CN102690583A

CN102690583A - Anti-corrosion coating composition

Info

Publication number: CN102690583A
Application number: CN2012101946666A
Authority: CN
Inventors: 骆玉明
Original assignee: TIANCHANG YINHU PAINT Co Ltd
Current assignee: TIANCHANG YINHU PAINT Co Ltd
Priority date: 2012-06-13
Filing date: 2012-06-13
Publication date: 2012-09-26

Abstract

The invention relates to an anti-corrosion coating composition, which mainly comprises the following ingredients in parts by weight: (A) 1-80 parts of epoxy resin; (B) 3-35 parts of amine curing agent; and (C) 0.2-200 parts of coumarone resin containing a hydroxyl group. According to the invention, the ingredients are mixed uniformly in proportion so as to obtain the anti-corrosion coating composition. The resin ingredients in the anti-corrosion coating composition have excellent compatibility; and in the curing film, cured epoxy resin and specific coumarone resin are in uniformly mixed state. The problems of insecurity and insanitation during coating operation are prevented; and a film which has excellent corrosion resistance, water resistance and adhesion force and is brighter than tar is formed through coating.

Description

A kind of anticorrosive coating composition

Technical field

The invention belongs to chemical material field, specifically relate to a kind of anticorrosive coating composition.The present invention relates to a kind of anticorrosive coating composition.The present invention has good sea water resistance, can form light tone such as grey and film, and can be used in the external coating of marine transition pipeline etc., the anticorrosive coating composition that especially inner application is very useful to boats and ships such as ballast tanks.

Background technology

Material surfaces such as metal, concrete, timber receive the physics of surrounding environment medium, chemical action through regular meeting corrosion damage to take place.The whole world all suffer of all kinds because of the massive losses that brought of corrosion.At oil, chemical industry, building materials field, the accident of various potential safety hazards, the initiation that is brought because of corrosion is startling especially.

In order to tackle corrosion, people have taked various measures, and are wherein most economical, actual effect or the most general to apply protective system.The ultimate principle of protective system is through Isolated Shield, passivation inhibition and three kinds of mechanism of electro-chemical protection material surface to be protected.Present protective system divides acid-proof, alkali prevention, anti-salt etc. substantially, and the easy alkali prevention of acid-proof is difficult.Protective system commonly used comprises: epoxy-based coatings, the advantage of this coating are that sticking power is good, solidity to corrosion is strong, but weathering resistance is poor, is commonly used to do priming paint; The alkyd varnish weathering resistance is better, but water-fast, anti-saponifiability is relatively poor; Coal tar coating, its water tolerance is better, but poor solvent resistance; Polyurethane coating, chlorosulfonated polythylene coatings, fluorocarbon coating; Water tolerance, the weathering resistance of this type coating are better; And have certain chemical resistance, but it does not have resistance to corrosion preferably to alkali and 40% above concentrated acid, and paint film is harder; To cement etc. sticking power is bad, can't directly be used as terrace paint.

In the past, the tar epoxy coating with good non-corrosibility was used in inner application always to boats and ships such as ballast tanks.Because this coating contains tar; The problem that therefore the safety and sanitation aspect is arranged, and because its color is and the proximate black of the color of body material steel plate therefore visually to be difficult to the film thickness that the branch pigtail is filmed; If want to carry out application with uniform film thickness, then its application operation and inspection are quite difficult.In addition, containing filming of tar has the visual inspection of utilizing and is difficult to distinguish that the burn into that has or not steel plate has or not the influence of steel plate when welding heat and produces the problem that is coated with maintenance care aspects such as membrane stage of film scaling loss and deterioration with time etc.And the coating that contains tar also has tar component and moves to (oozing out) gradually and be coated with in the top coat layer that is contained on this tar based film, and influence is attractive in appearance by the boats and ships of application or steel structure, and functions such as didirtresistance, weathering resistance are caused dysgenic problem.

CN 1056397A discloses a kind of anticorrosion, waterproof paint that uses epoxy resin and deposed polystyrene as major ingredient, but its solvent resistance is relatively poor; CN 1422914A disclose a kind of through add styrene-butadiene rubber(SBR), epoxy resin p-poly-phenyl ethenoid resin carries out the polystyrene styrene-butadiene rubber anticorrosive coating that modification obtains; Because it contains epoxy resin; Though increased the sticking power to base material, photostabilization will receive negative impact.

CN 101747835A relates to a kind of elastic anti-corrosion coating; Be that its prescription comprises: 30 ~ 70 weight part organopolysiloxane, 1 ~ 80 weight part color stuffing, 3 ~ 10 weight part linking agents, 1 ~ 10 weight part auxiliary agent and 10 ~ 80 parts by weight diluent with high-performance, functional compsn on room temperature vulcanized silicone rubber basis.But the corrosion-resistant time falls short of.

