JPS63371A - Underwater curing corrosion-resistant material composition - Google Patents

Abstract

PURPOSE:To obtain a corrosion-resistant material having excellent coating workability under water and on wetted surfaces, consisting mainly of a prepolymer obtd. by reacting an epoxy compd. with an unsaturated monocaboxylic acid and an epoxy acrylate resin. CONSTITUTION:An underwater curing corrosion-resistant material compsn. consists mainly of a prepolymer obtd. by reacting an epoxy compd. with an unsaturated monocarboxylic acid and an epoxy acrylate resin composed of a crosslinking vinyl monomer. In addition to the epoxy acrylate resin, the compsn. may contain a bisphenol unsaturated polyester resin consisting of a glycol component composed of at least 50mol% of a glycol having a skeleton of formula I and a dicarboxylic acid component. In the formula, Z is a group of formula I or II; R1 is H or methyl; R2 is H or halogen; and n is a number of 1.05-5.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to an underwater curable anticorrosive material composition. More specifically, the present invention relates to an epoxy acrylate resin-based underwater curable anticorrosion material composition used for corrosion protection in underwater areas, splash zones, and tidal zones of marine structures, port facilities, ships, and the like.

[Conventional technology]

In general, marine structures, port facilities, ships, etc. are exposed to more severe corrosive environments than other structures, so initial corrosion protection and maintenance are important issues.

A, Y ho l-Yukiichi's Lηt-Ba Kataharu Shiga+1shi1pugi II 72Ni ゛Underwater-curable anti-corrosion materials based on engineered boxy resin and unsaturated polyester resin have been put into practical use. .

[Problem that the invention seeks to solve]

However, polyamide epoxy resin-based underwater curing anticorrosive materials have poor wettability and adhesion to steel and concrete, which are the base materials to be coated, in water or on wet surfaces, and have the disadvantage that application workability with spatulas, rollers, etc. is extremely poor. have. Furthermore, corrosion resistance is not sufficient, and
It also poses a problem in terms of pollution prevention as it tends to cause water pollution.

On the other hand, underwater curing anticorrosion materials made of unsaturated polyester resin have excellent underwater painting workability and adhesion to substrates, as shown in the earlier application JP-A-81-4774, but The paint film becomes hard and is prone to cracking due to collisions with objects floating on the sea, and although corrosion resistance is improved compared to epoxy resin-based underwater curing anti-corrosion materials, it is still not sufficient. .

An object of the present invention is to provide an underwater curable anticorrosive material composition that has excellent coating workability underwater and on wet surfaces.

Another object of the present invention is to provide an underwater curing anticorrosive material that is excellent in adhesion between the anticorrosive material and the base material after application, impact resistance that does not cause cracks even under external mechanical impact, and corrosion resistance. The composition is provided.

Yet another object of the present invention is to provide an underwater curable anticorrosive material composition that does not cause water pollution.

Means for Solving Problem C] The underwater curable anticorrosion material composition of the present invention comprises an epoxy acrylate resin made of a prepolymer obtained by reacting an epoxy compound and an unsaturated monocarboxylic acid and a crosslinkable vinyl monomer. This is the generation/minute.

The underwater curable anticorrosion material composition of the present invention contains, in addition to the above-mentioned epoxy acrylate, a hydrogen atom or a methyl group of the primary general formula %, R2 may be the same or different, and R2 may be a hydrogen atom or a halogen, respectively. is an atom, and n is 1.05 to 5. ] The glycol that softens the skeleton is at least 50 mo1 of the total glycol components.
% of a glycol component and a dicarboxylic acid component.

The epoxy acrylate resin, which is the main component of the underwater curable anticorrosion material composition according to the present invention, is prepared by reacting an epoxy compound and an unsaturated monocarboxylic acid using a known method and dissolving the resultant mixture in a crosslinkable vinyl monomer.

Epoxy compounds include mainly bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol type epoxy, halogenated bisphenol A type epoxy, and these epoxy compounds have groups that react with epoxy groups such as Showa dibasic acid. A reaction product with a compound having a terminal epoxy group is preferred. Two or more types of these compounds can be used.

It goes without saying that epoxy compounds other than those exemplified above can also be used.

Acrylic acid is an unsaturated monocarboxylic acid.

Methacrylic acid and crotonic acid are preferably used.

