KR102573905B1 - Resin composition for injection molding having improved chemical resistance - Google Patents

Abstract

The present invention relates to a resin composition for plastic injection with excellent chemical resistance, and the resin composition for plastic injection according to the present invention has excellent chemical resistance and environmentally friendly effects.

Description

Resin composition for plastic injection with excellent chemical resistance {RESIN COMPOSITION FOR INJECTION MOLDING HAVING IMPROVED CHEMICAL RESISTANCE}

The following examples relate to resin compositions for plastic injection with excellent chemical resistance.

In the case of home appliances, there is a tendency to demand not only the functions of the home appliance itself but also functions such as interior accessories, and the demand for exterior quality is increasing. However, the painting or plating process applied to improve the exterior quality is not environmentally friendly and has a disadvantage in that it cannot be recycled when the product is disposed of. Accordingly, development of a resin composition that excludes a painting process or a resin composition that has reinforced weather resistance is actively being developed in the field of automobiles as well as electrical and electronic products. In addition, in order to eliminate the painting process, the chemical resistance and scratch resistance of the resin should be increased and the glossiness should be improved. In order to solve this problem, Korean Patent Publication No. 10-1997-0059220 discloses a high-density polyethylene (HDPE) composition for injection molding, but the chemical resistance deterioration problem is not recognized, and research to improve it is conducted. It is necessary.

Republic of Korea Patent Publication No. 10-1997-0059220

The following examples are made to solve the above problems, and an object of the present invention is to provide a resin composition for plastic injection with excellent chemical resistance.

In order to achieve the above object of the present invention, one embodiment of the present invention is 60 to 70 weight of polycarbonate (Polycarbonate) based on the total weight of the composition; 25 to 30% by weight of an acrylonitrile-butadiene-styrene copolymer (ABS) based on the total weight of the composition; and 5 to 10% by weight of an aromatic polyester based on the total weight of the composition, wherein the polycarbonate is a P-bisphenol A-phosgene polymer, and the aromatic polyester is poly(ethylene terephthalate), poly(1,4- Butylene terephthalate) and poly (trimethylene terephthalate), and at least one resin composition for plastic injection is provided.

The resin composition for plastic injection according to the present invention has excellent chemical resistance and environmentally friendly effects. However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.

In the following, embodiments are described in detail. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

Specific structural or functional descriptions of the embodiments are disclosed for illustrative purposes only, and may be modified and implemented in various forms. Therefore, the embodiments are not limited to the specific disclosed form, and the scope of the present specification includes changes, equivalents, or substitutes included in the technical spirit.

Although terms such as first or second may be used to describe various components, such terms should only be construed for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element.

When an element is referred to as being “connected” to another element, it should be understood that although it may be directly connected or connected to the other element, other elements may exist in the middle.

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “include” or “have” are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Advantages and features of the present invention, and how to achieve them, will become clear with reference to the detailed description of the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, only these embodiments make the disclosure of the present invention complete, and common knowledge in the art to which the present invention belongs. It is provided to fully inform the holder of the scope of the invention, and the present invention is only defined by the scope of the claims.

In the embodiments of the present invention, unless otherwise defined, all terms used herein, including technical or scientific terms, are the same as those commonly understood by one of ordinary skill in the art to which the present invention belongs. It has meaning. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the embodiments of the present invention, an ideal or excessively formal meaning not be interpreted as

In describing the present invention, if it is determined that a detailed description of related known technologies may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. When 'includes', 'has', 'consists of', etc. mentioned in this specification is used, other parts may be added unless 'only' is used. In the case where a component is expressed in the singular, the case including the plural is included unless otherwise explicitly stated.

In interpreting the components, even if there is no separate explicit description, it is interpreted as including the error range.

Each feature of the various embodiments of the present invention can be partially or entirely combined or combined with each other, and as those skilled in the art can fully understand, various interlocking and driving operations are possible, and each embodiment can be implemented independently of each other. It may be possible to implement together in an association relationship.

Hereinafter, the present invention will be specifically described with reference to examples. However, it is obvious that the present invention is not limited by the following examples.

In one aspect, the present invention comprises 60 to 70% by weight of polycarbonate based on the total weight of the composition; 25 to 30% by weight of an acrylonitrile-butadiene-styrene copolymer (ABS) based on the total weight of the composition; and 5 to 10% by weight of an aromatic polyester based on the total weight of the composition, wherein the polycarbonate is a P-bisphenol A-phosgene polymer, and the aromatic polyester is poly(ethylene terephthalate), poly(1,4- Butylene terephthalate) and poly (trimethylene terephthalate), and at least one resin composition for plastic injection is provided.

As used herein, "injection" means, for example, a molding method in which a relatively elastic plastic material among synthetic resins is fluidized by a heater installed in the machine inside the cylinder of an injection molding machine and pressurized into a mold with a pressurized plunger. there is. The resin composition for plastic injection according to an embodiment of the present invention has excellent mechanical properties and workability, so it is not only suitable for injection, but also has excellent chemical resistance and eco-friendly effects.

In one embodiment, the resin composition for plastic injection includes a PCR material (Post-Consumer Recycled material). As important environmental issues such as climate change and carbon neutrality, consumer awareness of eco-friendliness, and social standards increase, domestic and foreign companies are demanding ESG (Environmental, Social, Governance) management and development of eco-friendly plastic alternative material technology. Accordingly, domestic and foreign materials companies are attempting to develop eco-friendly products in various ways, such as developing bioplastics (bio-based plastics, biodegradable plastics) and recycling waste plastics (mechanical, chemical). Among them, PCR material (Post-Consumer Recycled material) products, which are produced by recycling waste plastic used and discarded by consumers, are progressing and being applied at a relatively rapid pace.

In one embodiment, as the Post-Consumer Recycle (PCR) resin, the melt index (190 ° C., 2.16 kg load) is 0.01 to 10 g / 10 min, and the density is 0.94 to 0.96 g / cm ³ The first 20 to 60% by weight of high density polyethylene; 25 to 70% by weight of a second high density polyethylene having a melt index (190° C., 2.16 kg load) of 0.15 to 10 g/10 min and a density of 0.960 to 0.965 g/cm ³ ; and 5 to 20% by weight of a third high density polyethylene having a melt index of 0.01 to 0.15 g/10min and a density of 0.950 to 0.955 g/cm ³ (190°C, 2.16 kg load).

In one embodiment, the content of the polycarbonate (Polycarbonate) is 60% by weight or more, 61% by weight or more, 62% by weight or more, 63% by weight or more, 64% by weight or more, 65% by weight or more based on the total weight of the composition; 70 wt% or less, 69 wt% or less, 68 wt% or less, 67 wt% or less, 66 wt% or less, 65 wt% or less, but is not limited thereto.

In one embodiment, the content of the acrylonitrile-butadiene-styrene copolymer (ABS) is 25% by weight or more, 26% by weight or more, 27% by weight or more based on the total weight of the composition; It may be 30 wt% or less, 29 wt% or less, 28 wt% or less, or 27 wt% or less, but is not limited thereto.

In one embodiment, the content of the aromatic polyester is 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more based on the total weight of the composition; 10 wt% or less, 9.5 wt% or less, 9 wt% or less, 8.5 wt% or less, 8 wt% or less, 7.5 wt% or less, 7 wt% or less, but is not limited thereto.

The polycarbonate has an oxygen index of about 25 to 29 and a melting index of about 8 to 12, and easily forms char during combustion to effectively block the movement of gas. , can exhibit high flame retardant properties by itself. Examples of the polycarbonate include a compound including a repeating unit represented by Formula 1 below, and the compound including a repeating unit represented by Formula 1 below can be obtained from the synthesis scheme of Scheme 1 below.

[Formula 1]

[Scheme 1]

In one embodiment, the polycarbonate is a P-bisphenol A-phosgene polymer of CAS number 103598-77-2 or 1664368-22-2 represented by Formula 2 below.

[Formula 2]

The acrylonitrile-butadiene-styrene copolymer (ABS) is a synthetic terpolymer formed from three different monomer types acrylonitrile, 1,3-butadiene and styrene. It is an amorphous thermoplastic material. Quantitative ratios can vary from 15-35% acrylonitrile, 5-30% butadiene and 40-60% styrene.

In one embodiment, the acrylonitrile-butadiene-styrene copolymer (ABS) is a compound of CAS number 9003-56-9 represented by Formula 3 below.

[Formula 3]

In one embodiment, the aromatic polyester is at least one selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate) and poly(trimethylene terephthalate), and in a preferred embodiment , poly(1,4-butylene terephthalate) (PBT) having CAS number 26062-94-2 represented by the following formula (4) is used.

[Formula 4]

In one embodiment, the resin composition for plastic injection according to one embodiment of the present invention further includes a plasticizer to implement various physical properties.

In one embodiment, the plasticizer comprises 0.5% to 9.5% by weight, 14.5% to 43.8% by weight of an alkyl-substituted terephthalate-based compound of unhybrid unbranched type, hybridized branched type, and unhybridized branched type, respectively, based on the total weight of the plasticizer. and in an amount of 46.7% to 85% by weight.

The term "unhybrid unbranched type" used in the present invention refers to a structure containing two types of linear hydrocarbons in which the alkyl group substituted at the symmetrical position of the phenyl group is the same and without a branched chain, unless otherwise specified. In addition, the term “hybrid branched type” used in the present invention refers to a structure in which the alkyl groups substituted at symmetrical positions of the phenyl group are different from each other and include one type of branched chain, unless otherwise specified. For example, in the hybrid branched alkyl-substituted terephthalate-based compound, if one of the two alkyl groups substituted at the symmetrical position of the phenyl group is a branched alkyl group, the other alkyl group is an unbranched type. It means that it is an alkyl group. In addition, in the hybrid branched alkyl-substituted terephthalate-based compound, the branched-type alkyl group may be the same as the branched-type alkyl group of the unhybrid branched-type alkyl-substituted terephthalate-based compound, and the unbranched type The alkyl group may be the same as the unbranched type alkyl group of the unhybrid unbranched type alkyl-substituted terephthalate-based compound. Furthermore, the term "non-hybrid branched type" used in the present invention refers to a structure including two types of branched chains in which the alkyl group substituted at the symmetrical position of the phenyl group is the same, unless otherwise specified.

When the plasticizer component is included within the specific weight ratio range, it is possible to provide excellent physical properties such as plasticization efficiency (hardness) and light resistance while having excellent compatibility with additives suitable for injection molding. In the case of using the plasticizer of the present invention, since the degree of softening can be increased even with the use of a small amount of plasticizer compared to the case of using a conventional phthalate-based or terephthalate-based plasticizer in the same amount, it is very effective in terms of cost. In addition, since it has melting characteristics suitable for low-pressure injection, applications such as automobile encapsulated glass molding and gear knobs may be possible.

In one embodiment, the plasticizer is an ether-free composition. The ether-free means that the ether component contained in the plasticizer is 1,000 ppm or less, 100 ppm or less, or 10 ppm or less. Within this range, there is an effect of good plasticization efficiency and excellent workability.

In one embodiment, the resin composition for plastic injection according to an embodiment of the present invention further includes a flame retardant and a flame retardant aid.

In one embodiment, the flame retardant is a terminally uncapped brominated epoxy compound.

In one embodiment, as the flame retardant adjuvant, antimony trioxide, antimony pentoxide, metal antimony or antimony trichloride may be used alone or in combination of two or more, and in particular, the use of antimony trioxide is excellent in flame retardant synergy . The flame retardant aid acts to cause a synergistic flame retardant action together with the flame retardant, the terminal uncapped epoxy compound.

In one embodiment, the resin composition for plastic injection may further include a component selected from the group consisting of a heat-resistant stabilizer, a lubricant, an antistatic agent, a nucleating agent, a slip agent, a pigment, and combinations thereof.

According to one embodiment of the present invention, a method of using the resin composition for plastic injection for injection may be provided.

According to one embodiment of the present invention, a method of injecting a raw material including the resin composition for plastic injection may be provided.

According to one embodiment of the present invention, an injection-molded product including the resin composition for plastic injection may be provided. The injection-molded article may be manufactured by a method commonly known in the art. The molded article may be in various forms, such as, for example, a film, sheet, or fiber. In addition, the molded product may be an injection molded product, an extrusion molded product, or a blow molded product. Specifically, in the case of manufacturing a molded product by injection molding, the mold temperature may be about 130° C. or higher. When the molded article is in the form of a film or sheet, it may be manufactured into various films or sheets by methods such as non-stretching, uniaxial stretching, and biaxial stretching. When the molded article is a fiber, it may be various fibers such as unstretched yarn, stretched yarn, or super-stretched yarn, and may be used as woven fabric, knitted fabric, nonwoven fabric (spun bond, melt blown, staple), rope, or net. These molded articles can be used for electrical parts such as computer accessories, electronic parts, building members, automobile parts, mechanical parts, daily necessities, coatings for parts in contact with chemicals, industrial chemical resistant fibers, and the like.

{Example}

Hereinafter, the present disclosure will be described in detail by examples. However, the following examples are only examples for helping the overall understanding of the present disclosure, and the content of the present disclosure is not limited to the following examples.

<Production Example> Production of pellets

Pellets were prepared by mixing the materials in the ratios shown in Table 1 below.

Ingredients (% by weight) CAS number Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 polycarbonate 103598-77-2 65 - - 20 70 50 polycarbonate 1664368-22-2 - 65 - - - - PVC - - - 65 - - - ABS 9003-56-9 27 27 27 72 22 49 PBT 26062-94-2 7 7 7 7 7 - plasticizer - 0.5 0.5 0.5 0.5 0.5 0.5 flame retardant - balance balance balance balance balance balance

<Experimental Example> Measurement of physical properties

Specimens were prepared by injection molding at 300 ° C. using the pellets prepared in the above Preparation Example, and each physical property was measured by the following method. Table 2 shows the measurement results. N.D. is not detect, meaning that it contains an amount less than the detection limit.

(1) Tensile strength

The tensile strength of the injection specimen was measured according to the ISO 527 method.

(2) impact strength

According to the ISO 179 method, the impact strength of injection specimens of 80 mm (length) Х 10 mm (width) Х 4 mm (thickness) was measured by the V-notch Charpy method.

(3) sodium content

10 ml each of nitric acid, perchloric acid, and sulfuric acid were added to 0.5 g of the injection specimen, and heated on a hot plate at about 350 ° C. to decompose organic matter and evaporated leaving only a small amount of the remaining acid. Thereafter, the mixture was cooled to room temperature, put into a 25 ml volumetric flask, diluted by adding distilled water to the 25ml scale of the volumetric flask, and the sodium (Na) content was measured by ICP-AES. At this time, N.D. refers to containing less than 5 ppm of sodium, which is the quantification limit.

(4) Chlorine content

50 mg of the injection specimen was completely burned while humidifying at 1,000 ℃ using AQF (Auto Quick Furnace), and the combustion gas was collected in an absorption solution (hydrogen peroxide solution 900 ppm), and then ion chromatography (Ion Chromatography, Auto Quick After automatic injection with Furnace), the chlorine (Cl) content was measured.

(5) Flexural strength

Flexural strength of the injection specimen was measured according to the ISO 178 method.

(6) Long life coolant (LLC)

After immersing the injection specimen in automobile antifreeze (composition: ethylene glycol 45 vol%, water 50 vol%, and phosphate-based corrosion inhibitor 5 vol% included) at 150 ° C for 3,000 hours, tensile strength and flexural strength after immersion compared to tensile strength and flexural strength before immersion The rate at which flexural strength is maintained was measured.

(7) Chemical resistance 1

The injection specimen was immersed in chloroform and heat-treated at 50° C. for 30 days, and then the weight change rate after heat treatment was measured based on before heat treatment.

(8) Chemical resistance 2

Injection specimens were immersed in 10% (w/v) CaCl ₂ aqueous solution and heat treated at 80° C. for 1,000 hours (41.6 days). The rate of change in flexural strength after heat treatment was measured with the flexural strength before heat treatment as 100%.

division unit Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 tensile strength kgf/cm ² 1830 1800 1520 1630 1590 1600 impact strength
(notched) kJ/m ² 9.5 9.3 7.2 7.1 7.0 7.2 impact strength
(un-notched) kJ/m ² 47 46 36 32 32 35 chlorine content ppm ND ND 1320 1050 2850 1200 sodium content ppm ND ND 1450 1700 1650 1350 LLC (Tensile Strength) % 95 94 58 62 60 65 LLC (flexural strength) % 96 94 75 76 73 70 chemical resistance 1 % 1.1 1.2 8.2 7.1 6.4 4.8 chemical resistance 2 % 98 95 86 88 87 85

As shown in Table 2, the resin composition for plastic injection according to the present invention contained very small amounts of chlorine and sodium and had excellent internal copper liquid and chemical resistance. In addition, it showed remarkably excellent anti-synchronization properties, tensile strength, impact strength, and strong chemical resistance to acid.

Although the present invention has been described with respect to the preferred embodiments mentioned above, various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, the scope of the appended claims is intended to include such modifications and variations insofar as they fall within the scope of the present invention.

Claims (3)

60 to 67% by weight of polycarbonate based on the total weight of the composition;
25 to 30% by weight of an acrylonitrile-butadiene-styrene copolymer (ABS) based on the total weight of the composition; and
5 to 10% by weight of an aromatic polyester based on the total weight of the composition;
Including,
Further contains a plasticizer,
The polycarbonate is a P-bisphenol A-phosgene polymer,
The aromatic polyester is at least one selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate) and poly(trimethylene terephthalate),
The plasticizer contains 0.5% to 9.5% by weight, 14.5% to 43.8% by weight and 46.7% by weight of an alkyl-substituted terephthalate-based compound of unhybrid unbranched type, mixed branched type and unhybrid branched type, respectively, based on the total weight of the plasticizer. % to 85% by weight,
A resin composition for plastic injection. According to claim 1,
The plasticizer is an ether-free composition, a resin composition for plastic injection. According to claim 1,
A resin composition for plastic injection, further comprising a flame retardant and a flame retardant aid.