KR101743794B1 - Metal pipe coating composition and method for preparing extruded products using them - Google Patents

Abstract

The present invention relates to a metal pipe coating composition and a process for producing an extruded product using the metal pipe coating composition, wherein a separate primer layer is provided on the metal pipe substrate by providing a metal pipe coating composition comprising a film-forming copolymer, a white light blocker and a network structure It provides the effect of realizing excellent corrosion prevention, weather resistance, chemical resistance, anti-static, contact feeling, appearance and the like without necessity.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal pipe coating composition and a method for manufacturing an extruded article using the same,

The present invention relates to a metal pipe coating composition and a process for producing an extruded article using the same, and more particularly, to a metal pipe coating composition which does not require a primer layer and is excellent in corrosion resistance, weatherability , Chemical resistance, antistatic property, contact feeling, appearance, and the like, and a method for producing an extruded article using the same.

Outdoor and indoor metal pipes are used for most railings, cargo holders, and structural aids. However, uncoated metal pipes are easily rusted by surface oxidation and require periodic painting. In this case, the simple paint operation only causes the static touch in the winter when the human body touches the dry weather in the winter, so it gets too cold feeling, which causes the contact to be avoided and there is a risk of accident due to slip when moisture or oil is on the surface of the pipe .

In the coating method for the metal pipe, it is possible to prevent the oxidation of the surface or give a soft feeling when the human body touches by simple coating of the resin. However, the possibility of being exposed to ultraviolet rays, the environmental pollution such as oil adhered by human hands or work gloves And cracks due to cracks, and safety problems due to sliding may occur.

In addition, as the interest in living environment increases, the demand for high-grade metal pipes is increased, so that the coating resin of metal pipe is not only excellent in corrosion resistance but also excellent in weather resistance, chemical resistance, antistatic performance, proper surface roughness, A smooth sensation, a beautiful appearance, and an easy extrusion processability are required.

As a related prior art, Korean Patent Laid-Open Publication No. 1996-0701707 discloses a three-layer metal pipe coating based on a thermoplastic hard adhesive and a powder primer on a polyolefin coating film, but it is intended to prevent corrosion, Prevention, weatherability, chemical resistance, anti-static and sense, appearance, etc.

Accordingly, the present invention has been made to overcome the problems of the prior art and to provide a metal pipe coating which is excellent in weather resistance, chemical resistance, antistatic performance, moderate surface roughness, smooth feeling upon contact with human body, And to provide a composition.

It is another object of the present invention to provide a method for producing an extruded product using the metal pipe coating composition and to provide the extruded product obtained therefrom as an outdoor or indoor metal pipe coating resin.

Thus, according to the metal pipe coating composition of the present invention,

From 65 to 90% by weight of a film-forming copolymer, from 5 to 15% by weight of a white light blocking agent, and from 5 to 20% by weight of a network structure.

Further, according to the method for producing an extruded article according to the present invention,

Mixing the film-forming copolymer and the white light blocking agent in the metal pipe coating composition described above and injecting the mixture into a main hopper of a twin screw extruder and extruding the same; And

Introducing a network structure among the metal pipe coating compositions of any one of the above-described methods into a side feeder of the biaxial extruder and extruding the same; And a control unit.

Further, according to the present invention, there is provided a resin for outdoor metal pipe coating or a resin for indoor metal pipe coating obtained by the above method.

Hereinafter, the present invention will be described in more detail.

In the present invention, a metal pipe coating capable of realizing excellent corrosion prevention, weather resistance, chemical resistance, static electricity prevention, contact feeling, and appearance without requiring a primer layer by appropriate combination of a film-forming copolymer, a white light shielding agent and a network structure Have technical features in providing the composition.

First, the term "film-forming copolymer " as used in the present invention refers to a copolymer that can be applied for outdoor or indoor metal pipe coating applications unless otherwise stated.

The term "white light blocking agent" used in the present invention refers to a material having a light blocking ability such as ultraviolet ray, unless otherwise stated.

Furthermore, the term "network structure" used in the present invention refers to a network structure that can form fine irregularities on its surface while being dispersed in the above-mentioned film-forming copolymer to form a network structure, Substance.

Specifically, the metal pipe coating composition according to the present invention includes, for example, from 65 to 90% by weight of the film-forming copolymer, from 5 to 15% by weight of the white light blocking agent, and from 5 to 20% by weight of the network structure do.

As another example, the metal pipe coating composition may comprise 70-84 wt% of the film-forming copolymer, 8-12 wt% of the white light blocker, and 8-18 wt% of the reticulated structure .

