JPS58179273A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating composition having excellent adhesivity and corrosion protecting property, and suitable for the coating of a rusted copper plate or an inadequately undercoated copper plate or aluminum plate, by compounding a specific chelatereactive epoxy resin, an active organic hardener, a bituminous material, etc. CONSTITUTION:The objective composition is prepared by compounding (A) a resin curable with an epoxy resin curing agent derived from (i) an acid of phosphorus having one or more P-OH bonds (e.g. orthophosphoric acid), (ii) an ester (e.g. n-butyl ester) of an acid of phosphorus, (iii) a salt (e.g. potassium salt) of an acid of phosphorus, and (iv) an epoxy resin (preferably the OH group of the phosphoric acid, etc. is 0.05-0.4 equivalent per 1 equivalent of the epoxy group) with (B) an active organic hardener for epoxy resin (e.g. aliphatic polymine) and (C) a bituminous substance (e.g. coal tar) and/or its substitute. EFFECT:An excellent coating film can be obtained even by spontaneous drying drying or forced drying with heat, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an IR coating for preventing metal corrosion. The present invention further relates to corrosion-resistant coatings containing certain medium-rate reactive epoxy resins, active organic curing agents, and bituminous materials and/or substitutes thereof. It has excellent adhesion and corrosion resistance to not only rusted steel plates that are sometimes rust-free, but also rusted steel plates or poorly treated steel plates, galvanized steel plates, Aluminum steel plates, stainless steel, etc. The present invention relates to a composition.

Conventional epoxy resin materials are used as metal preservatives in a wide range of fields because of their excellent corrosion resistance. However, in order to maintain its excellent corrosion resistance, it is necessary to carefully remove the rust on the surface of the steel plate and apply a sufficient amount of surface treatment. If this surface treatment is performed insufficiently, poor adhesion will occur and the corrosion resistance will be significantly reduced.

Therefore, the steel plate surface treatment is simplified or rusted steel plate Kli! Good adhesion even when installed, and excellent corrosion resistance! If Ij11I can be obtained, the benefits are great.

The purpose of the present invention is to provide not only steel plates and derusted steel plates that do not rust easily, but also simplifies the surface treatment of steel plates, and provides strong adhesion even when placed directly on rusted steel plates. An object of the present invention is to provide a coating resin composition having properties and corrosion resistance.

The composition of the present invention comprises as essential components (M) an epoxy resin and at least 1111 P
A resin that can be cured with a curing agent for epoxy resin prepared from a phosphorus acid having a -ON bond, an ester thereof, or a salt thereof (hereinafter abbreviated as precondensate); (Bl active organic curing agent for epoxy resin); , (0)
Contains bituminous substances and/or their substitutes.

Preliminary metals, which are essential components of the composition of the present invention, include epoxy resin, phosphorus, phosphoric acid esters containing hydroxyl groups, or salts thereof, and the presence of a bath agent in a proportion such that epoxy groups remain. It can be obtained by heat treatment in the presence or absence of the substance.

There is no limit to the percentage of heating mu, but it should be such that the epoxy resin does not decompose and the reaction is completed in an appropriate amount of time.
It is best to carry out at 50 to 1 sO<0>C.

As used herein, various compounds such as those having more than 1 substituted or unsubstituted glycidyl ether & represented by the formula in the molecule, such as bisphenol A diglycidyl ether, bisphenol r Diglycidyl ether, phenol novolac,
Epoxy resins, diglycidyl ethers of fullylene oxide adducts of bisphenols, etc. can be used, and there is no limit to the percentage of epoxy, but preferably epoxy 200 to 100 (ll&fJ) is preferred.

Examples of the phosphorus acid having at least one P-OH bond used in the present invention include orthophosphoric acid, memelic acid, birophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, phosphinic acid, etc. Orthophosphoric acid is preferred.

Further, as esters of phosphorus acids, esters of the above-mentioned phosphorus acids, preferably alkyl esters having up to a atomic number of 'a@ degrees (those having a hydroxyl group v1j/IA or more) and hydroxyalkyl esters, examples of which include tkf, , ethyl, n-
Examples include those having 1 such as 7'-ethyl, 2-ethylhexyl, hydroxyethyl, hydroxybutyl, hydroxypropyl, human-oxypentyl, etc. Phosphoric esters are preferred.

In addition, the phosphorus acid salts include the above-mentioned phosphorus acid salts, such as potassium, sodium, lithium, calcium, zinc,
Aluminum, tin, ) (lium group salts are mentioned, especially potassium, sodium or calcium $1 or #!
2 Rinken Hanawa is preferred.

In the reaction between epoxy resin and phosphoric acids, the amount of epoxy groups in 1 epoxy resin B is small, and the hydroxyl group of phosphoric acid is 0.05 ~
The amount of epoxy i in the produced modified epoxy resin (precondensate) is io.

The following should be used.

The oil-based organic curing agent used in the present invention includes:

All curing agents for common epoxy 611M1IIIiI materials can be used, such as mV polyamines, aromatic modified polyamines, aliphatic modified polyamines, boriaides, amine resins, carboxylic acids, etc. can be mentioned.

As the bituminous substance used in the composition of the present invention, coal tar, coal tar pitch, IS cactobacterial, expanded N verticals, asphalt, etc. can be used.

Also, there are various substitutes for bituminous substances, such as aromatic oil resins, etc. Ron Resin 1 Petroleum resins, DOP, DBP, which are generally used as diluents, and other high-boiling point neutral oils such as petroleum-based and stone-based oils can be used. The appropriate blending ratio of the bituminous substance and/or the substitute for the bituminous substance is ~2 times the amount of CO and S relative to the amount of precondensation.

In addition, the composition of the present invention must have 1! According to [4! rI
LiI & catalyst, filler, diluent, dehydrating agent, am, etc. can be added.

The coating composition of the present invention can be obtained by drying naturally, but if it is a coating composition, it can be obtained by heating etc.
Even with one drying, a desirable film formation can be obtained. The present invention can be directly coated on steel plates that are difficult to coat, such as young steel plates with rusted surfaces or simply coated steel plates, to provide high N-density and corrosion resistance.
The present invention has provided a resin composition for use in coatings that can form an IIL film.

The present invention will be described in detail in Example K below.

Note that the different type part is based on kJ11.

Example 1 Bisphenol moodiglycidyl ether (evo nakashima)
@-580) 100 parts and 7 decaglycylol Ell-5
01 (Epoxy amount-ink aS) 20s and orthorin m
d parts and 50 parts of xylene were mixed and reacted at 80°C for 5 hours to obtain a preliminary compound. The 4s synthesis that was prayed for [l
shall be. Precondensate [J) 100% epoxy'! M Polyamide (amine value -340) as fat removing agent
12s and a*tW, solvent, light horizontal steel, blended with 5 as shown in Table 1, rust box steel plate with this compound resin (1Φ steel plate that has been subjected to backwashing and removed floating rust) K* cloth, membrane When the thickness was 150 μm and the material was subjected to a hardening process as shown in Table 1, both adhesion and corrosion resistance were clearly superior to the comparative example.

li! Koji Example 2 Bisphenol Y/diglycidyl ether (epoxy equivalent: -4so) ioog, bisphenol A/p4pyrene oxide adduct diglycidyl ether (epoxy equivalent: -340) 20 parts, monoethyl phosphate 8s, and xylene 50 parts'Ik: The mixture was stirred and reacted at 85° C. for 4 hours to obtain a precondensate. The obtained precondensate is designated as α].

Preliminary 4J! epoxy tree m per 100 parts of l fine compound (4)
Adeka hardener with modified aromatic compound as a hardening agent
-b418 (amine value -280,71! Denka Kogyo Co., Ltd.)
IJ! Product name) 12s, retribution products, yukata, and fillers are listed in Table 1.
Example 1 was prepared using this blended resin.
Create a fill & in the same way as jIkjII8:lIl! As a result of the comparison, as shown in Table 1, the adhesion and
It was excellent in terms of corrosion resistance and wearability.

