JP3517933B2 - Epoxy group-containing polyhydroxypolyether resin and resin composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of paints such as can inner surface paint, zinc rich primer and the like, magnetic tape binder,
Electric appliances such as insulating varnish, self-fusing enamel wire varnish,
The present invention relates to an epoxy group-containing polyhydroxypolyether resin obtained by epoxidizing a hydroxyl group in a thermoplastic polyhydroxypolyether resin used in the electronic field, adhesives and films, and a resin composition thereof.

[0002]

2. Description of the Related Art Thermoplastic polyhydroxypolyether resins have hitherto been known as phenoxy resins and are excellent in flexibility, impact resistance, mechanical properties and the like, and therefore, in the paint field, they are zinc rich against metal supports. Corrosion resistant paint such as primer, can inner surface paint that requires processability, P
CM tape and magnetic tape binder in the electric and electronic fields
It has been used in a wide range of applications such as insulating varnish for electric equipment such as electric motors and motors. However, the conventional polyhydroxypolyether resin has a drawback that the adhesiveness is lowered and the physical properties are lowered in a high temperature and high humidity environment. For example, in the field of paints, when a polyhydroxypolyether resin is used for the purpose of improving the workability in the application of non-repair paint for the end surface of cans such as cans and beverage cans, the resin has almost no epoxy group in one molecule. Since it does not have it, it has poor adhesion to metals and poor reactivity with curing agents such as resole phenolic resins, urea resins and melamine resins, resulting in poor retort adhesion resistance.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an epoxy group-containing polyhydroxypolyether resin having excellent flexibility, impact resistance, mechanical properties and the like, and excellent adhesion even in a high temperature and high humidity environment. And a resin composition thereof.

[0004]

SUMMARY OF THE INVENTION The gist of the present invention is that a hydroxyl group in a thermoplastic polyhydroxypolyether resin is epoxidized, and the hydroxyl group in the thermoplastic polyhydroxypolyether resin is 1-30%
To epoxidize oxirane oxygen to 0.16 to 1.6
% Of the epoxy group-containing polyhydroxypolyether resin, and the epoxy group-containing polyhydroxypolyether resin composition comprising the resin and a curing agent. That is, in the present invention, the adhesion in a high temperature and high humidity environment is improved by epoxidizing the hydroxyl groups in the thermoplastic polyhydroxypolyether resin. The thermoplastic polyhydroxypolyether resin used in the present invention is a direct synthetic method in which a divalent phenol and epihalohydrin are subjected to a condensation reaction to a high molecular weight, or a low molecular weight diepoxy compound and
It is a polyhydroxypolyether resin having a weight-average molecular weight of 20,000 or more and having a self-film forming property, which is obtained by an indirect synthesis method in which a polyhydric phenol is subjected to a polyaddition reaction. When producing a thermoplastic polyhydroxypolyether resin, divalent phenols that can be used include mononuclear divalent phenols having one aromatic nucleus and polynuclears having two or more aromatic nuclei. There are divalent phenols. Examples of mononuclear divalent phenol include resorcinol and 4,6-dichloro-
Resorcinol, hydroquinone, 2-bromohydroquinone, 2,5-ditertiary-butylhydroquinone, dihydroxynaphthalene and the like can be mentioned. Examples of the polynuclear divalent phenol include bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol AD, bisphenol S and tetrabromobisphenol A, 4 Examples thereof include dihydroxybiphenyls such as -4'-dihydroxybiphenyl and dihydroxyphenyl ethers such as bis (4-hydroxyphenyl) ether, and it is possible to use one kind or several kinds of these divalent phenols. it can. Examples of epihalohydrin include epichlorohydrin, epibromhydrin, epiyohydrin and the like. The divalent phenols 1
40 mol of epihalohydrin in a non-reactive solvent in the presence of an alkali metal hydroxide.
At a temperature of 120 ° C., epihalohydrin is consumed, and a condensation reaction is performed so that the weight average molecular weight becomes 20,000 or more, whereby a polyhydroxypolyether resin by a direct synthesis method can be obtained. Further, the polyhydroxypolyether resin prepared by the indirect synthesis method does not react in the presence of a catalyst due to a substantially equimolar reaction between diglycidyl ether, which is a low molecular weight diepoxy compound divalent phenol, and divalent phenol. 50-200 using a reactive high boiling point solvent
It can be obtained by carrying out a polyaddition reaction so that the weight average molecular weight becomes 20,000 or more at ° C.

The epoxy group-containing polyhydroxypolyether resin of the present invention has one of the secondary hydroxyl groups in the resin.
-30% is epoxidized and contains oxirane oxygen in the range of 0.16-1.6%. This is because when the oxirane oxygen content is 0.16% or less, the effect of improving the adhesion, which is the object of the present invention, is not seen, and when it is 1.6% or more, the cured product becomes hard and brittle. The epoxy group-containing polyhydroxypolyether resin of the present invention preferably has a weight average molecular weight of 20,000 or more. 20,000
This is because the thermoplastic properties are not exhibited below, and more preferably 35,000 or more.

To epoxidize the hydroxyl groups in a thermoplastic polyhydroxypolyether resin, the resin is dissolved in an organic solvent, epihalohydrin is added dropwise in the presence of an acidic catalyst to form a halohydrin ether, and then an alkali metal is used. It can be produced by dehydrohalogenating with a hydroxide and epoxidizing. As epihalohydrin, epichlorohydrin, epibromohydrin,
Examples include epi-yohydrin, and epichlorohydrin is preferable. Boron trifluoride as an acidic catalyst
Tellurium complex compound, stannous chloride, tin tetrachloride, zinc chloride,
Lewis acids such as ferric chloride and aluminum chloride, and mixtures thereof can be used. The amount of the catalyst added is preferably in the range of 0.1 to 0.002 mol per mol of epihalohydrin. As the solvent during the reaction, a non-reactive solvent that does not react with epihalohydrin, such as methyl ethyl ketone, cyclohexanone, methylcyclohexanone, dioxane, toluene, xylene, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol- Lumonobutyl ether and the like and mixtures thereof can be used, and the concentration of the reaction product is in the range of 25 parts by weight to 60 parts by weight. The solvent must be selected so that it can be dissolved in the reaction product. After dissolving the polyhydroxypolyether resin in the solvent and adding the catalyst, 0.2 to 20 mol, more preferably 1 to 8 mol of epihalohydrin is added to the resin at 20 to 100 ° C. per 1 mol of the hydroxyl group in the resin. It is added dropwise at a temperature of 20 to 60 minutes and aged for 1 to 4 hours. Next, 1 to 5 mol of alkali metal hydroxide is added to 1 mol of hydrolyzable chlorine in the resin, and 1 to 5 at 20 to 100 ° C.
React for hours. Then, after neutralizing with phosphoric acid, sodium dihydrogen phosphate, or the like, washing with water, dehydration, filtration, and removal of the solvent by distillation, 1 to 30% of the hydroxyl groups are epoxidized, and oxirane oxygen is reduced to 0.16 to An epoxy group-containing polyhydroxypolyether resin containing 1.6% can be obtained.

The epoxy group-containing polyhydroxypolyether resin of the present invention can be variously modified by utilizing the reactivity of the epoxy group. For example, amines, carboxylic acids, isocyanates, phenols and the like can be reacted. Further, it can be made aqueous by neutralizing with an acid after the reaction with amines or neutralizing with a basic compound after the reaction with carboxylic acids.

As the curing agent used in the resin composition of the present invention, aliphatic polyamines, aromatic amines, secondary and tertiary amines, acid anhydrides and polyamide resins generally used as curing agents for epoxy resins are used. , Dicyandiamide, imidazole, urea resin, phenol resin, melamine resin, isocyanate resin, block isocyanate resin and the like. Further, the polyhydroxypolyether resin alone without using a curing agent can be used as a laminating material such as paper or aluminum foil in addition to a coating material, a molding process, an adhesive agent.

The composition of the epoxy group-containing polyhydroxypolyether resin of the present invention thus obtained can be used alone, but is selected from polyurethane resin, polyester resin, epoxy resin, alkyd resin, polyimide resin and the like. One or two or more kinds of the resins described above can be contained in a desired target range. Further, if necessary, a diluent, a dye, a pigment, a filler, a plasticizer and the like can be added. The composition of the present invention is useful as a precoat metal undercoat paint, electric wire coating paint, magnetic paint, can paint, adhesive and the like.

[0010]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, part and% show a weight part and weight%. Example 1 In a flask container equipped with a stirrer, a condenser and a thermometer, YP-50S (manufactured by Tohto Kasei Co .; direct synthesis method polyhydroxypolyether resin; weight average molecular weight = 4)
7,000, oxirane oxygen content = 0.0312%)
Charge 1000 parts and 2333 parts of methyl ethyl ketone,
It heated at 75 degreeC and melt | dissolved uniformly. Next, 20 parts of an ether complex of boron trifluoride was added, heated to 80 ° C., and then 324 parts of epichlorohydrin was added dropwise in 60 minutes. After aging for 2 hours, 56 parts of 10% aqueous sodium hydroxide solution was added and the reaction was carried out for 2 hours. Then, 616 parts of methyl ethyl ketone and 900 parts of ion-exchanged water are added for washing,
Epoxy group-containing polyhydroxypolyether resin containing 0.6750% of oxirane oxygen in which 12.0% of the secondary hydroxyl groups in the phenoxy resin are epoxidized by dehydration and filtration, and then methyl ethyl ketone is distilled off. Got

Example 2 An oxirane in which 6.2% of the secondary hydroxyl groups in the polyhydroxypolyether resin were epoxidized in the same manner as in Example 1 except that 129 parts of epichlorohydrin of Example 1 was used. An epoxy group-containing polyhydroxypolyether resin containing 0.347% oxygen was obtained.

Example 3 30 parts of the epoxy-containing polyhydroxypolyether resin obtained in Example 1 was dissolved in 70 parts of a butyl cellosolve / methylpropyne glycol / solvesso 100 = 1/1/1 weight mixed solvent. , 404 as a curing agent
0 (Hitachi Chemical Co., Ltd. resole phenol resin, resin content 50%) was added in an amount of 15 parts, and orthophosphoric acid as a catalyst was added in an amount of 0.7 part with respect to the resin solid content to obtain a coating material of Example 3.

Example 4 A coating material of Example 4 was obtained in the same manner as in Example 3 except that the epoxy group-containing polyhydroxypolyether resin obtained in Example 2 was used.

Comparative Example 1 A coating material of Comparative Example 1 was obtained in the same manner as in Example 3 except that the polyhydroxypolyether resin YP-50S was used.

Comparative Example 2 As a polyhydroxypolyether resin, YP-50 (manufactured by Tohto Kasei Co., Ltd .; indirect synthesis method; weight average molecular weight 58,000)
0, and the oxirane oxygen content was 0.0432%) to prepare a paint in the same manner as in Example 3 to obtain a paint of Comparative Example 2.

The coating materials obtained in Examples 3 to 4 and Comparative Examples 1 and 2 were evaluated for coating film physical properties by the following methods. Evaluation of physical properties of coating film 1) Conditions for preparing coated plate Material: Phosphoric acid chromate treatment (Alodine 1000 treatment)
Aluminum plate 0.3 × 100 × 200 mm. Dry film thickness: 5 ± 1 μ. Baking condition: 200 ° C. × 10 minutes. 2) Evaluation method-MEK rubbing test The coating film was rubbed with a gauze containing an MEK solvent to perform 100 times as one round trip, and it was visually judged whether or not the base was exposed. ○: No base exposure, × It was evaluated as a base exposure. Adhesion test 100 pieces of 1 mm x 1 mm grid are cut into the coating film with a cutter knife at a depth reaching the substrate, and then a cellophane tape is peeled off momentarily to leave it on the substrate. The number of squares on the grid was visually determined.・ Pressure-cooker-testing machine (Hirayama Seisakusho P
C-364R) temperature 125 ° C. pressure 1.3 kg / cm ²
After 30 minutes of treatment, the appearance and adhesion of the coating film were evaluated. The appearance of the coating film was evaluated as ◯: no change in the coating film, ×: whitening of the coating film. 3) Table 1 shows the evaluation results.

[0017]

[Table 1]

[0018]

As is apparent from the examples, 1 to 30% of the hydroxyl groups in the polyhydroxypolyether resin are epoxidized, and epoxy groups containing oxirane oxygen in the range of 0.16 to 1.6%. Containing polyhydroxypolyether
By using the tell resin, it is possible to improve the adhesion in a high temperature and high humidity environment, which has been a problem with conventional resins.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-57418 (JP, A) JP 63-199724 (JP, A) JP 4-128278 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 59/00-59/72 C08G 65/48

Claims (2)

(57) [Claims] 1. The thermoplastic polyhydroxyl polyether resin is characterized in that 1 to 30% of secondary hydroxyl groups are epoxidized and contain oxirane oxygen in the range of 0.16 to 1.6%. An epoxy group-containing polyhydroxypolyether resin having a weight average molecular weight of 20,000 or more . 2. An epoxy group-containing polyhydroxypolyether resin composition comprising the epoxy group-containing polyhydroxypolyether resin according to claim 1 and a curing agent.