KR20110017780A - Environment friendly resin composition for hollow molding product and hollow molding product using the same - Google Patents

Abstract

PURPOSE: An environment-friendly resin composition for hollow molding products is provided to ensure excellent mechanical strength, heat resistance and processability and to enable application to hollow molding products for vehicle, machine component, electrical and electronic component, communications device, office device, general merchandise, and construction materials. CONSTITUTION: An environment-friendly resin composition for hollow molding products includes 40-90 weight% of biodegradable or plant-derived environment-friendly resin and 10-60 weight% of natural reinforcing agent; or 40-90 weight% of synthetic resin and 10-60 weight% of natural reinforcing agent; or 20-40 weight% of biodegradable or plant-derived environment-friendly resin and, 20-70 weight% of synthetic resin and 10-40 weight% of natural reinforcing agent. The biodegradable or plant-derived environment-friendly resin is selected from the group consisting of a polylactic acid resin, polyhydroxy alkanoate resin, polybutylene succinate resin, starch resin, plant-derived polyamide resin, bio succinic acid resin, and combinations thereof.

Description

ENVIRONMENT FRIENDLY RESIN COMPOSITION FOR HOLLOW MOLDING PRODUCT AND HOLLOW MOLDING PRODUCT USING THE SAME}

The present disclosure relates to an environment-friendly resin composition for a hollow molded body and a hollow molded body using the same, and in particular, used for molding a hollow body embedded in a slab in order to reduce the amount of reinforced concrete, an eco-friendly resin composition for a hollow molded body and a hollow using the same It relates to a molded article.

Until recently, research focused on the development of robust specialty polymer materials and the safety of polymer materials. However, as the problem of environmental pollution caused by waste polymers has become a social problem all over the world, the necessity of environmentally friendly polymer materials is required in recent years.

Such environmentally friendly polymers can be broadly classified into photodegradable and biodegradable polymers. The double biodegradable polymers have functional groups capable of being decomposed by microorganisms in the main chain structure.

Among these polymers, aliphatic polyester polymers are the most researched as biodegradable polymers because of their excellent processability and easy control of their decomposition properties. Especially, polylactic acid (PLA) forms the 150,000 ton market worldwide. In addition, the scope of application is expanding to the field where general plastics such as food packaging materials, containers, and electronics cases were used. To date, the main use of polylactic acid resins is in disposable products utilizing the biodegradable properties of polylactic acid, such as food containers, wraps, films and the like. The polylactic acid is currently being produced by Natureworks in the US and Toyota in Japan.

However, existing polylactic acid resins are easily broken in the case of thin film products due to lack of moldability, mechanical strength and heat resistance, and have low temperature resistance. there was. In addition, the hydrolysis resistance is low, it does not endure for more than 48 hours in the environment of high temperature and high humidity has the disadvantage of decomposing itself.

Meanwhile, Japanese Patent Laid-Open Nos. 2005-220177, 2005-200517, and 2005-336220 disclose techniques for mixing glass fibers to improve heat resistance and mechanical strength at the same time. There is a disadvantage that is not.

In addition, Japanese Patent Laid-Open Nos. 2005-105245 and 2005-60556 propose methods for mixing natural fibers in order to increase environmental friendliness.

One aspect of the present invention is to provide an environmentally friendly resin composition for a hollow molded article excellent in mechanical strength, heat resistance and processability.

Another aspect of the present invention is to provide a hollow molded article prepared from the environmentally friendly resin composition for the hollow molded article.

One aspect of the present invention is a biodegradable or plant-derived eco-friendly resin 40 to 90% by weight; And it provides an environmentally friendly resin composition for a hollow molded body comprising 10 to 60% by weight of a natural reinforcing agent.

Another aspect of the invention the synthetic resin 40 to 90% by weight; And it provides an environmentally friendly resin composition for a hollow molded body comprising a natural reinforcing agent 10 to 60% by weight.

Another aspect of the present invention is biodegradable or plant-derived eco-friendly resin 20 to 40% by weight; 20 to 70 weight percent of synthetic resin; And it provides a natural eco-friendly resin composition for a hollow molded article comprising a natural reinforcing agent 10 to 40% by weight.

The biodegradable or plant-derived eco-friendly resin is polylactic acid (PLA) resin, polyhydroxy alkanoate (PHA) resin, polybutylene succinate (PBS) resin, starch resin, plant-derived polyamide resin, bio succinic acid resin And combinations thereof.

The natural reinforcing agent may include cellulose-based powder or fiber, the cellulose-based powder or fiber may be wood-based powder, pulverized paper, powder pulp, flax, hemp, jute, It may be selected from the group consisting of kenaf, ramie, curaua, ground walnut shell, and combinations thereof, the average particle diameter of the natural reinforcing agent may be 0.1 to 1000 ㎛.

The synthetic resin may be selected from the group consisting of polyolefin resins, polycarbonate resins, rubber-modified vinyl copolymer resins, polyamide resins, non-degradable resins, and combinations thereof, and the polyolefin resin may be selected from high density polyethylene, HDPE) resin, linear low density polyethylene (LLDPE) resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl alcohol copolymer resin, and combinations thereof.

