阅读说明：本技术 氟涂料组合物 (Fluorine coating composition ) 是由 郑容旭 金龙洙 金旼俊 于 2019-07-09 设计创作，主要内容包括：本发明涉及一种包含含氟共聚物及热固性丙烯酸树脂的氟涂料组合物,所述热固性丙烯酸树脂由包含甲基丙烯酸烷基酯、丙烯酸烷基酯及丙烯酰胺中的一个以上的单体制备。(The present invention relates to a fluorine coating composition comprising a fluorine-containing copolymer and a thermosetting acrylic resin prepared from a monomer comprising one or more of alkyl methacrylate, alkyl acrylate and acrylamide.)

1. A fluorine coating composition, wherein,

comprises a fluorine-containing copolymer and a thermosetting acrylic resin,

the thermosetting acrylic resin is prepared from monomers comprising 5 to 50 wt% of alkyl methacrylate, 5 to 25 wt% of alkyl acrylate, and 2 to 20 wt% of acrylamide.

2. The fluorine coating composition according to claim 1,

comprising 10 to 30 wt% of a fluorine-containing copolymer and 2 to 8 wt% of a thermosetting acrylic resin.

3. The fluorine coating composition according to claim 1,

the fluorine-containing copolymer is more than one of polyvinylidene fluoride and polyvinyl fluoride.

4. The fluorine coating composition according to claim 1,

the viscosity of the fluorocopolymer is from 25 to 35 kPs.

5. The fluorine coating composition according to claim 1,

the thermosetting acrylic resin is prepared from a monomer containing one or more of methyl methacrylate, ethyl acrylate and acrylamide.

6. The fluorine coating composition according to claim 1,

the thermosetting acrylic resin is prepared from monomers comprising methyl methacrylate, ethyl acrylate and acrylamide.

7. The fluorine coating composition according to claim 1,

the mixing ratio of the alkyl methacrylate, the alkyl acrylate and the acrylamide is 1: 0.1-10: 0.1 to 10.

8. The fluorine coating composition according to claim 1,

the thermosetting acrylic resin has a weight average molecular weight of 30000 to 85000 and a glass transition temperature of 30 to 60 ℃.

Technical Field

The present invention relates to a fluorine coating composition having excellent corrosion resistance and coating workability.

Background

The fluorine coating containing the fluorine resin has excellent chemical reagent resistance, weak water permeability and excellent corrosion resistance, so the fluorine coating can be applied to structures such as building appearances, street lamps, guardrails, advertising boards and the like, and has the effects of preventing surface oxidation and discoloration. Further, a fluorine coating material containing a fluorine resin such as polyvinylidene fluoride (PVDF) has high coating film strength and excellent durability such as corrosion resistance and weather resistance, and thus can be applied to automobile parts (for example, pipes for internal combustion engines).

Conventional fluorine paints are suitable for spraying a base material such as an aluminum plate, using a fluororesin and a thermoplastic acrylic resin as main agents. However, in order to apply such a fluorine Coating material to pipes for automobile internal combustion engines and the like, it is necessary to apply a Flow Coating (Flow Coating) method rather than a spray Coating method, and the conventional fluorine Coating material cannot satisfy Coating workability (Thixotropy) and the like) required by the Flow Coating (Flow Coating) method, and thus it is difficult to apply the fluorine Coating material to the above-mentioned applications.

Disclosure of Invention

Problems to be solved by the invention

The invention provides a fluorine coating composition having excellent coating film strength, durability such as corrosion resistance and weather resistance, and coating application property.

Means for solving the problems

The present invention provides a fluorine coating composition comprising a fluorine-containing copolymer and a thermosetting acrylic resin prepared from one or more monomers including alkyl methacrylate, alkyl acrylate and acrylamide.

Effects of the invention

The invention provides a fluorine coating composition having excellent coating film strength, durability such as corrosion resistance and weather resistance, and coating application property. The fluorine coating composition according to the present invention can be applied to automobile parts (for example, pipes of automobile internal combustion engines).

Detailed Description

The present invention will be explained below. However, the present invention is not limited to the following, and various modifications and selective combinations of the respective components may be made as required. Therefore, the present invention should be understood to include all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.

