KR100577920B1 - Coating Composition for Corrosion Proofing - Google Patents

Abstract

Phenolic hydroxyl group obtained by polymerizing an epoxy resin (A), a curing agent, preferably an amine curing agent (B), and a cracked oil fractionation fraction having an indenes content of 60 to 90% by weight in the presence of phenols with a Friedel-Craft catalyst. By containing less than 1.0 aromatic petroleum resin (C) per molecule and making the content of the aromatic petroleum resin (C) 1 to 500 parts by weight based on 100 parts by weight of epoxy resin, no tar is included. Epoxy paint compositions for anticorrosion applicable to the site of contact with seawater are obtained.

Paint, anticorrosive, epoxy resin, petroleum resin

Description

Anticorrosive coating composition {Coating Composition for Corrosion Proofing}

The present invention relates to an anticorrosive coating composition useful as a substitute for tar-based epoxy paints, in particular for coating in areas in contact with sea water, such as in ballast tanks of ships.

Conventionally, tar-based epoxy paints have been used as anticorrosive paints for ships and steel structures. This paint is excellent in corrosion resistance, water resistance, chemical resistance, etc., but because it contains tar, it is not only concerned with hygiene problems, but because it is black, it is difficult to maintain and darkened in a closed place. There was a problem.

In recent years, non-tar epoxy coatings using petroleum resins in place of tar have also been developed. For example, it is proposed by Japanese Unexamined-Japanese-Patent No. 59-52656, Unexamined-Japanese-Patent No. 9-263713. That is, the resin of Unexamined-Japanese-Patent No. 59-52656 contains a hydroxyl group, In the Example, the fractionation fraction containing the unsaturated component obtained from the cracking of naphtha was superposed | polymerized in phenol coexistence, and resin of softening point 93 degreeC is obtained. Japanese Patent Application Laid-Open No. 9-263713 discloses an epoxy resin anticorrosive coating using a divinyltoluene-indene copolymer (softening point 100 DEG C) having a hydroxyl group content of 1 to 1.1 mol in one molecule in Examples.

However, regarding the epoxy paint of the present material, there is a problem in compatibility between the curable resin composed of an epoxy resin, a curing agent, especially an amine curing agent and a petroleum resin, and especially in seawater where high corrosion resistance and water resistance are required. Insufficient coating in areas of direct contact, such as in ballast tanks of ships.

Disclosure of the Invention

As a result of earnestly examining in order to solve the above-mentioned problem, the inventors have found that epoxy resin can be obtained by using a resin having an indene content as a specific aromatic fraction as a raw material and using a resin having a relatively low content of phenolic hydroxyl groups. It is excellent in compatibility with the curing agent, especially the amine curing agent, and as a result, there is no hygiene problem, and the anticorrosive coating composition which is excellent in anticorrosiveness, water resistance, adhesion, etc., and which can form a bright color coating film is obtained. Discovered to complete the present invention.

That is, the 1st of this invention contains the component in the boiling range of 140-220 degreeC mainly in the decomposition oil obtained by the thermal decomposition of an epoxy resin (A), a hardening | curing agent, Preferably an amine-type hardening | curing agent (B), and petroleum. 0.1 or more phenolic hydroxyl groups formed per polymer by polymerizing a cracked oil fraction containing 60 to 90% by weight of the indene content obtained by distillation from fractionated fractions in the presence of phenols, using a Friedel-Crafts catalyst. It consists of aromatic petroleum resin (C) containing less than 1.0, and it contains an aromatic petroleum resin (C) 1-500 weight part with respect to 100 weight part of epoxy resins.

The second aspect of the present invention relates to the anticorrosive coating composition according to the first aspect of the present invention, wherein the conjugated diene content of the decomposed oil fractional component is 5% by weight or less.

Hereinafter, the present invention will be described in detail.

The epoxy resin (A) used in the present invention has at least two or more epoxy groups in one molecule, and an epoxy equivalent of 150 to 600 is appropriate, preferably 180 to 500. Examples of such epoxy resins include bisphenol epoxy resins, aliphatic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, phenol novolac epoxy resins, cresol epoxy resins, dimer acid modified epoxy resins, and the like. The conventionally well-known thing of these is mentioned, These can be used only by 1 type or in mixture of 2 or more types.

The hardening | curing agent (B) used by this invention is a conventionally well-known thing as a hardening | curing agent of an epoxy resin. For example, various aliphatic or aromatic amines, polyamide resins, acid anhydrides, phenol resins, polyisocyanates and the like are exemplified. These can be used only by 1 type or in mixture of 2 or more types.

