KR20170088488A - Anticorrosive Coating Composition comprising unsaturated polyester and vinyl ester - Google Patents
Anticorrosive Coating Composition comprising unsaturated polyester and vinyl ester Download PDFInfo
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- KR20170088488A KR20170088488A KR1020160008323A KR20160008323A KR20170088488A KR 20170088488 A KR20170088488 A KR 20170088488A KR 1020160008323 A KR1020160008323 A KR 1020160008323A KR 20160008323 A KR20160008323 A KR 20160008323A KR 20170088488 A KR20170088488 A KR 20170088488A
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- Prior art keywords
- unsaturated polyester
- resin
- weight
- vinyl ester
- coating composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
The present invention relates to an anti-corrosive coating composition comprising an unsaturated polyester and a vinyl ester resin.
The paint using unsaturated polyester resin is excellent in mechanical and chemical properties of the coating film and has excellent drying property even when coated with a back coating film so that the back coating can be performed within a short time due to a short waiting time in the subsequent coating operation. In addition, the dry film is excellent in impact resistance, so that the coating is applied to areas where frequent impacts are applied to protect the substrate.
However, due to the nature of the resin, the adhesion to the iron base and the rust resistance are poor, and its application tends to be limited to areas where high performance rustproofing is required.
The present invention relates to a paint composition comprising an unsaturated polyester resin, a vinyl ester resin, an extender pigment, a coloring pigment and a solvent on the basis of 100 wt% of the total composition, , And an object of the present invention is to provide an anticorrosive coating composition that exhibits improved shelf-life while satisfying water-resistant and water-resistant standards.
The rust-preventive coating composition of the present invention comprises an unsaturated polyester resin and a vinyl ester resin.
The rust-preventive coating compositions of the present invention may exhibit improved shelf-life while meeting the rust-preventive, water-resistant and adherence specifications specified in NORSOK, Norwegian offshore paint and coating specification test specification. In addition to its physical properties such as rust resistance and adhesion, it is also excellent in workability in field applications, and thus can be effectively applied to steel structures for off-shore or steel sheets as rust-preventive paints.
Hereinafter, the present invention will be described in more detail.
The rust-preventive coating composition of the present invention comprises an unsaturated polyester resin and a vinyl ester resin.
A conventional paint using an unsaturated polyester resin is a high-solids content paint which can be coated with a thick film by a single coating, has quick curing, has excellent abrasion resistance, impact resistance and chemical resistance, but has a large volume shrinkage during curing There is a disadvantage in that the adhesion to the substrate is relatively weak. On the other hand, the vinyl ester resin is superior to the conventional resin in the basic adhesion, but the storage stability is relatively short and the viscosity is low, so additional measures are needed to improve the workability.
The rust-preventive coating composition of the present invention can improve the rust-preventive property, the adhesion property, the workability and the storage property by applying the unsaturated polyester resin and the vinyl ester resin at an appropriate ratio.
In one embodiment, the rust-preventive coating composition of the present invention comprises 30 to 50% by weight of an unsaturated polyester resin, 10 to 30% by weight of a vinyl ester resin, 15 to 40% by weight of an extender pigment, (A) a polyfunctional alcohol having two or more hydroxyl groups, (b) an aromatic dicarboxylic acid, and (c) an unsaturated polyester resin having an unsaturated An aliphatic dicarboxylic acid having a carbon-carbon double bond or an anhydride thereof, and the vinyl ester resin is the resultant resin of a ring-opening reaction of an epoxy resin by addition of an unsaturated carboxylic acid.
The unsaturated polyester resin contained in the composition of the present invention is used for improving the storage stability. The viscosity of the unsaturated polyester resin is in the range of V to W (Gardner viscosity) at 25 ° C, an acid value of 5 to 25 mg KOH / g, 4 to 5 minutes, the peak time is 7 to 10 minutes, and the peak temperature is 175 to 185 ° C. The peak time refers to the time from the transition from gel to solid when ascertaining the gelation time of the resin to the temperature reaching the peak (peak temperature). If the viscosity is out of the range, the workability may be poor. If the acid value is higher than the above range, the molecular weight is low and the unreacted monomers are present and the appearance becomes worse. If the acid value is lower than the above range, Flowability may be reduced.
The unsaturated polyester resin includes (a) a multifunctional alcohol having two or more hydroxyl groups, (b) an aromatic dicarboxylic acid, and (c) an aliphatic dicarboxylic acid having an unsaturated carbon-carbon double bond or an anhydride thereof . Although not particularly limited, (a) a polyfunctional alcohol having two or more hydroxyl groups includes a polyhydric alcohol such as a dihydric alcohol, a trihydric alcohol, and a tetravalent alcohol. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, dimethylene glycol, trimethylolpropane , Neopentyl glycol, and the like. The aromatic dicarboxylic acid (b) may be, for example, benzene dicarboxylic acid, naphthalene dicarboxylic acid or isophthalic acid, but is not limited thereto. (c) The aliphatic dicarboxylic acid or its anhydride having an unsaturated carbon-carbon double bond may be selected from maleic acid, fumaric acid, gluconic acid, tromatin acid and an anhydride thereof.
In one embodiment, the unsaturated polyester may be prepared by the following reaction scheme (1).
[Chemical Formula 1]
In the above formula, n is an integer of 2 or more representing the number of polymerization units.
The composition of the present invention comprises 30 to 50% by weight of an unsaturated polyester resin based on 100% by weight of the total composition. If it is less than 30% by weight, the shelf-life improving effect is not exhibited, and when it exceeds 50% by weight, the workability is poor.
The vinyl ester resin is used for improving the rust prevention property. The viscosity is from H to J (Gardener viscosity) at 25 ° C, the acid value is 6 to 14 mg KOH / g, the gelation time is 11.5 to 19 minutes, the peak time is 5.5 to 8.5 minutes And a peak temperature of 160 to 185 ° C can be used. If the viscosity is out of the range, the workability may be poor. If the acid value is higher than the above range, the molecular weight is low and the unreacted monomers are present and the appearance becomes worse. If the acid value is lower than the above range, Flowability may be reduced.
Although not particularly limited, the vinyl ester resin may be a resin resulting from ring-opening reaction of an epoxy resin by addition of an unsaturated carboxylic acid. Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, aliphatic epoxy resin and alicyclic epoxy resin, and preferably, Novolac epoxy resin is used.
As the unsaturated carboxylic acid, at least one selected from the group consisting of phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, methacrylic acid and trimellitic anhydride may be used, Can be used.
In one embodiment, the vinyl ester can be prepared by the following reaction formula (2).
(2)
The composition of the present invention comprises 10 to 30% by weight of a vinyl ester resin based on 100% by weight of the total composition. If it is less than 10% by weight, the effect of improving the rustproofing property is not exhibited, and if it exceeds 30% by weight, the workability is poor.
The extender pigment contained in the composition of the present invention may be selected from the group consisting of mica, glass fiber, and combinations thereof. The mica may be used for improving scratch resistance, rust prevention property, and water resistance. The mica may have a water content of 0.5 wt% or less, a pH of 6 to 8, and a body balance (325 mesh) of 10% or less. The fiberglass may be used for improving impact resistance and abrasion resistance, and may have a water content of 0.15 wt% or less, an average thickness of 3 to 7 mu m, and a particle distribution (45 to 300 mu m) of 65% or more.
When a mixture of mica and glass fiber is used, the weight ratio of mica: glass fiber may be 1: 1 to 6: 1, for example, mica may be 10 to 30 wt% And 5 to 10% by weight based on 100% by weight of the total. When the content of the mica is out of the above range, scratching resistance, rust resistance and water resistance are lowered. When the content of the glass fiber is out of the above range, the impact resistance and the abrasion resistance may be lowered.
The colored pigment used in the composition of the present invention is used for enhancing hiding power, and is not particularly limited, but titanium dioxide, carbon black, and a combination thereof may be used. Specifically, titanium dioxide can have an oil absorption of 16 to 22 or less, a tinting strength of 104 to 113%, and a body residue (325 mesh) of 25 ppm or less.
The composition of the present invention comprises from 0.1 to 5% by weight of a color pigment based on 100% by weight of the total composition. If it is less than 0.1% by weight, the hiding power is lowered, and when it exceeds 5% by weight, the workability is poor.
The composition of the present invention may include a solvent for improving wettability and workability, and is not particularly limited. A styrene monomer having a purity of 99.6% or more and a TBC (4-Tert-BUTLY CATECHOL) content of 5 to 20 ppm or Ethyl acetate (less than 1% by weight) may be used.
And 10 to 30% by weight of a solvent based on 100% by weight of the total composition. Outside of the above range, the wettability and workability may become poor.