The eco-friendly resin composition for the hollow molded body is a polypropylene-maleic anhydride graft copolymer, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and a combination thereof. A coupling agent selected from the group consisting of 0.1 to 10 parts by weight relative to 100 parts by weight of the environmentally friendly resin composition for the hollow molded body may be further included.

The eco-friendly resin composition for the hollow molded body is a lubricant selected from the group consisting of hydrocarbon wax, fatty acid or higher alcohol wax, amide wax, ester wax, stearic acid metal salt wax, fluorine-containing polymer, silicone oil and combinations thereof. 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the eco-friendly resin composition for the hollow molded product may be further included.

The eco-friendly resin composition for the blow molded body is an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, a dye, a surfactant, a plasticizer, a admixture, a colorant, a stabilizer, a lubricant, and an antistatic agent based on 100 parts by weight of the eco-friendly resin composition for the blow molded body. It may further comprise 0.1 to 30 parts by weight of an additive selected from the group consisting of a pigment, a flame retardant, a weathering agent, a colorant, a sunscreen agent, a nucleating agent, an adhesion aid, an adhesive and a combination thereof.

Another aspect of the present invention provides a hollow molded article prepared from the eco-friendly resin composition for the blow molded article.

The hollow molded body may be applied to a concrete hollow slab, and may have a shape selected from the group consisting of spherical, mushroom, oval, square, rounded rectangle, hexagonal, donut, cylindrical, and combinations thereof.

Other aspects of the present invention are included in the following detailed description.

Eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention is excellent in mechanical strength, heat resistance and processability, car, mechanical parts, electrical and electronic parts, communication equipment, office equipment, sundries, building materials, civil engineering, etc. It can be applied to a hollow molded body of various fields such as. In particular, it can be usefully applied to the hollow slab of the construction field, which has an environmentally friendly environment to reduce the environmental burden when disposing of the building while reducing the amount of reinforced concrete.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Eco-friendly resin composition for a hollow molded body according to an embodiment of the present invention is a resin selected from the group consisting of biodegradable or plant-derived eco-friendly resin, synthetic resin and combinations thereof; And natural reinforcing agents.

Hereinafter, it looks at in detail with respect to each component included in the eco-friendly resin composition for hollow molded article according to an embodiment of the present invention.

(A) Biodegradable or plant-derived eco-friendly resin

The biodegradable or plant-derived eco-friendly resin is polylactic acid (PLA) resin, polyhydroxy alkanoate (PHA) resin, polybutylene succinate (PBS) resin, starch resin, plant-derived polyamide resin, bio succinic acid resin And it can use what is selected from the group consisting of these combinations.

(A-1) Polylactic Acid (PLA) Resin

The polylactic acid resin is a polyester-based resin prepared by ester reaction using lactic acid as a monomer obtained by decomposing methanol starch, and is easily commercially available. In other words, the polylactic acid resin is a biodegradable resin, which gives environmentally-friendly properties to the eco-friendly resin composition for the hollow molded product according to the exemplary embodiment of the present invention.

The polylactic acid resin may include a repeating unit derived from a lactic acid selected from the group consisting of L-lactic acid, D-lactic acid, L, D-lactic acid, and combinations thereof.

The polylactic acid resin may include 95 wt% or more of repeating units derived from L-lactic acid in terms of balance of heat resistance and moldability, and specifically, 95 to 100 wt% of repeating units derived from L-lactic acid and D-lactic acid Polylactic acid resins consisting of 0 to 5% by weight of repeating units derived from D can be used, more specifically 98 to 99.99% by weight of repeating units derived from L-lactic acid and 0.01 to 2% of repeating units derived from D-lactic acid Polylactic acid resin which consists of% can be used. When the polylactic acid resin is made of the above content, it is possible to obtain not only a balance of heat resistance and moldability but also excellent hydrolysis resistance.

In addition, the polylactic acid resin is not particularly limited in molecular weight or molecular weight distribution as long as the molding process is possible, and a weight average molecular weight of 80,000 g / mol or more may be used, and specifically, 80,000 to 300,000 g / mol may be used. When the weight average molecular weight of a polylactic acid resin has the said range, it is excellent in the balance of the mechanical strength and heat resistance of a molded object.

The polylactic acid resin may be selected from the group consisting of polylactic acid polymers, polylactic acid copolymers, and combinations thereof.

The polylactic acid polymer is preferably a polymer produced by ring-opening polymerization of a lactic acid selected from the group consisting of the L-lactic acid, D-lactic acid and combinations thereof.

The polylactic acid copolymer is a random or block copolymer with a component copolymerizable with the polylactic acid polymer. As another component copolymerizable with the said polylactic acid polymer, the compound which has a 2 or more ester bondable functional group in a molecule | numerator can be used.

Examples of the compound having a functional group capable of two or more ester bonds in the molecule include (i) -dicarboxylic acid, (ii)-polyhydric alcohols, hydroxy carboxylic acids other than (i) -lactic acid, (x) lactone, and ( I) Various polyesters, polyethers, polycarbonates, etc. which are manufactured from the said compound are mentioned.

