KR100269565B1 - Anticorrisive coating composition - Google Patents

Abstract

The present invention comprises (A) an epoxy resin, (B) an amine curing agent and (C) a hydroxyl group-containing petroleum resin or a decomposed residual oil at a softening point of 50 to 150 ° C., preferably an additional modifier (D), wherein the epoxy resin (A And 20 to 500 parts by weight of the component (C), based on l00 parts by weight of the cured resin solid content consisting of the amine curing agent (B).

Description

Anticorrosive coating composition {ANTICORRISIVE COATING COMPOSITION}

Conventionally, tar epoxy paint has been used as an anticorrosive paint for ships and steel structures. The paint is excellent in corrosion resistance, water resistance, chemical resistance, etc., but because it contains tar, not only the safety and hygiene problems caused by the carcinogenic substance benzopyrene contained in this tar, but also because of the black maintenance It was difficult to do so it became dark in a closed place, so there was inadequacy such as carrying a risk on the work.

Recently, non-tar paints using petroleum resins in place of tars have also been developed. However, since the paints have problems in compatibility between epoxy resins, amine-based curing agents and petroleum resins, particularly high corrosion resistance and water resistance are required. Insufficient for application in ship's ballast tanks.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, by using a specific amount of a hydroxyl-containing petroleum resin or a specific decomposition residual oil instead of tar, the present inventors have no safety and hygiene problem while maintaining compatibility with an epoxy resin and an amine curing agent, The present invention has been made by discovering that an anticorrosive coating composition excellent in anticorrosion and adhesiveness and also forming a light coating film in comparison with light to tar can be obtained.

The present invention relates to anticorrosive coating compositions which do not contain tar, and are particularly useful for painting inside ships, such as ballast tanks.

The present invention comprises (A) an epoxy resin, (B) an amine curing agent and (C) a hydroxyl group-containing petroleum resin or a decomposed residual oil at a softening point of 50 to 150 ° C., preferably an additional modifier (D), wherein the epoxy resin (A And 20 to 500 parts by weight of the component (C), based on l00 parts by weight of the cured resin solid content consisting of the amine curing agent (B).

Although the epoxy resin (A) used by this invention has at least 2 or more epoxy groups in 1 molecule, epoxy equivalent is suitably 150-600, Preferably it is 150-300. Examples of such epoxy resins include bisphenol type epoxy resins, aliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol block type epoxy resins, cresol type epoxy resins, and dimer acid modified epoxy resins. Although conventionally well-known things are mentioned, You may use these 1 type or in mixture of 2 or more types.

As an amine hardening | curing agent (B) used by this invention, a conventionally well-known hardening | curing agent for epoxy resins, for example, aliphatic, such as methaxylenediamine, isoprondiamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane Polyamines, aliphatic ring polyamines, aromatic polyamines; The epoxy resin adduct of the said polyamine, polyamide amines, polyamide resin, etc. are mentioned, These can be used 1 type or in mixture of 2 or more types. Among them, aromatic polyamines are suitable from the viewpoints of compatibility with the decomposition residual oil as the above-mentioned (C) component and reactivity with epoxy resins, and in particular, polyamines are selected from phenol and alkylphenol (for example, 3-n-pentadidinylphenol, etc.). Alkylated phenolic polyamines modified with) and formalin are suitable.

Although the mixing ratio of said (A) and (B) component is suitably selected according to both types of components used, Usually, the equivalence ratio of [active hydrogen equivalent in (B) / epoxy equivalent in (A)] is 0.5-1.0. It is appropriate to exist in.

The hydroxyl group-containing petroleum resin as the component (C) used in the present invention is a solid petroleum resin at room temperature containing a hydroxyl group, and may have a softening point of 50 to 150 캜, preferably 80 to l00 캜. have.

Examples of the petroleum resin constituting the hydroxyl group-containing petroleum resin of the component (C), such as an aromatic by polymerizing a C ₉ fractions, such as styrene derivatives, indene from heavy oil to by-product in petroleum naphtha pyrolysis petroleum resins, cyclopentadiene, Aliphatic petroleum resin in which conjugated diene of C ₅ fraction such as 1,3-pentadiene is partially ring-polymerized, copolymer petroleum resin copolymerized with C ₅ fraction and C ₉ fraction, resin hydrogenated to aromatic petroleum resin, And aliphatic cyclic petroleum resins obtained by polymerizing dicyclopentadiene, and the like, and hydroxyl groups are introduced therein. Of these, hydroxyl-containing aromatic petroleum resins are particularly suitable from the viewpoint of water resistance.

