JPS61218620A - Production of acrylic acid and/or methacrylic acid modified epoxy resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having improved stability by a simplified process without requiring removal of a residual catalyst by water washing, by reacting epoxy resin with (meth)acrylic acid in the presence of a metallic complex or anorganic phosphine compound. CONSTITUTION:Epoxy resin is reacted with acrylic acid and/or methacrylic acid in the presence of preferably 1-2wt% (based on epoxy resin) metallic complex (preferably compound containing Al, Ga, Sn, Zr, Zn, Cu, Fe, Ni, Co, Mn, Cr, V, Nb, Mo or In, especially trisacetylacetonatoaluminum) and/or organic phosphine compound (preferably triphenylphosphine), to give the aimed resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing an epoxy resin modified with acrylic acid and/or methacrylic acid, and more specifically.

This invention relates to a method for producing an epoxy resin modified with acrylic acid and/or methacrylic acid using a metal complex and/or an organic phosphine compound as a catalyst.0 [Technical background of the invention and its problems] Conventional acrylic acid and/or methacrylic acid Quaternary ammonium salts or amines are known as catalysts used when producing modified epoxy resins (hereinafter simply referred to as "modified epoxy resins") (Japanese Patent Publication No. 44-19038).
.

However, when these catalysts are used, the remaining catalyst cures the epoxy resin after the reaction is completed, so it is necessary to separate and remove the remaining catalyst from the modified epoxy resin that produced it by washing with water. Ta. Additionally, if the reaction is terminated while unreacted epoxy resin still exists, the unreacted epoxy resin will react further due to the action of the remaining catalyst, so a water washing step was essential. . Furthermore, there were also problems in terms of stability, such as the fact that the finished product was easily molded.

[Purpose of the invention]

By using a metal complex and/or an organic phosphine compound as a catalyst, the present invention eliminates the need for washing with water to separate and remove the modified epoxy resin and catalyst produced after the completion of the first reaction. The object of the present invention is to provide a method for producing a modified epoxy resin that can significantly improve product stability.

[Summary of the invention]

As a result of intensive research to achieve the above object, the present inventors found that when a gold i1 complex and/or an organic phosphine compound is used as a catalyst, the epoxy resin does not harden even if the catalyst remains. discovered that washing with water was unnecessary in order to separate and remove the catalyst from the modified epoxy resin, and completed the present invention. That is, the present invention relates to a method for producing a modified epoxy resin, which involves reacting an epoxy resin with acrylic acid and/or methacrylic acid in the presence of a metal complex and/or an organic phosphine compound.

The epoxy resin used in the present invention is not particularly limited as long as it is generally known as an epoxy resin.

Specific examples include bisphenol Afil.
Epoxy resin; Bisphenol F-type epoxy resin; Phenol-lac type epoxy resin; Alicyclic epoxy resin; Heterocyclic-containing epoxy resin such as triglycituruin cyanurate and hydantoin epoxy; Hydrogenated bisphenol A
type epoxy resin; aliphatic epoxy resin such as propylene glycol-soglycisol ether, be/taerythritol-bolyglycisol ether; aromatic.

Glycytyl ester type epoxy resin obtained by the reaction of aliphatic or alicyclic carboxylic acid and epichlorohydrin; Spiro ring-containing epoxy resin; Glycity ether type which is the reaction product of O-allyl-phenol novolak compound and epichlorohydrin Epoxy resins include glycityl ether type epoxy resins which are reaction products of epichlorohydrin and noaryl bisphenol compounds having an allyl group at the 0-position of each hydroxyl group of bisphenol A.

The metal complexes used in the present invention include aluminum,
A compound containing an element selected from the group consisting of gallium, tin, turconium, copper, iron, nickel, cobalt, manganese, chromium, vanadium, niobium, molybdenum and ion/sodium, e.g. T L, T, CH3
COCH2COCH3゜cF3cocu2cocn3.
CF3COCH2C0CF3. Spider (2COCH2Cc
ca3゜CH3COCH(CH3)COCH3,(CH
3) 2CHCOCH(CH3)2.

Examples thereof include a β-sonoketone complex, a β-ketoester complex, a salibutyraldehyde type complex, an N-nitroxyphenylhydroxylamine complex, and a Schiff ill complex, among which an acetylacetone complex is preferred. Also, these metal complexes.

They may be used alone or in a mixture of two or more.

The organic phosphine compound used in the present invention is represented by the chemical formula (1).

Δ R2-P (Ill Tertiary phosphine compound in which all stars R□ to R3 are organic groups 5 Secondary phosphine compound in which only R3 is hydrogen, df6. Specifically, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, methyl Examples include sophenylphosphine, butylphenylphosphine, sophenylphosphine/, phenylphosphine, octylphosphine, l,21's(sophenylphosphino)ethane, and bis(sophenylphosphino)methane. , organic tertiary phosphine compounds are preferred, and triphenylphosphine is particularly preferred.

In addition, these organic phosphine compounds are
It may be used in a mixed system of i or more.

The epoxy resin used in the present invention, acrylic acid and/or
Or, the ratio of methacrylic acid, whether used alone or in combination, is such that the ratio of the weight of the resin used/the number of moles of epoxy I and acrylic acid and/or methacrylic acid is 1.
:1~x:o, r, preferably l20.7~l:0.
It is 3.

The reaction temperature is above 20'C and below 150°C.

Preferably it is in the range of 90°C to 120°C. At temperatures below 20°C, it is difficult for one reaction to proceed, and at temperatures above 150°C, the reaction becomes turbulent.

The ratio of the metal complex and/or organic phosphine compound used as a catalyst to the epoxy resin is 0 to epoxy resin when used alone or in combination with fc and m.
6005 overlapping%~5 overlapping songs, preferably ii1~2**%
It is. If it is less than 0.005%, one reaction time will be long, and even if it is 5 times or more, the anti-6 rate will not increase beyond a certain value. When the metal complex and the organic phosphine compound are used together, the mixing ratio may be arbitrary as long as it is within the range of the above-mentioned usage ratio.

There is no special method for producing the modified epoxy resin gold of the present invention, and it can be produced by a conventional method under the above-mentioned reaction conditions. A modified epoxy resin can be obtained by stirring and mixing the prescribed amounts of epoxy resin, acrylic acid, and catalyst by an arbitrary method so as to be uniform, and then heating the mixture at 110°C for 8 hours and incubating it. . In this case, all of the Evokiku Jugetsu used may be modified Evoki Jugetsu, or the reaction may be terminated in the presence of unreacted epoxy resin.

The modified epoxy resin obtained by the above reaction is:

It refers to a substance having an acrylic group and/or a methacrylic group and an epoxy group in the same molecule, and it is sufficient that at least one of each of these groups exists in one molecule. The number of groups is not particularly limited.

The modified epoxy resin obtained by the production method of the present invention can be used as a coating material for paper, plastic films, metal plates such as iron, zinc, aluminum, copper, etc., for the purpose of preventing dirt and rust on the surface. be able to.

〔Effect of the invention〕

When producing the modified epoxy pattern fat by the production method of the present invention, there is no need to wash with water to separate and remove the remaining catalyst from the produced modified epoxy resin after the reaction is completed, which simplifies the production process. As a result, the manufacturing cost is reduced and the manufacturing time is shortened, and furthermore, the stability of the finished product is excellent, as is clear from the test examples described later.

[Embodiments of the invention]

Example 1 200y of bisphenol F type epoxy resin Ep807 (manufactured by Shell, epoxy fi1t170) was added with 54% acrylic acid and 4% trisacetylacetonate aluminum.
was added and reacted at 110°C for 10 hours to obtain a modified epoxy resin with an epoxy residual rate of 30%. Examples 2 to 7 The same procedure as in Example 1 was carried out using the composition and conditions shown in the table. A modified epoxy resin was obtained.

Test Examples Products 1 to 7 produced by the production method of the present invention obtained in Examples 1 to 7 and the compositions and conditions shown in the table were used as catalysts.
Using choline chloride, the same procedure as in Example 1 was carried out, and the resulting product was used as a comparative product to test its stability.

Stability was evaluated by putting 10y of each of Products 1 to 7 and the comparative product into test tubes, leaving them in a water bath at 25°C, and determining the period of time until the test tubes became liquid.

[Unity of invention]

As is clear from the table, the product manufactured by the manufacturing method of the present invention had excellent stability and could withstand long-term storage at room temperature.

Claims (1)

[Claims] 1. Acrylic acid and/or methacrylic acid-modified epoxy resin characterized by reacting an epoxy resin with acrylic acid and/or methacrylic acid in the presence of a metal complex and/or an organic phosphine compound. manufacturing method. 2. A patent claim in which the metal complex is a compound containing an element selected from the group consisting of aluminum, gallium, tin, zirconium, zinc, copper, iron, nickel, cobalt, manganese, chromium, vanadium, niobium, molybdenum, and indium. The manufacturing method according to item 1. 3. The manufacturing method according to claims 1 and 2, wherein the metal complex is trisacetylacetonatoaluminum. 4. The manufacturing method according to claim 1, wherein the organic phosphine compound is triphenylphosphine. 5. The manufacturing method according to claim 1, wherein the amount of the metal complex and/or organic phosphine compound used is 1 to 2% by weight based on the weight of the epoxy resin.