WO1997035931A1 - Anticorrosive coating composition - Google Patents

Abstract

An anticorrosive coating composition which comprises (A) an epoxy resin, (B) an amine hardener, and (C) a hydroxylic petroleum resin or a cracked residue having a softening point range of 50 to 150 °C, preferably contains (D) a modifier, and is characterized in that the amount of the component (C) is 20 to 500 parts by weight per 100 parts by weight of the cured solid resin formed from the epoxy resin (A) and the amine hardener (B).

Description

 Akira -Specification Anti-corrosion paint composition Technical field

 The present invention relates to an anticorrosion paint composition that does not contain tar, and is particularly useful for painting the interior of ships such as ballast tanks.

 Background art

 Conventionally, tar epoxy filler has been used as an anticorrosive paint for ships and structures. The paint is excellent in anticorrosion, water resistance, shochu chemical properties, etc., but since it contains tar, only the safety and hygiene problems are conceived due to the benzpyrene, a pain-causing substance contained in tar. In addition, it was difficult to maintain because it was amber, and it became too long in a closed place.

 In recent years, non-tar paints using petroleum-based resins instead of tars have been developed. However, these paints have problems with the compatibility of epoxy resins and amine-based curing agents with petroleum-based resins. It was not enough to be applied in ballast tanks of ships that require anticorrosion and water resistance.

 The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a specific amount of a hydroxyl group-containing petroleum resin or a specific cracking residual oil instead of tar, the compatibility with the epoxy resin and the amine-based curing agent has been improved. The present invention has been found to provide an anticorrosion coating composition which has excellent corrosion protection and adhesion properties while maintaining solubility, has no problems in safety and health, and is capable of forming a light-colored film or a light-colored film as compared with tar. Reached.

Disclosure of the invention

 That is, the present invention provides (A) an epoxy resin, (B) an amine-based curing agent, and (C) a hydroxyl group-containing petroleum resin or a residual oil decomposed at a softening point of 50 to 150, preferably a modifier (D ) Wherein the component (C) is contained in an amount of 20 to 500 parts by weight based on 100 parts by weight of a solid content of a cured resin comprising the epoxy resin (A) and the amine-based curing agent (B). The present invention relates to an anticorrosion paint composition characterized by the following.

BEST MODE FOR CARRYING OUT THE INVENTION

The epoxy resin (A) used in the present invention contains at least two epoxy resins per molecule. Suitable are those having an epoxy group and having an epoxy equivalent of 150 to 600, preferably 150 to 300. Such epoxy resins include, for example, bisphenol-type epoxy resins, aliphatic epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, phenol novolak-type epoxy resins, Crebur-type epoxy resins, and dimers. Known ones such as a monoacid-modified epoxy resin may be mentioned, and these may be used alone or in combination of two or more.

 Examples of the amine curing agent (B) used in the present invention include conventionally known curing agents for epoxy resins, for example, aliphatic acids such as metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, and diaminodiphenylmethane. Polyamines, alicyclic polyamines, aromatic polyamines; epoxy resin adducts of such polyamines, polyamide amines, boriamid resin, etc., and these can be used alone or in combination of two or more. . Among these, aromatic polyamines are preferred in view of compatibility with the decomposed residual oil as the component (C) and reactivity with epoxy resin, and particularly, polyamines are phenol or alkylphenol (for example, Alkylated phenolic polyamines modified with 3 n-pentazinylphenol) and formalin are preferred.

 The mixing ratio of the above-mentioned components (A) and (B) is appropriately selected depending on the type of use of both, but usually the equivalent ratio of [active hydrogen equivalent in (B) Z epoxy equivalent in (A)] is 0. It is appropriate to set it in the range of 5 to 1.0.

 The (C) component petroleum group-containing petroleum resin used in the present invention is a petroleum resin containing a hydroxyl group at room temperature and having a softening point of 50 to 150, preferably 80 to 1 Those having a temperature of 0 ° C. can be suitably used.

