KR101116841B1 - Paint composition of bisphenol f epoxy - Google Patents

Abstract

The present invention is 20 to 40% by weight of bisphenol F-type epoxy resin, sieving pigment 30 to 50% by weight, reactive diluent 1 to 5% by weight, non-reactive diluent 1 to 5% by weight, additives 2 to 10% by weight and solvent 5 to 20 A bisphenol F-type epoxy liquid coating composition comprising a weight%, a curing agent composed of 15 to 35 weight% of modified amide curing agent, 0.1 to 5 weight% of curing accelerator, 30 to 50 weight% of extender pigment, and 10 to 40 weight% of solvent; Bisphenol F-type epoxy liquid coating composition comprising a, the coating composition is excellent in workability and flow resistance when coating the coating, the dried coating is excellent in adhesion with the coating, chemical resistance, water resistance In addition, it is excellent in hardness and abrasion resistance, and since no harmful substances are detected in the dissolution test of the coating film, it can be preferably applied to a subject for drinking water pipe use.

Bisphenol F type epoxy, liquid paint, inner surface of steel pipe, environmental hormone

Description

Bisphenol F type epoxy liquid coating composition {PAINT COMPOSITION OF BISPHENOL F EPOXY}

The present invention relates to a two-component epoxy liquid coating composition, and more particularly to an epoxy liquid coating composition for the inner surface of the steel pipe.

The present invention relates to an epoxy liquid coating composition used for the inner surface of a steel pipe, generally epoxy resin has excellent hardness, durability, processability, and when bonded with a suitable curing agent has a large adhesion to the surface of the subject, mechanical and chemical properties It is excellent in general use and is widely used.

At present, Doctile cast iron pipes, steel pipes and fittings are anti-corrosion and protective coating agents, and bitumen paints or bisphenol A (BPA) epoxy liquid paints have already been developed and applied. Here, the bisphenol A type epoxy liquid paint is excellent in durability, workability and adhesion to the subject, and also has high mechanical and chemical resistance.

The resins used in the bisphenol A type epoxy liquid paints are the most important commercially available epoxy resins to date, mainly diphenylopropane (DPP) and epichlorohydrin (known as bisphenol A). It is a diglycidyl ether type epoxy resin produced by condensation reaction with ECH).

However, the bisphenol A type is a material that is gradually being disputed with respect to environmental friendliness.

Accordingly, there is a need for an alternative to an epoxy liquid coating composition that can be preferably used in place of a bisphenol A resin.

In order to solve the above problems, the present invention has an object of providing an epoxy liquid coating composition that is safe when used for water and sewage pipes using an epoxy resin having a physical property equivalent to or more than the bisphenol A and no human hazards.

Bisphenol F type epoxy liquid coating composition according to the present invention, 20 to 40% by weight of bisphenol F type epoxy resin, sieving pigment 30 to 50% by weight, reactive diluent 1 to 5% by weight, non-reactive diluent 1 to 5% by weight, additives It is characterized by comprising 2 to 10% by weight and 5 to 20% by weight of the solvent.

The reactive diluents described above are creylglycidyl ether, versatic acid glycidyl ester, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, parabutyl phenyl phenyl glycidyl ether, neopentyl digly It is characterized in that the at least one selected from the group consisting of cydyl ether, 1,4-butane diglycidyl ether, cyclohexane dimethanol diglycidyl ether,

Said non-reactive diluent is another specific feature that is at least one selected from the group consisting of benzyl alcohol and perfuryl alcohol.

In addition, the bisphenol F-type epoxy liquid coating composition further comprises a curing agent consisting of a modified amide-based curing agent 15 to 35% by weight, a curing accelerator 0.1 to 5% by weight, a sieving pigment 30 to 50% by weight and a solvent 10 to 40% by weight. It is characterized by including.

Here, the bisphenol F-type epoxy liquid coating composition and the curing agent is another feature that is mixed in an equivalent ratio of 1: 1.

And, the curing agent is at least one member selected from the group consisting of amide, anhydride, polymercaptan, polysulfide of the MODIFIED type, ADDUCT type, ACCELERATED type ,

The above-mentioned curing accelerator is at least one selected from imidazoles, imidazole modified epoxy, di-oil and non-sulphate salts, butyl triphenyl phosphonium bromide, butyl triphenyl phosphate oxalate, and butyl triphenyl phosphonium chloride. It is done.

