CN103013273A - Anticorrosive paint composition - Google Patents
Anticorrosive paint composition Download PDFInfo
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- CN103013273A CN103013273A CN2012104952616A CN201210495261A CN103013273A CN 103013273 A CN103013273 A CN 103013273A CN 2012104952616 A CN2012104952616 A CN 2012104952616A CN 201210495261 A CN201210495261 A CN 201210495261A CN 103013273 A CN103013273 A CN 103013273A
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Abstract
The invention discloses an anticorrosive paint composition which is characterized by comprising the following components in parts by weight: 10-30 parts of epoxy resin, 6-18 parts of amine curing agent, 5-20 parts of hydroxyl-containing coumarone resin, 1-4 parts of 2-mercaptobenzothiazole, 2-5 parts of organic silicon compound and 5-30 parts of solvent. A coating film provided by the invention has excellent anticorrosive property, water resistance and adhesive force.
Description
Technical field
The present invention relates to a kind of anticorrosive coating composition.Particularly, the present invention relates to a kind of good sea water resistance that has, can form the light tones such as grey and film, and can be used in the external coating of marine transition pipeline etc., the anticorrosive coating composition that especially application of the boats and ships inside such as ballast tank is very useful.
Background technology
In the past, the tar epoxy coating with good non-corrosibility was used in the application of the boats and ships inside such as ballast tank always.Because this coating contains tar, the problem that the safety and sanitation aspect is therefore arranged, and because its color is the black approximate with the color of body material steel plate, therefore the indistinguishable film thickness of filming visually, if want to carry out application with uniform film thickness, then its application operates and checks difficult.In addition, containing filming of tar has the impact of heat when utilizing the visual inspection impalpable to have or not the burn into of steel plate to have or not Plate Welding and produces film scaling loss and deteriorated etc. the problem that is coated with the maintenance care aspects such as membrane stage in time.And, the coating that contains tar also has tar component and moves to gradually (oozing out) and be coated in the top coat layer on this tar based film, the boats and ships that are coated of impact or steel structure attractive in appearance caused dysgenic problem to functions such as didirtresistance, weathering resistances.
Patent documentation 1(CN101443425A) disclosed a kind of anticorrosive coating composition and be characterised in that, comprised: (A) Resins, epoxy; (B) amine curing agent; And the coumarone resin that (C) contains hydroxyl, and with respect to the Resins, epoxy (A) of 100 weight parts, this coumarone resin (C) that contains hydroxyl is the amount of 1～500 weight part.In addition, the described coumarone resin (C) that contains hydroxyl is preferably, and contain 1～5% hydroxyl in a molecule, and its softening temperature is below 200 ℃.By this anticorrosive coating composition, can form well mixed uniformly cured coating film of a plurality of resin Compositions, related filming has good non-corrosibility, water tolerance and sticking power.And, because anticorrosive coating composition does not contain existing protection against corrosion with the contained tar of coating, therefore can form the cured coating film that oozes out without any component of light tone more, when operating, application do not have the problem in the safety and sanitation yet.
But non-corrosibility, water tolerance and sticking power to coating in the prior art have higher requirement.
Summary of the invention
The object of the invention is to provide a kind of non-corrosibility coating composition, its can form by application have fabulous non-corrosibility, water tolerance, sticking power and than tar filming of light tone more.
The inventor makes great efforts research and finds in order to solve the above problems: by improving on the basis of patent documentation 1 disclosed component, add 2-mercaptobenzothiazole and silicoorganic compound and form new non-corrosibility coating composition, can form by application have fabulous non-corrosibility, water tolerance, sticking power and than tar filming of light tone more, thereby finished the present invention.
Namely, anticorrosive coating composition involved in the present invention comprises: (A) Resins, epoxy; (B) amine curing agent; (C) contain the coumarone resin of hydroxyl; (D) 2-mercaptobenzothiazole; (E) silicoorganic compound; (F) solvent.Wherein Resins, epoxy is the 10-30 weight part; Amine curing agent 6-18 weight part; The coumarone resin that contains hydroxyl is the 5-20 weight part; 2-mercaptobenzothiazole is the 1-4 weight part; Silicoorganic compound are the 2-5 weight part; Solvent 5-30 weight part.
