JP3252168B2 - Novel polyether resin and resin paint containing the resin as an essential component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention can provide a cured product (particularly a coating film) having excellent flexibility, adhesion and boiling water resistance by curing with a polyether resin, more specifically a crosslinkable resin. Accordingly, the present invention relates to a polyether resin which can be advantageously used for paint and the like, and a resin paint using the polyether resin.

[0002]

2. Description of the Related Art Epoxy resins have been widely used in the fields of paints, adhesives, civil engineering, electricity, etc. because of their excellent properties. In this case, there was a defect that the flexibility and impact resistance were poor. As means for improving these disadvantages of the epoxy resin, means for improving the flexibility of the epoxy resin itself are known. For example, Japanese Patent Application Laid-Open
Japanese Patent No. 263222 proposes a polyether resin which is a reaction product of an epoxy resin and a specific kind of aliphatic polyhydric alcohol. The degree of improvement is still inadequate. In addition, when a high molecular weight epoxy resin is used to improve flexibility, the viscosity of the resin is increased accordingly, and when a paint is formed, the amount of solvent used increases or a gel is formed during the reaction. There may be cases.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to improve various physical properties, particularly flexibility, adhesion and boiling water resistance, by curing with a crosslinkable resin. An object of the present invention is to provide a polyether resin capable of providing an excellent cured product (particularly, a cured coating film). Another object of the present invention is to provide a resin paint using the same polyether resin.

[0004]

Means for Solving the Problems The present invention provides: 1. The following structural formula (A)

[0005]

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[Wherein -A- is ＝ C (CH ₃ ) ₂ , -C
H ₂ —, —O—, or —S—, and n is O or 1
And an epoxy resin represented by the following structural formula (B):

[0007]

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Wherein -R ₁ is -H or -CH ₃ , and n is an integer of 1-20, and a polyalkylene glycol diglycidyl ether represented by the following structural formula (C): C)

[0009]

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[Wherein -B- is ＝ C (CH ₃ ) ₂ , -C
H ₂ —, —O—, or —S—, and m is O or 1
A dihydric phenol represented by the following formula (A):
An epoxy equivalent of 350 to 10000 g in the presence of a catalyst at a ratio of 5 to 50% by weight of the combined weight of (B) and (C)
/ Eq to the product obtained by the reaction represented by the following general formula (D):

[0011]

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Wherein R ₂ represents an alkyl group having less than 5 carbon atoms, and an alcohol having an epoxy group content of 0.07 me
A polyether resin obtained by reacting in the presence of an etherification catalyst until q / g or less . 2. The polyether resin according to claim 1, wherein the polyalkylene glycol diglycidyl ether (B) is polypropylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether. 3. The polyether resin according to claim 1, wherein the dihydric phenol in the general formula (C) is bisphenol A or bisphenol F. 4. The polyether resin according to claim 1, wherein R ₂ in the general formula (D) is a methyl or ethyl group. 5. The polyether resin according to claim 1, wherein the alcohol of the general formula (D) is 1,1,1-tri (hydroxymethyl) propane. 6. A resin paint containing the polyether resin according to claim 1 and a crosslinkable resin. 7. The resin coating according to claim 6, wherein the crosslinkable resin is one or more selected from an amino resin, a phenol-formaldehyde resin, and a blocked polyisocyanate. About.

[0013]

The raw material epoxy resin for producing the polyether resin of the present invention is a bisphenol type epoxy resin, for example, commercially available Epicoat 806, Epicoat 82
8, one having various molecular weights and various epoxy equivalents such as Epicoat 1001, Epicoat 1004 (all of which are trade names of Yuka Shell Epoxy Co., Ltd.) may be used alone, or two or more may be mixed. You may use it.

The polyalkylene glycol diglycidyl ether used in the production of the polyether resin of the present invention is represented by the general formula (B). For example, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are flexible and impact-resistant. It is preferable in that it is excellent in such properties. Examples of the diglycidyl ether include commercially available products such as Glycier PP-300P (trade name of Sanyo Chemical Industries, Ltd.).