It is preferable that content of a hydroxyl group in the hydroxyl-containing petroleum resin which is the said (C) component contains 1-2 mol, Preferably it is 1-1.5 mol in 1 molecule of the said petroleum resin. When the content is 1 mol or less in one molecule, compatibility with the amine curing agent is lowered and adversely affects the coating film performance. On the other hand, when the content is 2 mol or more, the water resistance is not preferable. Moreover, when the softening point of the said hydroxyl-containing resin is 50 degrees C or less, the water resistance of a coating film falls, the said component may bleed out on the coating film surface, and adhesiveness may remain | survive, while when it is 150 degreeC or more, paint viscosity becomes high and works It is not preferable because the properties are lowered or the coating film properties are lowered.

The cracked residual oil (C) component used in the present invention is a by-product residue when obtaining various cracked fractions produced during the pyrolysis of petroleum naphtha, and the polynuclear aromatic compound is a main component and contains a large amount of impurities, and thus has a relatively large molecular weight. Have a distribution. It is preferable to remove this low molecular weight powder which is easy to permeate the surface of a coating film distilled especially from the said residue. Moreover, compared with tar, the said decomposition | restoration residual oil does not contain polar compounds, such as a sulfur compound, in an impurity, and an aromatic ring and a naphthenic ring are mixed in moderate degree in a polynuclear body. For this reason, it is excellent in water resistance, has a low content rate of benzopyrene which is a carcinogenic substance, and is a light brownish color compared with tar.

As the decomposition residual oil, a softening point of 50 to 150 ° C, preferably 80 to 100 ° C can be used. When the softening point of the decomposition residual oil is 50 ° C. or less, the water resistance of the coating film is lowered, and the component may bleed out on the surface of the coating film, and adhesiveness may remain. On the other hand, when 150 ° C. or more, the paint viscosity becomes high and workability is deteriorated. Not desirable

The composition of the present invention contains 20 to 500 parts by weight, preferably 50 to 300 parts by weight of the hydroxyl group-containing petroleum resin or the decomposition residual oil, which is the component (C), based on l00 parts by weight of the cured resin solid content. If the content is less than 20 parts by weight, sufficient water resistance cannot be obtained. If the content is more than 500 parts by weight, the coating film becomes weak and good physical properties cannot be obtained.

The composition of the present invention may use the decomposition residual oil as the component (C) and the petroleum resin having a softening point of 50 to 150 ° C. as necessary within the range that does not adversely affect the compatibility with the amine curing agent. .

In the composition of the present invention, further, in view of flexibility, other liquid modifiers such as xylene resin and toluene resin; Reaction diluents such as epoxy compounds such as butylglycidyl ether; Non-reactive diluents, such as a phenol modified condensation polymer, etc. may be added in 50 weight part or less with respect to 100 weight part of cured resin solid content. Among them, aromatics are suitably used in view of water-resistant oils and fats.

In the composition of this invention, if necessary, pigments, such as a extender pigment, an antirust pigment, and a coloring pigment; Reactive diluents; Ordinary paint additives such as organic solvents, antisettling agents, thickeners, wetting agents, reaction accelerators, adhesion imparting agents, and dehydrating agents may be appropriately contained.

In addition, the composition of this invention is a 2 type liquid coating which consists of a main body containing an epoxy resin, and an amine hardening | curing agent, and is normally coated on primary rust-proof coating films, such as a zinc primer. The coating method of the paint can be applied to a dry film thickness of 150 to 500 μm using conventionally known methods such as air spray, airless spray, brushing, and rollers.

In the following, the present invention will be described in more detail with reference to examples. In addition, "part" and "%" represent a "weight part" and "weight%", respectively.

Example 1

In a 1-liter container, l00 parts of epoxy resin (Note 1), 70 parts of white titanium, l00 parts of talc, 50 parts of hydroxyl-containing petroleum resin (Note 2), l0 part of xylene resin (Note 3), thickener (Note 4) l 0 The main part was made by adding and adding xylene 10 parts and mixing and stirring with a disper to disperse, and then adding 70 parts of an amine curing agent (Note 5) immediately before coating to mix and stir to obtain an anticorrosive coating.

* 1 "EPON # 828": epoxy equivalent 190, emulsified shell epoxy products.

(Note 2) "Neopolymer-K-2": divinyltoluene-indene copolymer having a hydroxyl group content of 1 to 1.1 mol in one molecule, a softening point of l00 ° C, manufactured by Nippon Petrochemical Co., Ltd.

* 3 "Nikanol L": product of Samneung Wasa Chemical Co., Ltd.

(Note 4) "Disperon A630-20XN": Polyamide wax, product of Nammok Chemical Co., Ltd.

(Note 5) "Acidamide CX110": Alkylated phenolic polyamine which modified | denatured aliphatic polyamine with 3-n-pentadinyl phenol and formalin, active hydrogen equivalent 130, the product of Samwha Chemical.

Examples 2-3 and Comparative Examples 1-7

With respect to Example 1, the composition and the compounding amount were as described in Table 1, except that the same operation as in Example 1 to obtain each anticorrosive coating. Note 6 to note 9 in Table 1 are as follows. As Comparative Example 5, "Eposil 6000PS" (manufactured by Kansai Paint Co., Ltd., tar epoxy resin paint) was used. Table 1 shows the solid content.

Note 6: EPON # 1001: Epoxy equivalent 475, emulsified shell epoxy company.

(NOTE 7) "Neopolymer-00": Aromatic petroleum resin (without hydroxyl group), softening point 100 degreeC, the product made by Nippon Petrochemical.

(Note 8) "Neopolymer-140": Aromatic petroleum resin (without hydroxyl group), softening point 150 degreeC, the Japan Petrochemical company make.

(Note 9) "Ditecral X778C": Mannich-modified metaxylenediamine, active hydrogen equivalent 70, product made from Daedo Industry.

Examples 4-6 and Comparative Examples 8-13

In Example 1, the composition and the compounding amount were as described in Table 2, except that the same operation as in Example 1 to obtain each anticorrosive paint. Note 1, note 3 to note 7, and note 9 in Table 2 are as described above, and note 10 is as follows.

(Note) “CR-Z”: Decomposed residual oil, Softening point 80 ° C, manufactured by Ring Sun Petrochemical Co., Ltd.

Performance test

Each anticorrosive coating obtained as above was subjected to a performance test as follows. The results are shown in Table 1 and Table 2.

(* 1) Flexibility

Each anticorrosive paint was coated on a degreased polished mild steel sheet (150 × 70 × 0.8 mm) by airless spray to approximately 250 μm (dry film thickness), dried in an atmosphere at 20 ° C. × 65% RH for 7 days, and then tested. The plate was prepared. The plate was bent at 90 ° with the drawing outward in a 20 ° C. atmosphere, and the coating film crack at this bent portion was visually evaluated (○: no crack, Δ: some crack, ×: significant crack has exist).

(* 2) Temperature difference Water resistance

Shot blasted steel sheet (300 × l00 × 3.2 mm) (test plate I) and “SD zinc l000” (manufactured by Kwansai Paint, silicate zinc primer) on the steel sheet to be about 25 μm (dry film thickness). On one dried test plate (Test Plate II), each of the anticorrosive paints obtained above was coated with airless spray to have a thickness of about 250 μm (dry film thickness), and dried in an atmosphere of 20 ° C. × 65% RH for 7 days. A test plate was obtained.

After the coating surface of this test plate was immersed in the immersion tank for 14 days such that the coated surface was in contact with hot water at 40 ° C. and the water at 20 ° C., the drawing state was visually evaluated (○: no abnormality, Δ: bubbles and rust slightly). Generated, ×: bubbles, rust is generated significantly).

(* 3) seawater resistance

Each test plate obtained in the same manner as the above (* 2) was immersed in seawater at 50 ° C. for 3 months, and the state of the drawings was visually evaluated (○: no abnormality, Δ: bubbles slightly generated, ×: bubbles) Occurs significantly).

[Effects of the Invention]

Since the anticorrosive coating composition of the present invention uses a specific amount of a hydroxyl group-containing petroleum resin or a specific decomposition residue in place of tar, the compatibility between the epoxy resin and the amine-based curing agent and the petroleum resin or the decomposition residue is good, and there are safety and hygiene problems. It is excellent in corrosion resistance, water resistance, and adhesiveness, and can form a light-colored coating film compared with light to tar.

The anticorrosive coating composition of the present invention is very useful as an anticorrosive coating for ships and steel structures.

Claims (4)

An anticorrosive coating composition comprising (A) an epoxy resin, (B) an amine-based curing agent, (C) a hydroxyl group-containing petroleum resin or a decomposition residue having a softening point of 50 to 150 ° C. as a resin component, and (D) a modifier. (A) has an epoxy equivalent of 150 to 300, wherein the amine curing agent (B) is an alkylated phenolic polyamine, and the modifying agent (D) is a xylene resin, and an epoxy resin (A) and an amine curing agent (B) An anticorrosive coating composition containing the component (C) in an amount of 20 to 500 parts by weight and the modifier (D) in an amount of 50 parts by weight or less per 100 parts by weight of the cured resin solid. The method of claim 1, The composition ratio of the said (A) component and the said (B) component is the equivalence ratio of the active hydrogen equivalent in the said (B) component and the epoxy equivalent in the said (A) component in the range of 0.5-1.0, The composition characterized by the above-mentioned. . The method of claim 1, The hydroxyl-containing petroleum resin which is the said (C) component is a petroleum resin containing 1-2 mol of hydroxyl groups in 1 molecule, and its softening point is 50-150 degreeC. The method of claim 1, The decomposition residue oil as the component (C) is a residue by-produced during the pyrolysis of petroleum naphtha, and has a polynuclear aromatic compound as a main component and does not include low molecular weight distilled from the residue.