The resin Composition that comprises in the anticorrosive coating composition of the present invention has good intermiscibility, and epoxy resin cured product will become mixed uniformly state with specific coumarone resin, 2-mercaptobenzothiazole, silicoorganic compound in cured coating film.Therefore, according to anticorrosive coating composition of the present invention, can not use tar and terpene phenolic resin, just can form and have filming of good flexibility, non-corrosibility, water tolerance etc., and specific coumarone resin can not ooze out from this is filmed.In addition, owing to anticorrosive coating composition of the present invention can be made the high solid type coating with higher-solid rate, therefore can carry out thick-film.
In addition, because mixed tar not in the coating composition of the present invention, so it is light tone, carries out easily visual inspection etc., can form and can not occur to damage filming of attractive in appearance and film performance because oozing out, when the application operation of coating, also not have the problem in the safety and sanitation.
Embodiment
Anticorrosive coating composition
Anticorrosive coating composition involved in the present invention comprises (A) Resins, epoxy; (B) amine curing agent; (C) contain the coumarone resin of hydroxyl; (D) 2-mercaptobenzothiazole; (E) silicoorganic compound.Below these components and blending ratio etc. are described successively.
＜Resins, epoxy (A) 〉
The Resins, epoxy that comprises in the anticorrosive coating composition of the present invention (A) is the resin that has at least two above epoxy group(ing) in a molecule.Can exemplify just like record in [0014]～[0016] section of TOHKEMY 2001-279167 communique, from the Resins, epoxy of bisphenol A-type, Bisphenol F type, dihydroxyphenyl propane D type, bis-phenol K type, bisphenol S type to Resins, epoxy dimer acid modified, the polysulphide modification, the resin that can also use Resins, epoxy with aromatic ring structure to be hydrogenated.From forming the viewpoint with filming of good sticking power etc., in these materials, preferably use the aromatic series based epoxy resins such as bisphenol A-type, Bisphenol F type as Resins, epoxy of the present invention (A).
In addition, the epoxy equivalent (weight) of Resins, epoxy of the present invention (A) is generally 150～600, is preferably 150～500, in addition, from obtaining the purpose of higher-solid coating, is preferably the bisphenol-type epoxy resin that is at normal temperatures liquid or solid shape.
As the Resins, epoxy of this type of bisphenol A-type, such as the bisphenol A-type diglycidyl ethers such as diglycidyl rthers of bisphenol-A, polymer with bis phenol A propylene oxide diglycidyl ether, bisphenol-A epoxy ethane diglycidyl ether, Hydrogenated Bisphenol A diglycidyl ether, Hydrogenated Bisphenol A propylene oxide diglycidyl ether etc. are arranged.
This based epoxy resin can be used alone or be used in combination.
＜amine curing agent (B) 〉
In the present invention, can use widely hardener for epoxy resin of existing known use as amine curing agent (B), as long as according to the kind of Resins, epoxy (A), suitably selection can be reacted with it and the amine curing agent of its sclerosis is got final product.
As amine curing agent of the present invention (B), comprise such as the polyamine class solidifying agent of in the section of [0017] of TOHKEMY 2001-279167 communique～[0021], putting down in writing, modified polyamine class solidifying agent, polyamide-based solidifying agent (such as polyamide-amide), modified polyamide class solidifying agent etc.
As " modified polyamine class solidifying agent ", comprise the aliphatic poly amines such as m-xylene diamine, isophorone diamines, diethylenetriamine, Triethylenetetramine (TETA), diaminodiphenyl-methane; Alicyclic polyamine class; The modifier of the polyamine classes such as aromatic series polyamine class.Particularly, utilize epoxide addition, Michael addition, Mannich addition, thiocarbamide addition, vinyl cyanide addition, ketone chelating (ketone terminating) etc. and polyamine is carried out the aliphatics of modification, alicyclic or aromatic series polyamine such as comprising.
As " polyamide-based solidifying agent ", such as polyamide-based with the reaction of dimeracid and amine (aliphatic poly amine same as described above, alicyclic polyamine class, aromatic series polyamine class etc.) arranged.In addition, as described polyamide-based modifier i.e. " modified polyamide class solidifying agent ", particularly, for example there is pair polymeric amide to carry out the epoxy compounds addition and the epoxy adduct that consists of; The Mannich modification body of modified polyamide.
The amine value of the described polyamine that the present invention uses, modified polyamine, polymeric amide, modified polyamide solidifying agent is generally 50～1000, is preferably 80～500.If the amine value of solidifying agent (B) is positioned at this scope, then has and improve the drying property film and the trend of the balance between the bounding force.In addition, these solidifying agent are generally liquid～solid.
For solidifying agent (B), if consider from viewpoints such as Physical properties of coating film and application operability, be preferably in anticorrosive coating composition of the present invention, be 0.4～1.0 amount with the Ahew number in this solidifying agent (B) (weight/Ahew of solidifying agent (B)) with respect to the value of the ratio of the epoxy equivalent (weight) number in the described Resins, epoxy (A) (weight/epoxy equivalent (weight) of Resins, epoxy (A)) and mix, 0.5～0.9 the amount of more preferably being is mixed.
＜contain the coumarone resin (C) of hydroxyl 〉
The present invention mixes in anticorrosive coating composition and has used the coumarone resin that contains hydroxyl.The viewpoint of the non-corrosibility of filming from gained sees and is preferably that in the measurement of being undertaken by acetylation method, this coumarone resin (C) that contains hydroxyl contains 1～5% hydroxyl in a molecule.
In addition, the softening temperature that contains the coumarone resin (C) of hydroxyl is preferably below 200 ℃, below 150 ℃, particularly preferably is below 100 ℃ more preferably, also can be liquid at normal temperatures.Surpass above-mentioned scope if contain the softening temperature of the coumarone resin (C) of hydroxyl, then and the intermiscibility between Resins, epoxy and the cured article thereof etc. will be lower or lack intermiscibility, therefore preferably do not surpass in the present invention above-mentioned scope.
In addition, the number-average molecular weight of passing through gpc measurement (Mn) that contains the coumarone resin (C) of hydroxyl is generally 80～700, is preferably 100～500.
Satisfy the coumarone resin that contains hydroxyl (C) of above-mentioned condition, can pass through ordinary method, for example carry out copolymerization by interpolation phenol when making coumarone resin and make.In addition, also can obtain its commodity.These contain the coumarone resin of hydroxyl, can use a kind of or are used in combination two or more.
＜2-mercaptobenzothiazole 〉
2-mercaptobenzothiazole can adopt and can prepare by ordinary method, perhaps adopts the commercial goods.
＜silicoorganic compound 〉
Silicoorganic compound from the cohort that organoalkoxysilane and hydrolyzate thereof consist of, select one or more form.Organoalkoxysilane is preferably with the compounds of general formula (X ') Si (x ") 3 expressions.
Herein, X ' is from hydroxyl, the lower alkoxy of methoxyl group, oxyethyl group, isopropoxy etc., the low alkyl group of ethyl etc., the low-grade alkenyl of vinyl etc., and contain and select in the low alkyl group of γ-Racemic glycidol oxygen propyl group, γ-methacryloxypropyl, γ-functional groups such as sulfydryl propyl group.X " be from the alkoxyl group of hydroxyl and methoxyl group, oxyethyl group, isopropoxy etc., to select 3 X " both can be the same or different.
The concrete example of organoalkoxysilane, can exemplify tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, vinyltrimethoxy silane, vinyltriethoxysilane, γ-Racemic glycidol oxygen propyl trimethoxy silicane etc., but be not limited to this.Can use commercially available various organoalkoxysilanes as silane coupling agent.
＜other component 〉
In anticorrosive coating composition of the present invention, except the coumarone resin (C) that contains hydroxyl, in the scope that does not affect with the intermiscibility of cured resin component, also may be used (not hydroxyl) coumarone resin, xylene resin, terpene phenolic resin etc.
And, in anticorrosive coating composition of the present invention, can suitably mix the pigment class such as pigment extender, rust-stabilising pigment, tinting pigment as required; The common additive for coatings such as reactive diluent, organic solvent, anti-sedimentation agent, anti-sagging agent, lubricant, reaction accelerator, adhesion promoter, dewatering agent etc.
The preparation method of coating composition and coating process
Anticorrosive coating composition of the present invention can mix described Resins, epoxy (A), amine curing agent (B), the coumarone resin (C), 2-mercaptobenzothiazole, silicoorganic compound and other the components such as solvent that contain hydroxyl by ordinary method and prepares.
Anticorrosive coating composition of the present invention is that the solid component content in the coating is higher than the higher-solid coating of existing coating (for example: solids component is 70～95 % by weight).
The anticorrosive coating composition of the present invention for preparing as mentioned above, can pass through ordinary methods such as hydraulic spraying, aerial spraying, brushing, roller coat, surface at boats and ships and steel structure etc. is coated with, make again its drying, curing, just can form the protection against corrosion with described premium properties and film.In addition, when application operates, also can be with re-using anticorrosive coating composition after the suitable dilutions such as thinner.
Embodiment
By the following examples, anticorrosive coating composition of the present invention is specifically described again, but the present invention is not subjected to the restriction of embodiment.
[embodiment 1～4, comparative example 1～5]
With stirrer mixing etc., prepared the anticorrosive coating composition with blending ingredients shown in the following table 1 by ordinary method.
By following test method, each anticorrosive coating composition for gained has carried out the test of the test subject shown in the table 1.Its result is as shown in table 1.
＜performance test 〉
(1) resistance to bend(ing) test
Utilize the aerial spraying device with the degree of about 250 μ m (desciccator diaphragm thickness), described each anticorrosive coating is coated with on the test board that is contained in 150mm * 50mm * 0.3mm, under 23 ℃, the environment of 50%RH, made various test boards in dry seven days.Use these test boards, according to following standard evaluation the resistance to bend(ing) of filming.(according to JIS K-56005-1)
(judgement criteria)
AA: do not have crackle and peel off.
BB: small crackle is arranged, but do not peel off.
CC: peel off.
(2) shock-resistance test
Utilize the aerial spraying device with the degree of about 250 μ m (desciccator diaphragm thickness), described each anticorrosive coating is coated with on the test board that is contained in 150mm * 70mm * 1.6mm, under 23 ℃, the environment of 50%RH, made various test boards in dry seven days.Use these test boards, according to ISO-6272 Du Pont type, by shock-testing machine (ProductName: Du Pont impact tester, helping very much machine material Co., Ltd. makes), under 1/4 inch, the condition of 1kg * 50cm, carry out the shock-resistance test, according to following standard evaluation the shock-resistance of filming.
(judgement criteria)
AA: peel diameter is less than 13mm.
BB: peel diameter more than or equal to 13mm less than 18mm.
CC: peel diameter is more than or equal to 18mm.
(3) resistance to salt water test
Use and above-mentioned " test of (2) shock-resistance " same test board of making according to following standard, have been estimated 150 days appearance of films afterwards of dipping in 40 ℃/3% salt solution.(according to JISK-56006-1)
(judgement criteria)
AA: pore, crackle, become rusty, peel off, any one of color all do not have to change.
BB: pore, crackle, become rusty, peel off, any one of color has a little defective (variation).
CC: pore, crackle, become rusty, peel off, any one of color produces significantly and changes.
(4) electrical anticorrosion (electric anticorrosion) test
Use and above-mentioned " test of (2) shock-resistance " same test board of making according to ASTMG-8, according to following standard, have been estimated 150 days appearance of films afterwards of dipping in 40 ℃/3% salt solution.
(judgement criteria)
AA: pore, crackle, become rusty, peel off, any one of color all do not have to change.
BB: pore, crackle, become rusty, peel off, any one of color has a little defective (variation).
CC: pore, crackle, become rusty, peel off, any one of color produces significantly and changes.
(5) high-temp resisting high-humidity resisting test
Use and above-mentioned " test of (2) shock-resistance " same test board of making according to following standard, have been estimated and preserved 150 days appearance of films afterwards in the testers of temperature 50 C, humidity 95%.(according to JIS K-56006-1)
(judgement criteria)
AA: pore, crackle, become rusty, peel off, any one of color all do not have to change.
BB: pore, crackle, become rusty, peel off, any one of color has a little defective (variation).
CC: pore, crackle, become rusty, peel off, any one of color produces significantly and changes.
(6) temperature head test
Use the test board with above-mentioned " test of (2) shock-resistance " same making, so that the application face of this test board contacts with 50 ℃ warm water, the mode that its back side is contacted with 20 ℃ water has been flooded in steeping vat 28 days.At first, according to the standard of having used following ASTM grade symbol (ASTMD714-56), estimated and be coated with membrane stage (size of pore and generation degree) behind the dipping.
(judgement criteria)
Size
No.10: without (None).
No.8: minimum size (Smallest Size).
No.6: middle size (Medium Size).
No.4: large size (Large Size).
The generation degree
D: intensive (Dense).
MD: medium intensive (Medium Dense).
M: medium (Medium).
F: few (Few).
Then, with cutter filming of these test films is cut into the X shape, according to following standard evaluation the sticking power of filming.(according to JIS K-56006-18.5.3)
(judgement criteria)
AA: on filming, do not peel off (adhering to good).
