JPH09263713A - Anticorrosive coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anticorrosive coating compsn. which contains a curable resin and a petroleum resin well compatible with each other, does not cause problems with safety and hygiene, and can form a light-colored coating film excellent in anticorrosive properties, water resistance, and adhesive properties by compounding an epoxy resin, an amine-base curative, and a specified amt. of a hydroxylated petroleum resin. SOLUTION: This composn. comprises an epoxy resin pref. having at least two epoxy groups in the molecule and an epoxy equivalent of 150-600 (e.g. a bisphenol epoxy rein), an amine-based epoxy resin curative (e.g. m- xylendiamine) in an equivalent ratio of active hydrogen of this curative to epoxy group of the resin of 0.5-1.0, and a hydroxylated petroleum resin which is solid at nomad temp., has a softening point of 50-150 deg.C, has 1-2 hydroxyl groups per molecule, and is contained in an amt. of 20-500 pts.wt. based on 100 pts.wt. curable resin solid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tar-free anticorrosive coating composition which is particularly useful for coating the interior of ships such as ballast tanks.

[0002]

2. Description of the Related Art Tall epoxy paints have been used as anticorrosion paints for ships and steel structures. The paint is excellent in corrosion resistance, water resistance, chemical resistance, etc., but since it contains tar, not only is it concerned about safety and health problems, but it is black and difficult to maintain. There was a problem that work was dangerous because it became dark in a closed place.

In recent years, non-tall paints using petroleum-based resins instead of tars have been developed.
There is a problem with the compatibility of the cured resin consisting of the epoxy resin and the amine curing agent with the petroleum-based resin, and particularly high corrosion resistance,
It was not enough to apply it in the ballast tank of a ship that requires water resistance.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that an epoxy resin and an amine curing agent are formed by using a specific amount of a hydroxyl group-containing petroleum resin instead of tar. The compatibility of the cured resin and petroleum resin is significantly improved, and there is no problem in terms of safety and hygiene, and it is possible to obtain an anticorrosion coating composition that is excellent in corrosion resistance, water resistance, and adhesion and that can form a light-colored coating film. And has reached the present invention.

That is, the present invention relates to (A) epoxy resin,
An anticorrosion comprising (B) an amine-based curing agent and (C) a hydroxyl group-containing petroleum resin, and containing the hydroxyl group-containing petroleum resin (C) in an amount of 20 to 500 parts by weight based on 100 parts by weight of the resin solid content. A coating composition is provided.

Hereinafter, the present invention will be described in detail.

Epoxy resin (A) used in the present invention
Is one having at least two epoxy groups in one molecule, and an epoxy equivalent of 150 to 600, preferably 130 to 300 is suitable. Examples of such epoxy resin include bisphenol type epoxy resin, aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin. Examples include conventionally known resins such as resins, and these may be used alone or in combination of two or more.

As the amine curing agent (B) used in the present invention, conventionally known curing agents for epoxy resins can be used.
For example, metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, and other aliphatic polyamines, alicyclic polyamines, aromatic polyamines; epoxy resin adducts of these polyamines, polyamide amines, polyamide resins, etc. Can be mentioned. These can be used alone or in combination of two or more.

The mixing ratio of the above components (A) and (B) is
Although it is appropriately selected depending on the species used, it is usual that the equivalent ratio of [active hydrogen equivalent in (B) / epoxy equivalent in (A)] is in the range of 0.5 to 1.0. Appropriate.

The hydroxyl group-containing petroleum resin (C) used in the present invention is a petroleum resin which contains hydroxyl groups and is solid at room temperature and has a softening point of 50 to 150 ° C., preferably 80.
Those having a temperature of up to 100 ° C can be preferably used.

The petroleum resin is, for example, an aromatic petroleum resin obtained by polymerizing a C ₉ fraction such as a styrene derivative or indene from a heavy oil by-produced by the decomposition of petroleum naphtha, the C ₅ fraction and the C ₉ fraction. Copolymerized petroleum resin obtained by copolymerizing distillates, cyclopentadiene, 1,3-pentadiene, etc. C ₅ fraction conjugated diene cycloaliphatic polymerized aliphatic petroleum resin, aromatic petroleum resin hydrogen Examples thereof include added resins and alicyclic petroleum resins obtained by polymerizing dicyclopentadiene, and hydroxyl groups are introduced into these. Of these, a hydroxyl group-containing aromatic petroleum resin is particularly preferable from the viewpoint of water resistance.

The content of the hydroxyl group in the resin (C) is 1 to 2 mol, preferably 1 to 1.5 mol per molecule of petroleum resin. If the content is less than 1 mol per molecule, the compatibility with the amine curing agent will be deteriorated and the coating performance will be adversely affected, while if it exceeds 2 mol, the water resistance will be deteriorated, which is not desirable. The softening point of the resin (C) is 5
If the temperature is lower than 0 ° C, the water resistance of the coating film may be deteriorated and the components may be bleeded on the surface of the coating film to leave tackiness.
If it exceeds the range, the viscosity of the coating composition is increased, the workability is deteriorated, and the physical properties of the coating film are deteriorated.

In the composition of the present invention, the above hydroxyl group-containing petroleum resin (C) is added in an amount of 20 to 5 with respect to 100 parts by weight of the solid content of the cured resin.
00 parts by weight, preferably 50 to 300 parts by weight.
If the content is less than 20 parts by weight, sufficient water resistance cannot be obtained, while if it exceeds 500 parts by weight, the coating film becomes brittle and good physical properties cannot be obtained, which is not preferable.

In the composition of the present invention, from the viewpoint of imparting flexibility, other liquid modifiers such as xylene resin and toluene resin; reactive diluents such as butylglycidyl ether and other epoxy compounds; A non-reactive diluent such as a modified polycondensate may be added in an amount of 50 parts by weight or less based on 100 parts by weight of the solid content of the cured resin. Of these, aromatic compounds are preferably used from the viewpoint of maintaining water resistance.

In the composition of the present invention, if necessary, pigments such as extender pigments, rust preventive pigments and coloring pigments; reactive diluents; organic solvents, anti-settling agents, anti-sagging agents, wetting agents,
Ordinary paint additives such as a reaction accelerator, an adhesion promoter, and a dehydrating agent may be appropriately contained.

The composition of the present invention is a two-pack type coating composition comprising an epoxy resin-based main agent and an amine-based curing agent, and is usually applied on a primary anticorrosive coating film such as a zinc primer. As a method for applying the paint, conventionally known methods such as an air spray, an airless spray, a brush coating, and a roller can be adopted, and the paint can be applied so as to have a dry film thickness of 150 to 500 μm. .

[0017]

EXAMPLES The present invention will be described in more detail with reference to examples. “Parts” and “%” are “parts by weight” respectively.
And "% by weight".

Example 1 100 parts of epoxy resin (Note 1), 70 parts of titanium white, 100 parts of talc, 50 parts of hydroxyl group-containing petroleum resin (Note 2), 20 parts of xylene resin (Note 3), and sag in a 1-liter container. Add 10 parts of a stopper (Note 4) and 10 parts of xylene, mix and stir in a disperser to disperse the main agent, and add 70 parts of an amine curing agent (Note 5) immediately before coating and mix and stir. I got an anticorrosion paint.

(Note 1) "Epon # 828": Epoxy equivalent 190, manufactured by Yuka Shell Epoxy Co., Ltd. (Note 2) "Neopolymer-K-2": divinyltoluene having a hydroxyl group content of 1 to 1.1 mol in one molecule. -Indene copolymer, softening point 100 ° C, manufactured by Nippon Petrochemical Co., Ltd. (Note 3) "Nicanol L": Mitsubishi Gas Chemical Co., Ltd. (Note 4) "Disparlon A630-20XN": Polyamide wax, Kusumoto Chemicals (Note 5) "Sunmide CX102": phenalkamine,
Active hydrogen equivalent 130, manufactured by Sanwa Chemical Co., Ltd. Examples 2 to 6 and Comparative Examples 1 to 5 In Example 1, each anticorrosion paint was prepared in the same manner as in Example 1 except that the composition and blending amount shown in Table 1 were used. Obtained. (Note 6) to (Note 9) in Table 1 are as follows. As Comparative Example 5, "Epocal 6000PS" (Tales epoxy resin paint manufactured by Kansai Paint Co., Ltd.) was used. Table 1 shows the solid content.

(Note 6) "Epon # 1001": Epoxy equivalent 475, manufactured by Yuka Shell Epoxy Co., Ltd. (Note 7) "Neopolymer-100": aromatic petroleum resin (without hydroxyl group), softening point 100 ° C, Nippon Oil Co., Ltd. Chemical company (Note 8) "Neopolymer-140": Aromatic petroleum resin (no hydroxyl group), softening point 150 ° C, Nippon Petrochemical Co., Ltd. (Note 9) "Daito Clar X778C": Mannich modified metaxylene diamine, Performance test with active hydrogen equivalent 70, Daito Sangyo Co., Ltd. Each anticorrosion paint obtained as described above was subjected to the following performance test. The results are shown in Table 1. (* 1) Flexibility Polished mild steel plate (150 x 70 x
0.8 mm) was coated with an airless sprayer to a thickness of about 250 μm (dry film thickness) and dried in an atmosphere of 20 ° C. × 65% RH for 7 days to prepare each test coated plate. The coated plate was bent at 90 ° with the coated surface facing outward in an atmosphere of 20 ° C, and cracks in the coating film at the bent portion were visually evaluated (○: no crack, Δ: slightly cracked, ×: considerably cracked. ).

(* 2) Temperature Difference Water Resistance Shot Blast Steel Sheet (300 × 100 × 3.2 mm)
(Test plate I), and "SD zinc 1000" on the steel plate
Each of the anticorrosive paints obtained above was coated on (Test plate II) which was coated with (Siliketo zinc primer manufactured by Kansai Paint Co., Ltd.) to a thickness of about 25 μm (dry film thickness) and dried for one day. Each test coated plate was obtained by coating with an airless sprayer to a thickness of about 250 μm (dry film thickness) and drying for 7 days in an atmosphere of 20 ° C. × 65% RH.

After dipping for 14 days in a dipping bath in which the coated surface of the coated plate was in contact with warm water of 40 ° C. and the back surface was in contact with water of 20 ° C., the coated surface condition was visually evaluated (◯: no abnormality, Δ) : Slight blistering and rusting are observed, ×: Blistering rusting is remarkable).

(* 3) Seawater resistance Each test coated plate obtained in the same manner as in (* 2) above was visually evaluated for coating surface condition after immersion in seawater at 50 ° C. for 3 months (◯: no abnormality) , △: A little blistering was observed,
X: significant blistering occurs).

[0024]

INDUSTRIAL APPLICABILITY The anticorrosion coating composition of the present invention uses a specific amount of a hydroxyl group-containing petroleum resin instead of tar, so that the compatibility between the cured resin comprising the epoxy resin and the amine curing agent and the petroleum resin is good. In addition, it is excellent in corrosion resistance, water resistance, and adhesion without any problems in safety and hygiene, and can form a light-colored coating film, and is very useful as an anticorrosion paint for ships and steel structures.

[0025]

[Table 1]

Claims (2)

[Claims] 1. A composition comprising (A) an epoxy resin, (B) an amine-based curing agent, and (C) a hydroxyl group-containing petroleum resin, wherein the hydroxyl group-containing petroleum resin (C) is used in an amount of 20 parts by weight per 100 parts by weight of the cured resin solid content. The anticorrosive coating composition is contained in an amount of up to 500 parts by weight. 2. The composition according to claim 1, wherein the hydroxyl group-containing petroleum resin (C) is a petroleum resin containing 1 to 2 moles of hydroxyl groups in one molecule and has a softening point of 50 to 150 ° C.