JPS62253669A - Coating epoxy resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition for paints containing as an essential component a novel epoxy resin which has low viscosity and excellent cured properties.

Various types of epoxy resins are industrially manufactured and commercially available, and among them, ν-glynolether of 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) (hereinafter referred to as bis A type epoxy resin) Resin and abbreviation t,>
Needless to say, it is a general-purpose epoxy resin, and in particular, liquid Bis A type epoxy resin has fluidity at room temperature, which is advantageous in terms of work. polycarboxylic acids, l
! Utilizing the excellent properties of cured products such as mechanical strength, heat resistance, adhesiveness, electrical insulation, and water resistance using hardening agents such as anhydrides, we can produce paint adhesives, electrical insulation materials, and FRP.
It is well known that they are used as matrices, flooring materials, and other applications.

However, this useful liquid bis-A type epoxy resin still has a disadvantage of high viscosity.

In other words, this liquid bis-A type epoxy resin is usually produced by reacting bisphenol A with excess epicumylhydrin, and as the amount of shrimp chlorohydrin used increases, the molecular weight and viscosity decrease. Are known. However, by increasing the amount of epichlorohydrin used, the resin viscosity decreased by about 7.000 CPS (25
℃) is the limit. and 7,000 to 10,000
OCPS, a liquid bis-A type epoxy resin with a relatively low viscosity, tends to crystallize, so it solidifies in the winter, loses its original fluidity at room temperature, and loses its value as a product, so it is usually manufactured industrially. The epoxy equivalent of the liquid type epoxy resin sold is around 190? 25
Viscosity at °C from about 9,000 to about 15,000 CPS
It has a relatively high viscosity. Therefore, for the purpose of reducing the viscosity of such liquid bis A type ebocarbohydrate, a low viscosity reactive diluent such as butyl glycylate ether or phenyl glycycle ether, or a heptalic acid ester,
Non-reactive diluents such as alkylphenols are also used, but the use of these diluents inevitably causes problems such as a decrease in the mechanical strength of the cured product, a decrease in heat resistance, a decrease in adhesiveness, etc. The physical properties of the cured epoxy resin product deteriorate, and depending on the type of diluent, the toxicity is high, causing health problems for workers.

In addition, in the field of paints, solvents such as aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols, and ketones are currently used in the coating process. However, there are health problems for workers and air pollution due to the release of solvents into the atmosphere, and there is a trend toward not using solvents or using only small amounts of solvents. In this direction, general-purpose liquid bis-A type epoxy resins cannot be used satisfactorily due to their inherent high viscosity, despite the excellent properties of their cured products.

As a low-viscosity epoxy resin that retains a considerable portion of the properties of the cured product of liquid bis-A type epoxy W resin, diglynn tulle ether of bis(4-hydrodonphenyl)methane (commonly known as s72/-ru F) is used. (hereinafter abbreviated as bis-F type epoxy resin) is known (Japan Chemical Industry Association Monthly Report, (10), 29 (
1975)), this bis-F type epoxy resin has a low viscosity of about 3,0OOCPS at 25°C at an epoxy equivalent of 180, and the cured product of No. 7 is quite similar to the liquid bis-A type epoxy resin, but has low heat resistance. It has a serious drawback. That is, according to the above-mentioned JCIA Monthly Report, when triethylenetetoteamine is used as a curing agent, the heat distortion temperature of the cured product of Bis-F type Egotoshi resin is 104°C, and that of Bis-A type Mexi resin. The disadvantage of such bis-F type epoxy resin, which is considerably lower than the heat distortion temperature of the cured product at 121°C, is that while it has the advantage of low resin viscosity, it has the same heat resistance as bis-A type epoxy resin. There are naturally limits to its application to applications that require yR7)-).

In view of the above-mentioned circumstances, the inventors of the present invention have conducted intensive studies to obtain an epoxy FMm that takes advantage of the high heat distortion temperature and other advantages of a liquid bis-A type epoxy resin cured product, and also has a low viscosity. The structural formula is substantially Q OH -CHt -CH-CHt (1)
I), where the epoxy equivalent is A and the hydrolyzable chlorine equivalent is B, the value expressed by A × B / (A + B) is about 170 to about 190, and X is the formula (n) The epoxy resin, which is a divalent residue obtained by removing the hydrogen atom of the water R group from 1,1-bis(hydroxyphenyl)ethane shown in We discovered the surprising fact that the heat resistance and other properties are equal to or better than those of bis A type epoxy resin, and arrived at an invention that can completely satisfy the requirements that have existed for a long time.