Central μ Example 3 Phenol Novolanc Novo medium 7 mk (epoxy equivalent -
180) 100ml of bisphenol A diglycidyl ether (epoxy Todoroki (i-550) 100ml, 50ml of xylene, 25s of methyl ethyl ketone, and 50ml of dibasic potassium phosphate were mixed and reacted with stirring at 110°C for 5 hours to form a precondensate. The obtained precondensate vr
Let's call it JD. Per 10 parts of the pre-compound ID, 15 parts of epoxy and modified polyandazoka-donor H-220 (amine value -575, part name manufactured by Asahi Denka Kogyo Co., Ltd.) as a curing agent and a bituminous material, As luck would have it, the light* agent was blended as shown in Table 1, and K was prepared in the same manner as in Example 1 using this blended resin.
As a result of making a molded plate and comparing the performance of the m-film, it was found to be better in terms of adhesion and corrosion resistance than the soft plate, as seen in INIK.

ratio IIR? IJ1 Unmodified bisphenol A diglycidyl ether (epoxy equivalent -58031001iiSK*11, polyamide (amine value -540) 25@ and bituminous material, yukata,
5 as shown in Hikari*Mv Table 1, and this compounded resin was applied to a rust-faced steel plate (a steel plate that had been exposed outdoors for 1 year and had floating rust VT4R), and the K coating percentage thickness was 150μ, and the coating was cured at room temperature for 1 week. The results of the total sex test are shown in Table 1.

Comparative Example 2 To 100,111 unmodified bisphenol y diglycidyl ether (epoxy equivalent -480), 541,125 parts of ADEKA Hardener 11, bituminous material, #I, and filler were blended as shown in Table 1, In the same manner as Comparative Example 1, it was applied to a rusted steel plate to create a coating *V. Coating film properties test result J
Jk is shown in Table 1.

Comparative Example 3 Phenol Novolank Epoxy Tree K (Epoxy Todoroki 1L
-1ap) So part and 50 parts of bisphenol A diglycidyl ether (epoxy Todoroki 1l-550), ADEKA Hardener IM-22026 parts and bituminous material, f
III rope, the filler was mixed in 5 as shown in Table 1, and ratio II
A navigation surface steel plate Kjllk cloth coated plate was prepared in the same manner as in R Example 1. Table 1 shows the total performance test #V results.

Table 1 Example 4 A 61 fat composition having the formulation shown in Table 2 was obtained in the same manner as in Example 1 except that White Cool, a historical material substitute, was used in place of the coal tar in Example 1, and the coating film was A sex purity test was conducted. The results are shown in Table 2.

Ishi JI1 Example 5 A resin composition having the formulation shown in Table 2 was obtained in the same manner as in Example 2, except that white tar was used instead of the coal tar in Sou'IIIA Example 2, and a 70 m membrane test was conducted. Ta. The results are shown in Table 2.

Example 6 Resin composition V having the formulation shown in Table 2 was obtained in the same manner as in Example 5 except that white tar was used instead of coal tar in Example S, and a coating film purity test was conducted. Table 2 shows the results.
Shown below.

Comparative Example 4 A resin composition having the formulation shown in Table 2 was obtained in the same manner as Comparative Example 1 and 1ii1 except that White Cool was used in place of the coal tar in Comparative Example 1, and the 111 performance rudder test was conducted. The results are shown in Table 2.

Comparative Example 5 The same as Comparative Example 2 except that White Cool was used instead of the coal tar in Comparative Example 2. A resin composition having a formulation of 73<< in Table 2 was obtained, and warpage film property purity test 1 was carried out. went. The results are shown in Table 2.

Comparison Example 6 A resin composition compounded with gas as shown in Table 2 was obtained in the same manner as in Comparative Example 5 except that White Cool was used instead of coal tar in Comparative Example 5, and a Sled I11 agricultural performance test was conducted. Table 2 shows the results.
Shown below.

Claims (1)

[Claims] As an essential component (phosphoric acid having at least one IP-OH bond,
a resin curable with an epoxy 11 curing agent obtained from its ester or salt and epoxy*m; fB) an active organic curing agent for epoxy resin; and (CJ
A coating composition containing a bituminous substance and/or its substitute.