The film-forming copolymer may include, for example, 30 to 80% by weight of a rubber-reinforced resin and 70 to 20% by weight of a matrix resin based on the total weight of the film-forming copolymer. Within this range, Chemical properties and the like can be appropriately provided.

As another example, the film-forming copolymer may include 30 to 50% by weight of the rubber-reinforced resin and 70 to 50% by weight of the matrix resin based on the total weight of the film-forming copolymer.

In particular, the rubber-reinforced resin may be obtained by graft copolymerizing 40 to 60% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyan compound in 30 to 50% by weight of a rubbery polymer latex based on the total weight of the rubber- It may be a thermoplastic resin.

The rubbery polymer latex may be, for example, an acrylate rubbery polymer latex having an average particle size of 3500 to 6000 Å. When the acrylate rubbery polymer latex is used, the resultant rubbery resin may be a long- It is suitable for use in covering metal pipes used in products which are mainly used for outdoor work and storage. In practice, the impact strength of the metal pipe coating composition is not degraded within the particle size range and the production of coagulum may not be increased.

The rubbery polymer latex may be, for example, a diene-based rubbery polymer latex having an average particle diameter of 2500 to 5000 ANGSTROM, and is suitable for producing an indoor metal pipe coating composition when a diene rubbery polymer latex is used as the rubbery polymer latex . This is because the diene rubber polymer latex is used and it is used in outdoor electrical, electronic, and automobile fields which are not directly exposed to sunlight because the physical properties are deteriorated over a long period of time due to problems such as discoloration and cracking during outdoor use .

Further, if the acrylate rubbery polymer latex and the diene rubbery polymer latex are mixed as needed as the rubbery polymer latex, they may be suitable for producing an indoor metal pipe coating composition which is exposed to ultraviolet rays.

The acrylate-based rubbery polymer may be an acrylate monomer having an alkyl group having 1 to 10 carbon atoms, for example, butyl acrylate. In addition, if necessary, a methacrylate monomer having an alkyl group having 1 to 10 carbon atoms may be contained as a comonomer, and specific examples thereof include methyl methacrylate as a comonomer.

Specific examples thereof include 30 to 50% by weight of an acrylate monomer having an alkyl group having 1 to 10 carbon atoms, or 20 to 49% by weight of an acrylate monomer having an alkyl group having 1 to 10 carbon atoms, 1 to 10% by weight of a methacrylate monomer having an alkyl group of 1 to 10 carbon atoms.

Further, the aromatic vinyl compound may be used alone or in admixture of two or more of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene or substituents thereof.

As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile, or their substituents may be used alone or in combination of two or more.

The graft copolymerization may be carried out at a ratio of 0.001 to 5 parts by weight, or 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of monomers for rubber-reinforced resins, of a reactive emulsifier containing at least one functional group selected from the group consisting of carbonate, sulfonate, To 2 parts by weight.

The reactive emulsifier may be, for example, sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, sodium dodectyl allyl sulfosuccinate, styrene and sodium dodecyl allyl sulfosuccinate copolymers, polyoxyethylene alkylphenyl ether ammonium, alkenyl C16 -18 succinic acid, alkenyl C16-18 succinic acid, di-potassium salt, and sodium methallyl sulfonate.

The rubber-reinforced resin may contain 0.001 to 5 parts by weight, or 0.1 to 2 parts by weight, based on 100 parts by weight of the total amount of monomers for rubber-reinforced resins, which is usually used in emulsion polymerization.

The rubber-reinforced resin may contain 0.001 to 5 parts by weight, or 0.1 to 2 parts by weight, based on 100 parts by weight of the total amount of monomers for rubber-reinforced resins, which is usually used in emulsion polymerization.

The matrix resin may be, for example, a copolymer of styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer and styrene-acrylonitrile-methyl methacrylate copolymer Or more. Here, the styrene-methyl methacrylate copolymer, the styrene-acrylonitrile-methyl methacrylate copolymer and the like can further improve the weather resistance, and the styrene-maleic anhydride copolymer can bond the metal pipe to the resin The strength can be increased.

As another example, the matrix resin may be a styrene-acrylonitrile copolymer having an acrylonitrile content of 20 to 35% by weight. Within the above range, the impact strength may be deteriorated due to the lower compatibility with the rubber reinforced resin, And the chemical resistance may not be lowered, or the disadvantage that over-use lowers the workability and color discoloration over time is also solved.

As another example, the matrix resin may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 160,000 g / mol, and the mechanical properties and processability may be improved within the above range.