It is known that an epoxy resin can be produced by reacting di(f172/-) represented by the formula (n) with epichlorohydrin or dichlorohydrin in the presence of an alkali.
scbucLIL (4) sl 71-174 (1961
LJ, Angel, chess, , Bd3
2, 1 1 2 4-1 1 29 (1959) lK
him, Prow, , 4 8 8 ~ 4 6 9 (
1961), 1゜1 in Japanese Patent Publication No. 26-4638, etc.
-Bis(4-hydroxyphenyl)ethane and epichlorohydrin or dichlorohydrin are reacted in the presence of an aqueous sodium hydroxide solution to produce an epoxy resin, and the properties of the produced epoxy resin, properties of the cured product, etc. are described. However, these known documents only describe examples of synthesis of epoxy wm using a small amount of 3 moles or less of epichlorohydrin or dichlorohydrin per 1 mole of 1,1-bis(human I2xyphenyl)ethane.
According to the descriptions of these known documents, the value expressed by A×B/(A+B) is 200 or more, and the inventor's additional tests revealed that it was 9200 or more. Furthermore, there is no detailed description of the viscosity of the synthesized epoxy resin in the known literature (
Also, there was no description regarding the heat resistance of the cured product of the epoxy resin. Furthermore, according to the inventor's additional tests, the epoxy resins produced by these methods are in a solid solution state with almost no fluidity at 25°C, and under the same conditions, Bis7 El/-A type epoxy resin also shows no fluidity at 25°C. Solid solution, both at 25℃
Almost no difference could be observed in terms of viscosity.

However, the inventors have discovered that the divalent phenol of formula (II)
Substantially the formula (
1) An epoxy resin having the structure shown in A×B/(
If the value displayed in A+B) is within the range mentioned above, it is BisF.
It has a low viscosity equivalent to the type liquid epoxy resin, and its cured product has physical properties equivalent to or better than the bis A type liquid epoxy resin. I gained some great knowledge.

That is, the present invention has a structure substantially represented by the above general formula (I), and when the epoxy equivalent is A1 and the hydrolyzable octalodene equivalent is B, it is expressed as A×B/(A + B). The present invention relates to providing a curable resin composition for coatings, which contains as an essential component a liquid epoxy resin having a value of about 170 to about 190.

In addition, in formula (1), X is 1,1- shown in the above formula (II)
It is a divalent residue obtained by removing the hydrogen atom of the hydroxyl group from bis(hydroxyphenyl)ethane, and n is the number of repeating units.

The viscosity of the epoxy resin used in the present invention is 2.50 at 25°C.
Is it 0? , has an extremely low viscosity of 0OOCPS, and its cured product exhibits heat resistance equivalent to that of conventional liquid Bis-A type epoxy resin, that is, a heat distortion temperature.
Much better than type epoxy resin. Of course, other properties are equivalent to or better than those of the bis A type epoxy resin, and the epoxy resin used in the present invention has a sufficiently low viscosity even without the use of a diluent, so there is no need to use a diluent. Even if it is used to lower the viscosity even further, the amount used to achieve the same viscosity is much smaller than Bis A type Evokin resin, which poses a health problem for workers. Of course, the WA mechanical strength and heat resistance of a cured product obtained from a compound whose viscosity has been lowered by a diluent will be superior to that of a bis-A type epoxy resin.

In addition, in the field of paints, it is possible to obtain a coating film that has the excellent properties of Bis A type epoxy resin, so according to the present invention, an epoxy resin can be used and an excellent solvent-free paint or solvent can be used. Also, a pollution-free paint can be obtained with a small amount of usage.

Other objects and advantages of the present invention will be better understood from the following detailed description of the present invention.

The formula m of the epoxy resin used in the present invention is substantially represented by the above formula (1) (1 formula<1), and X is the formula (If
) is the residue obtained by removing the hydrogen atom of the hydroxyl group -OH of the divalent 7-enol represented by formula (1), 1.1-bis(4-hydroxyphenyl)ethane, 1
．． 1-bis(2-hydroxyphenyl)ethane, 1.1
-bis(3-hydroxyphenyl)ethane, 1-(2-
hydroxy7enyl)-1-(4-hydroxyphenyl)ethane, 1-(3-hydroxyphenyl)-1-(4
Examples include -hydroxyphenyl)ethane, 1-(2-hydroxyphenyl)-'1-(3-hydroxyphenyl)ethane, and 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis( 2-hydroxyphenyl)ethane, 1-bis(2-hydroxyphenyl)-1
Preferred examples include -(4-hydroxyphenyl)ethane, and particularly preferred is 1,1-bis(4-hydiphenyl)ethane.

The fact that X is a divalent 7-ethyl residue represented by the formula ([[) gives the epoxy resin used in the present invention its advantages. : What a composition! This is one of the problems, and screw 7
The effects of the present invention cannot be achieved with residues of alcohol A or bisphenol F.

The epoxy resin used in the present invention is A×B/(A+B) where A is the epoxy equivalent and B is the hydrolyzable halogen equivalent.
) is about 170 to about 1901, preferably about 171 to about 185, more preferably about 171 to about 182.

The detailed explanation and measurement method is edited by Hiroshi Kakiuchi, Epoxy m*
(1? wo Gyosho, Shokodo), 161 Su&st, i 70
% and the primary measurement method is exemplified.

1°200@j! Triangle 7? Epoxy resin 0.2 on Sco
Weigh accurately 0.004 g and dissolve by adding 25 ml of dioxane.

Accurately add 25 to 25 ml of a 2°115N salt aWI solution (nooxane solution), seal tightly, mix thoroughly, and let stand for 30 minutes.

3. After adding 50% of toluene-ethanol (1:1, volume ratio) mixed solution, use cresol red as an indicator.
Titrate with 10N sodium hydroxide Sa.

4. Calculate the engineering mexi equivalent according to the following formula.

(Q-3) Xo, IXf W: Weight of sample (g) S: Titration amount of 1/10 normal sodium hydroxide solution (J
) Titer Q of Gl/10N sodium hydroxide solution; Blank test, 1/10N hydroxide) Titration of 13um solution * (@1 ”) Also, hydrolysis method n/S What is the equivalent weight of loden? It means the weight t (unit: g) per gram equivalent of hydrolyzable halogen.

Hydrolyzable no%a dene can be used, for example, when producing the epoxy resin used in the present invention by reacting epichlorohydrin with divalent 7 ether represented by the formula (II).
Epoxy resin is produced according to formula I) and formula C■), but the reaction of formula (1'V> is not completed and it mainly consists of the halogen remaining in the form of (II).This hydrolysis Possible halogen i± It is not always good for it not to exist at all, but it is determined in an appropriate amount depending on the application.

The following method is exemplified as a method for measuring the hydrolyzable halogen equivalent.

f, 300@j! Epoxy #i fat approx. 5 to round bottom 7 fusco
gt accurately weighed, toluene-methanol mixed solvent (1:1:
Volume ratio HOOmJ! Add and dissolve.

2. Metallic 1/10 normal potassium hydroxide solution 50
-! After precisely adding the
Heat to reflux in the dark for 0 minutes.

3. Thereafter, the mixture is allowed to cool and titrated with a 1/10N aqueous hydrochloric acid solution using 7 ethyl atarein as an indicator.

4. Calculate the hydrolyzable halogen equivalent according to the following formula.

wxioo.

(Q-8) xo, 1xf W: Weight of sample! l(g) S: Titration amount of 1/10N hydrochloric acid aqueous solution <*1) f: 1
/Titer of 10N hydrochloric acid aqueous solution Q: In a blank test, the titer of 1/10N hydrochloric acid aqueous solution (mj
) Epoxy equivalent IA and hydrolyzable halogen equivalent Bel! As a number, A×B/(A+8)? If the displayed value exceeds about 190, the epoxy resin has a high viscosity, and if the displayed value is less than about 170, the epoxy resin is produced by reacting the divalent 7 ether represented by formula (II) with epihalohydrin. When adopting a suitable manufacturing method, it is necessary to use epihalohydrin in a large amount that is unbearable for industrial implementation, which is a disadvantage of the present invention.