As said dicarboxylic acid, C4-C50 linear or branched saturated or unsaturated aliphatic dicarboxylic acid, C8-C20 aromatic dicarboxylic acid, polyether dicarboxylic acid, etc. are mentioned. .

The aliphatic dicarboxylic acid may include succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, and the like. The aromatic dicarboxylic acid may include phthalic acid, terephthalic acid, isophthalic acid, and the like. As polyether dicarboxylic acid, the dicarboxylic acid which has a carboxymethyl group in the both ends of polyalkylene ether, such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polyethylene polypropylene glycol, is mentioned.

Examples of the polyhydric alcohols (ii) include aliphatic polyols, aromatic polyhydric alcohols, polyalkylene ethers, and the like.

The aliphatic polyols are C2 having 2 to 4 hydroxyl groups such as butane diol, hexane diol, octane diol, decane diol, 1,4-cyclohexanedimethanol, glycerin, sorbitan, trimethylolpropane, neopentyl glycol, and the like. To C50 aliphatic polyols.

Examples of the aromatic polyhydric alcohols include C6 to C20 aromatic diols such as bis-hydroxy methyl benzene and hydroquinone, or bisphenols such as bisphenol A and bisphenol F, such as ethylene oxide, propylene oxide, and butylene. Aromatic diols which addition-reacted C2-C4 alkylene oxide, such as an oxide, are mentioned.

Moreover, as said polyalkylene ether, ether glycol, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, is mentioned.

Examples of the hydroxy carboxylic acid other than the lactic acid include C3 to C10 hydroxy carboxylic acids such as glycolic acid, hydroxy butyl carboxylic acid and 6-hydroxy caproic acid.

Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, δ -Valerolactone and the like.

The various polyesters, polyethers, and polycarbonates may be used without limitation as long as they are conventionally used in the production of lactic acid copolymers, but polyesters may be used.

As the polyester, an aliphatic polyester prepared from aliphatic dicarboxylic acid and aliphatic diol may be used.

In this case, succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, etc. may be used as the aliphatic dicarboxylic acid, and the aliphatic diol may be C2 such as ethylene glycol, propane diol, butane diol, hexane diol, or octane diol. Polyalkylene ethers (alone polymers or copolymers) such as aliphatic diols of C to C20, polyethylene glycols, polypropylene glycols, and polybutylene glycols, polyalkylene carbonates, and the like.

(A-2) Polyhydroxy Alkanoate (PHA) Resin

The polyhydroxy alkanoate resin is a biodegradable resin, which is an aliphatic polyester including a repeating unit represented by Formula 1 below, and the following repeating unit is derived from a hydroxy alkanoic acid monomer. do.

[Formula 1]

(In the formula 1,

R ₁ is a hydrogen atom or a substituted or unsubstituted C1 to C15 alkyl group,

n is an integer of 1 or 2.)

The polyhydroxy alkanoate resin is specifically a homopolymer of the hydroxy alkanoic acid monomer; Copolymers composed of two or more different hydroxy alkanoic acid monomers such as tri-copolymers, tetra-copolymers, and the like; Or blends of such homopolymers and copolymers.

Examples of the hydroxy alkanoic acid monomers, in the formula 1, n is 1 and R ₁ is 3-hydroxybutyric acid that result in a repeating unit group (3-hydroxy butyric acid), n is 1 and R ₁ is an ethyl group 3-hydroxy valeric acid to induce phosphorus repeat units, 3-hydroxy hexanoic acid to induce repeat units where n is 1 and R ₁ is a propyl group, n is 3-hydroxy octanoic acid which induces a repeating unit of 1 and R ₁ is a pentyl group, 3-hydroxy octadecanoic acid inducing a repeating unit of which n is 1 and R ₁ is an alkyl group of C15 ( 3-hydroxy octadecanoic acid). Specific examples thereof include 3-hydroxy butyric acid, and polyhydroxy butyrate (PHB) resin is polymerized from the monomer, and specifically, a kind of polyhydroxy alkanoate resin. Can be used.

In addition, specific examples of the copolymer consisting of two or more different hydroxy alkanoic acid monomers include poly (3-hydroxybutyric acid-co-3-hydroxy, which is a copolymer of 3-hydroxybutyric acid and 3-hydroxy hexanoic acid. Hexanoic acid) or poly (3-hydroxy butyric acid-co-3-hydroxy valeric acid) which is a copolymer of 3-hydroxy butyric acid and 3-hydroxy valeric acid. In this case, the copolymer may be composed of 80 to 99 mol% of 3-hydroxy butyric acid and 1 to 20 mol% of 3-hydroxy hexanoic acid or 3-hydroxy valeric acid.

(A-3) Polybutylene Succinate (PBS) Resin

The polybutylene succinate resin is prepared by a polycondensation reaction of succinic acid and 1,4-butanediol prepared by fermentation chemistry from sugars such as sugar cane and corn. That is, the polybutylene succinate resin is a plant-derived resin that is naturally decomposed when it is buried in the ground, thereby imparting environmental friendliness to the environment-friendly resin composition for the hollow molded product according to an embodiment of the present invention.

The polybutylene succinate resin is copolymerizable with other components to control crystallinity and flexibility. Examples of copolymerizable with succinic acid used in the polycondensation reaction include adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and the like, specifically, adipic acid. Examples of copolymerizable with 1,4-butanediol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, cyclohexane dimethanol, diethylene glycol, polyethylene glycol, polypropylene glycol, poly Tetramethylene glycol etc. are mentioned, Specifically, ethylene glycol, 1, 3- propylene glycol, etc. are mentioned.

The polybutylene succinate resin may have a melting point of 100 to 125 ℃. Molding is easy when the melting point of the polybutylene succinate resin is within the above range.

(A-4) starch resin

Examples of the starch resin include pure starch such as corn starch, rice starch, potato starch, tapioca starch, wheat starch and sweet potato starch; Modified starches such as α-starch, acid-treated starch, oxidized starch, amphoteric starch, ester starch, ether starch, etc. subjected to physicochemical treatment to the pure starch; And mixtures thereof. Specifically, corn starch may be used in terms of particle size or economical aspect of starch.

The starch resin is generally readily biodegradable, and is composed of linear amylose and branched amylopectin. Amylose has three hydroxyl groups per glucose unit, which is hydrophilic, and has strong hydrogen bonds.

(A-5) Plant-derived polyamide resin

The plant-derived polyamide resin may be selected from the group consisting of polyamide 4, polyamide 6, polyamide 66, polyamide 610, polyamide 1010, polyamide 11, and combinations thereof.

The polyamide 4 obtains glucose by a saccharification process of biomass such as cellulose or starch, and undergoes a glutamic acid fermentation process using the same, thereby obtaining γ-aminobutyric acid (GABA). It can be prepared by synthesizing and polymerizing it. The polyamide 4 is excellent in mechanical strength, heat resistance, oil resistance, chemical resistance, hydrophilicity and self-extinguishing, and biodegradation by microorganisms is possible.

The polyamide 6 is obtained by obtaining a glucose by a biomass saccharification process such as starch, and fermented with lysine, an amino acid, to prepare a caprolactam as a monomer, and ring-opening polymerization of the prepared caprolactam. Can be.

The polyamide 66 may be prepared by obtaining glucose by using a fermentation process using E-coli bacteria, preparing adipic acid using this as a raw material, and condensation polymerization of the prepared adipic acid with hexamethylenediamine.

The polyamide 610 comprises 60% by weight sebacic acid prepared from castor oil.

The polyamide 1010 may be prepared by condensation reaction of sebacic acid prepared from castor oil with 1,10-decamethylenediamine, which is aminated by sebacic acid, which is derived from 100% biomass.

The polyamide 11 is prepared from castor oil, which is a vegetable oil, and may be usefully applied to a product having low moisture absorption and requiring dimensional stability.

(A-6) Bio Succinate Resin

The bio succinic acid resin includes bio succinic acid and derivatives thereof, and may be prepared from starch using a fermentation process using an enzyme.

The biodegradable or plant-derived eco-friendly resin is included in an amount of 40 to 90% by weight based on the total amount of the eco-friendly resin composition for the hollow molded body according to one embodiment of the present invention, that is, the total amount of the biodegradable or plant-derived eco-friendly resin and natural reinforcing agent. It may be included, specifically, 50 to 80% by weight. In addition, the total amount of the eco-friendly resin composition for the hollow molded body according to another embodiment of the present invention, that is, may be included in 20 to 40% by weight relative to the total amount of biodegradable or plant-derived eco-friendly resin, synthetic resin and natural reinforcing agent, specifically May be included in an amount of 20 to 30 wt%. When the biodegradable or plant-derived eco-friendly resin is included in the above range, the eco-friendly resin composition of the eco-friendly resin composition for the hollow molded body, mechanical strength, heat resistance and moldability are all excellent.

(B) synthetic resin

The synthetic resin may be selected from the group consisting of polyolefin resins, polycarbonate resins, rubber-modified vinyl copolymer resins, polyamide resins, non-degradable resins, and combinations thereof.

(B-1) Polyolefin Resin

The polyolefin resin is a high density polyethylene (HDPE) resin, linear low density polyethylene (LLDPE) resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl alcohol copolymer resin and combinations thereof It may be used selected from the group consisting of, specifically, may be used polypropylene resin. In this case, the high density polyethylene resin means that it has a density range of 0.94 to 0.965, and the linear low density polyethylene resin means that it has a density range of 0.91 to 0.94.

(B-2) polycarbonate resin

The polycarbonate resin may be prepared by reacting a compound selected from the group consisting of diphenols represented by the following Chemical Formula 2 with phosgene, halogen acid esters, carbonate esters, and combinations thereof:

[Formula 2]

In Chemical Formula 2,

A is a single bond, substituted or unsubstituted C1 to C30 straight or branched alkylene group, substituted or unsubstituted C2 to C5 alkenylene group, substituted or unsubstituted C2 to C5 alkylidene group, substituted Or unsubstituted C1 to C30 straight or branched haloalkylene group, substituted or unsubstituted C5 to C6 cycloalkylene group, substituted or unsubstituted C5 to C6 cycloalkenylene group, substituted or unsubstituted C5 to C10 cycloalkylidene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C1 to C20 linear or branched alkoxylene group, halogen acid ester group, carbonate ester group, CO , S and SO ₂ is a connector selected from the group consisting of,

Each R ₁ and R ₂ are each independently a substituent selected from the group consisting of a substituted or unsubstituted C1 to C30 alkyl group and a substituted or unsubstituted C6 to C30 aryl group,

n ₁ and n ₂ are each independently an integer of 0 to 4,

The "substituted" is a hydrogen atom substituted with a substituent selected from the group consisting of a halogen group, C1 to C30 alkyl group, C1 to C30 haloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group and combinations thereof It means.

The diphenols represented by the formula (2) may combine two or more kinds to constitute a repeating unit of the polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also called 'bisphenol-A'), 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro 4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2 , 2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether and the like. Among the diphenols, specifically 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4- Hydroxyphenyl) cyclohexane can be used. Moreover, 2, 2-bis (4-hydroxyphenyl) propane can be used more specifically among these.

The polycarbonate resin may use a weight average molecular weight of 10,000 to 200,000 g / mol, specifically may be used 15,000 to 80,000 g / mol, but is not limited thereto.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. The polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. As said polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used.

(B-3) Rubber modified vinyl copolymer resin

The rubber-modified vinyl copolymer resin is a copolymer obtained by graft polymerization of 5 to 95% by weight of a vinyl polymer to 5 to 95% by weight of a rubbery polymer.

The vinyl polymer may include 50 to 95 wt% of a first vinyl monomer selected from the group consisting of aromatic vinyl monomers, acrylic monomers, and combinations thereof; And 5 to 50% by weight of a second vinyl monomer selected from the group consisting of unsaturated nitrile monomers, acrylic monomers, and combinations thereof. In this case, the first vinyl monomer and the second vinyl monomer are different from each other.

The aromatic vinyl monomer may be selected from the group consisting of styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, and combinations thereof. Specific examples of the alkyl-substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene and the like.

The acrylic monomer may be selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters, maleic anhydride, alkyl or phenyl N-substituted maleimide, and combinations thereof. In this case, the alkyl means C1 to C10 alkyl. Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. (Meth) acrylates can be used.

The unsaturated nitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and combinations thereof.

The rubbery polymer may be polybutadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / poly Alkyl (meth) acrylate rubber composites and combinations thereof may be used.

In manufacturing the rubber-modified vinyl copolymer resin 입, the particle diameter of the rubber particles may be in the range of 0.05 μm to 4 μm in order to improve mechanical strength and surface properties of the molded product. When the particle diameter of the rubber particles is in the above range it can be secured excellent impact strength.

The rubber-modified vinyl copolymer resin may be used alone or in the form of a mixture of two or more thereof.

Specific examples of the rubber-modified vinyl copolymer resin include graft copolymers of polybutadiene rubber, acrylic rubber or styrene / butadiene rubber with polymers of styrene, acrylonitrile and optionally methyl (meth) acrylate.

Specific examples of the rubber-modified vinyl copolymer resin may include those obtained by graft copolymerization of methyl (meth) acrylate on polybutadiene rubber, acrylic rubber or styrene / butadiene rubber.

The method for preparing the rubber-modified vinyl-based copolymer resin is well known to those skilled in the art, and may be any method of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization. And the above-mentioned aromatic vinyl monomer in the presence of a rubbery polymer, and emulsion polymerization or bulk polymerization using a polymerization initiator is mentioned.

(B-4) Polyamide Resin

The polyamide resin contains an amide group in the polymer main chain, and may be polymerized using amino acids, lactams or diamines and dicarboxylic acids as main components.

Specific examples of the amino acid include 6-aminocapronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Specific examples of the lactam include ε-caprolactam, ω-laurolactam, and the like, and specific examples of the diamine include tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, and undecamethylene. Diamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, methaxylenediamine, paraxylenediamine, 1,3-bis (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis ( Aliphatic, alicyclic or aromatic diamines such as 3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine Can be. Specific examples of the dicarboxylic acid include adipic acid, sericinic acid, azelaic acid, sebacic acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, cycloaliphatic, or aromatic dicarboxylic acids, such as 5-sodium sulfoisophthalic acid, 2, 6- naphthalenedicarboxylic acid, hexahydro terephthalic acid, and hexahydroisophthalic acid, are mentioned. Polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of mixtures, respectively.

(B-5) Non-degradable Resin

The non-degradable resin may be selected from the group consisting of polytrimethylene terephthalate (PTT) resin, polyurethane (PU) resin, bio polypropylene (bio PP) resin, bio polyethylene resin (bio PE), and combinations thereof. Can be.

The polytrimethylene terephthalate (PTT) resin is an aromatic polyester resin, and can be generally prepared by melt polycondensation of 1,3-propanediol and terephthalic acid, and has intermediate properties between polyester and polyamide.

The polyurethane (PU) resin has chemical resistance as a thermosetting resin.