Especially preferably, it is an amine hardening | curing agent, For example, aliphatic polyamines, such as metha xylene diamine, isophorone diamine, diethylene triamine, triethylene tetratamine, diamino diphenylmethane, alicyclic polyamine, aromatic polyamine, these Epoxy resin adducts of polyamines, polyamide amines, polyamide resins, and the like. These can be used only by 1 type or in mixture of 2 or more types.

The mixing ratio of the epoxy resin (A) and the curing agent (B) can be appropriately selected depending on the type of cationic component. Generally, it is selected in the range of 1 to 200 parts by weight of the curing agent per 100 parts by weight of epoxy resin. When using an amine hardening | curing agent suitable as a hardening | curing agent (B), it is usual to select so that the equivalence ratio of the active hydrogen equivalent in (B) / the epoxy equivalent in (A) may be in the range of 0.5-1.0.

As the aromatic petroleum resin (C) used in the present invention, as a solid petroleum resin at room temperature containing a phenolic hydroxyl group, one having a softening point of 50 to 150 ° C, preferably 80 to 110 ° C is used.

As the petroleum resin, a fractionated fraction containing a component having a boiling point in the range of 140 to 220 占 폚 is mainly used as a raw material in decomposition oil generated by thermal decomposition of hydrocarbons such as naphtha and butane in order to produce ethylene, propylene, and the like. . Such fractions include styrene, α- or β-methylstyrene, vinyltoluene, indene, methyl indene, unsaturated components such as dicyclopentadiene, dimethylcyclopentadiene, ethylbenzene, trimethylbenzene, indane, methyl indane, Saturated components, such as naphthalene, are contained. Moreover, conjugated dienes, such as cyclopentadiene and methylcyclopentadiene produced by thermal decomposition of dicyclopentadiene, dimethylcyclopentadiene, etc. at the time of distillation operation, are also included.

In this invention, the fractionation fraction obtained by the distillation of the said decomposition oil is a fractionation fraction whose indene content is 60 to 90 weight% as a raw material. Use of fractions out of this range is undesirable because of the deterioration of the performance as an anticorrosive coating composition. Here, indene content rate (weight%) is defined as (total unsaturated component content in the total amount / decomposition oil fractionation fraction of alkyl indenes, such as indene and methyl indene) x100.

Preferably, the fractionation fraction whose conjugated diene content rate, such as cyclopentadiene and methylcyclopentadiene, is 5 weight% or less is used. By adjusting the content of conjugated dienes to 5% by weight or less, the performance as an anticorrosive coating can be further improved. Here, conjugated diene content rate (weight%) is defined as (total unsaturated component content in the total amount / decomposition oil fractionation of conjugated diene) x100.

In addition, analysis of each said component can be easily performed by a well-known gas chromatography method.

The cracked oil fractionation fraction having the above composition can be easily obtained by appropriately combining a known distillation method with respect to the cracked oil by-produced by pyrolysis.

The raw material resin of the present invention coexists with 1.0 to 10.0 parts by weight of phenols in 100 parts by weight of the cracked oil fraction, and is in the range of 10 to 100 ° C. using a 0.01 to 3% by weight Friedel-Craft catalyst based on the cracked fraction. It can be prepared by polymerization in.

As phenols, phenol of alkyl group substitution, such as cresol, xylenol, tert-butylphenol, nonylphenol, can be illustrated besides phenol. These can also be mixed and used. Preferably, it is phenol. Phenols may be present in the reaction system as one component of the Friedel-Crafts catalyst, but usually a predetermined amount of phenol is often supplied to the reaction system independently of the catalyst.

As the Friedel-Crafts catalyst, a metal halide, preferably boron trifluoride, or a complex with an oxygen-containing compound such as phenol, ethyl ether, butyl ether, butyl alcohol or methyl alcohol is used.

The polymerization time can be selected in the range of 0.5 to 10 hours in the case of batch type.

Resin having a predetermined softening point is obtained by adding a predetermined amount of the cracked oil fraction, phenols, Friedel-Craft catalyst and the like and polymerizing it by a known method. After polymerization, the catalyst is deactivated appropriately using an alkali or the like, and then the unreacted oil or the low polymer is separated and removed by distillation or the like as appropriate, thereby obtaining the desired resin.

