JPS6063261A - Epoxy resin coating material composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting of an oxygen acid of phosphorus having P-OH bonds, a leafing type aluminum pigment and a triphosphorous ester, etc., and having improved leafing property, rust preventing property and metallic feeling, etc., and useful for steel towers, etc. CONSTITUTION:An epoxy resin coating material composition obtained by incorporating (A) a modified resin prepared by reacting (i) an oxygen acid of phosphorus having one or more P-OH bonds, e.g. orthophosphoric acid, or an ester or salt thereof with (ii) an epoxy resin to give 0.05 equivalent, based on one equivalent epoxy groups in the epoxy resin, hydroxyl groups of the phosphoric acid with (B) 0.5-1.0 equivalent, based on the epoxy equivalent of the component (A), curing agent, e.g. diethylenetriamine, (C) 5-100pts.wt., based on 100pts.wt. component (A), leafing type aluminum pigment and (D) 3-100pts.wt. triphosphorous ester, e.g. thioalcohol esters in one or more of ester parts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved coating composition that does not particularly require an undercoat or a topcoat and can be finished in one coat.

In general, leafing type epoxy resin paints containing aluminum pigments are used in a wide variety of applications, including steel towers, bridges, tanks, and vehicles. However, with conventional leafing type aluminum pigment-containing epoxy resin paints, it is not always possible to obtain a paint film with satisfactory leafing properties, and therefore a paint film with an aluminum feel is often not obtained, and weather resistance etc. It was also bad. Furthermore, since it is an epoxy resin paint, special care must be taken in treating the metal surface, and a high degree of surface treatment using blasting pressure such as sandblasting is required.

Therefore, in consideration of rust prevention properties, adhesion, etc., a method has been used in which an epoxy resin-based Zolimer is usually applied, and a leafing type epoxy resin paint containing an aluminum pigment is applied thereon.

In view of the above-mentioned current situation, the present invention has been developed to improve the adhesion properties of aluminum-lamb pigments, to coat a wide range of objects between metal substrates, and to create a leafing-type aluminum paint that can be used as both an undercoat and a topcoat. The object of the present invention is to provide a pigment-containing epoxy resin coating composition.

Such a purpose is to prepare a phosphorus oxyacid having at least one P-OH bond,
This is achieved by a coating composition characterized by comprising a modified resin which is a reaction product of the ester or salt thereof and an epoxy resin, a curing agent, a leafing type aluminum pigment, and a phosphorous acid triester.

Conventionally, paints whose main components are an epoxy resin base component, a curing agent component, and an argonium yeast component have been used in the form of a three-component paint, but with the paint composition of the present invention,
Even if the aluminum paste component is mixed in advance with the main component containing phosphite triester, gluing does not occur, and therefore it is possible to form an A-liquid type paint, so it has good painting workability and is easy to apply. A superimposed layer of aluminum flakes is formed on the film surface, resulting in a coating film with good appearance and excellent weather resistance and rust prevention properties.

Furthermore, as described above, since the paint according to the present invention functions as both an undercoat and a topcoat, it can be used as both an undercoat and a topcoat in one application, and the painting process can be shortened.

The modified resin has an epoxy resin and a P-OH bond,
Oxygen acids of phosphorus, their esters or salts (hereinafter these compounds are referred to as phosphoric acids) are obtained by heat treatment at Sθ to 73θC in a proportion such that epoxy groups remain, and are used as chelates. It has reactivity.

As the resin used here, various resins can be used, such as those having more than one glycidyl ether group in the molecule, and are preferred.
Appropriate values are approximately 5θ to 2/θθ.

Examples of phosphorus oxygen acids having a P-OH bond include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, tinnitus, polyphosphoric acid, phosphonic acid, and phosphinic acid.

Examples of the phosphorus acid ester include alkyl esters of the phosphorus oxygen acid having carbon number/-ff, and salts of lithium, sodium, potassium, calcium, zinc, barium, albanium, tin, and the like.

In the reaction between epoxy resin and phosphoric acids, the hydroxyl group of phosphoric acid is θO5 to θS per niboxy group/equivalent in the epoxy resin.
It is preferable to carry out the reaction in an equivalent ratio, and it is appropriate that the engineering equivalent of the obtained chelate-reactive modified resin is 3θθθ or less. If the epoxy equivalent exceeds 30θ0izr, the viscosity becomes too high and it cannot be used as a paint from the viewpoint of workability, etc., which is not preferable. This modified resin cannot be used.
It is now possible to coat a wider range of objects between metal base treatments,
A coating film with excellent rust prevention and adhesion properties can be obtained.

As the curing agent, a normal curing agent for epoxy resins can be used. For example, aliphatic polyamines such as diethylene triabane and triethylene tetrane, aromatic polyamines such as metaphenylene cyane and diaminodiphenylmethane, and polyamide resins can be used.

The amount of curing agent used is A5 for the modified resin epoxy resin.
A larger reserve of ~lO is appropriate.

As leafing type aluminum pigments, those normally used for this type of paint can be used, but special pigments can be used.
It is best to use a stick-like material whose surface has been treated with stearic acid or the like. For example, Altop (manufactured by Tokai Kinkyusha), Aluminum Base) Sap (manufactured by Showa Al<z9 Uda),
Commercial products such as Alpaste (manufactured by Toyo Aluminum Co., Ltd.), Eterna Bright (manufactured by Silver Line Co., Ltd.), and 5tapa (manufactured by Mukasei Kogyo Co., Ltd.) can be used.

The amount of leafing type aluminum pigment used is
W, 5-io to 10 parts by weight of modified resin.

Part N9 is suitable.

In the present invention, as the phosphite triester, a phosphorous acid dialcohol compound and a phosphite phenyl compound can be typically used.

As the phosphorous acid thioalcohol compound, a phosphorous acid trithioalcohol compound represented by the general formula (%) P-+5-CnH2°-5)3 can be typically used. Note that in the general formula, the n value is an integer of 26 or less. Compounds with an n value exceeding 26 are not preferred because they have poor compatibility with other components.

Further, as a derivative of the above compound, one in which one to two of the thioalcohol groups in the above general formula are replaced with phenol, thiophenol, aliphatic alcohol, polyhydric alcohol such as chiliethylene glycol, or a derivative thereof can be used.

(In the formula, n and n' may be the same or different, and both are integers of 26 or less.) Phosphite esters represented by the following can also be used.

The phenyl phosphite compounds or derivatives thereof include triphenyl phosphite [P+oc6H5)3], tricresyl phosphite [P+oc6+, c+3)3], tricylenyl phosphite [P+0C6H3(CH3)2)3]
], trisnonylphenyl phosphite CP+oc6+, 0
g81g)3], these trinisder phosphites are known compounds per se and are easily available. ! f!
jK In the present invention, phosphorous thioalcohol compounds are preferred from the viewpoint of rust prevention.

The amount of the phosphorous triester used is 3 to 1θ0 parts by weight, particularly preferably 3-2 parts by weight, per 700 parts by weight of the modified resin.
] Parts by weight are appropriate. If the amount of phosphite triester used is less than the above range, the above-mentioned effects cannot be expected, and if the back pressure is too high, the water resistance of the coating film will be extremely poor, so both are not preferred.

In the present invention, by blending the above-mentioned phosphite triester, even if the modified resin base component and the aluminum pigment component are mixed in advance, reaction between them during storage can be prevented, and therefore the modified resin's Chelate reactivity is maintained.Albanium pigments are stable even after long-term storage in paints, and do not easily lose their fusing properties, and do not require the harsh surface treatment required for conventional epoxy resin paints. This is unnecessary, and a coating film with excellent adhesion and yellowing resistance can be obtained.

In the present invention, hydrocarbon solvents which are non-polar solvents such as toluene, xylene, benzene and naphtha are suitable as the I/I agent. In addition, when using polar solvents such as ketone solvents, use aluminum 4-st,
Since the polar solvent reacts with the phosphite triester, it is necessary to mix the polar solvent with the curing agent component, for example, when the main components are mixed in advance and stored for a long period of time.

The amount of solvent used is 70 to 10 parts by weight of the modified resin.
70 parts by weight is suitable. In addition, when using a phosphorous acid triester at a pressure within the above-mentioned range and using a large amount of flK, it is not necessarily necessary to add a solvent.

Further, in the present invention, as described above, a °C rust preventive pigment and an extender pigment can be used if necessary. The amount of these rust preventive pigments and extender pigments to be used is suitably less than θθtit parts per 100M parts of the modified resin.

The present invention will be explained in detail below with reference to Examples. In addition, in the examples, "part" and "%" are shown based on the mold needle.

Example 1 Bisphenol F type epoxy resin (Ebichron Naza 3θ
[Manufactured by Dainippon Ink & Chemicals Co., Ltd.]; Epoxy equivalent/gO)
A modified resin (1) was obtained by condensing 100 parts and g parts of orthophosphoric acid at goC for S hours.

Leafing Taigu Aluminum Paste Pigment (Aluminum Paste 53-//'?C Manufactured by Toyo Aluminum Co., Ltd.) 2
After pre-kneading Part 1, 10 parts of trithiotrilauryl phosphite and Part S of xylene in a disper, the modified resin (50 parts of IL, 3 parts of xylene and 5 parts of anti-sagging agent) were mixed and kneaded in a disper. It was used as the main ingredient.

Separately, modified polyamide resin (ADEKA HARDNER EHX-
/,,? 0.2 [manufactured by Kadenka Kogyo Co., Ltd.]) 30 parts, calcium carbonate 35 parts, mica 23 parts, xylene S part, methyl isobutyl ketone S part, part anti-sagging agent and 1 part suspending agent were mixed in a disper. It was used as a curing agent component.

A paint was prepared by mixing the base component and the curing agent component in a ratio of (/:l).

Example A paint was prepared in the same manner as in Example 1 except that trithiotristearyl phosphite was used in place of trithiotrilauryl phosphite.

Example 3 A paint was prepared in the same manner as in Example 1 except that trithiotricapryl phosphite was used instead of trithiotrilauryl phosphite.

Example q A paint was prepared in the same manner as in Example 1, except that trithiotrilylnylsulfite was used instead of trithiotrilauryl phosphite.

Example S A paint was prepared in the same manner as in Example 1 except that triphenyl phosphite was used instead of trithiotrilauryl phosphite.

Example 6 Bisphenol A epoxy 4iM fat (Ebi Cortna g
21; Manufactured by C Shell Chemical Co., Ltd.]; Engineering number? xy equivalent/qO)7
00 parts and 10 parts of monoethyl phosphate were subjected to a linear combination reaction at 90C for 3 hours to obtain a modified resin (If).

20 parts of leafing type aluminum yeast pigment,
After kneading 10 parts of trithiolauryl phosphite and xylene Hirobe in a disper, the modified resin (
II) 60 parts of xylene, 3 parts of xylene, and 3 parts of anti-sag agent were mixed and kneaded in a dispensing machine to obtain a main component.

Separately, polyamide Azun (Tomide 2S old [Fuji Kasei Kogyo N)], 20 parts, calcium carbonate 33 parts, mica lO part, xylene/, S part, methyl ethyl ketone/3
1 part of the anti-sagging agent, and 1 part of the suspending agent were kneaded in a disc/4'- to prepare a curing agent component.

A paint was prepared by mixing the base agent component and the curing agent component in a ratio of (/:/).

Example A paint was prepared in the same manner as in Example 6 except that tricresol phosphite was used instead of trithiolauryl phosphite.

Example g Bisphenol F type epoxy resin (Ebiclone Naza 30
[Manufactured by Dainippon Ink & Chemicals Co., Ltd.]; Epoxy equivalent 1gθ)
A condensation reaction was carried out with 700 parts of dibasic potassium phosphate and 17 parts of dibasic potassium phosphate at ff/10C for a period of time to obtain a modified resin (I).

After previously kneading 25 parts of Leafing Tisial Miniram Paste, θ part of trithiotrilauryl subsulfite, and S part of xylene in a disper, the modified resin (
1) 30 parts of xylene S part and 3 parts of anti-sagging agent were mixed and kneaded in a disper to obtain a main ingredient.

Separately, modified polyamide resin (ADEKA HARDNER EHX-
43θ (manufactured by Kadenka Kogyo Co., Ltd.)) 2θ, 33 parts of calcium carbonate, 23 parts of mica, S part of xylene, S part of methyl isobutyl ketone, Hirobe anti-sagging agent, and 7 parts of anti-settling agent. - to form a curing agent component.

A paint was prepared by mixing the base agent component and the curing agent component in a ratio of (/:/).

Example 9 General formula (Cl2
H25-8+, POc, compound represented by H25 (J
A paint was prepared in the same manner as in Example g, except that P8.212-DC (manufactured by Johoku Kagaku Kogyo Co., Ltd.) was used.

Comparative Example 1 A paint was prepared in the same manner as in Example 1 except that petroleum resin was used instead of trithiotrilauryl phosphite.

Comparative Example In the main component of Example 1, bisphenol FW compound was used instead of modified resin (1). Kishiresin (Ebikronna G3
Example/ except that θ) (epoxy equivalent 1gθ) is used.
A paint was prepared in the same manner.

Comparative Example 3 Bisphenol F type epoxy resin (Ebiclona g3θ) was used instead of the modified resin (1) in the main component of Example 1.
A paint was prepared in the same manner as in Example 1, except that xylene 1S was used in place of trithiotrilaurylsulfite IO and xylene S.

After storing the base ingredients prepared in Examples 1-9 and Comparative Examples/~3 for a certain period of time, they were mixed with a curing agent component, and this paint was applied to a steel plate with a brush to a dry film thickness of about 100μ,
Leafing property was visually evaluated after air drying for one week. The results are shown in Table 1.

In addition, the paints prepared in Examples/~9 and Comparative Examples 1 to 3 were applied with a brush to a sandblasted iron plate (SIS, Sa 2/3A) and a rusted iron plate (2F4 Keren) so that the dry film thickness was /θ0μ, After air drying for 1 week, the samples were cross-cut and subjected to a salt spray test (1200 hours) and an outdoor exposure test (1 year).The results are shown in Table 2.

Table 1 Judgment Criteria ◎←0-△→× Meta 1 good anti-sensitivity Almost no metallic feel Table 2 ○: 13WR or less The paint had good leafing properties and a good metallic feel even after long-term storage, and also had excellent rust prevention properties.

On the other hand, in Comparative Example 1 and Comparative Example 3, which did not contain phosphite triester, the coating films by system after long-term storage had poor metallic feel and poor anti-freezing properties.

In addition, in Comparative Example 1 using an ordinary unmodified epoxy resin, the metallic feel was good, but the rust prevention property was poor.

Claims (2)

[Claims] (1) A modified resin that is a reaction product of a phosphorus oxygen acid, its ester or salt, and an epoxy resin, which has at least one P-OH bond, a curing agent, a leafing type aluminium pigment, and a triphosphorous acid. A polyurethane resin coating composition comprising an ester. (2) The epoxy resin coating composition according to claim (1), wherein at least seven of the ester moieties in the phosphorous acid triester are thioalcohol esters.