The synthetic resin may be included in an amount of 40 to 90% by weight relative to the total amount of the eco-friendly resin composition for the hollow molded product, that is, the total amount of the synthetic resin and the natural reinforcing agent according to an embodiment of the present invention, specifically 60 to 90% by weight May be included. In addition, the total amount of the eco-friendly resin composition for the hollow molded body according to another embodiment of the present invention, that is, may be included in 20 to 70% by weight relative to the total amount of biodegradable or plant-derived eco-friendly resin, synthetic resin and natural reinforcing agent, specifically May include 40 to 60 weight percent. When the synthetic resin is included in the above range, the environmentally friendly, mechanical strength, heat resistance and moldability of the environmentally friendly resin composition for the hollow molded body are all excellent.

(C) natural reinforcing agents

The natural reinforcing agent means a cellulose-based material derived from a plant, and specific examples thereof include cellulose-based powder or fibers.

That is, the natural reinforcing agent according to an embodiment of the present invention usefully used as a polymer composite material is used as the reinforcing agent in the eco-friendly resin composition for the hollow molded body as an environmentally friendly material.

The cellulose-based powder or fiber is mainly composed of cellulose (cellulose), lignin () and semicellulose (), of which the cellulose may be used containing 70% by weight or more. When using a cellulose-based powder or fiber containing 70% by weight or more of cellulose may improve mechanical strength and heat resistance, in particular, the problem of discoloration of the molded product due to pyrolysis of lignin during molding.

The cellulose-based powder or fiber may be wood-based powder, pulverized paper, powder pulp, flax, hemp, jute, kenaf, ramie, curaua , Crushed walnut shells and combinations thereof may be selected from the group consisting of.

The cellulose-based powder may be pulverized by a conventional pulverization method, for example, wood-based powder is dried after sufficient drying, specifically, the moisture content of 3% by weight or less, more specifically 2% by weight or less Can be used after.

The average particle diameter of the natural reinforcing agent may have a range of 0.1 to 1000 ㎛, specifically may have a range of 10 ~ 100 ㎛ ㎛. When the average particle diameter of the natural reinforcing agent is within the above range, the workability is excellent, and the surface gloss is excellent.

The natural reinforcing agent may be included in an amount of 10 to 60% by weight based on the total amount of the eco-friendly resin composition for the hollow molded body according to an embodiment of the present invention, that is, biodegradable or plant-derived eco-friendly resin and natural reinforcing agent, specifically 10 wt% to 40 wt% may be included. In addition, the total amount of the eco-friendly resin composition for the hollow molded body according to another embodiment of the present invention, that is, may be included in 10 to 60% by weight relative to the total amount of the synthetic resin and natural reinforcing agent, specifically, it may be included in 10 to 40% by weight have. In addition, the total amount of the eco-friendly resin composition for the hollow molded body according to another embodiment of the present invention, that is, may be included in 10 to 40% by weight relative to the total amount of biodegradable or plant-derived eco-friendly resin, synthetic resin and natural reinforcing agent, specifically As may be included in 20 to 40% by weight. When the natural reinforcing agent is included in the above range, the workability with the biodegradable resin or synthetic resin is excellent.

(D) coupling agent

Eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention may further include a coupling agent. The coupling agent is a compatibilizer used to improve the compatibility between the biodegradable resin and the cellulose-based powder.

The coupling agent is a group consisting of a polypropylene-maleic anhydride graft copolymer, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a combination thereof. Can be selected from.

The coupling agent may be included in an amount of 0.1 to 10 parts by weight, specifically, 0.5 to 4 parts by weight, based on 100 parts by weight of the total amount of the eco-friendly resin composition for the hollow molded product. When the coupling agent is included in the above-described range, the compatibility of the environmentally friendly resin or the synthetic resin with the natural reinforcing agent is improved, and thus the overall physical properties of the environmentally friendly resin composition for the hollow molded body are improved.

(E) lubricant

Eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention may further include a lubricant. The lubricant may further improve moldability by being used together in an environment-friendly resin composition for the hollow molded body.

The lubricant may be a hydrocarbon wax such as polyethylene wax; Fatty acids such as stearic acid, stearyl alcohol, 12-hydroxy stearic acid or higher alcohol waxes; Amide waxes such as stearic acid amide, oleic acid amide, L-carnitine amide, methylenebisstearic acid amide, ethylenebisstearic acid amide and ethylenebisoleic acid amide; Ester waxes such as butyl stearate, monoglyceride stearate, pentaerythritol-tetrastearate, stearyl moist stearic acid, etc .; Metal stearic acid waxes such as calcium stearate, zinc stearate, barium stearate and magnesium stearate; Fluorine-containing polymers; Silicone oils; And combinations thereof may be selected from the group consisting of.

The lubricant may be included in an amount of 0.1 kPa to 10 kPa with respect to 100 parts by weight of the total amount of the eco-friendly resin composition for the hollow molded product, and specifically, 0.5 kPa to 4 kW by weight. When a lubricant is included in the said range, processability (molding) of the eco-friendly resin composition for hollow molded objects is further improved.

(F) other additives

Eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention is an antibacterial agent, heat stabilizer, antioxidant, mold release agent, light stabilizer, dye, surfactant, plasticizer, admixture, colorant, stabilizer, lubricant, antistatic agent, pigment, flame retardant, And may include additives selected from the group consisting of weathering agents, colorants, sunscreens, nucleating agents, adhesion aids, pressure sensitive adhesives, and combinations thereof.

The antioxidant may be a phenol, phosphite, thioether or amine antioxidant, the release agent is a fluorine-containing polymer, silicone oil, metal salt of stearic acid, montanic acid Metal salts, montanic acid ester waxes or polyethylene waxes may be used. In addition, a benzophenone type or an amine type weathering agent may be used as the weathering agent, and a dye or a pigment may be used as the coloring agent. In addition, the sunscreen may be titanium oxide (TiO ₂ ) or carbon black, the nucleating agent may be used talc or clay.

The additive may be included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the eco-friendly resin composition for the hollow molded product. When the additive is included in the above range can be obtained the effect of the additive according to each use, it is possible to obtain the excellent mechanical properties and improved appearance of the environment-friendly resin composition for the hollow molded body.

Eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention can be prepared by a known method. For example, after mixing the components and additives according to an embodiment of the present invention described above, it may be melt-extruded in an extruder and manufactured in pellet form.

According to another embodiment of the present invention, there is provided a hollow molded product manufactured by molding the above-mentioned eco-friendly resin composition for the hollow molded product. The eco-friendly resin composition for the blow molded body may be applied to the blow molded body in various fields such as automobiles, machine parts, electrical and electronic parts, communication equipment, office equipment, sundries, building materials, civil engineering, etc., which requires excellent mechanical strength, heat resistance and processability. Can be. In particular, it can be usefully applied to the concrete hollow slab of the construction field, specifically by embedding the hollow body made of eco-friendly resin composition according to an embodiment of the present invention in the slab not only can reduce the amount of reinforced concrete, but also biodegradable By using excellent biodegradable resins and natural reinforcing materials as the main raw materials, it has an environmentally friendly nature to reduce the environmental burden when disposing of buildings.

The hollow molded body may have various shapes, and specifically, may have a shape selected from the group consisting of spherical shape, mushroom shape, oval shape, square shape, round square shape, hexagon shape, donut shape, cylinder shape, and combinations thereof. Specifically, it may have a donut shape.

In particular, when the hollow molded body applied to the hollow slab is a donut type, it is effective to block the vibration and noise by forming a hollow structure in the slab while minimizing the reduction of the ultimate load of the slab.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

[Example]

Each component used in the manufacture of the eco-friendly resin composition for a hollow molded article according to an embodiment of the present invention is as follows.

(A) Biodegradable or plant-derived eco-friendly resin

(A-1) Polylactic Acid (PLA) Resin

4032D manufactured by NatureWorks LLC, USA was used.

(A-2) Polyhydroxy Alkanoate (PHA) Resin

Mirel P1003 from Metabolix was used.

(A-3) Plant-derived Polyamide Resin

Rilsan PA11 manufactured by Arkema was used.

(B) synthetic resin

(B-1) Polyolefin Resin

As the polypropylene resin, HF409 manufactured by Samsung Total was used.

(B-2) polycarbonate resin

SC-1220 (medium viscosity) manufactured by Cheil Industries was used.

(B-3) Rubber modified vinyl copolymer resin

As the ABS resin, SD-0150 manufactured by Cheil Industries was used.

(C) natural reinforcing agents

A kenaf powder having an average particle diameter of 2.5 µm was used.

(D) coupling agent

As polypropylene-maleic anhydride graft copolymer, Clariant Licocene PPMA 6452 was used.

(E) lubricant

As ethylene bis stearic acid amide, LEBAX-140B manufactured by Uion Lion Chemical was used.

Examples 1-20 and Comparative Examples 1-5

The above mentioned components are fed to a conventional biaxial feed rate of 40 kg / hr, screw rpm 200, screw configuration 45φ Regular, L / D = 36 with the contents as shown in Table 1 below. After extruding in a temperature range of 180 to 240 ℃ in an extruder, the extrudate was prepared in pellet form.

[Test Example]

After drying the pellets prepared according to Examples 1 to 20 and Comparative Examples 1 to 5 at 80 ° C. for 4 hours, using a 6 oz injection molding machine, the cylinder temperature was 190 ° C., the mold temperature was 80 ° C., and the molding cycle was 120 seconds. After setting, injection molding the ASTM dumbbell test specimen to prepare a physical specimen. Physical properties of the prepared specimens were measured by the following method, and the results are shown in Tables 1 to 3 below.

(1) Flexural strength: measured according to ASTM D638.

(2) Flexural modulus: measured according to ASTM D638.

(3) Tensile strength: measured according to ASTM D638.

(4) Heat Deflection Temperature (HDT): Measured according to ASTM D648.

TABLE 1

* Parts by weight: The content unit is based on 100 parts by weight of the total amount of (A) eco-friendly resin, (B) synthetic resin and (C) natural reinforcing agent.

TABLE 2

* Parts by weight: Content units represented based on 100 parts by weight of the total amount of (A) eco-friendly resin, (B) synthetic resin, and (C) natural reinforcing agent.

[Table 3]

* Parts by weight: Content units represented based on 100 parts by weight of the total amount of (A) eco-friendly resin, (B) synthetic resin, and (C) natural reinforcing agent.

Through Table 1, Examples 1 to 8 using a biodegradable or plant-derived eco-friendly resin and a natural reinforcing agent can be confirmed that the mechanical strength and heat resistance excellent compared to Comparative Example 1 using only eco-friendly resin, eco-friendly resin and Comparative Example 2 using each of the natural reinforcing agents in an amount outside the range according to the embodiment of the present invention can be seen that the mixing process itself is impossible.

Through Table 2, Examples 9 to 16 using a synthetic resin and a natural reinforcing agent can be confirmed that the mechanical strength and heat resistance is superior to Comparative Example 3 using only synthetic resin, each of the synthetic resin and natural reinforcing agent Comparative Example 4 used in a content outside the range according to one embodiment of the mixing process itself can be seen that impossible.

Through Table 3, Examples 17 to 20 using a biodegradable or plant-derived eco-friendly resin, a synthetic resin and a natural reinforcing agent can be confirmed that the mechanical strength and heat resistance is excellent, and each of the eco-friendly resin, synthetic resin and natural reinforcing agent Comparative Example 5 used in a content outside the range according to an embodiment of the present invention can be seen that the mixing process itself is impossible.

In particular, Comparative Examples 2, 4 and 5 using an excessive amount of a natural reinforcing agent can be seen that due to the pressure rise in the extruder did not melt well, so that no physical properties were obtained.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

Biodegradable or plant-derived eco-friendly resin 40 to 90 weight percent; And Eco-friendly resin composition for a hollow molded body comprising 10 to 60% by weight of a natural reinforcing agent. 40 to 90 weight percent of synthetic resins; And Eco-friendly resin composition for a hollow molded body comprising a natural reinforcing agent of 10 to 60% by weight. Biodegradable or plant-derived eco-friendly resin 20 to 40 weight percent; 20 to 70 weight percent of synthetic resin; And Eco-friendly resin composition for a hollow molded body comprising a natural reinforcing agent # 10 to 40% by weight. The method according to claim 1 or 3, The biodegradable or plant-derived eco-friendly resin is polylactic acid (PLA) resin, polyhydroxy alkanoate (PHA) resin, polybutylene succinate (PBS) resin, starch resin, plant-derived polyamide resin, bio succinic acid resin And environmentally friendly resin compositions for hollow molded bodies, which are selected from the group consisting of a combination of these. The method according to any one of claims 1 to 3, The natural reinforcing agent is an environment-friendly resin composition for a hollow molded article containing a cellulose-based powder or fiber. The method of claim 5, The cellulose-based powder or fiber may be wood-based powder, pulverized paper, powder pulp, flax, hemp, jute, kenaf, ramie, curaua , Crushed walnut shell and environmentally friendly resin composition for a hollow molded body is selected from the group consisting of these. The method according to any one of claims 1 to 3, Eco-friendly resin composition for a hollow molded article that the average particle diameter of the natural reinforcing agent is 0.1 to 1000 ㎛. The method according to claim 2 or 3, The synthetic resin is a polyolefin resin, polycarbonate resin, rubber-modified vinyl copolymer resin, polyamide resin, non-degradable resin and environmentally friendly resin composition for a hollow molded article is selected from the group consisting of these. The method of claim 8, The polyolefin resin is a high density polyethylene (HDPE) resin, linear low density polyethylene (LLDPE) resin, polypropylene resin, ethylene-propylene copolymer resin, ethylene-vinyl alcohol copolymer resin and combinations thereof It is selected from the group consisting of a cyclic resin composition for a hollow molded body. The method according to any one of claims 1 to 3, The eco-friendly resin composition for the blow molded body is a polypropylene-maleic anhydride graft copolymer, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and their Eco-friendly resin composition for a hollow molded body further comprises a 0.1 to 10 parts by weight of the coupling agent selected from the group consisting of 100 parts by weight of the eco-friendly resin composition for blow molded products. The method according to any one of claims 1 to 3, The eco-friendly resin composition for the hollow molded body is a lubricant selected from the group consisting of hydrocarbon wax, fatty acid or higher alcohol wax, amide wax, ester wax, stearic acid metal salt wax, fluorine-containing polymer, silicone oil and combinations thereof. Eco-friendly resin composition for a blow molded article, which is further included in 0.1 to 10 kPa parts by weight based on 100 parts by weight of the eco-friendly resin composition for blow molded article. The method according to any one of claims 1 to 3, The eco-friendly resin composition for the blow molded body is an antibacterial agent, a heat stabilizer, an antioxidant, a mold release agent, a light stabilizer, a dye, a surfactant, a plasticizer, a admixture, a colorant, a stabilizer, a lubricant, and an antistatic agent based on 100 parts by weight of the eco-friendly resin composition for the blow molded body. And 0.1-30 parts by weight of an additive selected from the group consisting of a pigment, a flame retardant, a weathering agent, a colorant, a sunscreen agent, a nucleating agent, an adhesion aid, an adhesive, and a combination thereof. The hollow molded article manufactured from the eco-friendly resin composition for hollow molded articles of any one of Claims 1-3. The method of claim 13, The hollow molded body is applied to the concrete hollow slab. The method of claim 13, The hollow molded body has a shape selected from the group consisting of spherical, mushroom, oval, square, rounded square, hexagonal, donut, cylindrical, and combinations thereof.