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WO2016013819A1 - Composition comprenant au moins deux résines, des fibres de verre et une résine de caoutchouc à base d'oléfine - Google Patents

Composition comprenant au moins deux résines, des fibres de verre et une résine de caoutchouc à base d'oléfine Download PDF

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Publication number
WO2016013819A1
WO2016013819A1 PCT/KR2015/007481 KR2015007481W WO2016013819A1 WO 2016013819 A1 WO2016013819 A1 WO 2016013819A1 KR 2015007481 W KR2015007481 W KR 2015007481W WO 2016013819 A1 WO2016013819 A1 WO 2016013819A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
composition
resins
mixed
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2015/007481
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English (en)
Korean (ko)
Inventor
조윤숙
신양재
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Container Pool Co Ltd
Original Assignee
Korea Container Pool Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140094716A external-priority patent/KR101537193B1/ko
Priority claimed from KR1020150097683A external-priority patent/KR20170006683A/ko
Application filed by Korea Container Pool Co Ltd filed Critical Korea Container Pool Co Ltd
Publication of WO2016013819A1 publication Critical patent/WO2016013819A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a composition comprising two or more kinds of resins, glass filaments and olefinic rubber resins, and more particularly, adding glass filaments together with olefinic rubber resins to waste resins having low impact resistance and low bending characteristics when mixed.
  • the present invention relates to a composition comprising two or more kinds of mixed resins, glass long fibers and olefin rubber resins solved using an olefin resin and a glass long fiber.
  • Waste resins can be used as recycled raw materials, so they are collected separately, crushed, melted and provided for reuse. However, since the physical properties of these waste resins are very different depending on the type of polymer, various kinds of waste resins must be accurately separated according to the type of waste resin for recycling.
  • the waste resin is separated using a difference in specific gravity, but the problem is that polyethylene (PE) and polypropylene (PP) having a lower specific gravity than water are difficult to separate in this manner.
  • PE polyethylene
  • PP polypropylene
  • Utility Model Application No. 20-2001-24176 discloses a technique for manufacturing a pallet using recycled plastic to achieve cost reduction.
  • the recycled pallet of the cited invention is produced by pulverizing the waste resin material into a pallet shape. In this case, due to the compatibility and affinity between different waste resin materials, there is a problem that the impact resistance is inferior.
  • the problem to be solved by the present invention is to provide a composition comprising a heterogeneous waste resin, and a plastic product using the same, improved physical properties such as impact resistance, flexural strength.
  • the present invention is a composition comprising two or more resins, glass filament, olefin rubber resin, 100 parts by weight of a mixed resin consisting of two or more unit resins; 1 to 30 parts by weight of the glass filament having a length of 10 mm to 50 mm; And it provides a composition comprising a 0.5 to 25 parts by weight of olefinic rubber resin.
  • the composition further comprises 5 to 35 parts by weight of LDPE, the LDPE is contained in the olefin-based rubber resin of the pellet form, it is incorporated into the composition.
  • the mixed resin is made of waste polyethylene (PE) and waste polypropylene (PP).
  • the mixed resin comprises a first resin and a second resin, wherein the first resin is a resin having an elongation at break of 100% or more, the second resin is 20% or less at break
  • the weight average molecular weight of the rubber resin is 1,000 to 500,000.
  • the weight ratio of the first resin and the second resin is 20 to 59: 30 to 50.
  • one of the first resin and the second resin is polyethylene (PE), the other is polypropylene (PP), and the present invention provides a plastic product comprising the composition described above. .
  • the plastic product is a pallet or box.
  • the present invention also provides a method for producing a plastic product using the composition described above, comprising the steps of preparing the composition by mixing the mixed resin, the glass fiber and an olefinic rubber resin having a molecular weight of 1,000 to 500,000; Melting the mixed composition; And molding the molten composition to produce a plastic product.
  • the mixed resin comprises a first resin and a second resin, wherein the first resin is a resin having an elongation at break of 100% or more, the second resin is 20% or less at break
  • the weight average molecular weight of the rubber resin is 1,000 to 500,000.
  • an olefinic rubber resin is used to recycle waste resin, thereby improving the resinous dispersion of glass filament in the waste resin containing polyethylene, and can solve the problem of precipitation of the rubber resin on the surface. Furthermore, the problem of odor generation by carbonization of rubber resin can be solved. According to the present invention, the problem of compatibility and physical property deterioration caused by the use of two or more kinds of mixed resins having different elongation at break is solved using an olefin resin and a glass filament having a specific molecular weight range.