The rust-preventive coating composition of the present invention may further comprise at least one additive selected from the group consisting of anti-sagging agents, polymerization inhibitors, defoaming agents, and combinations thereof. Although not particularly limited, hydroquinone having a pH of 4 to 4.7, a purity of 99.4% or less, and a water content of 0.5% by weight or less may be used as the polymerization inhibitor. The additive may be included in an amount of 1 to 10% by weight based on 100% by weight of the composition.
The rust-preventive coating composition of the present invention can be used as a main part of a coating material and mixed with a curing agent. The curing agent is not particularly limited, but Methyl ethyl ketone peroxide (MEKPO) may be used. The composition of the present invention may be mixed with the curing agent at a weight ratio of 90 to 100: 1.
Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
[Example]
1. Preparation of Unsaturated Polyester Resin
0.3 mol of propylene glycol, 0.7 mol of neopentyl glycol, 0.5 mol of isophthalic acid and 0.001 mol of naphthobin KX405 (manufactured by Meltel Gesellschaft AG, Germany) as a reaction stabilizer were added. After that, the condensed water begins to flow out at 170 to 180 ° C while increasing the temperature, and when the condensed water is removed while raising the reaction temperature to 210 ° C, the reactant becomes transparent. This reaction was continued while increasing the nitrogen gas injection amount to complete the reaction at an acid value of 2 to 3, followed by cooling to 120 ° C or lower to prepare a prepolymer.
0.7 mol of propylene glycol, 1.7 mol of neopentyl glycol, 0.6 mol of tetrahydrophthalic anhydride, 2.16 mol of maleic anhydride and 0.002 mol of naphthobin KX405 (manufactured by Mertel Gesellschaft AG, Germany) as a reaction stabilizer were added to the prepolymer, And the condensation water was removed while raising the reaction temperature to 210 ° C. Nitrogen was added to the mixture while maintaining the reaction temperature at that temperature, and the reaction was continued until the dilution viscosity of the styrene monomer became 3.2-3.4 poise at an acid value of 25 or less to prepare 73 parts by weight of an unsaturated polyester resin.
Then, 0.001 mol of hydroquinone was added thereto to stop further reaction. The resin was cooled to 170 to 180 DEG C and diluted to the whole amount of the styrene monomer, and then cooled to a temperature of 40 DEG C or less to obtain a viscosity of 25 , An unsaturated ester resin having an acid value of 5 to 25 mg KOH / g was prepared from V to W (Gardner viscosity).
2. Preparation of vinyl ester resin
26 parts by weight of novolac epoxy resin DEN438 (manufactured by Dow Chemical Co.), 4 parts by weight of DEN431 (manufactured by Dow Chemical Co.) and 13 parts by weight of bisphenol A type epoxy resin YD-134 (National Kagaku Kogyo) . To this were added 0.3 part by weight of hydroquinone as a polymerization inhibitor, 0.1 part by weight of toluene hydroquinone and 0.5 part by weight of heat stabilizer triphenylantimony, and 20 parts by weight of methacrylic acid previously charged in a driving tank, 3 parts by weight were added dropwise for 1 hour while maintaining 85 to 95 占 폚. After completion of the dropwise addition, the temperature was elevated to 110 ° C, and the reaction was carried out until the acid value became 14 or less and the dilution viscosity of the styrene monomer became 4.4-4.6. After cooling to 105 ° C, 10 parts by weight of a styrene monomer and additives were added, and the mixture was rapidly cooled to 30 ° C or lower. The remaining amount of the styrene monomer and the additive were added to the mixture to adjust the viscosity to H to J (Gardener viscosity) , And an acid value of 6 to 14 mgKOH / g.
3. Preparation of anticorrosive coating composition
The rust-inhibiting coating composition according to the present invention was prepared with the composition shown in Table 1 below, and the physical properties thereof were measured and shown in Table 2.
Resin 1 : unsaturated polyester resin (acid value 25 mgKOH / g or less, viscosity VW, gelling time 4 to 5 minutes, peak time 7 to 10 minutes, peak temperature 175 to 185 캜)
Resin 2 : novolac type vinyl ester resin (acid value: 6 to 14 mgKOH / g, viscosity: H to J, gel time: 11.5 to 19 minutes, peak time: 5.5 to 8.5 minutes, peak temperature: 160 to 185 ° C)
Extractive pigment 1 : mica (water content 0.5 wt% or less, pH 6-8, sieve residue (325 MESH) 10% or less)
Extractive pigment 2 : Glass flake (moisture content 0.15% or less, average thickness 3 to 7 탆, particle distribution (45 to 300 탆) 65% or more)
Colored pigment: TiO 2 (oil absorption of 16 to 22 or less, coloring power of 104 to 113%, sieve residue (325 MESH) of 25 ppm or less)
Additives: Sagging agent (Garamite 1958)
Polymerization inhibitor: Hydroquinone
MEKPO: Methyl ethyl ketone peroxide
※ Property evaluation test / evaluation method
1. Storage
- Fill the resin to be analyzed with about 70% of the tin can, then immerse in about 70% in 70 ℃ oil bath shaker and fix. Open the tin cans for a certain period (every 12 hours) and check the resin condition. At this time, if the resin becomes a gel and does not have fluidity, the test is terminated.
2. Rust prevention
- Scribe the specimen and test it in the Salt Spray Chamber for a certain period of time.
- Conditions in Salt Spray Chamber: Solution (spraying 5% NaCl, pH: 6.5 ~ 7.2), temperature (about 35 ℃), relative humidity (95 ~ 98%
- Method of evaluation: Rus Creepage measurement after 4,200 hours of test.
Evaluation criteria: 1 mm to 5 mm (O), 6 mm to 8 mm (O?), 8 mm to 10 mm (?),> 10 mm (X)
3. Adhesiveness
- Test the adhesion of the film using Pull off Adhesion Tester
Evaluation criteria: 10 MPa to 15 MPa (O), 5 MPa to 10 MPa (O DELTA), 3 MPa to 5 MPa (DELTA)
≪ 3 MPa (X)
4. Workability
- When painting on smooth steel panel using airless sprayer, check the paint pattern, the appearance of the formed film, and the scratch resistance.
As can be seen from Table 2, the rust-preventive coating compositions of Examples 1 and 2 showed excellent storage stability, rust-preventive properties, adhesion and workability. However, in Comparative Examples 1 and 2 in which the content of unsaturated polyester resin was small, gelation occurred and workability was poor. In addition, Comparative Example 3 containing no vinyl ester showed poor rust prevention, adhesion and workability, and Comparative Example 4 in which unsaturated polyester was not included showed poor storage stability and workability.
Claims (6)
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KR1020160008323A KR101869591B1 (en) | 2016-01-22 | 2016-01-22 | Anticorrosive Coating Composition comprising unsaturated polyester and vinyl ester |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20220139519A (en) * | 2021-04-08 | 2022-10-17 | (주)켐베이스 | Unsaturated polyester resin composition with high strength and manufacturing method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000072957A (en) * | 1998-08-28 | 2000-03-07 | Hitachi Chem Co Ltd | Vinyl ester resin composition |
JP2001226523A (en) * | 2000-02-17 | 2001-08-21 | Tamada Kogyo Kk | Rust prevention additive, resin composition containing the same, and rust prevention structure therewith |
JP2001279190A (en) * | 2000-01-28 | 2001-10-10 | Dainippon Toryo Co Ltd | Antifouling coating material composition |
KR20060046372A (en) * | 2004-06-02 | 2006-05-17 | 간사이 페인트 가부시키가이샤 | Unsaturated polyester resin composition and coating method by use of the same |
KR20110050508A (en) * | 2008-08-21 | 2011-05-13 | 쇼와 덴코 가부시키가이샤 | Anti-corrosion paint composition and anti-corrosion paint film structure using the same |
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2016
- 2016-01-22 KR KR1020160008323A patent/KR101869591B1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000072957A (en) * | 1998-08-28 | 2000-03-07 | Hitachi Chem Co Ltd | Vinyl ester resin composition |
JP2001279190A (en) * | 2000-01-28 | 2001-10-10 | Dainippon Toryo Co Ltd | Antifouling coating material composition |
JP2001226523A (en) * | 2000-02-17 | 2001-08-21 | Tamada Kogyo Kk | Rust prevention additive, resin composition containing the same, and rust prevention structure therewith |
KR20060046372A (en) * | 2004-06-02 | 2006-05-17 | 간사이 페인트 가부시키가이샤 | Unsaturated polyester resin composition and coating method by use of the same |
KR20110050508A (en) * | 2008-08-21 | 2011-05-13 | 쇼와 덴코 가부시키가이샤 | Anti-corrosion paint composition and anti-corrosion paint film structure using the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220139519A (en) * | 2021-04-08 | 2022-10-17 | (주)켐베이스 | Unsaturated polyester resin composition with high strength and manufacturing method thereof |
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