The fluorine coating composition according to the present invention comprises a fluorine-containing copolymer and a thermosetting acrylic resin. The thermosetting acrylic resin may be prepared from a monomer including one or more of alkyl methacrylate, alkyl acrylate, and acrylamide. The fluorine coating composition of the present invention may further contain a pigment, a solvent and additives generally used in the coating field as necessary. The composition of the fluorine coating composition of the present invention is as follows:

fluorine-containing copolymer

In the present invention, the fluorocopolymer functions to improve the corrosion resistance of the coating composition. The fluorine-containing copolymer, for example, may use a polymer (copolymer) prepared from one or more monomers selected from the following group: vinylidene fluoride (VDF), Vinyl Fluoride (VF), Hexafluoropropylene (HFP), Tetrafluoroethylene (TFE), Chlorotetrafluoroethylene (CTFE), and Perfluoromethylvinylether (PMVE). The fluorine-containing copolymer may be, for example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), or a mixture thereof. Polyvinylidene fluoride (PVDF) and polyvinyl fluoride (PVF) combine excellent chemical resistance and good mechanical, thermal and electrical properties.

The fluorocopolymer may have a Melt Index (Melt Flow Index) of 2.0 to 6.0g/10min and a viscosity of 25 to 35 kPs.

The polyfluoro copolymer may be present in an amount of about 10 to about 30 weight percent, for example, about 15 to about 20 weight percent, based on the total weight of the fluorine-containing coating composition. If the fluorine-containing copolymer component in the fluorine-containing coating component exceeds 30% by weight, it becomes difficult to sufficiently disperse the fluorine-containing coating, and it becomes difficult to form a uniform coating film, the appearance of the coating film becomes poor, the bonding force between resins decreases, and there is a possibility that the adhesion to the object to be coated and the mechanical and physical properties of the coating film decrease. On the other hand, if the content of the fluorocopolymer is less than 10% by weight, chemical resistance, corrosion resistance and weather resistance may be deteriorated.

Thermosetting acrylic resin

As the resin in the coating composition according to the present invention, a thermosetting acrylic resin is used together with the fluorine-containing copolymer. The thermosetting acrylic resin plays a role in improving the appearance of the coating film and increasing the hardness.

The thermosetting acrylic resin may be prepared using a monomer including one or more of alkyl methacrylate, alkyl acrylate, and acrylamide.

As the alkyl methacrylate, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate can be used, and they can be used singly or in combination of two or more. As the alkyl acrylate, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate can be used, and they may be used singly or in combination of two or more. N- (butoxymethyl) -2-acrylamide can be used as the acrylamide.

The thermosetting acrylic resin may be prepared from monomers including one or more of methyl methacrylate, ethyl acrylate, and acrylamide.

In addition, the thermosetting acrylic resin may be prepared from monomers including methyl methacrylate, ethyl acrylate, and acrylamide.

The thermosetting acrylic resin may comprise: alkyl methacrylate 5 to 50 wt%, e.g., 10 to 30 wt%; alkyl acrylate 5 to 25 wt%, e.g., 8 to 18 wt%; and 2 to 20 wt% acrylamide, for example, 3 to 10 wt%.

If the content of the alkyl methacrylate in the thermosetting acrylic resin is less than 5% by weight, the flexibility of the coating film may be reduced, and if it exceeds 50% by weight, the adhesion may be reduced. If the alkyl acrylate content is less than 5% by weight, the compatibility with the fluororesin may be lowered, and if it exceeds 25% by weight, the weather resistance may be lowered. If the acrylamide content is less than 2 wt%, the reactivity may be lowered and the hardness may be deteriorated, and if it exceeds 20 wt%, the hardening may be excessively caused depending on the temperature.

The mixing ratio of the alkyl methacrylate, the alkyl acrylate and the acrylamide in the thermosetting acrylic resin can be as follows by weight ratio: for example, 1: 0.1-10: 0.1 to 10, such as 1: 0.1-5: 0.1 to 3. If the mixing ratio of the thermosetting acrylic resin is out of the above range, the corrosion resistance and coating workability of the coating composition may be deteriorated.

The thermosetting acrylic resin may have a weight average molecular weight of about 30000 to 85000, for example, 35000 to 85000, and further for example, 35000 to 75000. The thermosetting acrylic resin has a glass transition temperature (Tg) of 30 to 60 ℃, for example, about 40 to 50 ℃.

The thermosetting acrylic resin is used in an amount of about 2 to 8% by weight, for example, about 3 to 6% by weight based on the total amount of the fluorine coating composition. When the thermosetting acrylic resin is used in the above-mentioned range, the fluorine coating material can be prevented from cracking, and the coating workability and hardness can be effectively improved.

Pigment (I)

The fluorine coating composition according to the present invention may further contain a pigment as necessary. The pigment is contained herein for the purpose of developing the paint into a desired color (color) or enhancing the strength or gloss of the coating film.

The pigment may use organic pigments, inorganic pigments, metallic pigments, aluminum paste (Al-paste), Pearl pigments (Pearl), base pigments, etc. which are generally used in the coating field without limitation, and they may be used singly or in combination of two or more. As the pigment, there can be used, by way of non-limiting example, pigments of red series, yellow/orange series, blue series, black series, white series, pearl pigment, metallic series, and the like.

In the present invention, the content of the pigment is not particularly limited, and may be about 5 to 15% by weight based on the total amount of the fluorine coating composition. When the pigment content is within the above range, the appearance and mechanical and physical properties of the coating film can be improved without lowering the dispersibility and storage stability.

Additive agent

The fluorine coating composition according to the present invention may optionally contain conventional additives known in the art, in addition to the aforementioned components, as required. Non-limiting examples of additives that may be used in the present invention are: thixotropic agents, antifoaming agents, leveling agents, surface modifiers, ultraviolet absorbers, ultraviolet stabilizers, drying agents, moisture absorbents, waxes, and the like.

The content of the additive is not particularly limited, and may be 0.1 to 5% by weight based on the total amount of the fluorine coating composition.

Solvent(s)

The fluorine coating composition according to the present invention may further comprise a solvent as necessary. The solvent can adjust the viscosity of the coating composition to facilitate coating operation, and can adjust the volatilization speed of the solvent to improve the leveling property and coating application property of a coating film (coating).

There is no particular limitation on the solvent that can be used in the present invention, which is a conventional solvent known in the art. For example, ketone solvents, ester solvents, ether solvents, hydrocarbon solvents, alcohol solvents, or mixtures thereof may be used.

By way of non-limiting example of such solvents, there are: butyl acetate, propylene glycol methyl ether, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzene, acetone, tetrahydrofuran, dimethylformamide, dimethyl phthalate, cyclohexanone, methanol, ethanol, and the like. They may be used singly or in combination of two or more.

In the present invention, the content of the solvent is not particularly limited, and may be a margin for adjusting the total amount of the fluorine coating composition to 100% by weight, for example, may be 50 to 70% by weight. When the solvent content is within the above range, workability and appearance characteristics of the coating film can be improved.

The present invention is specifically illustrated by the following examples. The following examples are merely intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention in any sense.

Examples 1 to 5 and comparative examples 1 to 4

The fluorine coating compositions of examples 1 to 5 and comparative examples 1 to 4 were prepared by blending the respective components according to the compositions described in the following Table 1.

[ TABLE 1 ]

1) Fluorine-containing copolymer 1: polyvinylidene fluoride resin (Hylar 5000, ARKEMAINC, viscosity 31kPs)

2) Fluorine-containing copolymer 2: polyvinyl fluoride resin (ZFT-9, LANITAN, viscosity 30kPs)

3) Thermosetting acrylic resin 1: methyl methacrylate (25%), ethyl acrylate () 11%, N- (butoxymethyl) -2-acrylamide (N- (butoxymethyl) -2-propenamide) 5% (CRT00431, KCC Corp., weight average molecular weight: 68000, Tg: 51 ℃ C.)