The white light blocking agent used in the present invention is capable of producing a product having excellent color contrast with a network structure and having an excellent appearance and further enhancing weatherability due to light blocking effect, For example, it may be at least one selected from the group consisting of TiO ₂ , BaSO ₄ , SiO ₂ , B ₂ O ₃ and Al ₂ O ₃ , and another example may be TiO ₂ .

Also, as described above, the white light blocking agent is preferably in the range of 5 to 15% by weight or 8 to 12% by weight based on the total weight of the metal pipe coating composition. If the amount is less than 5% by weight, the color may darken and the appearance may be deteriorated or long-term weatherability may be deteriorated. If the amount is more than 15% by weight, the mechanical properties may be deteriorated or the unit cost of the final product may be increased.

In addition, the network structure used in the present invention can disperse static electricity generated on the surface of the coating layer in dry weather, and furthermore, by forming fine irregularities on the surface of the coating layer to prevent slipping phenomenon. Lt; / RTI > to 10 mm. In fact, the conductive carbon fibers having a length of 3 to 10 mm can effectively form a network structure in the film-forming copolymer to efficiently perform electrostatic dispersion and maintain a beautiful surface.

As described above, the network structure can provide sufficient electrostatic dispersion and uniform quality in the range of 5 to 20 wt% or 8 to 18 wt% based on the total weight of the metal pipe coating composition, .

The metal pipe coating composition can be used as needed for lubricants, heat stabilizers, weather resistance stabilizers and the like which are commonly used in processing, and coloring agents can also be used.

The method for preparing an extruded product using the metal pipe coating composition according to the present invention comprises mixing a film-forming copolymer and a white light blocking agent in the metal pipe coating composition, injecting the mixture into a main hopper of a twin screw extruder, And feeding the mesh structure of the metal pipe coating composition into a side feeder of the biaxial extruder and extruding the mesh structure; . ≪ / RTI >

For reference, it is possible to effectively prevent the network structure from being cut in the biaxial extruder by feeding it into the side feeder through the kneading block of the biaxial extruder screw. In fact, when the mesh structure is passed through the kneading block of the twin-screw extruder, the mesh structure is not cut at the kneading block of the twin-screw extruder, and the mesh structure is efficiently formed. Thus, the desired antistatic property can be obtained even at a small input amount, It can be confirmed that a beautiful product is obtained (see Fig. 1).

On the other hand, when the mesh structure is inserted before passing through the kneading block of the biaxial extruder, the mesh structure is cut off from the kneading block of the biaxial extruder, so that it is difficult to achieve an efficient network structure and the cutting rate of the mesh structure is changed according to the operation conditions of the extruder. It is not uniform and the appearance becomes dark, and the value of the product is lowered (see Fig. 2).

In particular, when the rubber-reinforced resin containing the acrylate-based rubbery polymer latex is used as the film-forming copolymer in the metal pipe coating composition, an outdoor pipe-coated resin can be provided.

When the rubber-reinforced resin containing the above-mentioned diene-based rubbery polymer latex is used as the film-forming copolymer in the metal pipe coating composition, the indoor pipe-coated resin can be provided.

As described above, for the indoor pipe-coated resin having no ultraviolet ray, a press-molded article can be produced using the rubber-reinforced resin produced by blending the acrylate-based rubbery polymer latex and the diene-based rubbery polymer latex.

In particular, the surface resistivity of the final product obtained in the present invention can be excellent to ¹ x ¹⁰ < ¹⁰ >

According to the present invention, there is provided a metal pipe coating composition comprising a combination of a film-forming copolymer, a white light shielding agent and a reticulate structure, so that a separate primer layer is not required on the metal pipe substrate and excellent corrosion resistance, weather resistance, Static electricity, contact feeling, appearance, and the like.

FIG. 1 is a photograph enlarged by a 200-times microscope in the case of Example 1 in which a network structure is put into a side feeder through a kneading block of a twin screw extruder screw.
FIG. 2 is a photograph enlarged by a 200-fold microscope in the case of a further experimental example in which a network structure is inserted before passing through a kneading block of a twin-screw extruder.

Hereinafter, the present invention will be described in more detail with reference to the following examples. The following examples illustrate the invention and are not intended to be limiting thereof.

<Raw materials>

The raw materials used in the following examples are as follows.

&Lt; Coated film-forming copolymer &

Rubber reinforced resin:

Butyl acrylate was emulsified and polymerized to obtain a copolymer powder in which styrene-acrylonitrile was graft copolymerized with an acrylate-based rubbery polymer latex. The monomer used to obtain the copolymer powder was butyl methacrylate / methyl methacrylate / styrene / acrylonitrile. The content of the monomer was butyl methacrylate / methyl methacrylate / styrene / acrylonitrile = 40/2/38/18. The average particle size (measured with a NICOMP 380 instrument) of the prepared rubber-reinforced resin was 5200 Å.

Specifically, 70 parts by weight of deionized water, 1 part by weight of butyl acrylate, 0.02 part by weight of ethylene glycol dimethacrylate, 0.1 part by weight of sodium hydrogencarbonate and 0.04 parts by weight of potassium persulfate were polymerized in one step.

Separately, 34 parts by weight of deionized water, 0.4 parts by weight of dioctylsulfosuccinate, 29 parts by weight of butyl acrylate, 3 parts by weight of acrylonitrile, 2 parts by weight of methyl methacrylate, 0.09 parts by weight of ethylene glycol dimethacrylate, 0.03 part by weight of methacrylate, and 0.1 part by weight of sodium hydrogencarbonate were mixed.

Then, 0.06 part by weight of the mixture and 0.06 part by weight of potassium persulfate as a catalyst were added to the first-stage polymerizate at a temperature of 70 ° C for 3 hours, and polymerization was carried out to obtain a second-stage reaction product.

13 parts by weight of deionized water, 0.1 part by weight of dioctylsulfosuccinate, 10 parts by weight of butyl acrylate, 0.03 part by weight of ethylene glycol dimethacrylate and 0.01 part by weight of arylmethacrylate were added to the above two-stage reaction product, For 1 hour and 30 minutes. At this time, the particle diameter was 4500 Å, the pH was 8.0, and the polymerization conversion rate was 98%.

Further, 63 parts by weight of deionized water, 0.4 part by weight of potassium rosinate, 0.042 part by weight of KOH, 40 parts by weight of styrene, 15 parts by weight of acrylonitrile and 0.05 part by weight of tertiary dodecyl mercaptan (TDDM) 0.1 part by weight of the above mixture as a catalyst and potassium persulfate (KPS) as a catalyst were continuously added at 70 DEG C for 3 hours, followed by further reaction at 80 DEG C for 1 hour in order to increase polymerization conversion, Respectively. The polymerized latex had a particle diameter of 5300 Å, a polymerization conversion of 99.1%, and a pH of 9.5.

The obtained latex was subjected to atmospheric pressure agglomeration at 85 ° C using an aqueous solution of calcium chloride, and aged at 95 ° C for dehydration and washing.

Matrix resin:

As a block copolymer, LG Chem 90HR was used. Specifically, the kind of the monomer used to obtain the matrix resin was styrene / acrylonitrile, and the content was styrene / acrylonitrile = 73/27 by weight.

The weight average molecular weight of the prepared matrix resin was 140,000 g / mol

<White light blocker>

As the titanium oxide, R-104 product of DuPont Co. was used.

<Reticular structure>

Zoltec chopped pellet (-65) product having a length of 6 mm was used as a conductive carbon fiber.

For reference, auxiliary materials such as stabilizers, lubricants and weathering stabilizers required for other processing were generally used for the production of ASA resin.

[Example 1]

32 parts by weight of a rubber reinforced resin, 48 parts by weight of a matrix resin and 12 parts by weight of a white light blocking agent were weighed, and 1 part by weight of ethylene bisstearamide and 0.5 parts by weight of IR-1076 as a stabilizer, And 0.25 parts by weight of Tin-327 and Tin-770 as weather-resistant stabilizers were put in a 40-pie extruder and then mixed and supplied to the main hopper of the twin-screw extruder.

8 parts by weight of a separately weighed mesh was put into the side feeder of the twin screw extruder and the cylinder temperature of the twin screw extruder was adjusted to 200 to 230 캜 to prepare pellets.

The properties of the extruded pellets were evaluated according to the following physical property evaluation method, and the surface smoothness of the final product coated with the extruder for pipe coating was visually evaluated and summarized in Table 1 below.

As a result of observing the resultant coated surface with a 200x magnifying glass, it was confirmed that the carbon fiber was not cut and the surface resistivity did not decrease as shown in Fig.

[Examples 2 to 5, Comparative Examples 1 to 2]

Repeated experiments were conducted in the same manner as in Example 1, according to each of the prescriptions shown in Table 1 below.

&Lt; Property evaluation method &

* Izod impact strength : conducted according to ASTM D 256

* Flowability : ASTM D 1238 (G).

It was carried out according to ASTM D 638: Tensile Strength *.

* Elongation : according to ASTM D 638.

* Surface resistivity (surface resistivity ) : The surface resistivity of each specimen was measured using a KEITHLEY 6517A equipped with a Fixture 8009, and a voltage of 500 V was applied. After 60 seconds, the resistance value was read.

* Surface smoothness of pipe products : Visual judgment was made.

ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 The film-forming copolymer Rubber reinforced resin 32 32 32 32 32 32 32 Matrix resin 48 48 40 48 48 48 48 White light blocker 12 11 10 9  8 4 16 Network structure 8 9 18 11 12 16 4 Lubricant 1.0 1.0 1.0 1.0 1.0 1.0 1.0 stabilizator 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Weathering stabilizer (Tin-327) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Weathering stabilizer (Tin-770) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Properties Izod impact strength (kg.cm/cm) 4.8 4.7 4.5 4.3 4.2 4.6 3.5 Flowability (g / 10 min) 8.2 8.2 6.3 8.0 8.0 7.2 8.5 Tensile strength (kg / cm ² ) 460 470 480 470 470 480 475 Elongation (%) 12 10 10 8 8 6 4 Surface resistivity (Ω) 3.2 * 10 ⁹ 2.3 * 10 ⁹ 1.2 * 10 ⁸ 1.2 * 10 ⁹ 1.7 *
10 ⁹ 5.3 * 10 ⁸ 3.4 * 10 ¹³ Surface smoothness (visual determination) Great Great Great Great Great grey White

As shown in Table 1, in Examples 1 to 5, superior surface resistivity and surface smoothness were confirmed.

On the other hand, in Comparative Example 1, the hue decreased due to dark hues, and in Comparative Example 2, the surface resistivity of the final product was remarkably lowered.

[Additional Experimental Example]

Further, as a further experimental example, the same method was repeated except that the network structure in Example 1 was mixed at the same time and charged into the main hopper of the twin-screw extruder.

As a result of observing the resultant coated surface with a 200-fold magnifying glass, as shown in Fig. 2, the carbon fibers were often cut, and the surface resistivity was also lowered.

The specific physical properties were Izod impact strength of 4.6 kg.cm/cm, fluidity of 8.0 g / 10 min, tensile strength of 470 kg / cm ² , elongation of 7%, surface resistivity of 2.3 x 10 ¹² Ω, The surface smoothness was excellent in visual observation.

Claims (17)

A rubber-reinforced resin having an aromatic vinyl compound and a vinyl cyanide compound as a shell having an acrylate rubbery polymer latex as a core and surrounding the core; And 70 to 84% by weight of a film-forming copolymer comprising styrene-acrylonitrile-based matrix resin, 8 to 12% by weight of a white light blocker and 8 to 18% by weight of a reticulated structure, 40 to 60% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyanide compound are added to 30 to 45% by weight of an acrylate rubbery polymer latex having an average particle diameter of 3500 to 6000 Å based on the total weight of the reinforced resin, Shell structure, wherein the film-forming copolymer comprises 30 to 50% by weight of a rubber-reinforced resin and 50 to 70% by weight of a styrene-acrylonitrile matrix resin based on the total weight of the film-forming copolymer, and the styrene- The acrylonitrile-based matrix resin is a styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 160,000 g / mol, Wherein the network structure is a conductive carbon fiber having a length of 3 to 10 mm.
delete delete delete delete delete The method according to claim 1,
The graft copolymerization may include a reactive emulsifier containing at least one functional group selected from the group consisting of a carbonate, a sulfonate, and a sulfate in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total of the monomers for the rubber- &Lt; / RTI &gt;
The method according to claim 1,
Wherein the styrene-acrylonitrile-based matrix resin is at least one block copolymer selected from styrene-acrylonitrile copolymer and styrene-acrylonitrile-methyl methacrylate copolymer.
The method according to claim 1,
Wherein the styrene-acrylonitrile-based matrix resin is a styrene-acrylonitrile copolymer having an acrylonitrile content of 20 to 35% by weight.
delete The method according to claim 1,
Wherein the white light blocking agent is at least one selected from TiO ₂ , BaSO ₄ , SiO ₂ , B ₂ O ₃ and Al ₂ O ₃ .
delete Mixing the film-forming copolymer of claim 1 with a white light blocking agent, introducing it into a main hopper of a twin screw extruder and extruding it; And feeding the mesh structure of claim 1 to a side feeder of the biaxial extruder and extruding the same; Wherein the extruded article is formed by extrusion.
delete delete 13. A resin for outdoor metal pipe coating obtained by the method of claim 13 and having a surface resistivity of 1.2 x ¹⁰ &lt; ⁸ &gt; to ¹ x ¹⁰ &lt; ¹⁰ &gt;
delete

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