The petroleum resin (C) used for the coating composition of this invention contains 0.1 or more and less than 1.0 phenolic hydroxyl group in 1 molecule of petroleum resin. Preferably, it is 0.5-0.9. And in superposition | polymerization, resin in which the quantity of a phenolic hydroxyl group exists in the said range can be obtained by adjusting suitably the filling amount of each raw material, superposition | polymerization conditions, etc ..

If 1.0 or more phenolic hydroxyl groups exist in 1 molecule of the said petroleum resin (C) used by this invention, it is not preferable as resin for anticorrosive coating. Moreover, when less than 0.1, compatibility with epoxy resin falls and it is likewise unpreferable. And the quantity of the phenolic hydroxyl group which exists in obtained resin is IE 17 , C. Anal. Ed. It can be measured by the method described in (1945) p.394.

Moreover, the softening point of the said resin (C) is 50-150 degreeC as mentioned above, Preferably it is the range of 80-110 degreeC. If the softening point is less than 50 ° C, the water resistance of the anticorrosive coating film is low, and a resin component may leak on the surface of the coating film, and adhesiveness may remain. On the other hand, if the coating point exceeds 150 ° C, the coating viscosity becomes high, resulting in poor workability or deterioration in coating properties. Therefore, it is not preferable. And the molecular weight of resin (C) used for this invention is a range of 500-3000 as a number average molecular weight.

To obtain the composition of the present invention, 1 to 500 parts by weight, preferably 10 to 300 parts by weight of the petroleum resin (C) containing the phenolic hydroxyl group is added to 100 parts by weight of the epoxy resin (A). When the said compounding quantity is less than 1 weight part, sufficient water resistance cannot be obtained for the obtained composition, On the other hand, when it exceeds 500 weight part, since a coating film becomes weak and a favorable physical property cannot be obtained, either is not preferable.

The anticorrosive coating composition of the present invention includes other liquid modifiers such as xylene resin and toluene resin in order to impart more plasticity; Reactive diluents, such as an epoxy compound, such as butyl glycidyl ether, may be added in 50 weight part or less with respect to 100 weight part of hardening resin solid content. Of these, aromatics are suitably used in terms of water resistance retention.

The composition of the present invention may further include pigments such as extender pigments, rust preventive pigments and colored pigments as necessary; Reactive diluents; Ordinary paint additives such as organic solvents, sedimentation inhibitors, flow inhibitors, wetting agents, reaction promoters, adhesion imparting agents, and dehydrating agents may be appropriately blended.

In addition, the composition of the present invention is a two-component coating composed of a main material containing an epoxy resin and a curing agent, preferably an amine curing agent, and is usually coated on primary rust-preventive coating films such as zinc primers. That is, first, shot blasting is performed on the steel sheet to remove the mill scale, and inorganic zinc primers such as ethyl silicate are applied, and then the coating composition of the present invention is applied.

The primer is not limited to zinc silicate and the like, and various primers can be used. Moreover, even a steel plate without a primer can be applied, and sufficient anticorrosive effect is obtained.

As a coating method, conventionally well-known methods, such as an air spray, an airless spray, a brush coating, and a roller, can be employ | adopted, and the said coating composition can be apply | coated so that it may become 150-500 micrometers in dry film thickness.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail with reference to Examples. "Part" and "%" represent "weight part" and "weight%", respectively.

[Production example]

From the cracked oil obtained by pyrolysis of naphtha, fractionated fractions having a boiling point range of 140 to 220 ° C were fractionated to obtain cracked fraction fractions adjusted to 51% total unsaturated component content, 70% indenes content, and 0.5% conjugated diene content.

Next, 5 g of phenol was added to 100 g of the fractionated oil fractionated powder, 0.5 g of a trifluoride boron-phenol complex was added and polymerized at 30 ° C. for 3 hours, followed by removing the catalyst with an aqueous sodium hydroxide solution, followed by washing with water. The unreacted oil and the low polymer were removed by distillation to obtain 56 g of petroleum resin (A).

The softening point of the obtained resin was 103 degreeC, and as a result of analysis, it was confirmed that it has 0.8 phenolic hydroxyl groups per molecule.

[Comparative Manufacturing Example]

In the same manner as in the above-mentioned production example, cracked oil fractionation powder having an indene content of 20% and a conjugated diene content of 6% was obtained.

By polymerizing this in the same manner, a petroleum resin (B) having a softening point of 85 占 폚 and 0.8 phenolic hydroxyl groups per molecule was obtained.