The dihydric phenol used in the production of the polyether resin of the present invention is represented by the general formula (C), and for example, bisphenol A and bisphenol F are preferred. The mixing ratio of the bisphenol-type epoxy resin, the polyalkylene glycol diglycidyl ether and the dihydric phenol is such that the content of the polyalkylene glycol diglycidyl ether is 5 to 50% by weight, preferably 10 to 10% by weight of the total charge.
30% by weight. If the content of the polyalkylene glycol diglycidyl ether is too low, a sufficient improvement effect of the coating properties such as flexibility and boiling water resistance cannot be obtained, and even if the content is too high, the improvement effect commensurate with it is not obtained. No improvement is obtained.

The epoxy equivalent can be adjusted by adjusting the mixing ratio of the dihydric phenol.
It is 10,000 g / eq. When the epoxy equivalent is 350 or less, the physical properties (especially, flexibility) of the coating film are inferior.
If it is 0 or more, the second stage reaction becomes difficult due to high viscosity and tendency to gel.

The catalyst used in the first-stage reaction includes a catalyst generally known in this type of reaction, for example, tetramethylammonium bromide,
Quaternary ammonium salts such as tetrabutylammonium bromide and tetramethylammonium chloride; tertiary amines such as dimethylbenzylamine and trimethylamine; quaternary phosphonium salts such as ethyltriphenylphosphonium iodide and tetraphenylphosphonium chloride are used. You. The amount of the catalyst used is 50 to 1 with respect to the charged amount of the bisphenol type epoxy resin and the polyalkylene glycol diglycidyl ether.
000 ppm, preferably selected from the range of 100 to 600 ppm. The reaction temperature in this reaction is 110 to 2
The temperature is 00 ° C, preferably 130 to 180 ° C.

Next, in the second step for producing the polyether resin of the present invention, an aliphatic resin represented by the general formula (D) is added to the epoxy resin obtained in the first step. React with polyhydric alcohol. R in the general formula (D)
_The alkyl group represented by ₂ is preferably a methyl or ethyl group, and the alcohol is 1,1,1-tri (hydroxymethyl) propane or 1,1,1-tri (hydridoxymethyl) ethane. Particular preference is given to the former alcohol, which melts at 58 ° C. and can act as a solvent for the epoxy resin to be reacted, simplifying the production of polyethers.

As the etherification catalyst used in the second step reaction, amines, Lewis acids (for example, iron,
Alkanone salts of zinc, aluminum and boron, and their halides), and alkali metal alcoholates of polyoxyalkylene polyols. Preferred etherification catalysts are stannous salts, such as stannous dichloride, stannous salts of alkanoic acids (eg, octanoic acid). The amount of the catalyst used is 0.05 to 2.0 with respect to the total charged amount.
% By weight. The reaction temperature is 140-200 ° C,
Preferably it is 160-180 degreeC. If desired, the process according to the invention may comprise a suitable non-reactive solvent, for example toluene,
The reaction can be performed in the presence of xylene, cyclohexanone, ethylbenzene, monochlorobenzene, diethyl ether of ethylene glycol, diethyl ether of diethylene glycol, or the like.

The polyether resin of the present invention can be used in various applications, but is particularly suitable for coatings and, when cured with a crosslinkable resin, has excellent flexibility, adhesion and boiling water resistance. Can be given. Examples of suitable crosslinkable resins are amino resins, urea-formaldehyde resins, phenol-formaldehyde resins and blocked polyisocyanates. In preparing various paints, other epoxy resins can be used in combination, if necessary, and various additives such as various solvents, diluents, pigments, and stabilizers can be added. .

[0021]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples, Test Examples and the like. Example 1 Epicoat 828 (trade name of Yuka Shell Epoxy Co., epoxy equivalent: 186 g / eq) was placed in 11 separable flasks equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
7.0 g polypropylene glycol glycidyl ether (trade name of Sanyo Chemical Co., Ltd., Glycier PP-300)
P) 33.5 g and 114.1 g of bisphenol A were added and dissolved at 100 ° C. in a nitrogen gas stream. Then
0.22 g of tetramethylammonium chloride
(50% aqueous solution) and added at 160-165 ° C. for 5 hours 3
The reaction was performed for 0 minutes (first-stage reaction). The obtained epoxy resin had an epoxy equivalent of 3045 g / eq. Next, after the first-stage reaction, cyclohexanone and further 9.2 g of trimethylolpropane were added and dissolved. Then, 1.72 g of tin octylate was added thereto, and
The reaction was carried out at 175 ° C. for 4 hours (second stage reaction). After completion of the reaction, the resultant was dissolved in a solvent so that the weight ratio of the solid resin component / cyclohexanone / xylene became 40/30/30. The obtained polyether resin had an epoxy group content of 0.07 meq / g and a solution viscosity of Z ₆ ⁺ (Gardner Holtz).

Example 2 In the same manner as used in Example 1, a separable flask was filled with Epicoat 828, 118.0 g and Glycier PP-30.
After adding 0P, 50.0 g and bisphenol A 82.0 g, and dissolving by heating, 0.17 g (50% aqueous solution) of tetramethylammonium chloride was added, and 160 to 165 ° C.
For 5 hours and 30 minutes. The obtained epoxy resin is
The epoxy equivalent was 3553 g / eq. After the completion of the first-stage reaction, cyclohexanone and 5.9 g of trimethylolpropane were added and dissolved. Next, 1.28 g of tin octylate was added thereto and reacted at 170 to 175 ° C for 4 hours. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.05 meq / g and a solution viscosity of Z ₄ ⁺ (Gardner Holtz).

Example 3 In a separable flask, epicoat 828, 96.6 g, glycier PP-300 were used in the same manner as in Example 1.
P, 75.0 g and 78.4 g of bisphenol A were added, and after heating and dissolving, 0.17 g (50% aqueous solution) of tetramethylammonium chloride was added, and the mixture was heated to 160 to 165 ° C
For 5 hours and 30 minutes. The obtained epoxy resin is
The epoxy equivalent was 3089 g / eq. After the completion of the first-stage reaction, cyclohexanone and 6.8 g of trimethylolpropane were added and dissolved. Next, 1.28 g of tin octylate was added thereto and reacted at 170 to 175 ° C for 4 hours. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.04 meq / g and a solution viscosity of X ⁺ (Gardner Holtz).

Example 4 Epicoat 1001 (trade name of Yuka Shell Epoxy Co., Ltd.) was placed in a separable flask in the same manner as in Example 1.
Epoxy equivalent 470 g / eq) 235.0 g, glycier PP-300P, 76.7 g and bisphenol A
After adding 71.8 g and dissolving by heating, 0.31 g (50% aqueous solution) of tetramethylammonium chloride was added, and 1
The reaction was performed at 60 to 165 ° C. The obtained epoxy resin had an epoxy equivalent of 3286 g / eq. After the completion of the first-stage reaction, cyclohexanone and 9.8 g of trimethylolpropane were added and dissolved. Next, 1.97 g of tin octylate was added thereto and reacted at 170 to 175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.06 meq / g and a solution viscosity of Z ₃ ⁺ (Gardner Holtz).

Example 5 Epicoat 1004 (trade name of Yuka Shell Epoxy Co., Ltd.) was placed in a separable flask in the same manner as in Example 1.
229.8 g of epoxy equivalent (919 g / eq), 67.8 g of glycier PP-300P, and bisphenol A
After adding 41.6 g and dissolving by heating, 0.30 g (50% aqueous solution) of tetramethylammonium chloride was added, and 1
The reaction was performed at 60 to 165 ° C. The obtained epoxy resin had an epoxy equivalent of 3417 g / eq. After completion of the first-stage reaction, cyclohexanone and further 8.3 g of trimethylolpropane were added and dissolved. Next, 1.74 g of tin octylate was added thereto and reacted at 170 to 175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The resulting polyether resin had an epoxy group content of 0.07 meq / g and a solution viscosity of Z ₄ (Gardner Holtz).

Example 6 170.0 g of Epicoat 806 (trade name of Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 170 g / eq), 70.5 g of glycier PP-300P were placed in a separable flask in the same manner as in Example 1. And bisphenol A1
After adding 11.9 g and dissolving by heating, 0.24 g (50% aqueous solution) of tetramethylammonium chloride was added, and 1
The reaction was performed at 60 to 165 ° C. The obtained epoxy resin had an epoxy equivalent of 3492 g / eq. After the completion of the first-stage reaction, cyclohexanone and 8.5 g of trimethylolpropane were added and dissolved. Next, 1.80 g of tin octylate was added thereto and reacted at 170 to 175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The resulting polyether resin had an epoxy group content of 0.06 meq / g and a solution viscosity of Z ⁻ (Gardner Holtz).

Example 7 In the same manner as used in Example 1, 130.0 g of Epicoat 806 and Glycier PP-30 were placed in a separable flask.
After adding 56.4 g of TP and 89.5 g of bisphenol F and dissolving by heating, 0.19 g (50% aqueous solution) of tetramethylammonium chloride was added, and the mixture was heated at 160 to 165 ° C.
Was reacted. The obtained epoxy resin had an epoxy equivalent of 3258 g / eq. After the completion of the first-stage reaction, cyclohexanone and 7.0 g of trimethylolpropane were further added.
And dissolved. Then, tin octylate was added to this.
41 g was added and reacted at 170-175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin has an epoxy group content of 0.06.
meq / g and solution viscosity V (Gardner Holtz).

Examples 8 to 17 Each of the resins obtained in Examples 1 to 7 was replaced with a urea resin Euvan 20.
SE60 (trade name of Mitsui Toatsu Chemicals) and weight ratio of 90
/ 10 to give a paint.

Comparative Example 1 This example does not use the component (B) which is an essential component of the present invention. In the same manner as used in Example 1, 275.0 g of Epicoat 1004 and 18.2 g of bisphenol A were put in a separable flask and dissolved by heating, and then 0.17 g of tetramethylammonium chloride (50% aqueous solution)
And reacted at 150 to 155 ° C. for 3 hours and 30 minutes.
The obtained epoxy resin has an epoxy equivalent of 2703 g /
eq. After the completion of the first-stage reaction, cyclohexanone,
Further, 9.1 g of trimethylolpropane was added and dissolved. Next, 0.83 g of stannous chloride dihydrate was added thereto and reacted at 170 to 175 ° C for 4 hours. After the completion of the reaction, the resin was dissolved so that the weight ratio of the solid resin content / cyclohexanone / xylene became 35 / 32.5 / 32.5.
The resulting polyether resin has an epoxy group content of 0.0
The solution viscosity was 8 meq / g and the solution viscosity was Z ₄ ⁺ (Gardner Holtz).

Comparative Example 2 This is an example in which the component (B) is below the range used in the present invention. Epicoat 828, 186.0 g, Glycier PP- was added to a separable flask in the same manner as in Example 1.
300P, 12.2 g and bisphenol A 107.1
g, and after heating and dissolving, add 0.20 g (50% aqueous solution) of tetramethylammonium chloride and add 160-1
The reaction was performed at 65 ° C. The obtained epoxy resin had an epoxy equivalent of 3309 g / eq. After the completion of the first-stage reaction, cyclohexanone and 7.7 g of trimethylolpropane were added and dissolved. Next, 1.57 g of tin octylate was added thereto and reacted at 170 to 175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.08 meq / g and a solution viscosity of Z ₇ ⁻ (Gardner Holtz).

Comparative Example 3 This is an example in which the component (B) exceeds the usage range of the present invention. Epicoat 828, 46.5 g, Glycier PP-3 was placed in a separable flask in the same manner as in Example 1.
00P, 215.6 g and bisphenol A 97.3 g
And heated and dissolved, and 0.26 g (50% aqueous solution) of tetramethylammonium chloride is added thereto.
The reaction was performed at 5 ° C. The obtained epoxy resin had an epoxy equivalent of 3428 g / eq. After the end of the first stage reaction,
7. cyclohexanone, and also trimethylolpropane.
8 g was added and dissolved. Next, 1.84 g of tin octylate was added thereto and reacted at 170 to 175 ° C. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.03 meq / g and a solution viscosity of W ⁻ (Gardner Holtz).

Comparative Example 4 This is an example in which the component (A) is not used. In a separable flask similar to that used in Example 1, glycier PP-300P, 208.6 g and bisphenol A8 were added.
After adding 6.6 g and dissolving by heating, 0.21 g (50% aqueous solution) of tetramethylammonium chloride was added, and 16
The reaction was performed at 0 to 165 ° C for 5 hours and 30 minutes. The obtained epoxy resin had an epoxy equivalent of 4439 g / eq. After the completion of the first-stage reaction, cyclohexanone and 5.6 g of trimethylolpropane were added and dissolved. Then, 1.50 g of tin octylate was added thereto, and 170-1
The reaction was performed at 75 ° C. for 4 hours. After the completion of the reaction, the resultant was dissolved in cyclohexanone / xylene. The obtained polyether resin had an epoxy group content of 0.03 meq / g and a solution viscosity of A or less (Gardner-Holtz).

Comparative Example 5 This example is an example using no component (D). The first-stage reaction was performed under the same blending conditions and reaction conditions as in Example 2. After the reaction is completed, dissolve in cyclohexanone / xylene,
A resin solution was obtained.

Comparative Examples 6 to 10 Each of the resins obtained in Comparative Examples 1 to 5 was used
SE60 (trade name of Mitsui Toatsu Chemicals) and weight ratio of 90
/ 10 to give a paint.

Test Example 1 The paints obtained in the above Examples 8 to 14 and Comparative Examples 6 to 10 were applied to a tin plate using a bar coater so that the film thickness would be 5 to 10 μm. Bake at C for 10 minutes. Each of the obtained baked coating films was tested for pencil hardness, flexibility, adhesion, and boiling water resistance. The results were as shown in Table 1.

[0036]

[Table 1]

The resin of Comparative Example 4 did not completely cure, and did not form a cured coating film. The test method and evaluation criteria for each test were as follows. i) Pencil hardness According to JIS K5400. ii) Flexibility After leaving the coated plate in a constant temperature and humidity chamber at −30 ° C. for about 1 hour, it is folded in ^two , pressed at 40 to 50 kg / cm ² , and pressed at 5%
After immersion in an aqueous solution of copper sulfate for 1 minute, the degree of cracking of the coating film is checked. iii) Adhesion According to a cross cut tape peel test. iv) Boiling water test After immersion in boiling water for 10 hours, whitening was visually observed.
For the adhesion, a cross cut tape peel test is performed. Evaluation criteria ◎ …… Very good ○ …… Excellent △ …… Normal × …… Poor

[0038]

The cured coating film of the polyether resin of the present invention is excellent in flexibility, adhesion and boiling water resistance.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 171/10 C09D 171/10 175/08 175/08 (56) References JP-A-4-36307 (JP, A) JP-A-4-36307 62-263222 (JP, A) JP-A-62-195019 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 65/00-65/48

Claims (7)

(57) [Claims] 1. The following structural formula (A): Structural formula (A) [Wherein -A- is （C (CH ₃ ) ₂ , -CH _2- , -O
-Or -S- and n are O or an integer of 1 to 14], and the following structural formula (B): [Wherein -R ₁ is -H or -CH ₃ , and n is 1 to
A polyalkylene glycol diglycidyl ether represented by the following structural formula (C): [Wherein -B- is ＝ C (CH ₃ ) ₂ , -CH _2- , -O
-, Or -S-, and m is O or an integer of 1 to 5], wherein the content of (B) is (A)
An epoxy equivalent of 350 to 10000 g in the presence of a catalyst at a ratio of 5 to 50% by weight of the combined weight of (B) and (C)
/ Eq to the product obtained by the following general formula (D): [Wherein R ₂ represents an alkyl group having less than 5 carbon atoms] and an alcohol having an epoxy group content of 0.07 me
A polyether resin obtained by reacting in the presence of an etherification catalyst until q / g or less . 2. The polyether resin according to claim 1, wherein the polyalkylene glycol diglycidyl ether (B) is polypropylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether. 3. The dihydric phenol in the general formula (C) is bisphenol A or bisphenol F.
The polyether resin according to the above. 4. The polyether resin according to claim 1, wherein R ₂ in the general formula (D) is a methyl or ethyl group. 5. The method according to claim 1, wherein the alcohol of the general formula (D) is 1,1,1
The polyether resin according to claim 1, which is -tri (hydroxymethyl) propane. 6. A resin paint containing the polyether resin according to claim 1 and a crosslinkable resin. 7. The crosslinkable resin is an amino resin, phenol-
The resin paint according to claim 6, wherein the resin paint is one or more selected from a formaldehyde resin and a blocked polyisocyanate.