BB: some is peeled off on filming.
CC: filmed and peeled off (adhering to bad).
In addition, to being illustrated as of embodiment and the employed blending ingredients of comparative example (note of table 1) as described below.
The solid type Resins, epoxy of (annotating 1) bisphenol A-type, epoxy equivalent (weight) is 600, solids component is 75%.
The semi-solid type Resins, epoxy of (annotating 2) bisphenol A-type, epoxy equivalent (weight) is 300, solids component is 85%.
The liquid Resins, epoxy of (annotating 3) bisphenol A-type, epoxy equivalent (weight) is 210, solids component is 90%.
(annotating 4) contains the coumarone resin of hydroxyl, and softening temperature is 100 ℃, and hydroxy radical content is 2.2～2.7%, and solids component is 100%.
Table 1
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (4)
1. an anticorrosive coating composition is characterized in that, comprises:
(A) Resins, epoxy;
(B) amine curing agent;
(C) contain the coumarone resin of hydroxyl;
(D) 2-mercaptobenzothiazole;
(E) silicoorganic compound;
(F) solvent;
Wherein Resins, epoxy is the 10-30 weight part; Amine curing agent 6-18 weight part; The coumarone resin that contains hydroxyl is the 5-20 weight part; 2-mercaptobenzothiazole is the 1-4 weight part; Silicoorganic compound are the 2-5 weight part; Solvent 5-30 weight part.
2. anticorrosive coating composition according to claim 1 is characterized in that, the coumarone resin (C) that contains hydroxyl is, contains 1～5% hydroxyl in a molecule, and its softening temperature is below 200 ℃.
3. anticorrosive coating composition according to claim 1 is characterized in that, solvent is dimethylbenzene.
4. anticorrosive coating composition according to claim 1 is characterized in that, silicoorganic compound are γ-glycidyl ether oxygen propyl trimethoxy silicane.
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| CN2012104952616A CN103013273A (en) | 2012-11-28 | 2012-11-28 | Anticorrosive paint composition |
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| CN2012104952616A CN103013273A (en) | 2012-11-28 | 2012-11-28 | Anticorrosive paint composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725144A (en) * | 2013-11-19 | 2014-04-16 | 谭文平 | Anticorrosive paint and preparation method thereof |
| CN104479505A (en) * | 2014-12-08 | 2015-04-01 | 中国船舶重工集团公司第七二五研究所 | Rapid curing high-tenacity epoxy anticorrosive coating for ship cabin and preparation method |
| CN115605553A (en) * | 2020-06-22 | 2023-01-13 | 日涂工业涂料有限公司（Jp） | Aqueous anticorrosive coating composition |
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| CN101061194A (en) * | 2004-11-17 | 2007-10-24 | 大日本涂料株式会社 | Corrosionproof coating composition |
| CN101443425A (en) * | 2006-05-10 | 2009-05-27 | 中国涂料株式会社 | Anticorrosive coating composition |
| CN102378793A (en) * | 2009-04-03 | 2012-03-14 | 阿克佐诺贝尔国际涂料股份有限公司 | Anti-corrosive coating composition |
| CN102690583A (en) * | 2012-06-13 | 2012-09-26 | 天长市银狐漆业有限公司 | Anti-corrosion coating composition |
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2012
- 2012-11-28 CN CN2012104952616A patent/CN103013273A/en active Pending
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| CN101061194A (en) * | 2004-11-17 | 2007-10-24 | 大日本涂料株式会社 | Corrosionproof coating composition |
| CN101443425A (en) * | 2006-05-10 | 2009-05-27 | 中国涂料株式会社 | Anticorrosive coating composition |
| CN102378793A (en) * | 2009-04-03 | 2012-03-14 | 阿克佐诺贝尔国际涂料股份有限公司 | Anti-corrosive coating composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725144A (en) * | 2013-11-19 | 2014-04-16 | 谭文平 | Anticorrosive paint and preparation method thereof |
| CN104479505A (en) * | 2014-12-08 | 2015-04-01 | 中国船舶重工集团公司第七二五研究所 | Rapid curing high-tenacity epoxy anticorrosive coating for ship cabin and preparation method |
| CN115605553A (en) * | 2020-06-22 | 2023-01-13 | 日涂工业涂料有限公司（Jp） | Aqueous anticorrosive coating composition |
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Application publication date: 20130403 |