The reaction molar ratio of epoxy group and acid group is epoxy group/acid group:
Preferably 1.2-0.8, more preferably 1.1-0
．． It is 9. An excess of epoxy groups provides better underwater coating workability, but if the molar ratio of epoxy groups/acid groups is 1.2 or more, curing of the final anticorrosive material composition is slow. Furthermore, if the molar ratio of epoxy group/acid group is 0.8 or less, there is a large amount of unsaturated carboxyl residue remaining, which tends to produce a strong bad odor.

The reaction between the epoxy compound and the unsaturated monocarboxylic acid is carried out by a known method. For example, when an epoxy compound and an unsaturated carboxylic acid are mixed in a molar ratio of 1.2 to 0.8 in the presence of a known esterification catalyst at a temperature of 80 to 150"C, the resulting ester has a drunkenness value of about 15 to 0. 2. The reaction time at this time is usually 8 to 15 hours. The 0 reaction is preferably carried out in air.

Examples of crosslinkable vinyl monomers include styrene, vinyltoluene, divinylbenzene, methyl methacrylate, reaction products of glycol and methacrylic acid or acrylic acid, and monocarboxylic acid oligomers. Two or more of these may be used in combination. The amount of crosslinkable vinyl monomer in the epoxy acrylate resin is preferably 20 to 80% by weight.

In this invention, when an epoxy acrylate resin and a bisphenol-based unsaturated polyester resin disclosed in JP-A-4774 are used together, they can be used in any ratio, but the ratio of the unsaturated polyester resin is It is preferable that the total amount is 90% by weight or less.

The underwater curable anticorrosive material composition according to the present invention may contain pigments, aggregates, crosslinkable vinyl heptamer 1 polymerization accelerators, curing agents, etc., as appropriate, which are used in conventional underwater curable anticorrosive materials. Good too.

The pigments and aggregates used have the function of coloring the anticorrosive material composition, and also prevent the coating material from floating due to the difference in specific gravity with water when applied in water, and have a high specific gravity and corrosion resistance. Pigments that are generally used in anticorrosive materials can be used, such as titanium oxide, zinc oxide, iron oxide, aluminum oxide,
Examples include aluminum powder, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, talc, clay, kaolin, mica, graphite, silica, diatomaceous earth, and asbestos. Examples of the aggregate include silica sand, glass flakes, glass rPtla, synthetic fibers, natural or artificial MIO (mica dius iron oxide), and the like. The amount of pigment and aggregate in the total composition is
The volume concentration of the aggregate is preferably 60% or less.

Cobalt naphthenate, cobalt octenoate, copper naphthenate, manganese naphthenate, dimethylaniline, diethylaniline, etc. are used as polymerization accelerators, and the amount added is determined by the amount of the anticorrosive material composition (epoxy acrylate resin, this and bisphenol unsaturated polyester). The amount is preferably 0.1 to 2.0 parts per 100 parts (resin used in combination with resin, or a mixture of these and pigments, aggregates, etc.).

Examples of curing agents include peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, isobutyl methyl ketone peroxide, benzoyl peroxide, E-butyl perbenzoate, t-butyl hydroperoxide, lauryl peroxide, cyclohexanone peroxide, and cumene hydroperoxide. Oxide is used, and the amount added is preferably 0.3 to 3.0 parts per 100 parts of the anticorrosive material composition.

The anticorrosion material composition according to the present invention is usually made of epoxy 7/7
Relateki njisuta 1ji A combination resin of epoxy acrylate resin and bisphenol unsaturated polyester resin is further blended with pigment and aggregate, and a polymerization accelerator and curing agent are added at the time of use. Depending on the situation, it is also possible to add a polymerization accelerator in advance. Furthermore, the blending method,
The order of blending is not particularly limited as long as it can be used.

Furthermore, if desired, a thixotropic agent may be added to this anticorrosive material composition.
It is also possible to add modifiers such as light stabilizers, silane coupling agents, and inhibitors.

The underwater curable anticorrosion material composition according to the present invention can be easily applied to steel materials, concrete, etc. underwater using a spatula, roller, trowel, etc.

〔Effect of the invention〕

The underwater curable anticorrosive material composition according to the present invention has the following advantages over conventional epoxy underwater curable anticorrosive materials.

(1) Good wettability with the substrate to be coated and excellent coating workability.

(2) High electrical resistance film with excellent corrosion resistance.
Ru.

(3) Less water pollution during painting.

It also has the following advantages compared to bisphenol-based unsaturated polyester resin-based underwater curing anticorrosion materials.