  • olefinic rubber resins having a specific molecular weight range are used in recycling mixed resins having extremely low elongation at break, such as waste resins, to solve the problem of deterioration of mixing characteristics due to the use of recycled and new materials generated during the melting process.
  • Figure 4 is a SEM image after molding of the composition using an olefin rubber resin containing LDPE.
  • Figure 5 is a step diagram of a plastic product manufacturing method according to an embodiment of the present invention.
  • this inventor provides the composition which mixed the glass fiber and olefinic rubber resin which are glass fiber of a predetermined length (10 mm or more) with 2 or more types of waste resin mixture materials.
  • the olefin rubber resin was an ethylene-butene copolymer, but the scope of the present invention is not limited thereto.
  • the present invention uses an olefinic rubber resin to recycle waste resin, and improves the resinous dispersibility of the glass fiber in the waste resin containing polyethylene in addition to the impact resistance by a high carbon polymer such as butane.
  • the problem of precipitation on the surface of the final product can be solved. Furthermore, it solves the problem of odor generated by carbonization of rubber resin added to enhance impact resistance.
  • the present invention is a non-olefin rubber-based resin such as SBS, SEBS in general in the melting process in the plastic product using waste resin, the carbonization phenomenon occurs by heat (carbide and odor generation), and also the decomposition rate during the melting process
  • an olefinic rubber resin was used in the composition to reduce the possibility of agglomeration of the rubber resin during melting of the waste resin, and also a smell generated during the carbonization process. Reduced.
  • Composition according to an embodiment of the present invention comprises a composition comprising two or more resins, glass fiber, LDPE and olefinic rubber resin, 100 parts by weight of a mixed resin consisting of two or more unit resins; 1 to 30 parts by weight of the glass filament having a length of 10 mm to 50 mm; 0.5 to 25 parts by weight of olefinic rubber resin.
  • the LDPE is added to the olefinic rubber resin, in which the LDPE is 5 to 35 parts by weight, and in particular, the dispersion degree of the glass fiber is greatly increased by using an olefinic rubber resin and LDPE mixed. It is improved, which is explained in more detail below.
  • the two or more unit resins were polyethylene (PE) and polypropylene (PP) having a specific gravity lower than that of water, and the two kinds of resins were waste resins disposed of after use.
  • the present invention uses two or more waste resins having different structures, physical properties and molecular weights together, but also suffers from a decrease in compatibility caused by the simultaneous use of two or more waste resins, namely, brittleness, impact resistance, Problems such as weakening of flexural strength were solved by using glass fibers having a specific length and an olefinic rubber resin.
  • the present inventors solve the problem that when the long glass fiber is mixed with the molten resin, the dispersion of the long glass fiber is low, and thus it is difficult to achieve uniform strength of the plastic product. It is made to contain in resin, and it mixes with the mixed resin which consists of two or more waste resins. LDPE mixed with the olefinic rubber resin improves the dispersibility of the glass fiber, thereby improving the strength of the finally obtained plastic product.
  • the effect of improving the glass fiber dispersion degree by using the LDPE-containing olefinic rubber resin is described in more detail in the following experimental example.
  • the mixed resin includes any one of waste polyethylene (PE) and waste polypropylene (PP) as a unit resin, and the molecular weight of the unit resin is generally used in the molecular weight of general PE and PP.
  • the unit resin of the mixed resin has a specific gravity of less than 1, it is difficult to separate the resin of PE and PP by the conventional waste resin separation method using the specific gravity difference with water.
  • the compatibility between the resin and the chemical bonding strength is lowered, as a result, there is a problem that the molded article made of the mixed resin is easily broken by the impact applied to the outside.
  • the glass filaments of a certain length are physically mixed before melting and then melted, so that the glass filaments function as a kind of main chain to which the unit resin of the mixed resin is bonded.
  • different types of unit resins are combined with glass filaments, and the glass filaments function as a linkage connecting two types of unit resins.
  • the present inventors in the case of glass filaments connecting different types of waste resins, the effect varies depending on the length and the degree of dispersion, and by dispersing the glass filaments by containing LDPE in an olefinic rubber resin which improves impact resistance characteristics. To improve the degree, the strength of the composition was greatly improved.
  • the present invention further recognizes the problems of compatibility and physical property degradation caused by the use of two or more kinds of mixed resins having different elongation at break, and solves this problem by using olefinic resins and glass filaments in a specific molecular weight range.
  • the mixed resin is mixed with a first resin having an elongation at break of 100% or more and a second resin having an elongation at break of 20% or less at a weight ratio of 20 to 59:30 to 50.
  • the weight average molecular weight of the rubber resin is 1,000 to 500,000, more preferably 10,000 to 200,000, the compatibility of the first resin and the second resin having an excessively different chain length and the lowering of compatibility due to impact strength reduction Solve the problem.
  • the elongation at break is a result measured according to ASTM D638 in the tensile elongation at the point of breaking the specimen.
  • the first resin of the present invention is a new material
  • the second resin may be a reclaimed material
  • the first resin, a new material and the reclaimed material is a polyolefin-based resin
  • polyethylene, polypropylene may be the new material and reclaimed material.
  • the present invention uses a mixture of at least one of polyethylene and polypropylene new material, and recycled material recycled for the other one.
  • the present inventors have found that the general-purpose regenerated material used for other purposes has a breakage elongation of 20% or less. I found out that this is abnormal. This means that the recycled material has a shorter chain length compared to the new material, and in particular, it has been recognized that the bending strength and the impact strength of the recycled plastic product (for example, the container) fall due to the excessively short chain length during melting.
  • the present invention is to solve the problem arising from the difference in the chain length when using a recycled material having a break elongation of only 20% or less and a new material having a break elongation of 100% or more, the glass fiber and olefin resin Using a mixed solution solves the problem of excessively different chain lengths between new and recycled materials.
  • Glass filaments used in the present invention according to the man-made vitreos fibers (MMVF) specified by the World Health Organization (WHO), the average diameter is 6 ⁇ 15 ⁇ m.
  • MMVF man-made vitreos fibers
  • WHO World Health Organization
  • Ethylene-butene copolymer which is a glass filament (10 parts by weight) and an olefinic rubber resin in a mixed resin in which the ratio (weight ratio) of PP and PE is 5: 5 to 9: 1 according to an embodiment of the present invention. (Average molecular weight 2000, 10 parts by weight) was added, followed by melting to prepare a pallet (Example). On the contrary, instead of the olefinic rubber resin, SBS was added in the same weight part to prepare a pallet in the same manner as in Example 1 (comparative example).
  • the following table shows the results of three experiments sensoryly determined by placing the pallets of the Examples and Comparative Examples prepared according to the present invention in a closed room for 10 hours.
  • Figure 4 is a SEM image after molding of the composition using an olefin rubber resin containing LDPE.
  • the glass filaments are uniformly dispersed, and in the composition, the cavity is formed to have a uniform size and a small size. have.
  • the glass filaments added together with the olefin-based rubber resin containing LDPE in the molten state are uniformly dispersed in the resin, and thus it can be expected to produce an effect of improving both impact and bending strength.
  • the present invention provides a plastic product having improved strength, flexural strength and the like by using the composition having the above-described effect.
  • the compositions according to the invention can be used in various forms of products that have to withstand a certain load, for example by loading cargo such as pallets, crates, boxes, all of which are within the scope of the invention.
  • Figure 5 is a step diagram of a plastic product manufacturing method according to an embodiment of the present invention.
  • the above-described composition is prepared by mixing the above-described mixed resin, glass filament, and an olefinic rubber resin.
  • the olefinic rubber resin is used when the waste resin is melted according to the present invention, the problem of agglomeration and precipitation of the rubber resin on the surface of the plastic product can be solved, and generation of odor due to carbonization can be suppressed.
  • LDPE LDPE
  • the olefin-based rubber resin in a pellet form, it is mixed in the mixed resin, and the dispersion of glass filaments is greatly improved according to the use of LDPE as described above.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition comprenant : au moins deux résines ; des fibres de verre ; et une résine de caoutchouc à base d'oléfine, plus particulièrement, une composition comprenant : 100% en poids d'une résine mixte constituée de résines à au moins deux motifs ; de 3 à 30% en poids de fibre de verre ayant une longueur de 10 mm à 50 mm ; et de 0,5 à 25% en poids d'une résine de caoutchouc à base d'oléfine.
PCT/KR2015/007481 2014-07-25 2015-07-20 Composition comprenant au moins deux résines, des fibres de verre et une résine de caoutchouc à base d'oléfine Ceased WO2016013819A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020140094716A KR101537193B1 (ko) 2014-07-25 2014-07-25 2종 이상의 수지, 유리장섬유 및 올레핀계 고무수지를 포함하는 조성물
KR10-2014-0094716 2014-07-25
KR10-2015-0097683 2015-07-09
KR1020150097683A KR20170006683A (ko) 2015-07-09 2015-07-09 재생재를 포함하는 2종 이상의 혼합 수지, 유리장섬유 및 올레핀계 고무수지를 포함하는 조성물