Wherein (C) Examples of petroleum resin constituting the component serving hydroxyl-containing petroleum resin, eg if a styrene derivative from heavy oil by-produced in petroleum naphtha cracking, aromatics obtained by polymerizing C ₈ fraction such as indene system petroleum resin, cyclopentadiene, 1, 3-Pentaje down fat proof aliphatic conjugated diene of C ₅ fraction are polymerized over part cyclization and petroleum榭脂, by copolymerizing the C ₅ fraction minutes fraction And hydrogenated aromatic petroleum resins and alicyclic petroleum resins obtained by polymerizing dicyclopentene. Hydroxyl groups are introduced into these. Among them, especially the hydroxyl group-containing aromatic petroleum resin It is suitable from the viewpoint of water resistance. one

 The content of the hydroxyl group in the hydroxyl group-containing petroleum resin as the component (C) is preferably 1 to 2 mol, and more preferably 1 to 1.5 mol, in one molecule of the petroleum resin. If the content is less than 1 mol per molecule, the compatibility with the above-mentioned amine-based curing agent is reduced and the coating film performance is adversely affected. On the other hand, if it exceeds 2 mol, the water resistance is undesirably reduced. If the softening point of the hydroxyl group-containing resin is less than 50, the water resistance of the coating film may be reduced, and the component may bleed on the surface of the coating film and the tackiness may remain. It is not desirable because the viscosity of the coating material increases and the workability decreases, and the physical properties of the coating film decrease. The cracked resid as the component (C) used in the present invention is a residue produced as a by-product when obtaining various cracked oil fractions generated during the thermal cracking process of petroleum naphtha, and polynuclear aromatic compounds contain It has a relatively wide molecular weight distribution containing a large amount of impurities as a main component. In particular, those obtained by removing from the residue by distillation the bleeding easily on the surface of the coating film and low molecular weight components are preferable. Further, the cracked residual oil does not contain polar compounds such as sulfur compounds in impurities as compared with tar, and the aromatic and naphthene rings are appropriately mixed in the polynuclear body. For this reason, it has excellent water resistance, has a low content of the ventilating substance benzopyrene, and has a lighter and browner color than tar.

As the cracked residue, those having a softening point of 50 to 150, preferably 80 to 100 can be used. Softening point of the decomposition residue oil 5 (sometimes tacky bleed ingredients on the surface of the coating film reduces the酎水of coating is less than TC remains, whereas 1 5 0 exceeds ^e C the paint In the composition of the present invention, the hydroxyl group-containing petroleum resin or the decomposed residual oil as the component (C) is added in an amount of 2 parts by weight based on 100 parts by weight of the hardened resin solids. 0 to 500 parts by weight, preferably 50 to 300 parts by weight If the content is less than 20 parts by weight i, sufficient water resistance cannot be obtained, whereas if it exceeds 500 parts by weight. It is not preferable because the coating film is brittle and good physical properties cannot be obtained.

 In the composition of the present invention, the petroleum resin having a softening point of 50 to 150 may be added to the above-mentioned cracked residual oil as a component (C), if necessary, to adversely affect the compatibility with the amine-based curing agent. They may be used together in a range or range.

In the composition of the present invention, further from the viewpoint of imparting flexibility, other liquid modifiers, for example, Xylene resin, toluene resin; reactive diluents such as epoxy compounds such as butyl glycidyl ether; non-reactive diluents such as phenol-modified polycondensate; cured resin 5 parts per 100 parts by weight of solids You may add in the range of 0 weight part or less. Of these, aromatic ones are preferably used from the viewpoint of maintaining water resistance.

 The composition of the present invention may further contain, if necessary, pigments such as extender pigments, water-proof pigments, and color pigments; reactive diluents; organic solvents, anti-settling agents, anti-sagging agents, wetting agents, and reaction promoters. Ordinary paint additives such as agents, adhesion-imparting agents, and dehydrating agents may be appropriately contained.

 Further, the composition of the present invention is a two-pack type paint composed of a main agent containing an epoxy resin and an amine-based curing agent, and is usually applied on a primary protective film such as a zinc primer. As the coating method of the paint, a conventionally known method such as air spray, airless spray, brush break, roller, or the like can be adopted, and the paint is adjusted to have a dry film thickness of 150 to 500 / m. Can be intercepted.

 Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, “part J and Γ%” indicate “part by weight” and “% by weight”, respectively.

 Example 1

 Epoxy resin (Note 1) 100 parts, titanium white 70 parts, talc 100 parts, hydroxyl-containing petroleum resin (Note 2) 50 parts, xylene resin (Note 3) 100 Parts, 10 parts of anti-sagging agent (Note 4) and 10 parts of xylene were added, mixed with a disperser, stirred and dispersed to form a main agent, and 70 parts of an amine-based curing agent (Note 5) was added immediately before coating. The mixture was added, mixed and stirred to obtain an anticorrosion paint.

(Note 1) "Ebon # 8228": Epoxy equivalent: 190, manufactured by Yuka Sil Epoxy. (Note 2) "Neo Polymer K-2":. 1 molecule of hydroxyl group-containing Il～l 1 mole of Jibini Rutoruen one indene copolymer, a softening point 1 0 0 ^e C, Nippon Petrochemicals Co., Ltd..

 (Note 3) “Nicanol L j: manufactured by Mitsubishi Gas Chemical Company.

 (Note 4) “Dispalon A630-20XN”: A polyamide wax manufactured by Kusumoto Kasei.

(Note 5) "Sunmide CX 102": An alkylated phenolic polyamine obtained by modifying an aliphatic polyamine with 3-—n-pentinyl phenol and formalin; active hydrogen equivalent: 130; Sanwa Chemical Company. Examples 2 to 6 and Comparative Examples 1 to 5

In Example 1, each anticorrosion paint was obtained in the same manner as in Example 1 except that the composition and the amount were as shown in Table 1. In Table 1, (Note 6) through (Note 9), _c Note as follows, "Eposhiru 6 0 0 0 PS" (05 West Paint Co., Tarue Bokishi resin coating) as Comparative Example 5 was used . Table 1 shows the solid content.

 (Note 6) “Ebon # 1001”: Epoxy equivalent of 475, manufactured by Yuka Seal Epoxy. (Note 7) “Neopolymer 100”: aromatic petroleum resin (no hydroxyl group), softening point 100, manufactured by Nippon Petrochemical Co., Ltd.

 (Note 8) "Neopolymer 140": Aromatic petroleum resin (no hydroxyl group), softening point 150, manufactured by Nippon Petrochemical Co., Ltd.

 (Note 9) Daitoklar X 778 CJ: Mannich-modified meta-xylylenediamine, active hydrogen equivalent 70, manufactured by Daito Sangyo Co., Ltd.

 Examples 7 to 12 and Comparative Examples 6 to 8

 Each anticorrosive paint was obtained in the same manner as in Example 1 except that the composition and the amount shown in Table 2 were used. In Table 2, (Note 1), (Note 3) to (Note 7) and (Note 9) are as described above, and (Note 10) is as follows.

 (Note 10) “CR-Z”: Cracking residue, softening point 80, manufactured by Maruzen Petrochemical Company.

performance test

 Each anticorrosion paint obtained as described above was tested in the following performance test. The results are shown in Tables 1 and 2.

 (* 1) Flexibility

 Each anticorrosive paint was applied to a degreased polished mild steel plate (150 x 70 x 0.8 mm) by airless spraying to a thickness of about 250 (dry film thickness). After drying for days, each test coated plate was prepared. The coated plate was bent at 90 ° with the side facing outward in a TC atmosphere and the cracks in the bent portion were visually evaluated (〇: no cracks, Δ: slight * cracks, X: considerable) There are cracks).

 (* 2) Temperature difference

Shot-blasted steel plate (300 × 100 × 3.2 mm) (Test plate I) and “SD Zinc 100000” (Kansai Paint Co., Ltd., Siligate Zinc Bridger) on the steel plate _c- 1) is applied to a thickness of about 25 乾燥 m (dry film thickness) and dried for one day. On a test plate (test plate II), each of the anticorrosion paints obtained above is applied by airless spray. About 25

0 m was applied to the (dry film thickness), to obtain each test coated plate was dried for 7 days at 2 O ^e Cx 6 of 5% RH atmosphere.