In the present invention, having substantially the structure of the above formula (I) means that a small amount of the hydrolyzable halogen represented by the above formula (ml) remains due to the method adopted when producing the epoxy resin used in the present invention, or It may be intentionally left behind,
This means that such epoxy resins are also included in the epoxy resins used in the present invention.

Epoxy hit! The iA and the hydrolyzable halogen 31B are appropriately selected depending on the use of the epoxy resin used in the present invention, but the epoxy iiiA is preferably about 170 to about 190, particularly about 171 to about 185. The hydrolyzable halogen equivalent B is preferably 3,500 or more, particularly about 10,000 or more.

The viscosity of the epoxy resin used in the present invention is approximately 2.5 at 25°C.
00 to about 7,0OOCPS, but about 2,500
The effect of the present invention is best achieved by using a polyurethane resin having a concentration of from about 5,0 OOCPS to about 5,000 CPS, which is extremely preferable.

The epoxy resin used in the present invention can be produced by reacting #moles of the dihydric phenol represented by the formula (If) with shrimp halohydrin and/or dihalohydrin.

Examples of the shrimp halohydrin include epichlorohydrin and epibromohydrin. or 1,3-dichloro-2-propatol as dihalohydrin, 2.
3-ychlor-1-propatur, 1t3-nobrome-
Examples include 2-propertool and 2,3-kujirom-1-propertool. These epihalohydrins and dihalohydrins may be used as a mixture. Among these, it is preferable to use epihalohydrin, but the use of epichlorohydrin is most preferable.

The amount of shrimp halohydrin or zohalohi doria to be used is usually 4.5 mol or more, preferably about 5 to about 40 mol, more preferably about 5.5 mol, based on the divalent 7 enol≠(le). 30 moles to about 30 moles are used.

Dihydric phenol and shrimp halohydrin of formula (■) /
Alternatively, various methods can be used to react with dihalohydrin.

One of them is a method of directly reacting the dihydric phenol with shrimp halohydrin or dihalohydrin in the presence of an alkaline substance. This method is a method in which the etherification step of formula (1) and the dehydrohalogenation step of formula (IV) are performed simultaneously. At this time, the alkali compound is the divalent 7
Usually about 1 mole or more, preferably about 1 mole or more, based on the enol.
Used at about 8 to 2 times the mole, about 60 to about 90°C
is carried out in the presence of water at a temperature of . As the alkali compound, it is preferable to use alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide.
Industrially, the use of sodium hydroxide is recommended. 0 After the reaction is complete, unreacted shrimp halohydrin/or nohalomodrine, water, produced salts, etc. are removed from the reaction product, and the product used in the present invention is dried. A colored epoxy resin is obtained. When this method is adopted, the amount of ILA per epoxy and one hydrolyzable halogen equivalent can be adjusted to 11 depending on the amount of the alkali compound used.

However, the dihydric phenol and shrimp halohydrin are reacted in the presence of an etherification catalyst to carry out the etherification step of the formula (III), and then an alkaline compound is used. ) It is extremely preferable to employ a method of carrying out the dehydrohalogenation step of formula (■).

Suitable catalysts used in the etherification process include tertiary amines such as trimethylamine, triethylamine;
J-Phenyl-7-osphine, tributyl-7-osphine, and other third group aosphines; Tetra/tylammonium chloride, Tetofmethylammonium bromide, Tetraethylammonium chloride, Tetraethylammonium bromide, Choline chloride, and other quaternary ammonium compounds; Sonotetra Methyl 7-osulfonium, bromide or iodide, triphenylbuvir 7-osnium, bromide, benzylbutyl sulfonium chloride, benzylmethylsulfonium chloride, etc. The use of ammonium compounds is recommended.

The amount of these etherification catalysts used is about 0.25 to about 5 mole percent, preferably about 0.25 to about 5 mole percent, based on the dihydric phenol.
About 5 to &eJ3 mol% is used in the etherification process.

In the etherification step, the reaction is carried out until at least about 50% or more, preferably 80% or more, of the hydroxyl groups of the divalent 7 ether are etherified. Also typically 70 to about 11
The run is carried out at a temperature of 0° C. for about 1 to about 3 hours. It is preferable that water is substantially absent, and it is recommended that the amount of water be 3.0% or less based on the total amount of the reaction system.

The reaction product from the etherification step is directly supplied to the next dehydrohalogenation step, that is, containing unreacted shrimp halohydrin. An alkali compound is used in the dehydrohalogenation step, but the same alkali compound as used in the first method described above can be used, and industrially it is hydroxylated) +7'/
It is preferable to use The value of iB per hydrolyzable helodene of the epoxy resin used in the present invention can be arbitrarily adjusted by adjusting the amount of the alkali compound used. Normally, the amount of alkaline compound used is 7 ether divalent used in the etherification process/-
The amount used is at least 1 times the mole, preferably at least 1.6 times the mole. However, in order to avoid problems such as delification, it is preferred that the molar amount be less than 2 times the mole.The dehydrohalogenation step is usually carried out at a temperature of 60 to about 100°C for about 1 to about 3 hours. Depending on the type of alkaline compound,
For example, when I used sodium hydroxide, the water in the cram school turned into water.
It is recommended to remove this water from the reaction system.

After completion of this dehydrohalogenation step, the epoxy resin used in the present invention is obtained by removing unreacted shrimp halohydrin, removing the generated salt, and drying. Shrimp halohydrin is removed by vacuum distillation, and desalination is removed by washing with water or the like. If necessary, a neutralization step using a weak acid such as phosphoric acid or sodium dihydrogen phosphate is added at an intermediate stage.

When it is desired to further reduce the hydrolyzable halogen content of the obtained epoxy resin, especially when it is desired to increase the iB value per hydrolyzable halogen to approximately io, ooo or more, the second desorption process is performed using the alkali compound described above. This can be achieved by injecting hydrogen halide. This step can be carried out simultaneously with the desalting or as an intermediate step thereafter.

In the present invention, the above-mentioned epoxy resin is mixed with a curing agent and, if necessary, each of 4 to 1 lilj materials, and is used for paint purposes.

As the curing agent, known curing agents used for curing bis-A type epoxy resins, such as polyamines, modified polyamines, poly7V polyamines, modified polyamide polyamines, polycarboxylic acids, acids, etc. Anhydrous substances, etc., 37
Boron tsunide-amine complex, imidazoles,
Any curing agent such as Bis-A liquid epoxy resin can be used, and the selection of these curing agents is appropriately selected depending on the application, as is the case with Bis-A liquid epoxy resin.
The type can be determined from the same viewpoint as liquid Evokin resin. For example, when polyamines are used as a curing agent, the amount to be used can be determined by the ratio of the epoxy equivalent of the epoxy resin used in the present invention to the active water lk equivalent of the polyamine. A curing accelerator may also be used if necessary.

The diluent is epoxy! (Used to reduce the viscosity of mixtures containing fatty acids or oxidizing agents; non-reactive diluents such as 7-talic acid esters, ethers or esters of glycolic acid, 7 ethers, etc.) Reactive diluents such as ren oxide; glycidyl ethers such as butyl glycidyl ether, phenyl glycidyl ether, p-butyl 7-el glycidyl ether, and frenol glycinole ether are exemplified.The use of these diluents is usually Chemicals reduce the strength of the cured epoxy resin, and reactive diluents are harmful to the human body, so it is desirable not to include them, or even if they are used, they should be used in small amounts. However, the epoxy resin used in the present invention has a low viscosity, so it is necessary to include them. There are cases where it is not necessary, and even when it is necessary to incorporate it, only a small amount is required, and therefore the cured product can maintain sufficient strength.

Examples of fillers that can be used include calcium carbonate, clay, asbestos, silica, mica, quartz powder, cement, aluminum powder, gutsphite, titanium oxide, alumina, iron oxide, and tes powder. The type of filler is appropriately selected as in the case of the bis-A liquid epoxy resin.

For the purpose of coloring, coloring agents such as titanium oxide, 7-inch carbon oxide, Toilison red, Hansa yellow, iron oxide powder, 7-cyanine blue, 7-cyanine green, and carbon black may be added.

Further, when the epoxy resin of the present invention is used for paint, additives such as a leveling agent, an antifoaming agent, a pigment dispersant, and an antisettling agent are used in addition to the curing agent.

It is preferable that the m-acid for paint containing these compounding agents has a concentration of about 2,000 CPS or less at room temperature, but if a curing agent of about 200 CPS or less is used, a solvent-free paint can be obtained. . This was not possible with liquid epoxy resin without using a diluent, but with the epoxy resin used in the present invention, it is possible to achieve this without using a diluent that would impair the physical properties of the coating film. A solvent-free paint is obtained.

Additionally, when using a highly viscous curing agent, it is necessary to use a solvent such as xylene, toluene, methyl isobutyl ketone, cellosolve, or alcohol, but compared to using conventional bis A type liquid epoxy resin, hand,
A coating composition with the same viscosity can be obtained using approximately Zf) amount of solvent used.

In addition, the Evokin w resin used in the present invention can be used in combination with a Bis A type liquid Evokin resin or a Bis F type epoxy resin, and even if the epoxy resin used in the present invention has the above formula (■) Although the W# usage differs depending on the type of divalent 7 er/- alcohol, it is also possible to mix and use those with different an values.

The present invention will be explained below with reference to a major gaseous embodiment.

Comparative Example 1 Epichlorohydrin (sometimes abbreviated as ECH) 27
7.5g & 11.1-bis(4-hydroquine 722)
Ethane (sometimes abbreviated as BisAD) 160°5g (
The molar ratio of ECH and bisAD (ECH/bisAD) is 4)
and 0 for BisAD. 0.63 g of choline chloride corresponding to f1 mol % using 11 stirring J/P machines and recirculation TIL equipment! I! The mixture was charged into a fourth glass GI flask, and the reaction was carried out at 90° C. for 4 hours with stirring. While continuing to maintain the temperature at 90°C, add 58.8 g of solid sodium hydroxide (bisAD=
(corresponding to 1.96 mol to 71 R-mol) was added continuously over 90 minutes. At this time, the pressure was reduced to 600 mmHg to remove the generated water from the system, and the azeotropic epichlorohydrin was returned to the system. Even after the addition of sodium hydroxide was completed, water was removed from the system, and after the formation of water was no longer observed, unreacted ECH was distilled out of the system, and the distillation of ECH was almost confirmed. After becoming unable to do so, 5
The mixture was heated to 120° C. under a reduced pressure of m@Hg to completely remove epichlorohydrin.

To the obtained reaction product, xylene 300 [1, water 320,
was added and stirred, the generated common salt was transferred to the aqueous phase, and the aqueous phase was removed after standing.

Next, 4 for the oil phase! aJt% hydroxide) 17umtf
75 g of liquid # was added and stirred at 70° C. for 1 hour to perform the second dehydrochlorination. After oil and water separation, a 3% by weight sodium dihydrogen phosphate aqueous solution 10-1 was added to the oil phase for neutralization, water was subsequently removed by azeotropic distillation, and the oil phase was then treated with 4G
The salt was removed by filtration through a glass filter. The salt-removed oil phase was then heated under reduced pressure (150°C/2 mmH).
g) By completely removing xylene, 198% of epoxy resin was obtained.

Table 1 shows the properties of the obtained epoxy resin.

Incidentally, the viscosity was measured using a B-type viscometer (manufactured by *Kyo#ki Co., Ltd.).

Next L: Curing the epoxy resin used above using EPOMIKoQ-643 (Mitsui Petrochemical Epoxy Co., Ltd., modified polyamine; active hydrogen equivalent: 55) as Jfi (1) Measurement of bending strength and compressive strength according to JIS K69j1 The heat distortion temperature was measured according to AS'l'M D648.The results are shown in Table 1.The compounding ratio of the curing agent and epoxy resin is the ratio of the active hydrogen equivalent of the curing agent and the epoxy resin of the epoxy resin. The same.

Further, curing was performed by heating at 100°C for 2 hours and then further heating at 150°C for 4 hours.

