JPS6236051B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new epoxy resin composition with improved heat resistance, mechanical properties, and chemical resistance. Epoxy resins have excellent adhesive properties, heat resistance, chemical resistance, electrical properties, etc., and are therefore used in a wide range of fields such as paints, adhesives, various electrical insulation materials, and structural materials. However, in recent years, there has been an increasing demand for higher performance resin materials, and improvements in heat resistance, chemical resistance, impact resistance, etc. of epoxy resins are also desired. By the way, bisphenol A type epoxy resin is known as an epoxy resin that is widely used in practical use. When this epoxy resin is used at a high temperature of 150° C. or higher for a relatively long period of time, its mechanical properties and electrical properties deteriorate, so there has been a demand for improved heat resistance. Furthermore, further improvements in mechanical properties and chemical resistance have been desired. The present inventors conducted studies in view of these points, and found that a specific epoxy resin represented by the general formula [] exhibits good compatibility with bisphenol A type epoxy resin, and also has the ability to contain these components. The present inventors have discovered that the resin composition containing the present invention exhibits excellent heat resistance, mechanical properties, and chemical resistance, and have completed the present invention. An object of the present invention is to provide a new epoxy resin composition with excellent heat resistance, mechanical properties, and chemical resistance. This object of the present invention is based on the following constituent components (a) having the general formula (However, in the formula, Ar ¹ is a residue of a divalent phenol derived from a compound having one or two benzene nuclei, and Ar ² is a residue of a halogen-substituted benzenoid compound having two halogens on the nucleus. and is represented by -Ar ³ -Y-Ar ⁴ -, where Ar ³ and Ar ⁴ are hydrocarbon groups having a divalent benzene nucleus, Y is a sulfone group or a carbonyl group, and n is 1 An integer within the range of ~50.) Epoxy resin represented by. This can be achieved by blending (b) a bisphenol A type epoxy resin and (c) a curing agent. The epoxy resin containing a sulfone group or a carbonyl group represented by the general formula [], which is one of the constituent components in the present invention, can be produced by the method described in detail in Japanese Patent Application No. 14827/1983. That is, first in a highly polar solvent such as dimethyl sulfoxide, dimethyl sulfone, or sulfolane,
Or in a solvent containing these highly polar solvents under substantially anhydrous conditions, the general formula [] MO-Ar ¹ -OM [] (wherein Ar ¹ has one or two benzene nuclei The residue of divalent phenol derived from the compound, M represents an alkali metal atom), and the compound represented by the general formula ^{[ ]} It is a residue of a benzenoid compound having two halogens, -Ar ³ -Y
−Ar ⁴ −. Here, Ar ³ and Ar ⁴ are hydrocarbon groups having a divalent benzene nucleus, and Y is a sulfone group or a carbonyl group. Further, X represents fluorine, chlorine or bromine. ) and then reacting the reaction product with epichlorohydrin. The resin thus obtained has a skeletal structure of a condensate of an alkali metal salt of divalent phenol represented by the general formula [] and a halogen-substituted benzenoid compound represented by the general formula [], and has glycidyl at both ends. consists essentially of a compound to which a group is attached. The compound Ar ¹ of the general formula [] means the residue of divalent phenol after removing two aromatic hydroxyl groups. That is, Ar ¹ is a mononuclear phenylene group obtained from hydroquinone or resorcinol, for example. Further, Ar ¹ may be a residue of a phenol compound having two nuclei. Further, Ar ¹ may be one in which hydrogen on the nucleus is substituted with a substituent such as a halogen or an alkyl group. Examples of divalent phenols include 4,4'-dihydroxybiphenyl, dihydroxydiphenyl alkanes, etheric oxygen (-O-), carbonyl (-CO-), sulfone (-SO ₂ -), and sulfide (-S-). ) A dinuclear divalent phenol in which two phenols are bonded via a bond is preferred. in particular,
2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane,
1,2-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone,
Examples thereof include 3-chloro-4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ketone, and 4,4'-dihydroxydiphenyl sulfide. Compounds of general formula [] can be produced by reacting divalent phenols with compounds such as alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal carbonates, alkali metal alkoxides, or alkali metal alkyl compounds. . Preferably, alkali metal hydroxides are used and expediently reacted with dihydric phenols in the reactor used for the polymerization. In order to achieve the purpose of this application, 2.
It is also possible to use a mixture of one or more different divalent phenols. The compound of the general formula [] is a benzenoid compound in which one halogen atom and an electron-withdrawing group such as a sulfone group or a carbonyl group are bonded to at least one position ortho or distal to the nuclear halogen atom on the benzene nucleus. It is. Furthermore, the residue Ar ² in the compound of general formula [] is a benzenoid residue after removing the halogen atom on the benzene nucleus, and is represented by -Ar ³ -Y-Ar ⁴ -. Here, Ar ³ and Ar ⁴ are hydrocarbon groups having a divalent benzene nucleus, and Y is a sulfone group or a carbonyl group. Of course, this halogen-substituted benzenoid compound can be used regardless of whether it has a symmetrical structure or an asymmetrical structure. Specific examples include 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4,4'-dichlordiphenyl ketone, 4,
Examples include 4'-difluorodiphenyl ketone. The epoxy resin (component (b)) constituting another component in the present invention is a bisphenol A type epoxy resin obtained by reacting bisphenol A and epichlorohydrin. Further, the curing agent used in the present invention includes those used as curing agents for ordinary epoxy resins, and specific examples thereof include boron trifluoride monoethylamine complex, boron trifluoride piperidine complex, etc. Amine complex, triethylamine,
Tertiary amines such as benzyldimethylamine,
Borate compounds such as triphenylborate and tricresylborate, N-methylimidazole,
Examples include imidazole compounds such as N-ethylimidazole and N-phenylimidazole. Furthermore, phenylene diamine, diaminodiphenylmethane, diaminodiphenyl ether,
Aromatic amine compounds consisting of diaminodiphenyl sulfone, diaminodiphenyl sulfide, and their halogen or alkyl substituted products; aliphatic amine compounds such as ethylenediamine, hexamethylene diamine, etc.; or N-alkyl substitution of these aromatic and aliphatic amines. Amine compounds, as well as phthalic anhydride, hexahydrophthalic anhydride,
Methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, methyl-nadic anhydride, chlorendic anhydride, methylsuccinic anhydride, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride and acid anhydrides such as maleic anhydride. Furthermore, phenolic compounds such as various phenolic resins obtained by reacting phenol, hydroquinone, catechol, pyrogallol, resorcinol, bisphenol A, bisphenol F, and bisphenol S with aldehydes; diphenylmethane diisocyanate; Examples include isocyanate compounds such as enyl ether diisocyanate, diphenyl sulfone diisocyanate, and tolylene diisocyanate; various amide compounds and polyamide compounds obtained from dicyandiamide, amine compounds, and carboxylic acid compounds; and also melamine compounds, urea compounds, and the like. These curing agents can be used in combination of two or more types or in combination with a curing accelerator, and depending on the case, good results can be obtained. In the present invention, an epoxy resin represented by the general formula [], that is, component a, and other epoxy resins
The composition ratio with component (b) can be appropriately selected depending on the application and desired heat resistance, mechanical strength, etc., but generally, component a is about 10 to 80% by weight, and component (b)
It is preferable that each component is selected to have a content of about 20 to 90% by weight. This is because if the a component is less than 10% by weight, the desired performance improvement will not be sufficient;
This is because when the amount exceeds % by weight, a problem arises in that a considerably higher processing temperature is required than in a general epoxy resin composition when a cured molded article is obtained. On the other hand, the curing agent, which is another component of the present invention, is also appropriately selected depending on the application, required performance including heat resistance, molding conditions, etc. Third as a hardening agent
When using grade amines, boron trifluoride amine complexes, imidazole derivatives, borate compounds, etc., 0.001 parts by weight per 100 parts by weight of epoxy resin in total.
About 10 parts by weight is suitable. 1st class and 2nd class
When using a class amine compound, an acid anhydride, a phenolic compound, an isocyanate compound, etc. as a curing agent, the functional value of each curing agent is usually calculated based on the total epoxy equivalent of 1 of the epoxy resin selected from the above two groups. The chemical equivalent derived from the group is 0.6 to 1.3
It is preferable that The heat-resistant epoxy resin composition of the present invention can be used in fields such as electrical insulation materials, structural materials, paints and adhesives. At this time, reactive diluents, non-reactive diluents, inorganic fillers such as talc, slag, alumina, asbestos, or pigments may be added in accordance with conventional methods, and furthermore, phenolic resins, urea resins, Ketone resin, polyamide,
Resins such as various rubbers can be blended as modifiers and flexibility imparters. Further, the resin composition according to the present invention can be made solvent-free by selecting the composition ratio, and can be applied to a wide range of fields such as casting, impregnation, and molding. Also, methyl ethyl ketone,
Since it is soluble in solvents such as tetrahydrofuran and dimethylformamide, or mixed solvents thereof, it can be easily impregnated and applied to glass cloth, paper, etc., and can also be used to form laminates. However, since the resin composition of the present invention has good compatibility of each component,
Even when heat-cured, it forms a homogeneous structure. Moreover, the cured resin exhibits excellent heat resistance, mechanical properties, and chemical resistance. The present invention will be explained in more detail with reference to Examples below. Reference example 1 “Manufacture of epoxy resin represented by the general formula []” 2 equipped with a continuous moisture collector equipped with a stirrer, a thermometer and a cooling condenser, and a nitrogen gas inlet pipe
A flask was charged with 1.44 mol of bisphenol S, 0.8 mol of dimethyl sulfoxide, and 0.8 mol of chlorobenzene. After heating to 60℃, add 270ml of caustic potassium solution.
(2.88 mol as caustic potassium) was added dropwise. While heating the mixed solution, water contained in the solution was distilled off by azeotropy with chlorobenzene, and only the distilled chlorobenzene was returned to the reaction system. After almost completely removing the water in the reaction system, the temperature was raised to 162°C by distilling off part of the chlorobenzene, and then 0.96 mol of 4.4'-dichlorodiphenylsulfone dissolved in 360 ml of chlorobenzene was added. dripped. After reacting at 170°C for 6 hours, the mixture was cooled to 70°C and 380ml of epichlorohydrin was added. Subsequently, the temperature was raised to 100°C and the mixture was reacted for 2 hours. After cooling, the salt by-produced during the reaction was removed by filtration, the liquid was poured into a large amount of methanol, and the precipitated epoxy resin was collected by filtration and drying.
This resin had an epoxy equivalent weight of 726 and a melting point of 155-159°C. Moreover, the glass transition temperature was 136°C. Example 1 Epoxy resin with the above polysulfone structure, bisphenol A type epoxy resin (trade name Epicote)
828), a curing agent, and a curing accelerator were blended in the composition ratios (parts by weight) shown in Table 1 to prepare a solvent-free resin composition. The resin composition thus obtained was poured into a casting mold under heating, heated in an oven at 100°C for 2 hours, and then further heated to 175°C.
C. for 6 hours to obtain a cured resin plate with a thickness of 3 mm. Test pieces were cut out from this molded plate, and various physical properties were measured. The physical properties were measured using heat distortion temperature JIS K7207, bending strength JIS K-6911, Izod impact strength JIS K-6760, and volume resistivity JIS K-
Based on 6911. In addition, the organic solvent resistance was determined by the test piece (dimensions
50 mm x 50 mm) was immersed in methyl ketone at 25°C for 7 days, and the degree of weight increase was measured. Table 1 shows the measurement results of physical properties. In addition, the epoxy resin, curing agent, and
The blending ratio of the curing accelerator is parts by weight. Comparative Example 1 A cured resin board was produced in the same manner as in Example 1, except that only Epikote 828 was used as the epoxy resin. The results are shown in Table 1, and when these results are compared, the heat distortion temperature, bending strength retention rate, and Izot impact strength of the examples according to the present invention are all high, and they are also excellent in terms of organic solvent resistance.

【table】

[Table] Example 2 The epoxy resin used in Example 1 and the curing agent and curing accelerator shown in Table 2 were heated in the same manner as in Example 1 at 100°C for 2 hours and then further heated to 150°C.
℃ for 6 hours to prepare a cured resin plate.
The measurement results of physical properties are shown in Table 2. Comparative Example 2 A cured resin board was produced in the same manner as in Example 2, except that only Epikote 828 was used as the epoxy resin. The measurement results are shown in Table 2, and the examples of the present invention are superior in terms of heat distortion temperature and organic solvent resistance. Reference Example 2 "Production of epoxy resin represented by the general formula 2.50 mol of chlordiphenyl sulfone was added, and the mixture was reacted at 160°C for 2 hours. Next, 435g of epichlorohydrin
was added and reacted at 100°C for 2 hours. Subsequently, it was post-treated in the same manner as in Reference Example 1, and the epoxy resin was recovered. The obtained epoxy resin has an epoxy equivalent
483, with a melting point of 79-82°C. Example 3 In Example 2, 60 parts of the epoxy resin obtained in Reference Example 2 was used as the epoxy resin (component (a)), and 40 parts of Epicoat 828 was used as the component (b). A cured resin plate was prepared in the same manner as above. The heat deformation temperature of this resin plate is 143℃,
The measurement result of organic solvent resistance was 0.15wt%.

Claims (1)

[Claims] 1. As an essential component (a) General formula (However, in the formula, Ar ¹ is a residue of a divalent phenol derived from a compound having one or two benzene nuclei, and Ar ² is a residue of a halogen-substituted benzenoid compound having two halogens on the nucleus. , expressed as -Ar ³ -Y-Ar ⁴ -, where
Ar ³ and Ar ⁴ are hydrocarbon groups having a divalent benzene nucleus, and Y is a sulfone group or a carbonyl group. Further, n is an integer within the range of 1 to 50. ) Epoxy resin represented by (b) Bisphenol A type epoxy resin (c) Contains a curing agent, and the blending ratio of (a) and (b) is (a)
An epoxy resin composition characterized in that (b) is 90 to 20% by weight while (b) is 10 to 80% by weight.