In warm water at the coated surface of the test coated plate is 4 0 ^e C, after Hita演1 4 days in a pride演槽as backside is in contact with the water at 2 0, were evaluated coated surface state was visually (○: No abnormality, Δ: slight occurrence of swelling and rust, X: significant occurrence of swelling and rust).

 (* 3) Seawater resistance

Each test coated plate obtained in the same manner as in (* 2) above was visually evaluated for the coated surface after immersion in seawater at 50 for 3 months (〇: no abnormality, △: slight occurrence of blisters) X: Significant blistering occurs).

Table 1 Comparative examples

1 2 3 4 5 6 1 2 3 4 5 Eboxy resin (Note 1) 100 100 100 100 100 100 100】 00 100 Epoxy resin (Note 6) 100

 Titanium white 70 70 70 70 70 70 70 70 70 70 70

 1 Talc 100 100 100 100 100 100 100 100 100 100 l Petroleum resin (a) (Note 2) 50 150 300〗 50 150 150 600

Food petroleum resin (b) (Note 7) 150

 Petroleum resin (c) (Note 8) 150 pairs Xylene resin (Note 3) 10 10 10 10 10 10 10 10 10 10 Anti-sagging agent (Note 4) 10 10 10) 0 10 10 10 10 10 10

Xylene 10 10 10 10 10 10 10] 0 10 10 material Curing agent ① (Note 5) 70 70 70 70 70 70 70 70 Hardening thorn ② (Note 9) 40 40 Shaking color White White White White White White White White White白 屈曲 〇 〇 〇 〇 〇 〇 〇 OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX OX Test plate IO 〇 〇 〇 〇 〇 △ △ △ 〇 〇 Test plate II 〇 〇 〇 〇 〇 〇 Δ Δ Δ Δ Δ

Table 2

発明の効果

The invention's effect

 Since the anticorrosion coating composition of the present invention uses a specific amount of a hydroxyl group-containing petroleum resin or a specific decomposed residual oil instead of tar, the compatibility between the epoxy resin and the amine-based curing agent and the petroleum resin or the decomposed residual oil is used. It has good anti-corrosion properties, water resistance and adhesion, and can form a light-colored or light-colored film compared to tar.

Industrial applicability

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

Claims

The scope of the claims 1. (A) an epoxy榭脂, (B) consists Amin curing agent and (C) a hydroxyl group-containing petroleum榭fat or softening point 5 0~1 5 0 ^e C decomposition residue oil, the said component (C) An anticorrosion paint composition characterized by containing 20 to 500 parts by weight based on 100 parts by weight of a cured resin solid consisting of an epoxy resin (A) and an amine curing agent (B).  2. The mixing ratio of the component (A) to the component (B) is in the range of 0.5 to 1.0 as the equivalent ratio of the active hydrogen equivalent in the component (B) to the epoxy equivalent in the component (A). 2. The composition according to claim 1, wherein the composition is:  8. It is characterized in that the composition further comprises a modifier (D), and the modifier (D) is contained in an amount of 50 parts by weight or less based on 100 parts by weight of the cured resin solid content. The composition according to claim 1, wherein  4. The epoxy resin (A) has at least two epoxy groups in one molecule, 3. The composition according to claim 1, wherein the composition has an epoxy equivalent of 150 to 600.  5. The composition according to claim 4, wherein said epoxy resin (A) has an epoxy equivalent of 150 to 300.  6. The composition according to claim 1, wherein the component (C) is a cracked residual oil, and the amine-based curing agent (B) is an alkylated phenolic polyamine. 7. a petroleum resin in which the (C) hydroxyl-containing petroleum resin as component contains 1-2 moles of hydroxyl groups per molecule, and characterized in that the softening point of 5 0~1 5 0 ^e C The composition according to claim 1.  8. The cracked residual oil as the component (C) is a residue produced as a by-product in the thermal cracking process of petroleum naphtha, and is composed mainly of polynuclear aromatic compounds, and is obtained by removing low molecular components from the residue by distillation. 2. The composition according to claim 1, wherein the composition comprises: