KR100729013B1 - Polymer resin composition having resistance to epoxy group paints and polymer resin material manufactured using the same - Google Patents

Abstract

Provided are a polymer resin composition which is resistant against an epoxy-based paint and minimizes the mechanical properties resistance due to an epoxy-based resin, and a polymer resin material prepared by using the composition. The composition comprises 100 parts by weight of a poly(vinyl chloride) base resin; 20-80 parts by weight of a plasticizer selected from phthalate-based, phosphoric acid-based, fatty acid-based, mellitate-based and polymer-based plasticizers; 1-15 parts by weight of at least one stabilizer selected from lead-based, lead-free based, epoxy-based, stearate-based and metal soap-based stabilizer; 3-100 parts by weight of at least one inorganic filler selected from calcium carbonate, clay and talc; and 1-50 parts by weight of at least one organic filler selected from an ethylene-vinyl acetate copolymer containing 28-80 wt% of vinyl acetate, a nitrile rubber, a hydrogenated nitrile rubber, an ethylene-vinyl acetate carbon monoxide copolymer and a polyethylene chloride/ethylene-vinyl acetate/vinyl chloride terpolymer.

Description

Polymer resin composition having resistance to epoxy group paints and polymer resin material manufactured using the same

The present invention relates to a polymer resin composition having a resistance to epoxy paint and a polymer resin produced using the same, and more particularly, to manufacture the sheath body of a ship electric wire in order to have durability against the epoxy paint. The present invention relates to a composition for producing a sheath body of a ship electric wire which is excellent in compatibility with a polyvinyl chloride resin used and has a high polarity group, and a polymer resin material manufactured using the same.

In general, an epoxy-based paint is painted on the outer surface of the ship for the purpose of preventing corrosion and protecting the exterior of the ship. However, various wires, interior materials, and exterior materials manufactured using the polyvinyl chloride resin exposed to the outside as a main material in the process of coating the epoxy paint on the ship may contact the paint. As such, in order to prevent the epoxy paint from coming into direct contact with the wire sheath or the internal / exterior materials manufactured by using polyvinyl chloride resin as a main material, a method of minimizing contact when the epoxy paint is coated outside is used. However, this is because the additional installation of the protective member is greatly reduced work efficiency, and it is not desirable in several economic aspects, such as time and expenses required for the related work.

On the other hand, when the epoxy paint is in direct contact with the polyvinyl chloride resin constituting the wire sheath or the interior and exterior materials, physicochemical changes occur at the contact interface between these materials, and the physical properties of the polyvinyl chloride resin are caused by the epoxy paint. This can be changed. In particular, when specific conditions related to these physical property changes are satisfied, the physical properties of products manufactured using polyvinyl chloride resin as a main material may be aged. Due to this aging phenomenon, various physical conditions, for example, mechanical properties such as tensile strength and elongation can be rapidly deteriorated, and serious problems may occur when a standard value required for a product is set.

In such a situation, the epoxy paint is brought into contact with the wire sheath or the interior and exterior materials, resulting in aging of the product and, in fact, shortening the service life of these products. Considering the fact that it acts as a path for supplying the power required for the system, it is too obvious that it may cause an accident.

Therefore, efforts have been made to solve such problems in the related art, and the present invention has been made under such a technical background.

The technical problem to be solved by the present invention based on the above-mentioned conventional problems is caused by the contact with the marine wire sheath manufactured with polyvinyl chloride resin as the main material or the marine paint whose main material is an epoxy-based material. The purpose of the present invention is to provide a polymer resin composition having resistance to an epoxy-based paint and a polymer resin material prepared using the same. .

In order to achieve the technical problem to be achieved by the present invention, a polymer resin composition having resistance to an epoxy paint according to the present invention includes a polyvinyl chloride resin as a base resin, and a plasticizer 20 based on 100 parts by weight of the base resin. To 80 parts by weight; 1 to 15 parts by weight of the stabilizer; 3 to 100 parts by weight of the filler; And 1 to 50 parts by weight of organic additives.

In this case, the plasticizer is preferably a substance belonging to any one of the plasticizer groups selected from the group consisting of phthalates, phosphoric acids, fatty acids, meritates and polymers. More specifically, the phthalate plasticizer, DINP (Diisonony Phthalate), DIDP (Diisodecyl Phthalate), DUP (Diundecyl phthalate), DBP (Di-butyl phthalate), DIBP (Diisobutyl phthalate), DIOP (Diisooctyl phthalate), C9 type Any one or two or more materials selected from phthalate, Ditridecyl phthalate (DTDP) and Butyl Benzyl Phthalate (BBP) are preferable, and the phosphate plasticizer may be triaryl phosphate, trialkyl phosphate, mixed alkylaryl phosphate, and halogenated alkyl. It is preferable that any one or two or more substances selected from phosphate, and the fatty acid-based plasticizer, Di-2-Ethylhexyl Adipate (DOA), Di-2-Ethylhexyl Sebacate (DOS), Di-isodecyl Adipate (DIDA) and DOZ (Di) It is preferable that any one or two or more substances selected from -2-Ethylhexyl Azebacate), and the meritate-based plasticizer, Tri-2-ethyl hexyl Trimellitate (TOTM), Tri-2-ethyl hexyl Trimellitate (TOTM) mixed And Tri-isononyl Trimellitate (TINTM).

On the other hand, the plasticizer is preferably a substance belonging to any one selected from the group consisting of saturated polyester, individual polyester, elastomer, epoxy, extender, glycol ester, citrate, and paraffin chloride. Do. The plasticizer is preferably used 20 to 80 parts by weight based on 100 parts by weight of the base resin. When the plasticizer content is less than 20 parts by weight, the plasticizing effect on the PVC, which is a plasticizer, is lowered, thereby increasing the hardness of the composition. When the plasticizer content exceeds 80 parts by weight, the tensile strength of the mechanical properties is low and the heat resistance is also lowered, which is not preferable.

The stabilizer is preferably any one or two or more materials selected from lead-based, lead-free, epoxy stearate and metal soap-based materials. It is preferable to use 1 to 15 parts by weight of the stabilizer. If the content of the stabilizer is less than 1 part by weight, the heat resistance of the material is sharply lowered, and thus it is not preferable because the required properties are not satisfied. If the content of the stabilizer exceeds 15 parts by weight, the effect of improving the heat resistance due to the excessive use can be expected. None is undesirable.

The filler is preferably any one or two or more inorganic selected from calcium carbonate, cray and talc. It is preferable to use 3 to 100 parts by weight of the filler. When the content of the filler is less than 3 parts by weight, the effect of lowering the cost of the material due to the application of a low-cost filler is not expected, and it is not preferable. When the content of the filler exceeds 100 parts by weight, the tensile strength due to the excess inorganic material And elongation rate is drastically lowered and extrusion process property is also lowered, which is undesirable.

The organic additive is an ethylene vinyl acetate copolymer having an ethylene vinyl acetate content of 28 to 80% by weight, nitrile rubber, hydrogenated nitrile rubber, ethylene vinyl acetate carbon monooxide copolymer, polyethylene chloride, ethylene vinyl acetate vinyl chloride terpolymer It is preferred if it is any one or two or more materials selected. The organic additive is preferably used in an amount of 1 to 50 parts by weight. When the content of the organic additive is less than 1 part by weight, it is not preferable because it is impossible to secure resistance to the epoxy-based paint according to the application of the organic additive, and when the organic additive content is used in excess of 50 parts by weight, the plasticizing action of the organic additive is used. Due to the phenomenon that the tensile strength and heat resistance is lowered is not preferable.

In order to achieve the technical problem to be achieved by the present invention using a polymer resin composition having a resistance to the epoxy paints according to the present invention as a polymer resin material, it is specifically an internal / exterior material or an electric wire that can be exposed to epoxy paints It is preferable if it is used to manufacture a sheath.

Hereinafter, the present invention will be described with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Preparation of Epoxy Paint

Epoxy-based paints according to Table 1 below are examples of paints generally used, and are used to coat the exterior of ships.

Chemical name tinnitus Content (%) xylene Dimethylbenzene 1-10 Naphtha for light aromatic compounds 1-10 N-butyl alcohol Butyl alcohol 1-10 Talc, non-asbestos Talcum, non-asbestos form 41-50 Titanium dioxide Titanium oxide 11-20 Epoxy Bisphenol-A-bisphenol A diglycidyl ether polymerization 21-30 Etc 1-10

Example (1-6) and Comparative example (1 ~ 3)

Meanwhile, as shown in Table 2 below, test specimens of the wire sheath body prepared using the composition prepared by the examples according to the present invention and the comparative examples were prepared. The composition was blended for about 10 minutes in an open roll having a surface temperature of about 130 ° C., and then molded in a pressurized press at 170 ° C. to prepare test pieces. The epoxy paint composition prepared by mixing a curing agent and thinner (thinner) in a certain ratio to the epoxy paint according to Table 1 was applied to the outer surface of each test specimen, respectively.

division Example (1-6) Comparative example (1-3) One 2 3 4 5 6 One 2 3 Polyvinyl clyde 100 100 100 100 100 100 100 100 100 Chlorinated Polyethylene 20 - - - - - - - - Nitrile Rubber (NBR) - 10 30 - - - - - - Ethylene Vinyl Acetate Copolymer 1 -20 ----- ------ 20 ---- --- - - - - Ethylene Chloride Acetate - - - - 10 30 - - - Ethylene Vinyl Acetate Copolymer 2 - - - - - - - 20 - DINP 40 45 30 40 50 40 40 30 - TOTM - - - - - - - - 40 Lead-Based Stabilizer 5 - - - - - 5 5 5 Calcium carbonate 30 - - - - - 30 30 30

In Table 2, ethylene vinyl acetate copolymer 1 refers to ethylene vinyl acetate copolymer resin containing 46% by weight of vinyl acetate (VA), and ethylene vinyl acetate copolymer 2 to 19% by weight of vinyl acetate (VA). It means containing ethylene-vinyl acetate copolymer resin.

Physical characterization

Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to the following tests on the material specimens respectively treated to evaluate the physical properties, the evaluation results are shown in Table 3 below. Desirably required room temperature characteristic criteria, after heating characteristic criteria, heating loss criteria and insulation resistance reference values are as follows.

(1) Room temperature standard

Tensile strength should be more than 1.25 kgf / mm2 and elongation should be more than 150% when measured by tensile speed 500mm / min according to IEC 60811-1-1.

(2) Characteristics criteria after heating

After leaving the specimen at a temperature of 100 ° C. for 168 hours, the residual rate should be at least 70% when the change in tensile strength and elongation is measured.

(3) Heating loss standard

After leaving the specimen at a temperature of 100 ° C. for 168 hours, the weight lost after heating with respect to the unit surface area of the specimen should be 1.5 mg / cm 2 or less.

(4) Insulation resistance standard

When insulation resistance of wire is measured at 90 ℃, the resistance value should be over 3.67 ㏁.km.

division Example (1-6) Comparative example (1-3) One 2 3 4 5 6 One 2 3 Room temperature The tensile strength 1.7 1.85 1.67 1.76 1.9 1.82 1.8 2.1 1.92 Elongation 250 248 310 236 242 281 284 225 216 heating Tensile residual rate 98 88 85 91 92 87 58 41 67 Elongation 85 89 94 83 92 90 34 53 46 Heating loss 1.03 1.12 1.11 1.04 0.94 0.97 1.7 1.5 1.3

As can be seen through Table 3, in Examples 1 to 6 according to the present invention, the room temperature tensile strength and elongation of the material coated with the epoxy-based paint is 1.25kgf / mm2 and 150, which are required values, to be measured. It can be seen that the value is more than%. In addition, it can also be confirmed that the tensile residual ratio and the elongation residual ratio after heating at 100 ° C. for the specimens according to each example showed 75% or more of the required value. Lastly, even in the case of the heating loss described above, it can be seen that all the examples satisfy the reference value.

Through the above results, it can be seen that the composition for producing a ship wire sheath according to the present invention and the ship wire prepared using the same exhibit sufficient resistance to epoxy paint.

On the other hand, as a result of examining the physical property change when the epoxy-based paints according to Table 1 were applied to the material specimen prepared using the composition according to the comparative examples in contrast to the present invention, in the case of Comparative Example 1 polyvinyl chloride After adding a low molecular weight plasticizer to the resin, the durability of the epoxy paint was evaluated. As a result, the heat resistance after heating was rapidly decreased. In the case of Comparative Example 2, the low molecular weight plasticizer was applied to the same resin as Comparative Example 1. And it can be seen that even in the case of applying the ethylene vinyl acetate copolymer having a certain degree of polar group, the durability for the paint is not secured, in the case of Comparative Example 3 for the purpose of improving the durability for the paint In the case of a material to which a high molecular weight plasticizer was applied, the durability to the paint was lowered. .