Example 1.2.3.4 Comparative Example 11; The molar ratio of epichlorohydrin to bis-80 (ECH/bis-AD) was 6 (Example 1) and 10 (
Exactly the same operation as in Comparative Example 1 was performed except that the epichlorohydrin used and FTJt were changed to give Examples 2), 12 (Example H3), and 22 (Example 4).

The results are shown in Table 1.

Comparative Example 2 In Example 3, bis(4-human l:
159 g of (ECH/bisphenol) methane (corresponding to an ECH/bisphenol (molar ratio) of 12) was used, and the same operation was performed on the pond used. The results are shown in Table 1.

Comparative Example 3 In Comparative Example 1, 2,2-bis(4-
Hydrodouphenyl)propane 189.5gB: 2c)
! /bisphenol (mole ratio corresponding to 12) was used, but the same operation was performed. The results are shown in Table 1.

Comparative Example 4 Commercially available screw A type epoxy resin
EPOMI K■R-440 (Mitsui Petrochemical Epoxy (
A cured product was obtained by the same operation as in Comparative Example 1 using the same method as in Comparative Example 1, and its physical properties were measured. The results are shown in Table 1.

Comparative Example 5 Reaction with the epoxy I# fat 100 heavy leaf part of Comparative Example 4. ,
An epoxy resin formulation with a viscosity of 3,0OOCPS (25°C) was prepared by mixing with butylglycyl ether It was measured. The results are shown in Table 1. In addition, the properties of Ebikin 41411t in Table 1 of this comparative example
H*EPOM I KoR-140,! - Description of the mixture with butyl glycytyl ether"chjh.

From the results in Table 1 above, it can be seen that the epoxy resin of the present invention has bisA
Mold epoxy! MffI? The viscosity is lower, and the heat distortion temperature and other physical properties of the cured product are equivalent to the Bis A type Evokin resin, and therefore it is clear that it is superior to the Bis F type and Bis A type epoxy resins.

Comparison V45 also shows that when the viscosity of the Bis A type epoxy resin is simply lowered with a reactive diluent, it is inferior to the cured product of the epoxy resin of the present invention.

Comparative Example 6 Publication J, Angew, Cbem, Bd32.
The molar ratio of epichlorohydrin and bisAD (ECH/
An epoxy resin with a crest of O was prepared, i.e., after dissolving a molar part of bisADI in 3 molar parts of epichlorohydrin, 15% by weight of the equivalent amount of epichlorohydrin was prepared.
Sodium hydroxide solution sa was added while keeping the flask temperature at 25°C. Then, the W material in the flask was heated to 25°C for about 10 minutes.
Stir for a minute, then raise the temperature to 52-55°C and
The mixture was stirred for a minute, then the temperature was raised to 85°C, and the mixture was stirred at that temperature for 90 minutes. Then 7? Wash the contents with warm water until neutral, and then add ethyl acetate (50%)
- Extract the resin with a mixed solvent of toluene (25%) - 77 tons (25%), remove water by azeotropic dehydration, and remove the solvent from the solution after filtration to obtain a solid solution. A resin was obtained. The epoxy equivalent weight A of this epixy resin is 2
68, the amount of hydrolyzable chlorine was 0.01 fifi%, the amount of hydrolyzable halogen was ff1Blffi350,000, and AxB-/(A+B) was 268. In addition, the viscosity could be measured in a solid solution state.

As described above, the epixy resins disclosed in conventional known documents are completely different from the epixy resins of the present invention.

Example 5, Comparative Example 7.8 The properties of a cured product obtained by curing the formulation shown in Table 2 under curing conditions of 21° C. for 5 days are shown. In addition, the coating film thickness at the time of measurement of cured physical properties was 100 to 150 JJs.

Claims (1)

[Claims] (1) has a structure substantially represented by general formula (I),
And the epoxy equivalent is A, and the hydrolyzable halogen equivalent is B
, the value displayed as A×B/(A+B) is 1
A curable resin composition for paints containing a liquid epoxy resin having a molecular weight of 70 to 190 as an essential component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In formula (I), X is a divalent residue obtained by removing the hydrogen atom from the hydroxyl group of 1,1-bis(hydroxyphenyl)ethane, and n is This is the number of repeating units. ]