The present invention is a bisphenol F type epoxy liquid coating composition for inner surface of steel pipes using a bisphenol F type epoxy liquid coating composition having a limited equivalent range and a special epoxy curing agent, and can exhibit excellent physical properties in chemical resistance, solvent resistance, abrasion resistance, and the like. By not containing harmful controversial bisphenol A epoxy, it can be safely used not only for water pipes but also for sewage pipes, thereby expanding the range of use of liquid paints.

The bisphenol F type epoxy liquid coating composition of the present invention is composed of a bisphenol F type epoxy resin, a sieving pigment, a reactive diluent, a non-reactive diluent, an additive, and a solvent.

The epoxy resin used for the composition according to the present invention is a bisphenol F type epoxy resin represented by the following general formula (1).

(In Formula 1, n is an integer of 1 to 10)

Bisphenol F-type epoxy resin of Formula 1 is a diglycidyl ether type epoxy resin produced by the condensation reaction of diphenylomethane and epichlorohydrin (epichlorohydrin). The bisphenol F-type epoxy resin is a resin having hydrogen (H) instead of the methyl group (-CH ₃ ) among the bisphenol A-type molecules, and has a lower viscosity than the bisphenol A type, excellent compatibility with other resins, and mechanical The chemical resistance is also excellent. Moreover, it does not contain bisphenol A which is an existing environmentally controversial issue.

In particular, the present invention uses a bisphenol F type epoxy resin having an epoxy equivalent of 160 to 180 g / eq as the bisphenol F type epoxy resin. The epoxy resin is used 20 to 40% by weight based on the total weight of the liquid coating composition, if less than 20% by weight of the coating film due to the increase in the relative pigment content is lowered, the physical properties such as chemical properties, such as 40 weight When it exceeds%, it is difficult to secure an appropriate coating thickness due to the flowability of the paint, which lowers the painting workability, and causes a problem of poor appearance of the coating.

In the present invention, the extender pigment that fills pores in the coating film and controls the supplementation and gloss of hardness and chemical properties, etc., in particular, a pigment having excellent durability should be selected in consideration of the durability of the coating film. It has a big impact. The extender pigment may be used, for example, one or more selected from silica, barium sulfate and calcium carbonate. The extender pigment may be used in the main portion containing the epoxy resin 30 to 50% by weight, the extender pigment may be used in the curing agent portion containing the amine-based curing agent 30 to 50% by weight. At this time, when the use range is less than the problem of the film (sagging) of the coating occurs, the mechanical properties are lowered, when the use range is exceeded, the content of the epoxy resin is relatively lowered, the physical properties of the coating film is lowered, the viscosity is increased a lot Miscompatibility and workability are caused.

In addition, the bisphenol F-type epoxy liquid paint is used to maintain a high solid content while maintaining a relatively low viscosity to improve workability. The diluent has an epoxide group and is classified into a reactive diluent which participates in the reaction with the curing agent and a non-reactive diluent which does not participate in the reaction but remains in the coating film and affects the physical properties. Types of the reactive diluents include mono epoxides such as cresylglycidyl ether, versatic acid glycidyl ester, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, parabutyl phenyl phenyl glycidyl Ethers and the like, and diepoxides such as neopentyl diglycidyl ether, 1,4-butane diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and the like. The reactive diluent may be used at least one type, in particular, more preferably using a versatic acid glycidyl ester of a viscosity of 5 ~ 10cps (25 ℃) and epoxy equivalent (EEW). Also, the non-reactive diluent may be used one or more selected from, for example, benzyl alcohol and perfuryl alcohol.

The reactive diluent is 1 to 5% by weight based on the total weight of the liquid coating composition, 1 to 5% by weight of the non-reactive diluent, and less than the range of use of the extender pigment relative to the amount of physical pigments available, the mechanical properties There is a problem that can be lowered, relatively less viscosity lowering effect, when exceeding the range, mechanical properties such as hardness is lowered and the curing rate is lowered.

In the present invention, as the additive, a low molecular weight carboxylic acid type dispersant, a polysiloxane type antifoaming agent, a non-silicone polymer type defoamer, a clay type sedimentation inhibitor, and a polyacrylic type leveling agent are respectively contained in the liquid coating composition. 10% by weight is used.

In particular, when the antifoaming agent, the defoamer, and the leveling agent are not used properly, coating film defects such as defoaming defects and crettering may occur. In general, in the case of an epoxy liquid paint, an antifoaming agent and a defoamer must be used in combination so that bubbles in the coating film can quickly rise to the surface together with the bubble removal on the surface of the coating film. If bubbles inside do not rise quickly and remain in the coating film, they may cause poor adhesion to the substrate or deterioration of physical properties.However, even if the surface bubbles are hardened, the flow of the coating film decreases as the flow of the coating film decreases. Can remain.

In addition, when the content of the anti-settling agent is less than 1% by weight, the leveling of the coating film is very good, but the storage property of the paint is poor and problems of flowing down during the coating of the paint occur. It is excellent and the problem of flowing down during paint coating is reduced, but the leveling of the coating film may be poor. Therefore, an appropriate amount of anti-settling agent should be used to ensure the storage stability of the paint and the leveling of the coating at the same time.

In the present invention, the solvent is generally used as a solvent used in epoxy liquid paints, Ketones, Esters, Alcohols, Glycols and the like are used, it is preferable to be used in combination of one or more, based on the total weight of the coating composition 5 to 20% by weight.

Next, the bisphenol F-type epoxy liquid coating composition of the present invention is a modified amide-based curing agent, a curing accelerator, a sieving pigment in the main portion containing a bisphenol F-type epoxy resin, a sieving pigment, a reactive diluent, a non-reactive diluent, an additive and a solvent. The hardening agent consisting of a solvent may be mixed.

The curing agent should be used to best exhibit the properties of the resin used. In addition, the content of the curing agent depends on the type and amount of the epoxy resin and the reactive diluent used as the subject, and in general, the equivalent ratio in consideration of the epoxy equivalent ratio (EEW) of the epoxy resin and the reactive diluent and the active hydrogen equivalent ratio (AHEW) of the curing agent. The formulation is adjusted to be 1: 1, and the modified amide curing agent in the present invention uses 15 to 35% by weight in the curing agent of the paint.

Hardening accelerators are used when rapid curing and low temperature curing are necessary because the room temperature curing of the epoxy resin generally requires a temperature of 15 ° C. or more and the curing time requires 24 hours or more. In order to accelerate the curing of the epoxy resin, those containing chemical groups which have an promoting effect on the terminal groups are used.

End groups having such a promoting effect include -OH, -COOH, -SO ₃ H, -CONH ₂ , -SO ₃ NH ₂ and the like, including 2-methylimidazole, 2-phenylimidazole, 2- Imidazoles such as isopropyl imidazole and 2-undecyl imidazole, imidazole modified epoxy, di- and non-sulphate salts, butyl triphenyl phosphonium bromide, butyl triphenyl phosphate oxalate, butyl triphenyl phosphonium It is possible to select from the group consisting of chlorides and mixtures thereof. Generally, a curing accelerator may be a compound having an -OH group, and the like, and Mercaptanes having a -SH group may be used as a low temperature and rapid curing accelerator.

The said hardening accelerator is used at 0.1 to 5 weight% in a hardening | curing agent. If the content of the curing accelerator is less than the above range, the curing time is long, and on the contrary, even if the curing accelerator is used over the above range, there is no significant difference in effect, which is uneconomical.

In addition, the solvent in the curing agent is generally used in the epoxy liquid paints Ketones, Esters, Alcohols, Glycols, etc. are used, preferably used by mixing one or more, based on the total weight of the curing agent 10 40 wt%.

The modified amide curing agent and the extender pigment may be mixed in an amount of 15 to 35:30 to 50% by weight, and then added in an equivalence ratio of 1: 1 to the total mixed component to prepare an epoxy coating composition.

As described above, the coating film made of the epoxy liquid coating composition prepared according to the present invention is excellent in adhesion to the object, excellent in durability and chemical properties, and no harmful substances are detected in the dissolution test of the coating film. There is a characteristic. Therefore, it can be preferably applied as a coating material on the inner surface of the water and sewage pipe.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Thematic  My article

[ Preparation Example 1 ]

29 weight% of bisphenol-F type epoxy resin (EEW: 160-180e / q, Kukdo Chemical Co., Ltd.), 3 weight% of reactive diluents of Versatic acid glycidyl ester (EEW: 250e / q, Shell product), non-reactive 3 weight% of diluent (benzyl alcohol), 0.5 weight% of carboxylic acid type dispersant (BYK, BYK-P-104S), 1.0 weight% of clay type anti-settling agent (Rheox, Benton-27), antifoaming agent of polysiloxane type (BYK Co., Ltd., BYK-066N), a non-silicone defoamer (BYK Co., Ltd., BYK-501) were each mixed with 0.3 wt% and sufficiently stirred to prepare a reaction solution. The sieving pigment was slowly added to the reaction solution and stirred, and the white pigment (TiO ₂ ) and the black pigment (Carbon Black) were slowly added and stirred as the color pigment. After dispersing the reaction solution using a sand mill until the particle size became 35 μm or less, 0.2 wt% of a silicon-based leveling agent (BYK, BYK-333) was added and stirred to prepare a main body.

[ Preparation Example 2 ]

Prepared in the same manner as in Preparation Example 1, but prepared by replacing the reactive diluent 1% by weight, the non-reactive diluent 1% by weight.

[ Preparation Example 3 ]

Prepared in the same manner as in Preparation Example 1, but replaced with a sieving pigment 48% by weight.

[ Production Example 4 ]

Manufactured in the same manner as in Preparation Example 1, 43 weight% of bisphenol F-type epoxy resin, 7 weight% of reactive diluent, 9 weight% of non-reactive diluent, and 15 weight% of extender pigment.

The results of the above-mentioned [Example 1] to [Example 4] are shown in the following [Table 1].

Chart / Combination (Weight Ratio) Preparation Example 1 Production Example 2 Production Example 3 Preparation Example 4 Bisphenol F type epoxy resin 29 29 29 43 Reactive diluent 3 One 3 7 Non-reactive diluent 3 One 3 9 Dispersant 0.5 0.5 0.5 0.5 Sedimentation inhibitors 1.0 1.0 1.0 1.0 Antifoam 0.3 0.3 0.3 0.3 Defoamer 0.3 0.3 0.3 0.3 Sieving pigment 39 43 48 15 Color Pigment 8 8 8 8 Leveling agent 0.2 0.2 0.2 0.2 toluene 4 4 One 4 Butyl cellosolve 3 3 One 3 M.I.B.K 0.5 0.5 0.5 0.5 xylene 8.2 8.2 4.2 8.2 Sum 100 100 100 100

Of hardener  Produce

[ Production Example 5 ]

After mixing 25% by weight of modified amide resin (100% of solid content, AHEW: 65-85 g / eq, HEXION product), sieving pigment 40% by weight, 0.1% by weight of non-silicone defoamer (BYK, BYK-501) After stirring at a speed of 2000 rpm or more and stirring until the particle size became 35 µm or less, a curing agent which was a second composition was prepared.

Preparation of Paint Composition

[ Example 1 ] ~ [ Example 4 ]

The coating composition was prepared by mixing the main agent prepared in [Preparation Example 1] to [Preparation Example 4] and the curing agent of the polyamine system prepared in [Preparation Example 5] in an equivalent ratio of 1: 1, and the results are shown in the following [Table 2]. ].

Experimental Example

After coating the liquid coating composition prepared in the above [Example 1] to [Example 4] with a dry film thickness of about 400㎛ each, dried at room temperature (20 ~ 25 ℃) for 7 days and then measured physical properties by the following method The results are shown in [Table 2].

Property test method

1. pencil hardness

The coating composition was coated on a steel panel (STEEL PANEL) having a thickness of 2 mm or more, and hardness was measured using a Mitsubishi (MITSU-BISHI) pencil.

2. Chemical resistance

The coating composition was coated on the night light, and spotting was performed for 1 week to observe color, gloss change and other coating defects.

3. Solvent resistance

The paint composition was coated on the chestnut and the specimen was completely deposited and tested for one week to observe color, gloss change and other defects.

4. Water resistance

The coating composition was coated on a glass plate and a immersion test was performed for 1 week to observe color, gloss change, and other coating defects.