Summary of the invention

The object of the invention is exactly the limitation that overcomes present traditional coating; A kind of non-corrosibility coating composition is provided; The resin Composition that is comprised in its anticorrosive coating composition has good intermiscibility; And can a plurality of resin Compositions that be included in the cured coating film be carried out the good homogeneous mixing; Do not have oozing out of arbitrary component, when application is operated, do not have the problem in the safety and sanitation, can form through application have good non-corrosibility, water tolerance, sticking power and than tar filming of light tone more.

For reaching this purpose, the present invention adopts following technical scheme:

A kind of anticorrosive coating composition, said compsn mainly comprises by weight:

(A) 1 ~ 80 parts by weight of epoxy resin;

(B) amine curing agent of 3 ~ 35 weight parts; And

(C) coumarone resin that contains hydroxyl of 0.2 ~ 200 weight part,

Above-mentioned each composition is evenly mixed in proportion, obtain anticorrosive coating composition.

The epoxy resin (A) that is comprised in the anticorrosive coating composition of the present invention is the resin that in a molecule, has at least two above epoxy group(ing).From the epoxy resin of bisphenol A-type, Bisphenol F type, dihydroxyphenyl propane D type, bis-phenol K type, bisphenol S type to epoxy resin dimer acid modified, the polysulphide modification, the resin that can also use epoxy resin to be hydrogenated with aromatic ring structure.See from forming viewpoint, in these materials, preferably use aromatic series based epoxy resins such as bisphenol A-type, Bisphenol F type as epoxy resin of the present invention (A) with filming of good sticking power etc.Its parts by weight are 1.2 ~ 78,5 ~ 70,14 ~ 58,25 ~ 43,34 ~ 38 etc.

As the epoxy resin of this type of bisphenol A-type, 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 99 diglycidyl ether, Hydrogenated Bisphenol A 99 propylene oxide diglycidyl ether etc. are for example arranged.

This based epoxy resin can use one or more combinations to use separately.

The epoxy equivalent (weight) of described epoxy resin (A) is 150 ~ 600, is preferably 150 ~ 500, further preferred 230 ~ 270.

From obtaining the purpose of higher-solid coating, be preferably the bisphenol-type epoxy resin that is liquid or solid shape at normal temperatures.

Can use existing known use hardener for epoxy resin widely as amine curing agent (B), need only the kind according to epoxy resin (A), suitably selection can be reacted with it and its hardened amine curing agent is got final product.

Said amine curing agent (B) is the mixture of a kind of in polyamine class solidifying agent, modified polyamine class solidifying agent, polyamide-based solidifying agent or the modified polyamide class solidifying agent or at least two kinds, further preferred modified polyamine class solidifying agent.Its parts by weight can select 3.1 ~ 34.5,6 ~ 28,11 ~ 22,16 ~ 18 etc.

As modified polyamine class solidifying agent, comprise aliphatic poly amines such as m-xylene diamine, isophorone diamines, NSC 446, Triethylenetetramine (TETA), diaminodiphenyl-methane; Alicyclic polyamine class; The modifier of polyamine classes such as aromatic series polyamine class.Particularly, for example comprise and utilize your addition of epoxide addition, Mike, Mannich addition, thiocarbamide addition, vinyl cyanide addition, ketone chelating etc. and polyamine is carried out the aliphatics of modification, alicyclic or aromatic series polyamine.

The amine value of amine curing agent according to the invention (B) is 50 ~ 1000, is preferably 80 ~ 500, further preferred 100 ~ 150.

Further, said amine curing agent (B) is liquid or solid-like.

The said coumarone resin (C) that contains hydroxyl is for to contain 1 ~ 5% hydroxyl in a molecule.Its parts by weight are 0.22 ~ 199,0.8 ~ 175,3 ~ 142,10 ~ 120,27 ~ 85,45 ~ 60,53 etc.

Further, said coumarone resin (C) softening temperature that contains hydroxyl is below 200 ℃, and is further preferred below 145 ℃, most preferably 60 ~ 100 ℃.Surpass above-mentioned scope if contain the softening temperature of the coumarone resin (C) of hydroxyl, then and the intermiscibility between epoxy resin and the cured article thereof etc. will be lower, or lack intermiscibility, therefore preferably do not surpass above-mentioned scope in the present invention.

The said number-average molecular weight that contains the coumarone resin (C) of hydroxyl is 55 ~ 900, and is preferred 120 ~ 300, most preferably 200.

As optimal technical scheme, a kind of anticorrosive coating composition, said compsn mainly comprises by weight:

(A) bisphenol-type epoxy resin of 12 ~ 50 weight parts;

(B) the modified polyamine class solidifying agent of 10 ~ 25 weight parts; And

(C) coumarone resin that contains hydroxyl of 8 ~ 160 weight parts,

Compsn according to the invention also comprises color stuffing, auxiliary agent, thinner.

Further; Described color stuffing is the mixture of a kind of in WHITE CARBON BLACK, nano-calcium carbonate, titanium oxide, talcum powder, silicon powder, the permanent white or at least two kinds; Talcum powder for example, silicon powder and permanent white, the mixture of WHITE CARBON BLACK, nano-calcium carbonate and permanent white.

Further, described auxiliary agent comprises the mixture of a kind of in catalyzer, promotor, dispersion agent, flow agent, skimmer and the thickening material or at least two kinds.

Further; Described thinner is selected from the mixture of a kind of in dimethyl silicone oil, YLENE, toluene, acetone, ether, sherwood oil, glycerine, aromatic alcohol, the vinyl acetic monomer or at least two kinds; For example glycerine and aromatic alcohol, vinyl acetic monomer, the mixture of YLENE, toluene and sherwood oil.

(A) bisphenol-type epoxy resin of 28 ~ 36 weight parts;

(B) the modified polyamine class solidifying agent of 16 ~ 20 weight parts;

(C) coumarone resin that contains hydroxyl of 35 ~ 60 weight parts;

(D) talcum powder of 8 ~ 45 weight parts;

(E) auxiliary agent of 1 ~ 13 weight part; And

(F) vinyl acetic monomer of 10 ~ 38 weight parts,

" comprising " of the present invention, mean it except that said component, can also comprise other components, these other components are given said coating composition different characteristic.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... form ".

Compare with the prior art scheme, the present invention has following beneficial effect:

The resin Composition that is comprised in the anticorrosive coating composition of the present invention has good intermiscibility, and epoxy resin cured product and specific coumarone resin will become mixed uniformly state in cured coating film.Therefore,, 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 according to anticorrosive coating composition of the present invention.In addition, owing to can anticorrosive coating composition of the present invention be processed the high solid type coating with higher-solid rate, therefore can carry out thick filmization.Paint film all has outstanding sticking power to glass, pottery, steel construction piece, concrete and various types of resins priming paint etc.; Paint film elasticity, hydrophobic nature are good; Tensile strength, elongation at break are higher, can be widely used in anticorrosion, the leakproof of anticorrosion and ground, the sk-etc. of bridge, storage tank, various steel construction pieces.

Down in the face of further explain of the present invention.But following instance only is a simple and easy example of the present invention, does not represent or limits rights protection scope of the present invention, and interest field of the present invention is as the criterion with claims.

Embodiment

For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:

Embodiment 1

(A) bisphenol A type epoxy resin of 1 weight part, its epoxy equivalent (weight) are 150;

(B) the polyamine class solidifying agent of 35 weight parts, its amine value is 50; And

(C) coumarone resin that contains hydroxyl of 0.2 weight part, its softening temperature is 145 ℃, number-average molecular weight is 55,

Embodiment 2

(A) bisphenol F epoxy resin of 80 weight parts, its epoxy equivalent (weight) are 600;

(B) the polyamide-based solidifying agent of 3 weight parts, its amine value is 1000; And

(C) coumarone resin that contains hydroxyl of 200 weight parts, its softening temperature is 200 ℃, number-average molecular weight is 900,

Embodiment 3

(A) bisphenol-type epoxy resin of 50 weight parts, its epoxy equivalent (weight) are 500;

(B) the modified polyamine class solidifying agent of 10 weight parts, its amine value is 500; And

(C) coumarone resin that contains hydroxyl of 8 weight parts, its softening temperature is 100 ℃, number-average molecular weight is 300,

Embodiment 4

(A) bisphenol-type epoxy resin of 12 weight parts, its epoxy equivalent (weight) are 230;

(B) the modified polyamine class solidifying agent of 25 weight parts, its amine value is 100; And

(C) coumarone resin that contains hydroxyl of 160 weight parts, its softening temperature is 60 ℃, number-average molecular weight is 120,

Embodiment 5

(A) bisphenol-type epoxy resin of 36 weight parts, its epoxy equivalent (weight) are 270;

(B) the modified polyamine class solidifying agent of 16 weight parts, its amine value is 80;

(C) coumarone resin that contains hydroxyl of 60 weight parts, its softening temperature is 180 ℃, number-average molecular weight is 200;

(D) talcum powder of 45 weight parts;

(E) auxiliary agent of 13 weight parts; And

(F) vinyl acetic monomer of 10 weight parts,

Embodiment 6

(A) bisphenol-type epoxy resin of 28 weight parts, its epoxy equivalent (weight) are 380;