Example 1

100 parts of epoxy resin, 30 parts of titanium white, 100 parts of talc, 100 parts of petroleum resin (A) obtained in the production example, 20 parts of hydrocarbon-based plasticizer, 5 parts of anti-flow agent and equivalent mixing solvent of xylene, MIBK and cyclohexane 150 Part was added, and the mixture was stirred and mixed with a stirrer to prepare a main material. 80 parts (solid content conversion) of polyamide resin was added to this as mixing agent, and it stirred and mixed, and obtained the anticorrosive coating composition. The compositions and results are shown in Table 1.

Example 2, Comparative Example

Compositions were prepared in the same manner as in the formulation shown in Table 1.

In the comparative example, the petroleum resin (B) of the comparative manufacturing example was used. The results are shown in Table 1.

Table 1

Example Comparative example One 2 One    Paint composition (parts by weight) Epoxy Resin (1) 100 100 100 Titanium white 30 30 30 Talc 100 100 100 Petroleum Resin (A) (2) 100 200 - Petroleum Resin (B) (3) - - 150 Plasticizer (4) 10 10 10 Flow Retardant (5) 5 5 5 Mixed solvent 150 150 150 Curing Agent (Consolidated) (6) 80 80 80 Impact Resistance: 500g × 30cm pass pass Broken Cold resistance repeatability test: -20 ℃ × 1 hour ⇔ 60 ℃ × 1 hour three times pass pass Broken Seawater resistance O O △

Note (1) epoxy equivalent 475; "Epon # 1001", product made in yucca shell epoxy company

   (2) Petroleum resin (A) obtained in the production example

   (3) Petroleum resin (B) obtained by comparative manufacturing example

   (4) hydrocarbon plasticizers; "Hyazole SAS LH", Nippon Petrochemical Co., Ltd. make

   (5) fatty acid derivatives; `` ASA T-55-20BX '', manufactured by Ito Oil Co., Ltd.

  (6) polyamide resin curing agents; Trade name "Basamide 115", Henkel White Water Co., Ltd. product; It was provided as a 50% solution of the same mixed solvent of xylene, MIBK and cyclohexane.

And, the method of the performance test of the anticorrosive coating composition is as follows.

(1) Impact resistance test (dupont type)

Each sample was coated on a polished mild steel sheet (200 x 100 x 0.6 mm) degreased so as to have a dry film thickness of about 250 mu m, and dried in an atmosphere of 20 DEG C x 65% RH for 7 days to prepare each test plate. .

The plate was subjected to the DuPont impact test specified in JIS K5400-1990 in an atmosphere at 20 ° C.

(2) Cold and heat repeatability test

A silicate zinc primer was coated on the degreased polished mild steel sheet so as to have a dry film thickness of about 25 μm, and dried for 1 day. Each sample was coated on this with an applicator so as to have a dry film thickness of about 250 μm, and dried in an atmosphere of 20 ° C. × 65% RH for 7 days to obtain each test piece.

These test pieces were subjected to the cold and heat repeatability test according to JIS K5400-1990.                 

(3) seawater resistance test

The same test piece as made in the cold-heat repeatability test of (2) above was immersed in 50 ° C seawater for 6 months, and the state of the drawings thereafter was visually evaluated. The criteria of evaluation are as follows.

O: No abnormality

△: some expansion occurs

X: Swelling occurs remarkably

Since the anticorrosive coating composition of the present invention uses a phenolic hydroxyl group-containing petroleum resin having a specific indene content, it has good compatibility with epoxy resins and curing agents, particularly amine-based curing agents and petroleum resins, and has no hygienic problems. It is excellent in water resistance, adhesion, and the like, and can form a bright colored film, which is very useful as an anticorrosive coating for ships or structures.

Claims (4)

60-90 weight% of indenes content obtained by distillation from the fractionation component containing the component which is mainly in the boiling point range of 140-220 degreeC among the epoxy resin (A), the hardening | curing agent (B), and the decomposition oil obtained by thermal decomposition of petroleum. It consists of aromatic petroleum resin (C) which contains 0.1 or more and less than 1.0 phenolic hydroxyl groups per molecule obtained by superposing | composing the decomposition oil fractionation of this by a Friedel-Craft catalyst in presence of phenols, B) 1 to 200 parts by weight based on 100 parts by weight of the epoxy resin (A), and 1 to 500 parts by weight of the aromatic petroleum resin (C) based on 100 parts by weight of the epoxy resin (A). Anticorrosive coating composition, characterized in that. delete The anticorrosive coating composition according to claim 1, wherein the curing agent (B) is an amine curing agent. The anticorrosive coating composition according to claim 1 or 3, wherein the conjugated diene content of the decomposed oil fraction is 5 wt% or less.