5. Wear resistance

The coating composition is coated on a polyester film and tested using a TABER ABRASION tester.

NO. The loss amount of the coating film was measured by using the ablation wheel (ABRASION WHEEL) of CS-17 and testing 10000 revolutions under a load of 1000 g.

6. Impact resistance

After coating the coating composition on a steel panel (STEEL PANEL) having a thickness of 2 mm or more and applying an impact of 70 lb-in, the coating film was damaged and the adhesion was observed.

7. Workability

Spray was applied to the night light, and the mixing properties of the main and hardener portions, ease of operation, thickness, gloss, leveling, and other appearance of the coating film formed were observed.

8. Flow resistance

The steel panel (STEEL PANEL) having a thickness of 2 mm or more was erected and coated using a spray, and then the flowability of the coating film was observed.

9. Zhejiang

After the main material was contained in a volume of 0.5L tin can about 80% by volume and stored in a sealed state for 7 days at 60 ℃, the paint thickening, sedimentation, and the degree of layer separation was measured.

10. Dissolution test

It measured according to KSD 8502.

No. Test Items Example 1 Example 2 Example 3 Example 4 Remarks One Pencil strength ○ ○ ○ ○ 2 Chemical resistance HCL ○ ○ △ △ 10% solution SPOTTING 3 Solvent resistance xylene ◎ ◎ ○ ○ DIPPING 4 Water resistance ◎ ◎ ◎ ○ DIPPING 5 Wear resistance ◎ ◎ ○ ○ 6 Impact resistance ◎ ○ △ △ 7 Workability ◎ ○ △ △ 8 Flow resistance ◎ ◎ ○ △ 9 Zhejiang ◎ ◎ △ ○ 60 ℃ × 7 days 10 Dissolution Test ◎ ◎ ◎ ◎ ◎: Excellent, ○: Good, △: Normal, ×: Poor

As shown in Table 2, the bisphenol F-type epoxy liquid coating composition according to the present invention not only has excellent chemical resistance and solvent resistance, but also exhibited excellent physical properties in hardness and wear resistance, and the dissolution test resulted in dissolution of harmful substances. There was no.

[Effects of the Invention]

The present invention produced a BPF EPOXY liquid coating composition for the inner surface of the steel pipe using a bisphenol F-type epoxy resin and a special epoxy curing agent of the equivalent range, and by using this to form a coating film on the surface of the steel pipe and fittings (fittings).

The coating film not only shows excellent physical properties in chemical resistance, solvent resistance, abrasion resistance, etc., but also does not contain bisphenol A-type epoxy, which is controversial in environmental hazards, so that it can be safely used as a water pipe as well as a sewage pipe. The range can be expanded.

Claims (7)

In the bisphenol F type epoxy liquid coating composition applied as a coating material on the inner surface of water and sewage pipe, 20-40 wt% of bisphenol F-type epoxy resin; Sieving pigments 30-50 wt%; 1-5% by weight reactive diluent; 1-5% by weight non-reactive diluent; Additive 2-10 wt%; Solvent 5-20% by weight; And Curing agent; Including, The curing agent, 15 to 35% by weight of modified amide curing agent; 0.1 to 5 wt% of a curing accelerator; Sieving pigments 30-50 wt%; Characterized in that the solvent consists of 10 to 40% by weight, The bisphenol F-type epoxy resin composition and the curing agent are mixed in an equivalent ratio of 1: 1, The curing accelerator is at least one selected from imidazoles, imidazole modified epoxy, di- and non-sulphate salts, butyl triphenyl phosphonium bromide, butyl triphenyl phosphate oxalate, butyl triphenyl phosphonium chloride Bisphenol F type epoxy liquid coating composition. The method of claim 1, The reactive diluents are creylglycidyl ether, versatic acid glycidyl ester, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, parabutyl phenyl phenyl glycidyl ether, neopentyl diglyci Bisphenol F-type epoxy liquid coating composition, characterized in that at least one selected from the group consisting of dill ether, 1,4-butane diglycidyl ether, cyclohexane dimethanol diglycidyl ether. The method of claim 1, The non-reactive diluent is bisphenol F type epoxy liquid coating composition, characterized in that at least one selected from the group consisting of benzyl alcohol, perfuryl alcohol. delete delete delete delete