt used as a catalyst, 50 parts of methyltetrahydrophthalic anhydride and 0.5 parts of benzyldimethylamine were added as a curing agent, and the heat curing conditions were as shown in Table 1. A cured resin material was obtained by carrying out an experiment in the same manner as in Example 1, except that .

The obtained resin material and it was placed in hot water at 30,090° C.
Table 1 shows the tensile strength at 2580 after immersion for 00 hours.

Comparative Example 2 The same procedure as Example 1 was carried out, except that 17 parts of diacenodiphenylmethane was added as a curing agent in place of the diethyldithiocarbamic acid zinc salt used as a catalyst, and the heat curing conditions were changed to those shown in Table 1. We conducted experiments and obtained a cured resin material.

The obtained resin material and it were placed in hot water at 600°0.
Table 1 shows the tensile strength at 25°0 after immersion for 00 hours.

Example 4 1 Liethersulfone resin 200F (manufactured by Imperial + Michal Industries, UK) 20 parts Boxy resin Ateldite ny-032 (manufactured by Ciba, Switzerland) 6
After melting and mixing at 150'O, 150°
Cycloaliphatic epoxy resin 221 (U.S. -
- 20 parts of C.C. Co., Ltd.) were added and mixed uniformly, and further 5 parts of tin caprylate was added as a catalyst and mixed uniformly to obtain a resin composition.The resulting resin composition was heated at 150°C.
The resin material was cured by heating for 8 hours at 175°O, 4 hours at 175°O, and 2 hours at 250°O to obtain a cured resin material.

The resin material seen and it in an autoclave for 60
The tensile strength was measured after 600 hours of immersion in hot water at a temperature of 0.000 C. according to the method of IITM-1638. As a result, the initial value was 9001 dj/am'', and the value after immersion was 820 kg/'cJ-.

Examples 5 to 6 Cured resin materials were obtained by carrying out experiments in the same manner as in Example 4, except that the catalyst and heat curing conditions were changed to those shown in Table 2.

The obtained resin material and it were placed in hot water at 600°0.
Table 2 shows the tensile strength after immersion for 00 hours. A cured resin material was obtained by carrying out an experiment in the same manner as in Example 4, except that the heat curing conditions were changed to those shown in Table 2.

The obtained resin material and it was placed in hot water at 50,080 °C.
Table 2 shows the tensile strength at 2500 after soaking for 00 hours.

Example 7 180 parts of Susteel 0p-4 (manufactured by Hodogaya Chemical Industry Co., Ltd.) (54 parts as a resin component) of a 60% polyphenylene sulfide m-fat water dispersion was mixed with 100 parts of butyl alcohol, and then mixed as a polyoxy resin. 46 parts of bisphenol type epoxy resin Epicoat 828 were mixed. Further, 2.5 parts of dibutyldithiocarbamic acid tin salt was added as a catalyst and thoroughly mixed to obtain a uniform resin composition.

The obtained resin composition was cured by heating at 90° for 4 hours, at 110° for 4 hours, at 150° for 8 hours, at 200 oa'''c for 2 hours, and at 70' for 50 minutes to obtain a cured resin material. The tensile strength at 25°0 after immersing the obtained resin material in hot water of 60,000 in an autoclave for 300 hours is A8'l''M-D6.
It was measured according to the method of 5B. As a result, the initial value is 600 to 9101112 and the value after soaking is 550k
It was P/am2.

Examples 8 to 9 Cured resin materials were obtained by carrying out experiments in the same manner as in Example 7, except that the catalyst and heat curing conditions were changed to those shown in Table 3.

The resin material seen and it placed in hot water at 60,000 °C
Table 6 shows the tensile strength after immersion for 00 hours.

Table 3 Example 10 50-:J
(manufactured by Tamaoshi Flori Chemical ■) 100 parts (65 parts as a resin component) were mixed with a mixed solvent consisting of 60 parts of butyl alcohol and 30 parts of methyl alcohol, and then glycidyl ester type epoxy resin Ateldite OY182 (Japan Ciba Geigy ■) was mixed as an epoxy resin. 65 parts (manufactured by Manufacturer Co., Ltd.) were added and mixed. Furthermore, as a catalyst, 1-cyanoethyl-
2-phenyl-4,5-di(cyanoethoxymethyl)
3 parts of imidazole was added and thoroughly mixed to obtain a uniform resin composition.

The obtained resin composition was heated at 100'O for 4 hours at 150qO.
The resin material was cured by heating at 360° for 4 hours and at 360° for 1 hour to obtain a cured resin material.

The obtained resin material and it was heated in an autoclave for 60 minutes.
250 after being immersed in hot water at 0°0 for 600 hours
The tensile strength at 0 was measured according to the method of ASTM-D6KB. As a result, the initial value is 400 kg/a
m2, and the value after immersion was 366 kvcm2.

Agent: Ge Shuxin - (1 person) Procedural amendment (voluntary) ↑Y-Yuo Director's Palace 1, case indication Patent application No. 54-148210
No. 2, Title of the invention Hot water-resistant resin material 3, Relationship to the case of the person making the amendment Patent applicant address 2-2-3 Marunouchi, Chiyoda-ku, Tokyo Name (601) Mitsubishi Electric Co., Ltd. Representative Yunihachi Kata Department/10 Agent Address: 2-2-3-5 Marunouchi, Chiyoda-ku, Tokyo, Subject of amendment (1) “Detailed Description of the Invention” column 6 of the specification, Contents of amendment (1) Page 11 of the specification Correct "2-ethyl-4-imidazole" in the 7th line from the bottom to "2-ethyl-4-methyl-imidazole.""acid" is corrected to "methyltetrahydro7talic anhydride".

(8) Correct "diaminodiphenylamine" in Comparative Example 2 of Table 1, page 17, to "diaminodiphenylmethane."

that's all

Claims (1)

[Claims] (1) polysulfone resin, polyethersulfone resin,
A six-dimensional network is formed by forming ether bonds between the molecules of the epoxy resin in a resin composition obtained by mixing an epoxy resin with a thermoplastic resin selected from the group consisting of polyphenylene sulfide resin, resin, and polytetrafluoroethylene resin. A hot water-resistant resin material obtained by adding a catalyst that can form a structure and then curing it by heating. (2) The hot water-resistant resin material according to claim (1), wherein the epoxy resin is a bisphenol type epoxy resin, an alicyclic type epoxy resin, a glycidyl ester hmz mexi resin, or a novolak type Evo 41m resin. (8) The catalyst is a dialkyldithiocarbamate metal salt, a metal carboxylate, an iodazole compound, a triethanolanotitanate triphenylholet complex, an amine M form of boron trifluoride, or rimethoxybonexine. or the hot water-resistant resin material according to claim (1) or (2), which is boric anhydride◇