Publications (1)

Publication Number Publication Date
WO2016013819A1 true WO2016013819A1 (fr) 2016-01-28

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Application Number Title Priority Date Filing Date
PCT/KR2015/007481 Ceased WO2016013819A1 (fr) 2014-07-25 2015-07-20 Composition comprenant au moins deux résines, des fibres de verre et une résine de caoutchouc à base d'oléfine

Country Status (2)

Country Link
TW (1) TWI613242B (fr)
WO (1) WO2016013819A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040029566A (ko) * 2002-10-01 2004-04-08 주식회사 엘지화학 사출성형공법에 의한 유리 장섬유 강화 복합소재 적용자동차 플라스틱 시트백 프레임 판넬
KR20080061077A (ko) * 2006-12-28 2008-07-02 호남석유화학 주식회사 섬유강화 폴리프로필렌 수지조성물
KR100886497B1 (ko) * 2007-08-09 2009-03-05 현대이피 주식회사 자동차 내장재용 폴리올레핀계 복합수지 조성물
KR20100075227A (ko) * 2008-12-24 2010-07-02 제일모직주식회사 열전도성 절연 수지 조성물 및 플라스틱 성형품
KR20110076341A (ko) * 2009-12-29 2011-07-06 현대이피 주식회사 폴리올레핀계 복합수지 조성물
KR101353815B1 (ko) * 2013-07-12 2014-01-23 한국컨테이너풀 주식회사 2종 이상의 수지 및 유리장섬유를 포함하는 조성물 및 이로부터 제조된 파렛트

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10084451T1 (de) * 2000-02-14 2002-09-26 Asahi Chemical Ind Formkörper aus thermoplastischem Harz mit hoher Steifigkeit und hoher Festigkeit
BRPI0913018A2 (pt) * 2008-05-15 2015-10-13 Saudi Basic Ind Corp artigo moldado resistente a riscos fabricado a partir de uma composição de polipropileno carregado

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040029566A (ko) * 2002-10-01 2004-04-08 주식회사 엘지화학 사출성형공법에 의한 유리 장섬유 강화 복합소재 적용자동차 플라스틱 시트백 프레임 판넬
KR20080061077A (ko) * 2006-12-28 2008-07-02 호남석유화학 주식회사 섬유강화 폴리프로필렌 수지조성물
KR100886497B1 (ko) * 2007-08-09 2009-03-05 현대이피 주식회사 자동차 내장재용 폴리올레핀계 복합수지 조성물
KR20100075227A (ko) * 2008-12-24 2010-07-02 제일모직주식회사 열전도성 절연 수지 조성물 및 플라스틱 성형품
KR20110076341A (ko) * 2009-12-29 2011-07-06 현대이피 주식회사 폴리올레핀계 복합수지 조성물
KR101353815B1 (ko) * 2013-07-12 2014-01-23 한국컨테이너풀 주식회사 2종 이상의 수지 및 유리장섬유를 포함하는 조성물 및 이로부터 제조된 파렛트

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TW201604230A (zh) 2016-02-01
TWI613242B (zh) 2018-02-01

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