(B) the modified polyamine class solidifying agent of 20 weight parts, its amine value is 150;

(C) coumarone resin that contains hydroxyl of 35 weight parts, its softening temperature is 80 ℃, number-average molecular weight is 750;

(D) talcum powder of 8 weight parts;

(E) auxiliary agent of 1 weight part; And

(F) vinyl acetic monomer of 38 weight parts,

The comparative example

With the embodiment among the CN 101747835A 1 as comparative example of the present invention:

Elastic anti-corrosion coating with good weathering resistance, water tolerance, solvent resistance, oil-proofness and while acid-fast alkali-proof provided by the invention is that its prescription comprises following component (weight part) with the compsn on room temperature vulcanized silicone rubber basis:

Each embodiment performance test table of table 1

Project	The embodiment of the invention	The comparative example
			Set time/h	15	24
Salt water resistance (20%NaCl)	More than the 3200h	2000h
			Acid resistance (50% dense H ₂SO ₄)	More than the 2650h	2000h
Alkali resistance (10%NaOH)	More than the 2800h	2000h
			Tensile strength	≥5.8MPa	≥2.0MPa
Tear strength	≥10KN/m	≥3KN/m

Applicant's statement; The person of ordinary skill in the field is on the basis of the foregoing description, and is with the concrete content point value of the foregoing description component, combined with the technical scheme of summary of the invention part; Thereby the new numerical range that produces; Also be one of record scope of the present invention, the application is no longer enumerated these numerical ranges for making specification sheets simple and clear.

Claims

1. an anticorrosive coating composition is characterized in that, said compsn mainly comprises by weight:

(A) 1 ~ 80 parts by weight of epoxy resin;

(B) amine curing agent of 3 ~ 35 weight parts; And

(C) coumarone resin that contains hydroxyl of 0.2 ~ 200 weight part,

2. compsn according to claim 1; It is characterized in that; The resin of described epoxy resin (A) in a molecule, having at least two above epoxy group(ing), preferred bisphenol-type epoxy resin, further preferred bisphenol A type epoxy resin and/or bisphenol f type epoxy resin.

3. compsn according to claim 1 and 2 is characterized in that, the epoxy equivalent (weight) of described epoxy resin (A) is 150 ~ 600, is preferably 150 ~ 500, further preferred 230 ~ 270;

Preferably, said epoxy resin (A) is for be the bisphenol-type epoxy resin of liquid or solid shape at normal temperatures.

4. according to the described compsn of one of claim 1-3; It is characterized in that; Said amine curing agent (B) is the mixture of a kind of in polyamine class solidifying agent, modified polyamine class solidifying agent, polyamide-based solidifying agent or the modified polyamide class solidifying agent or at least two kinds, further preferred modified polyamine class solidifying agent.

5. according to the described compsn of one of claim 1-4, it is characterized in that the amine value of said amine curing agent (B) is 50 ~ 1000, is preferably 80 ~ 500, further preferred 100 ~ 150;

Preferably, said amine curing agent (B) is liquid or solid-like.

6. according to the described compsn of one of claim 1-5, it is characterized in that the said coumarone resin (C) that contains hydroxyl is for containing 1 ~ 5% hydroxyl in a molecule;

Preferably, said coumarone resin (C) softening temperature that contains hydroxyl is below 200 ℃, and is further preferred below 145 ℃, most preferably 60 ~ 100 ℃.

7. according to the described compsn of one of claim 1-6, it is characterized in that the said number-average molecular weight that contains the coumarone resin (C) of hydroxyl is 55 ~ 900, preferred 120 ~ 300, most preferably 200.

8. according to the described compsn of one of claim 1-7, it is characterized in that said compsn mainly comprises by weight:

(A) bisphenol-type epoxy resin of 12 ~ 50 weight parts;

(B) the modified polyamine class solidifying agent of 10 ~ 25 weight parts; And

(C) coumarone resin that contains hydroxyl of 8 ~ 160 weight parts,

9. according to the described compsn of one of claim 1-8, it is characterized in that said compsn also comprises color stuffing, auxiliary agent, thinner;

Preferably, described color stuffing is the mixture of a kind of in WHITE CARBON BLACK, nano-calcium carbonate, titanium oxide, talcum powder, silicon powder, the permanent white or at least two kinds;

Preferably, described auxiliary agent comprises the mixture of a kind of in catalyzer, promotor, dispersion agent, flow agent, skimmer and the thickening material or at least two kinds;

Preferably, described thinner is selected from the mixture of a kind of in dimethyl silicone oil, YLENE, toluene, acetone, ether, sherwood oil, glycerine, aromatic alcohol, the vinyl acetic monomer or at least two kinds.