4) Thermosetting acrylic resin 2: methyl methacrylate 10%, ethyl acrylate 15%, N- (butoxymethyl) -2-acrylamide 10% (CRT00329, KCC, weight-average molecular weight: 37000, Tg: 45 ℃ C.)

5) Thermosetting acrylic resin 3: 20% of methyl methacrylate, 11% of ethyl acrylate, 25% of N- (butoxymethyl) -2-acrylamide (weight-average molecular weight: 43000, Tg: 45 ℃ C.)

6) Thermosetting acrylic resin 4: methyl methacrylate 30%, ethyl acrylate 2%, N- (butoxymethyl) -2-acrylamide 9% (weight-average molecular weight: 54000, Tg: 51 ℃ C.)

7) Thermoplastic acrylic resin: SS-4007, DONGINCCHEMICAL Co. (viscosity Z, solids 40)

8) Pigment 1: chrome antimony titanium rutile (chrome antimony titanium buff rutile) (BBY24828)

9) Pigment 2: camouflage Green (Camuulage Green) No.179(BBG23063)

10) Pigment 3: zinc phosphate (zinc phosphate) (BBZ53642)

11) Additive 1: thixotropic Agent (Thixotropy Agent)1(BYK 410)

12) Additive 2: thixotropic agent 2(BYK430)

13) Additive 3: surface modifier (Slip Agent) (AEK56889)

14) Solvent: phthalic acid dimethyl ester

[ Experimental example-evaluation of physical Properties ]

The physical properties of the fluorine coating compositions prepared in examples 1 to 5 and comparative examples 1 to 4, respectively, were measured as follows, and the results thereof are shown in Table 2.

Adhesion property

After the Tape was applied to 100 scales (1 mm × 1 mm) in accordance with ASTM D3359 (Cross-cut Tape Test), the number of scales (N) remaining after the Tape was peeled off was measured and represented as N/100.

Newton's hardness

When the newton hardness was measured, the newton value at which the coating film was not broken was measured.

Flexibility

The test piece was bent (bending) in accordance with ASTM D4145, and the degree of cracking (crack) of the coating film at the bent portion and the peeling (peel-off) of the coating film after taping (taping) were evaluated.

MEK Rubbing (degree of cure)

After the gauze was sufficiently soaked with a Methyl Ethyl Ketone (MEK) solution, a load of 1 to 1.5kg was applied and the gauze was rubbed on the test piece at a speed of 100 reciprocations per minute by a length of 10cm and a predetermined number of times (rubbi ng), and the test piece was observed and evaluated after the end of the test.

Viscosity of the oil

Measured at 25 ℃ with Ford Cup No. 4.

TI (swinging modification)

TI (shaking property) was determined by measurement with LVT viscometer (BROOKFIELD).

Shaking property (viscosity at 5 revolutions/viscosity at 50 revolutions)

Bendability

A Test piece (having a length of 35mm or more and a thickness of 4mm or less) was bent at 120 ℃ once using a bending tester, and then Tape Test was performed three times. The samples before and after the test were compared, and the processed surface was evaluated as good (OK) if no peeling occurred, and as bad (NG) if a peeled surface existed.

Corrosion resistance

After forming an X-shaped cut in the center of the test piece with a knife according to ASTM B117, a corrosion resistance test was conducted for 1000 hours, and then whether or not blisters occurred was evaluated (Blister).

Storage stability

The presence of precipitates was observed after heat storage in an oven at 60 ℃ for seven days. If no precipitate is present, the determination is good.

[ TABLE 2 ]

The fluorine coating compositions according to examples 1 to 5 of the present invention showed excellent physical properties in all physical properties measured. In contrast, the fluorine coating composition of comparative example 1, in which the thermosetting acrylic resin was replaced with the thermoplastic acrylic resin, was inferior in the measured curability and the shaking property. Further, the fluorine coating composition of comparative example 2, which does not contain the fluorine-containing copolymer, is poor in the overall physical properties such as hardness, bendability, degree of curing, shaking property and corrosion resistance measured. The thermosetting acrylic resin having a monomer composition (content range) outside the fluorine coating compositions of comparative examples 3 and 4 of the present invention was poor in the overall physical properties such as adhesion and hardness as measured.