(1) It is an electrically high resistance film and has poor corrosion resistance.

(2) It is flexible and has excellent impact resistance.

As mentioned above, the anticorrosion material composition of the present invention has excellent underwater coating workability, and the formed coating film has a large anticorrosion effect over a long period of time and has excellent mechanical strength, so it can be used in port facilities, marine structures, etc. It is suitable as a maintenance material.

〔Example〕

The present invention will be explained in more detail by showing Examples and Comparative Examples below. In Examples and Comparative Examples, all parts are by weight.

In addition, the evaluation method in Examples and Comparative Examples is as follows.

Underwater coating properties: 100% coating surface can be covered with one stroke with a spatula. Δ 100% coating surface can be coated with 2 strokes with a spatula. Δ 3 or more strokes with a spatula. Condition in which 100% of the surface to be coated can be covered by coating × Water pollution property: Condition in which contamination cannot be visually confirmed during underwater painting operation ○ Condition in which contamination can be visually confirmed during underwater painting operation × Adhesion to the surface layer of the paint film A film with Δ uncured film
) Measuring device (CJA-3 type anticorrosion coating tester, manufactured by Shindenshi Kogyo) Appearance: Visually observe the coating after removing biological deposits such as barnacles, and no rust, peeling, blistering, or cracking is observed. Condition: O, acceptable condition: × Impact test: Based on the falling ball test J Is-5400 test (height: 1 m, load: 5 kg), mm indicates the maximum radius of the paint film damage from the center of impact.

Example 1-5 A pigment, an aggregate, a polymerization accelerator, and a curing agent were added to an epoxy acrylate resin made of a prepolymer obtained by reacting the epoxy compound shown in Table 1 with methacrylic acid and styrene as a crosslinkable vinyl monomer. A submersible curable anticorrosion material composition was prepared by blending in the proportions shown in 1.

On the other hand, a 3.2o+m thick copper plate that had been rusted in seawater for one year was polished with a wire brush to St 3 (SIS 05-590).
Using a treated steel plate (according to 0.0) as a base material, the above-mentioned underwater curing anticorrosive material composition was applied to a thickness of about 3 cm in seawater using a spatula, and the underwater coating workability, water pollution resistance and vt 7I
J nh Ill'l OX ,','lu,
p? VITI；lshioshi + thou d seven=+
4 * r + w ``L pickle l''
The state of the coating film in the afternoon was visually observed, and the adhesion between the coated substrate and the cured coating film was determined by an impact test, and the corrosion resistance was determined by the electrical resistance of the coating film. The above results are shown in Table 1.

Example 6-7 The bisphenol A type epoxy acrylate resin of Example 1 and the bisphenol-based unsaturated polyester resin (prepared according to Run No. 2 of JP-A No. 61-4774) were blended in the proportions shown in Table 1. A pigment, an aggregate, a polymerization accelerator, and a curing agent were blended in the proportions shown in Table 1 to prepare an underwater curable anticorrosive material composition. The obtained composition was prepared in Example 1.
It was evaluated in the same way. The results are shown in Table 1.

Comparative Example 1 Table 1 shows the results of the same evaluation as in Example 1 using a double-translated epoxy resin-based underwater curing anticorrosion material.

Comparative Examples 2 and 3 The same bisphenol-based non-corrosive polyester resin used in Example 6 was blended with IrJ diagonal, aggregate 1 polymerization accelerator and curing agent in the proportions shown in Table 1 to produce underwater curing type corrosion protection. It was made into a material composition. The obtained composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(1 procedural amendment) July 25, 1986

Claims (1)

[Claims] 1. An underwater curable anticorrosive material composition whose main component is an epoxy acrylate resin made of a prepolymer obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid and a crosslinkable vinyl monomer. 2. An epoxy acrylate resin consisting of a prepolymer and a crosslinkable vinyl monomer obtained by reacting an epoxy compound and an unsaturated monocarboxylic acid, and the following general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
There are tables etc. ▼, R_1 is a hydrogen atom or a methyl group, R_2 may be the same or different and are each a hydrogen atom or a halogen atom, and n is 1.05 to
It is 5. ] An underwater curable anticorrosion material composition containing as a main component a bisphenol-based unsaturated polyester resin consisting of a glycol component and a dicarboxylic acid component, in which a glycol having a skeleton represented by the formula occupies at least 50 mal% of the total glycol components.