That is, as can be seen from the characteristics evaluation results of Comparative Examples 1 to 3, when applying a variety of existing plasticizers to the polychloride resin it was not possible to secure the resistance to the epoxy-based paints, which is why It can be seen that the reliability cannot be obtained.

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art, and are not used to limit the scope of the present invention as defined in the meaning or claims.

The polymer resin composition having a resistance to the epoxy paint according to the present invention and the polymer resin prepared by using the epoxy resin, even if exposed to the epoxy paint, by introducing a high polar group polymer having excellent compatibility with the polyvinyl chloride resin epoxy By lowering the bond due to the reaction at the interface with the paint system has the advantage of minimizing the mechanical properties resistance by the epoxy paint. In particular, according to the present invention can extend the service life of ship wires or interior materials with a high frequency of exposure to the epoxy-based paints, and various safety accidents that may occur due to aging can be prevented in advance or the incidence of such safety accidents Can be lowered effectively.

Claims (12)

In the polymer resin composition having a resistance to the epoxy-based paint comprising a polyvinyl chloride resin as a base resin, Based on 100 parts by weight of the base resin, 20 to 80 parts by weight of a plasticizer which is a substance belonging to any one of the plasticizer groups selected from the group consisting of phthalate, phosphoric acid, fatty acid, meritate and polymer; 1 to 15 parts by weight of a stabilizer, which is any one or two or more selected from lead-based, lead-free, epoxy stearate, and metal soap-based materials; 3 to 100 parts by weight of a filler of any one or two or more selected from calcium carbonate, cray and talc; And Either or two selected from ethylene vinyl acetate copolymer, nitrile rubber, hydrogenated nitrile rubber, ethylene vinyl acetate carbon monooxide copolymer and vinyl chloride / ethylene vinyl acetate / vinyl chloride terpolymer having a vinyl acetate content of 28 to 80% by weight. 1 to 50 parts by weight of an organic additive, which is the above material; a polymer resin composition having resistance to an epoxy-based paint, comprising a. The method of claim 1, The phthalate plasticizer, DINP (Diisonony Phthalate), DIDP (Diisodecyl Phthalate), DUP (Diundecyl phthalate), DBP (Di-butyl phthalate), DIBP (Diisobutyl phthalate), DIOP (Diisooctyl phthalate), C9-based phthalate, DTDP ( Ditridecyl phthalate) and BBP (Butyl Benzyl Phthalate) of any one or two or more materials selected from the polymer resin composition having resistance to the epoxy-based paint. The method of claim 1, The phosphoric acid plasticizer is a polymer resin composition having resistance to an epoxy paint, characterized in that any one or two or more selected from triaryl phosphate, trialkyl phosphate, mixed alkyl aryl phosphate and halogenated alkyl phosphate. The method of claim 1, The fatty acid-based plasticizer, any one or two or more selected from DO-2 (Di-2-Ethylhexyl Adipate), DOS (Di-2-Ethylhexyl Sebacate), DIDA (Di-isodecyl Adipate) and DOZ (Di-2-Ethylhexyl Azebacate) Polymer resin composition having a resistance to the epoxy-based paint, characterized in that the material. The method of claim 1, The meritate plasticizer is any one or two or more materials selected from tri-ethyl hexyl trimellitate (TOTM), mixed tri-ethyl hexyl trimellitate (TOTM), and tri-isononyl trimellitate (TINTM). A polymer resin composition having resistance to an epoxy paint. The method of claim 1, The plasticizer is a substance belonging to any one selected from saturated polyesters, individual polyesters, elastomers, epoxys, extenders, glycol esters, citrates, and paraffin chlorides. A polymer resin composition having resistance to an epoxy paint. The method according to any one of claims 1 to 6, The polymer resin material is a polymer resin material, characterized in that used as an interior material or wire sheath that can be exposed to the epoxy paint. delete delete delete delete delete