JPS5910738B2 - polyhydroxy polyether - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to substantially linear polyhydroxy polyethers.

Conventionally, the following formula +~()I? derived from bisphenol A is used.
) ~ (However, q = 80 to 160) A substantially linear polyhydroxy polyether having a repeating structural unit represented by the following formulas has excellent adhesion to the substrate, chemical resistance, salt spray resistance, and moisture resistance. resistance, impact resistance, abrasion resistance,
Because of its excellent flexibility, gloss, and overbake resistance, it is used as a coating resin component for metal coatings, metal primers, and lacquers for wood and metal substrates.

It is also useful for hard or soft food packaging containers because of its excellent oxygen barrier properties, heat sealability, stain resistance, tasteless and odorless properties, and low temperature properties.

Furthermore, the polyhydroxy polyether represented by formula [I] has many hydroxyl groups.
'A77 [ ] also has the property of being crosslinkable with polyisocyanates, melamine formaldehyde resins, phenol formaldehyde resins, urea formaldehyde resins, etc., making it extremely useful in a wide range of applications.

Specific uses of the polyhydroxy polyether include clear metal coatings, magnetic tapes, primers for metals, decorative coatings for metals, clear coatings for wood, and flexible substrates such as cellophane and aluminum foil. , cardboard, kraft paper, gear; canvas cloth, phenolic resin impregnated paper, glass fiber cloth or polyethylene terephthalate,
Coating or laminating of molded products such as polystyrene, polycarbonate or polymethyl methacrylate, coating of food packaging supplies,
These include laminating or adhesive agents, varnishes for electric wires, and modifiers for various resins such as epoxy resins, phenol resins, and polyester resins.

However, in recent years, when applied to each of these fields, the required performance has become particularly sophisticated, and further drastic improvements in performance have been desired.

In view of the above circumstances, the present inventors have made extensive studies to improve the basic properties of the polyhydroxy polyether represented by the formula [1], which is suitable for a wide range of uses.
By replacing a part of the bisphenol A skeleton with resorcinol in the main chain structure of polyhydroxy polyether represented by They discovered that basic physical properties could be greatly improved and completed the present invention.

That is, the present invention uses the formula (where N and n' represent positive numbers, and 35≦n+n'≦400.

), and the object of the present invention is to provide coating laminates, adhesives, films,
We provide polyhydroxy polyethers that are suitable for a wide range of applications such as fibers and molding materials, and have excellent basic properties such as adhesion to substrates, chemical resistance, salt spray resistance, and impact resistance. The present invention also aims to provide a polyhydroxy polyether that can be used as a modifier for various resins such as epoxy resins, phenolic resins, and polyester resins.

The polyhydroxy polyether of the present invention having repeating units of the above formula includes any of random, block and alternating copolymers.

The polyhydroxypolyether of the present invention can be produced by reacting a mixture of resorcin and bisphenol A with epihalohydrin in the presence of a catalyst, or by reacting a diepoxide obtained by reacting resorcin and epihalohydrin with bisphenol A in the presence of a catalyst. Alternatively, it can be produced by reacting diepoxy obtained by reacting bisphenol A and epihalohydrin with resorcinol in the presence of a catalyst. In the present invention, the amount of resorcin used is at least 1 weight e, based on polyhydroxypolyether.
Preferably it is 5% by weight or more.

As the epihalohydrin used in the production of the polyhydroxypolyether of the present invention, epichlorohydrin is the most industrially advantageous, and the amount used is substantially equivalent to the sum of the moles of resorcinol and bisphenol A, and usually 0. The amount ranges from 98 mol to 1.02 mol.

Similarly, when diepoxide is used, the epoxy group and the phenolic hydroxyl group of resorcinol or bisphenol A are substantially equimolar, usually 0.9
The amount is 8 mol to 0.02 mol. The above reaction between resorcinol and bisphenol A and epihalohydrin, or between diepoxide and resorcinol or bisphenol A, is carried out in the presence of a catalyst such as an alkali metal hydroxide, an alkali metal halide, tertiary amines, or quaternary ammonium salt. This can be carried out without using a solvent or with a ketone such as methyl ethyl ketone, or an organic solvent such as dioxane or dimethylformamide.

The polyhydroxypolyether of the present invention exhibits its improved properties even though its molecular weight is lower than that of conventional polyhydroxypolyethers derived from bisphenol A, but it also exhibits a higher degree of improvement effect. In order to obtain
It is necessary that it is above.

That is, if the number of repeating units is less than 35, a sufficient improvement effect cannot be expected. On the other hand, if the number of repeating units exceeds 400, it is disadvantageous in terms of manufacturing or operation. Therefore, in the present invention, the number of repeating units must be 35 to 400, and this number of repeating units can be easily controlled by changing the reaction temperature, reaction time, etc. The polyhydroxypolyether thus obtained is put to practical use as a resin composition according to the usual methods known to those skilled in the art depending on the various uses mentioned above, but if necessary, it can be derived from bisphenol A or other polynuclear dihydric phenols. Modification methods for polyhydroxypolyether compounds include crosslinking with already known polyisocyanates, melamine formaldehyde resins, phenol formaldehyde resins, urea formaldehyde resins, etc., modification with carboxylic acids as seen in Japanese Patent Publication No. 49-1449, or Depending on the application, it can be modified using various modification methods, such as a modification method that improves flexibility by adding a lower molecular weight polyfunctional hydroxyl reactive modifier, as seen in No. 40-6990. can.

Next, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

In the text, parts represent parts by weight unless otherwise specified. Example 1 In a flask equipped with a condenser, 131.1 g of diglycidyl ether of bisphenol A (epoxy equivalent: 1879/E9, Sumiepoxy ELA-128, Sumitomo Chemical Co., Ltd.) was added.
part, and 38.6 parts of resorcinol, 1 part of methyl ethyl ketone.
69.7 parts and 5 parts by volume of a 5N aqueous sodium hydroxide solution were charged and reacted at reflux temperature for 24 hours.

The obtained resin liquid was subjected to the same post-treatment as in Example 1, and the molecular weight was 3.
5000 powdered polyhydroxy ethers were obtained (approximately 135 repeating units). This is designated as sample A. Example 2 In an apparatus similar to Example 1, a solid epoxy from bisphenol A and epichlorohydrin (epoxy equivalent weight 481 g) was added.
/Eg, Sumiepoxy ESA-011, Sumitomo Chemical product)
289 parts, 33 parts of resorcinol, 3 parts of methyl ethyl ketone
Prepare 22 parts and 8 parts by volume of a 5N aqueous solution of caustic soda,
The reaction was carried out at reflux temperature for 22 hours.

The obtained polyhydroxyether had a molecular weight of 30,000 (number of repeating units: about 120). This is called sample B.
Comparative Example 1 Sumiepoxy ELA-1281 was added to the same equipment as in Example 1.
12.4 parts, bisphenol A 68.4 parts, methyl ethyl ketone 180.8 parts, 5N caustic soda aqueous solution 4.
5 parts by volume were charged and reacted at reflux temperature for 20 hours.

The obtained resin liquid was subjected to the same post-treatment as in Example 1, and the molecular weight was 3.
A polyhydroxy polyether of 8000 was obtained (approximately 135 repeating units). This is designated as sample C. Comparative Example 2 The same procedure as in Example 1 was carried out except that the reaction time was changed to 8 hours to obtain a powdered polyhydroxy polyether having a molecular weight of 7000.

(Number of repeat units is approximately 30). This will be referred to as trial 1S1D. Measurement results of various physical properties of each sample obtained in the above Examples and Comparative Examples and Bakelite phenoxy resin PKHH (this will be referred to as Sample E), which is a polyhydroxy polyether made from Union Carbide's bisphenol A. is as shown below.

1. Solution viscosity and coloration Ethylene glycol monomethyl ether solution of each sample [
The viscosity and degree of coloration of resin concentration (solid content) 25% by weight were as shown in the following table.

2. The molecular weights determined by gel permeation chromatography were as shown in the table below.

(All molecular weights are expressed in terms of polystyrene)3
．． Resorcin content The resorcin content was determined by hydrogen nuclear magnetic resonance spectroscopy as follows.

Reference examples Samples A and B obtained in the above examples, Samples C and D obtained in comparative examples
and Sample E were each dissolved in ethylene glycol monomethyl ether, and the same amount of titanium oxide as the resin was added to form a paint.

This coating solution was applied to a steel plate, dried, and the physical properties of the coating film were evaluated. The paint formulation is as follows: The above formulation is sufficiently shaken with glass beads to form a paint, and then applied to a steel plate with a thickness of 0.8 and 0.4 mm using a percoater, and air-dried after application.
It was force-dried at 0° C. for 60 minutes and used as a test piece for evaluating the physical properties of the coating film.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, ¥n¥, n' represent a positive number, and 35≦n+n
'≦400). A polyhydroxy polyether having a repeating structural unit represented by: