KR20100021714A - Polymer adhesive from high density polyethylene power and preparing method - Google Patents

Polymer adhesive from high density polyethylene power and preparing method Download PDF

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KR20100021714A
KR20100021714A KR1020080080284A KR20080080284A KR20100021714A KR 20100021714 A KR20100021714 A KR 20100021714A KR 1020080080284 A KR1020080080284 A KR 1020080080284A KR 20080080284 A KR20080080284 A KR 20080080284A KR 20100021714 A KR20100021714 A KR 20100021714A
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density polyethylene
polyethylene powder
high density
polymer adhesive
reactor
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KR1020080080284A
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KR101003552B1 (en
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신승호
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(주)동원엔텍
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/06—Polyethene
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

PURPOSE: A polymer adhesive is provided to ensure excellent adhesive property properties with fibers, metals, concrete, and polar polymers, and to increase good chemical resistance, heat resistance, moisture protectionwet-proof property, impact resistance, and durability. CONSTITUTION: A method for manufacturing a polymer adhesive comprises: (S101) a radical generation step for generating radicals by irradiation irradiating anof electron beam to with high density polyethylene powder; (S103) a polyethylene injection step for injecting high density polyethylene powder, passing through the radical generation step, to a first reactor; (S105) a heating step for heating the high density polyethylene powder passing through the polyethylene injection step at 70-80 °C; (S107) a spraying step for spraying 0.2-55 parts by weight of additives to a first reactor; (S109) a circulation step which circulates the high density polyethylene powder using a circulator; and (S111) a second heating step for heating the high density polyethylene powder in a second reactor at 100-200 °C.

Description

고밀도폴리에틸렌 분말을 이용한 고분자 접착제 및 그 제조방법{polymer adhesive from high density polyethylene power and preparing method} Polymer adhesive using high density polyethylene powder and its manufacturing method {polymer adhesive from high density polyethylene power and preparing method}

본 발명은 섬유, 금속, 콘크리트 및 극성 고분자를 접착할 수 있는 고분자 접착제 및 그 제조방법에 관한 것으로, 고밀도폴리에틸렌 분말을 전자빔 가속기로 조사하여 라디칼(Radical)을 생성하고 단량체를 그래프팅(Grafting)하여 물성이 개질된 고분자 접착제 및 그 제조방법에 관한 것이다.The present invention relates to a polymer adhesive capable of adhering fibers, metals, concrete, and polar polymers, and a method for manufacturing the same, wherein a high density polyethylene powder is irradiated with an electron beam accelerator to generate radicals and grafting monomers. It relates to a polymer adhesive modified physical properties and a method of manufacturing the same.

종래에 사용되던 고분자 접착제의 경우는 펠렛(Pellet) 형태로 제조된 것이 대부분이였다. 그러나 이러한 펠렛 형태의 고분자 접착제는 압출기를 통해서 공압출 된다는 한계성 때문에 이용에 불편함이 있었고, 이것을 개질한 방법으로 트윈스크류(Twin Screw)를 이용하는 방법이 사용되었는데, 이 방법은 트윈스크류를 통해 압출하는 과정에서 고열이 발생하여 산 분해가 진행되거나 솔벤트가 증발하면서 발생하는 유해한 증기로 인해 작업환경이 오염되는 문제점이 있었다.In the case of the polymer adhesive used in the prior art was mostly manufactured in the form of pellets (Pellet). However, these pellet-type polymer adhesives were inconvenient to use due to the limitation of co-extrusion through an extruder, and a method using a twin screw was used as a modified method. There was a problem that the working environment is contaminated due to the harmful steam generated by the decomposition of the acid proceeds or the evaporation of the solvent due to high heat generated in the process.

본 발명의 목적은 전술한 문제점을 해결하기 위한 것으로, 전자빔 가속기로 고밀도폴리에틸렌 분말을 조사하여 라티칼을 생성하고 기상, 고상 반응을 통해 단량체를 그래프팅하는 과정이 이루어져 솔벤트가 사용되지 않는 고분자 접착제 및 그 제조방법을 제공하는 것이다.An object of the present invention is to solve the above-mentioned problems, the polymer adhesive is a solvent is not used because the process of grafting the monomer through the irradiation of high-density polyethylene powder with an electron beam accelerator to produce a radical and gas phase, solid phase reaction and It is to provide a manufacturing method.

본 발명의 다른 목적은 섬유, 금속, 콘크리트 및 극성 고분자에도 접착성이 우수한 고분자 접착제 및 그 제조방법을 제공하는 것이다.Another object of the present invention is to provide a polymer adhesive having excellent adhesion to fibers, metals, concrete and polar polymers, and a method of manufacturing the same.

본 발명의 또 다른 목적은 내화학성, 내열성, 내습성, 내충격석 및 내구성이 우수한 고분자 접착제 및 그 제조방법을 제공하는 것이다.Still another object of the present invention is to provide a polymer adhesive having excellent chemical resistance, heat resistance, moisture resistance, impact resistance and durability, and a method of manufacturing the same.

전술한 본 발명의 목적은, 고밀도폴리에틸렌 분말에 전자빔을 조사하여 라디칼을 생성시키는 라디칼생성단계, 전술한 라디칼생성단계를 거친 고밀도폴리에틸렌 분말을 제 1 반응기로 투입하는 폴리에틸렌투입단계, 전술한 폴리에틸렌투입단계를 거친 고밀도폴리에틸렌 분말을 70 내지 80℃의 온도로 가열하는 제 1 가열단계, 전술한 제 1 반응기에 첨가제 0.2 내지 55 중량부를 분무하는 분무단계, 전술한 분무단계를 계속 진행하면서 고밀도폴리에틸렌 분말은 순환기를 이용하여 순환시키는 순환단계 및 전술한 순환단계를 거친 고밀도폴리에틸렌 분말을 제 2 반응기로 이송하여 100 내지 200℃의 온도로 가열하는 제 2 가열단계를 포함하여 이루어지는 고 밀도폴리에틸렌분말을 이용한 고분자 접착제의 제조방법에 의해 달성된다.An object of the present invention as described above, a radical generation step of generating a radical by irradiating an electron beam to the high-density polyethylene powder, a polyethylene input step of introducing the high-density polyethylene powder passed through the radical generation step to the first reactor, the polyethylene input step described above The first heating step of heating the high density polyethylene powder to a temperature of 70 to 80 ℃, the spraying step of spraying 0.2 to 55 parts by weight of the additive in the first reactor described above, the high density polyethylene powder is a circulator A polymer adhesive using a high density polyethylene powder comprising a circulation step of circulating using a second step of transferring the high density polyethylene powder that has passed through the above-mentioned circulation step to a second reactor and heating to a temperature of 100 to 200 ° C. It is achieved by the manufacturing method.

본 발명에 바람직한 특징에 따르면, 전술한 라디칼생성단계에서 전자빔의 조사 범위는 3 내지 30 kGy(kilogray)인 것으로 한다.According to a preferred feature of the present invention, the irradiation range of the electron beam in the above-described radical generation step is 3 to 30 kGy (kilogray).

본 발명에 더 바람직한 특징에 따르면, 전술한 고밀도폴리에틸렌 분말의 입자크기는 200 마이크론 이하인 것으로 한다.According to a further preferred feature of the present invention, the particle size of the aforementioned high density polyethylene powder is 200 microns or less.

본 발명에 더욱 바람직한 특징에 따르면, 전술한 첨가제는 단량체 0.1 내지 40 중량부 및 분산제 0.1 내지 15 중량부를 포함하여 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the above-mentioned additive comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of dispersant.

본 발명에 더욱 더 바람직한 특징에 따르면, 전술한 단량체는 디부틸말레인산 및 무수말레인산으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지는 것으로 한다.According to a still further preferred feature of the present invention, the monomers described above comprise at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride.

본 발명에 더욱 더 바람직한 특징에 따르면, 전술한 분산제는 아세톤 및 자일렌으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지는 것으로 한다.According to a further preferred feature of the present invention, the above-mentioned dispersant is to comprise at least one selected from the group consisting of acetone and xylene.

본 발명에 더욱 더 바람직한 특징에 따르면, 전술한 첨가제에는 개시제 1 내지 10 중량부가 더 포함되며, 전술한 개시제는 디부틸퍼옥사이드, 벤조일퍼옥사이드 및 2,2-아조비스이소부틸로니트릴로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지는 것으로 한다.According to a still further preferred feature of the present invention, the above-mentioned additive further comprises 1 to 10 parts by weight of an initiator, and the above-mentioned initiator is a group consisting of dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutylonitrile It is to include one or more selected from.

본 발명에 더욱 더 바람직한 특징에 따르면, 전술한 순환단계는 25 내지 35분 동안 이루어지며, 상기 분무단계 실시하는 동안 순환기를 이용하여 고밀도폴리에틸렌 분말의 3 내지 8중량%를 순환시키는 것으로 한다.According to a further preferred feature of the present invention, the above-mentioned circulation step is performed for 25 to 35 minutes, and during the spraying step, it is to circulate 3 to 8% by weight of the high density polyethylene powder using the circulator.

또한, 전술한 본 발명의 목적은 전술한 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법으로 제조된 접착제를 제공함에 의해서도 달성될 수 있다.In addition, the above object of the present invention can also be achieved by providing an adhesive prepared by the method for producing a polymer adhesive using the high-density polyethylene powder described above.

본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제 및 그 제조방법에 의하면, 솔벤트가 사용되지 않는 고분자 접착제를 제공하여 환경친화력을 향상시키는데 탁월한 효과가 있다.According to the polymer adhesive using the high-density polyethylene powder according to the present invention and a method for manufacturing the same, there is an excellent effect to improve the environmental friendliness by providing a polymer adhesive that is not used solvent.

또한, 섬유, 금속, 콘크리트 및 극성 고분자에도 접착성이 탁월한 효과를 나타낸다.It also exhibits excellent adhesion to fibers, metals, concrete and polar polymers.

또한, 내화학성, 내열성, 내습성, 내충격석 및 내구성이 탁월한 효과를 나타낸다.In addition, it exhibits excellent effects of chemical resistance, heat resistance, moisture resistance, impact resistance and durability.

이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.In the following, preferred embodiments of the present invention and the physical properties of each component will be described in detail, which is intended to explain in detail enough to be able to easily carry out the invention by one of ordinary skill in the art, This does not mean that the technical spirit and scope of the present invention is limited.

본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법은 고밀도폴리에틸렌 분말에 전자빔을 조사하여 라디칼을 생성시키는 라디칼생성단 계(S101), 전술한 라디칼생성단계(S101)를 거친 고밀도폴리에틸렌 분말을 제 1 반응기(10)로 투입하는 폴리에틸렌투입단계(S103), 전술한 폴리에틸렌투입단계(S103)를 거친 고밀도폴리에틸렌 분말을 70 내지 80℃의 온도로 가열하는 제 1 가열단계(S105), 전술한 제 1 반응기에 첨가제 0.2 내지 55 중량부를 분무하는 분무단계(S107), 전술한 분무단계(S107)를 계속 진행하면서 고밀도폴리에틸렌 분말은 순환기(11)를 이용하여 순환시키는 순환단계(S109) 및 전술한 순환단계(S109)를 거친 고밀도폴리에틸렌 분말을 제 2 반응기(20)로 이송하여 100 내지 200℃의 온도로 가열하는 제 2 가열단계(S111)를 포함하여 이루어진다.Method for producing a polymer adhesive using a high density polyethylene powder according to the present invention comprises a radical generation step (S101) for generating a radical by irradiating an electron beam to the high density polyethylene powder (S101), the high-density polyethylene powder through the above-described radical generation step (S101) 1 polyethylene injection step (S103) to be introduced into the reactor 10, the first heating step (S105) for heating the high-density polyethylene powder passed through the above-described polyethylene injection step (S103) to a temperature of 70 to 80 ℃, the first described above The spraying step (S107) for spraying 0.2 to 55 parts by weight of the additive in the reactor, while continuing the spraying step (S107) described above, the high-density polyethylene powder is circulated by using the circulator 11 (S109) and the above-mentioned circulation step It comprises a second heating step (S111) for transferring the high density polyethylene powder passed through (S109) to the second reactor 20 and heated to a temperature of 100 to 200 ℃ The.

전술한 라디칼생성단계(S101)는 전술한 고밀도폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 3 내지 30 kGy의 전자빔을 조사하여 고밀도폴리에틸렌에 라디칼이 형성되는 단계로, 전술한 전자빔의 조사는 활성산소의 농도가 15 vol% 이하인 환경에서 분당 1 내지 1 × 103 메가레드(Mrgarad) 범위의 조사 속도와 에틸렌 폴리머 사슬이 분기 되면서도 가교가 일어나지 않는 양으로 진행된다.The radical generation step (S101) is a step of forming a radical in the high-density polyethylene by irradiating an electron beam of 3 to 30 kGy to the high-density polyethylene powder described above using a direct current type high voltage electron beam accelerator (ELV-0.5 Type). The irradiation of the electron beam proceeds at an irradiation rate in the range of 1 to 1 × 10 3 Megared (Mrgarad) per minute and crosslinking of the ethylene polymer chain without causing crosslinking in an environment where the concentration of active oxygen is 15 vol% or less.

전술한 폴리에틸렌투입단계(S103)는 전술한 라디칼생성단계(S101)를 거쳐 라디칼이 형성된 고밀도폴리에틸렌 분말을 기체상 반응기인 제 1 반응기(10) 내로 투입하는 단계로, 전술한 제 1 반응기(10) 내에는 활성산소가 없이 반응이 진행되어 야 하는데, 활성산소를 제거하기 위해서는 제 1 반응기(10) 내에 질소를 소량투입하여 밀봉하고 5분간 방치하는 과정을 거치게 된다.The above-described polyethylene input step (S103) is a step of introducing the high-density polyethylene powder in which the radical is formed through the above-described radical generation step (S101) into the first reactor 10, which is a gas phase reactor, and the first reactor 10 described above. The reaction should proceed in the absence of active oxygen, and in order to remove the active oxygen, a small amount of nitrogen is injected into the first reactor 10 and sealed for 5 minutes.

전술한 제 1 가열단계(S105)는 전술한 폴리에틸렌투입단계(S103)를 거쳐 제 1 반응기(10) 내로 투입된 고밀도폴리에틸렌 분말을 70 내지 80℃의 온도로 가열하는 단계로, 전술한 가열온도는 고밀도 폴리에틸렌 분말이 단량체와 그래프팅 반응을 하기에 가장 적합한 온도다.The above-described first heating step (S105) is a step of heating the high-density polyethylene powder introduced into the first reactor 10 through the above-described polyethylene input step (S103) to a temperature of 70 to 80 ℃, the above heating temperature is high density Polyethylene powder is the most suitable temperature for the grafting reaction with the monomers.

전술한 분무단계(S107)는 첨가제 0.2 내지 55 중량부를 분무하는 단계로, 전술한 첨가제는 단량체 0.1 내지 40 중량부 및 분산제 0.1 내지 15 중량부를 포함하여 이루어지는데, 전술한 단량체는 디부틸말레인산 및 무수말레인산으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지고 전술한 분산제는 아세톤 및 자일렌으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어진다.The above spraying step (S107) is a step of spraying 0.2 to 55 parts by weight of the additive, the above-mentioned additive comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of the dispersant, the monomer described above is dibutyl maleic acid and anhydrous And at least one selected from the group consisting of maleic acid and the aforementioned dispersant comprises at least one selected from the group consisting of acetone and xylene.

전술한 첨가제는 제 1 반응기(10) 내에 설치된 내경이 1 내지 3 마이크론인 노즐을 통해 기체상으로 분무되며, 이렇게 분무된 기체상의 첨가제는 전술한 고밀도폴리에틸렌 분말에 도포 된다.The above-described additive is sprayed into the gas phase through a nozzle having an inner diameter of 1 to 3 microns installed in the first reactor 10, and the sprayed gaseous additive is applied to the aforementioned high density polyethylene powder.

전술한 순환단계(S109)는 전술한 분무단계(S107)를 통해 첨가제가 도포된 제 1 반응기(10) 내에 고밀도폴리에틸렌 분말을 순환기(11)를 이용해 순환시키는 단계로, 제 1 반응기(10) 내에 고밀도폴리에틸렌 분말 3 내지 8 중량%를 로타리 피 더(rotary feeder) 순환기(11)를 이용하여 순환배관을 통해 다시 제 1 반응기(10) 내로 투입하여 분무단계(S107)를 거치게 된다.The above-mentioned circulation step (S109) is a step of circulating the high density polyethylene powder using the circulator 11 in the first reactor 10 to which the additive is applied through the above-described spraying step (S107), in the first reactor 10 3 to 8% by weight of the high density polyethylene powder is introduced into the first reactor 10 through the circulation pipe again using a rotary feeder circulator 11 to undergo a spraying step (S107).

이러한 순환단계(S109)를 통해 하부면에 쌓여있던 고밀도폴리에틸렌 분말이 다시 상부면으로 이동하는데, 이러한 순환단계(S109)를 실시하는 동안에도 전술한 분무단계(S107)는 연속으로 실시되기 때문에 이러한 순환단계(S109) 과정을 25 내지 35분 동안 지속하게 되면, 첨가제가 고밀도폴리에틸렌 분말에 고르게 도포 된다.The high density polyethylene powder accumulated on the lower surface is moved back to the upper surface through the circulation step (S109), while the aforementioned spraying step (S107) is continuously performed during the circulation step (S109). If the process (S109) is continued for 25 to 35 minutes, the additive is evenly applied to the high density polyethylene powder.

전술한 제 2 가열단계(S111)는 전술한 순환단계(S109)를 거친 고밀도폴리에틸렌 분말을 제 2 반응기(20)로 이송하여 100 내지 200℃의 온도 30 분간 가열하는 단계로, 전술한 조건으로 가열하게 되면 고밀도폴리에틸렌 분말에 남아있는 라디칼이 제거되어 안정화되고, 고밀도폴리에틸렌 분말에 도포되어 있던 아세톤 및 산 물질이 증발되게 된다.The above-described second heating step (S111) is a step of transferring the high-density polyethylene powder passed through the above-mentioned circulation step (S109) to the second reactor 20 and heating it for 100 minutes at a temperature of 100 to 200 ° C. As a result, the radicals remaining in the high density polyethylene powder are removed and stabilized, and the acetone and acid materials applied to the high density polyethylene powder are evaporated.

전술한 제 2 가열단계(S111) 이후에는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 질소가스로 냉각시킨다.After the second heating step S111 described above, the polymer adhesive using the high density polyethylene powder is cooled with nitrogen gas.

전술한 과정을 통해 제조된 고밀도폴리에틸렌 분말을 이용한 고분자 접착제는 가용온도인 60 내지 70℃의 온도로 가열하여 사용하게 된다.Polymer adhesive using a high-density polyethylene powder prepared by the above-described process is used by heating to a temperature of 60 to 70 ℃ the available temperature.

또한, 본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법으로 제조된 접착제는 전자빔 가속기로 조사된 고밀도폴리에틸렌(HDPE, Linear High Density Polyethylene)분말 60 내지 100 중량부, 첨가제 0.2 내지 55 중량부를 포함하여 이루어진다.In addition, the adhesive prepared by the method of preparing a polymer adhesive using the high density polyethylene powder according to the present invention includes 60 to 100 parts by weight of HDPE (Linear High Density Polyethylene) powder irradiated with an electron beam accelerator, and 0.2 to 55 parts by weight of an additive. It is done by

여기서 고밀도폴리에틸렌 분말은 가지 사슬이 거의 없는 선형이며, 분자량은 20만 이하이고, 60 내지 100 중량부가 첨가되는데, 전술한 고밀도폴리에틸렌 분말은 고분자 접착제에 내화학성, 내열성, 내습성, 내충격석 및 내구성을 제공하게 된다.Here, the high density polyethylene powder is linear with almost no branched chain, the molecular weight is 200,000 or less, and 60 to 100 parts by weight is added. The high density polyethylene powder described above has a chemical resistance, heat resistance, moisture resistance, impact resistance and durability to the polymer adhesive. Will be provided.

또한, 전술한 고밀도폴리에틸렌 분말에 전자빔 가속기를 이용하여 3 내지 30 kGy의 전자빔을 조사하면 고밀도폴리에틸렌에 라디칼이 형성되어 첨가되는 단량체가 그래프팅 된다.In addition, when the electron beam of 3 to 30 kGy is irradiated to the aforementioned high density polyethylene powder by using an electron beam accelerator, monomers are added to form the radicals in the high density polyethylene.

전술한 과정을 거친 고밀도폴리에틸렌의 입자크기는 200 마이크론 이하가 된다.The particle size of the high-density polyethylene that passed through the above process is less than 200 microns.

전술한 고밀도폴리에틸렌 이외에 탄소수 4 내지 10으로 이루어진 폴리올레핀(Poly Olefin)계의 고분자 물질이 사용될 수도 있다.In addition to the high density polyethylene described above, a polyolefin (Poly Olefin) -based polymer material having 4 to 10 carbon atoms may be used.

전술한 첨가제는 고밀도폴리에틸렌 분말에 그래프팅되는 단량체 0.1 내지 40 중량부 및 분산제 0.1 내지 15 중량부를 포함하여 이루어진다.The aforementioned additive comprises 0.1 to 40 parts by weight of monomers grafted onto the HDPE powder and 0.1 to 15 parts by weight of the dispersant.

전술한 단량체는 0.1 내지 40 중량부가 첨가되는데 디부틸말레인산 및 무수말레인산으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지며, 고밀도폴리에틸렌 분말에 형성된 라디칼과 반응하여 그래프팅 된다.The monomer described above is added in an amount of 0.1 to 40 parts by weight and includes at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride, and is grafted by reacting with radicals formed on the high density polyethylene powder.

전술한 단량체 이외에 불포화 카르복실산, 불포화 카르복실산 안하이드라이드, 불포화 카르복시산 에테르, 불포화 카르복시산 아마이드, 불포화 카르복시산 이미드 및 불포화 카르복시산 금속염 등이 사용될 수도 있다.In addition to the above-mentioned monomers, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid ethers, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides and unsaturated carboxylic acid metal salts and the like may be used.

전술한 분산제는 0.1 내지 15 중량부가 첨가되는데 아세톤 및 자일렌으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지며, 전술한 고밀도폴리에틸렌과 전술한 단량체의 용해도를 높이는 역할을 한다.The dispersant described above is added in an amount of 0.1 to 15 parts by weight, and includes at least one selected from the group consisting of acetone and xylene, and serves to increase the solubility of the aforementioned high density polyethylene and the aforementioned monomer.

전술한 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법으로 제조된 접착제에는 개시제 1 내지 10 중량부가 더 포함될 수도 있는데, 전술한 개시제는 디부틸퍼옥사이드, 벤조일퍼옥사이드 및 2,2-아조비스이소부틸로니트릴로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지며, 이러한 개시제는 고밀도폴리에틸렌 분말의 소수성을 개선하고, 분산된 상의 크기를 줄이며, 고밀도폴리에틸렌 분말과 그래프팅 되는 모노머 사이의 반응면적을 증가시키는 역할을 한다.The adhesive prepared by the method of preparing the polymer adhesive using the high density polyethylene powder described above may further include 1 to 10 parts by weight of an initiator. The above-mentioned initiator may be dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutyl. It comprises one or more selected from the group consisting of nitriles, and these initiators serve to improve the hydrophobicity of the HDPE powder, reduce the size of the dispersed phase, and increase the reaction area between the HDPE powder and the grafted monomer. do.

이하에는 본 발명의 따른 고밀도폴리에틸렌을 이용한 고분자 접착제의 제조방법을 실시예를 들어 설명한다.Hereinafter, a description will be given of an example of a method for producing a polymer adhesive using a high density polyethylene according to the present invention.

<실시예 1><Example 1>

고밀도폴리에틸렌 분말 100 중량부를 질소가스로 세척된 제 1 반응기에 넣어 75℃로 가열하고, 무수말레인산 6.0 중량부, 자일렌 0.5 중량부, 아세톤 10 중량부 및 디부틸퍼옥사이드 1.5 중량부를 혼합하여 혼합액을 형성하여 제 1 반응기에 설치된 내경이 2 마이크론인 분사노즐을 통하여 기체상으로 분무하고, 분무액에 도포된 고밀도폴리에틸렌 분말을 로타리 피더(rotary feeder) 순환기를 이용하여 순환배관을 통해 다시 제 1 반응기 내로 투입하는 순환단계를 30분간 실시하고, 순환단계를 거친 고밀도폴리에틸렌 분말을 제 2 반응기로 이송하여 160℃의 온도로 30 분간 가열하여 질소가스로 냉각시킨 후에 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.100 parts by weight of the high density polyethylene powder was put in a first reactor washed with nitrogen gas and heated to 75 ° C., 6.0 parts by weight of maleic anhydride, 0.5 parts by weight of xylene, 10 parts by weight of acetone and 1.5 parts by weight of dibutyl peroxide were mixed. It is formed and sprayed into the gas phase through a spray nozzle having an inner diameter of 2 microns installed in the first reactor, the high-density polyethylene powder applied to the spray liquid is returned to the first reactor through the circulation pipe using a rotary feeder circulator After the circulating step was carried out for 30 minutes, the high-density polyethylene powder passed through the circulation step was transferred to the second reactor and heated to a temperature of 160 ℃ for 30 minutes to cool with nitrogen gas to prepare a polymer adhesive using a high-density polyethylene powder.

<실시예 2><Example 2>

실시예 1과 동일하게 실사하되 무수말레인산을 디부틸말레인산으로 치환하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.In the same manner as in Example 1, maleic anhydride was substituted with dibutyl maleic acid to prepare a polymer adhesive using high density polyethylene powder.

<실시예 3><Example 3>

실시예 1로 제조된 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 L/D=36, 실린더 및 다이(Dies) 온도가 190℃이며, 스크류(Screw)의 회전속도가 60 rpm인 압출기를 이용하여 압출하여 고분자 접착제를 제조하였다.The polymer adhesive using the high density polyethylene powder prepared in Example 1 was extruded using an extruder having an L / D = 36, a cylinder and die temperature of 190 ° C., and a screw rotation speed of 60 rpm. Adhesive was prepared.

<실시예 4><Example 4>

실시예 3과 동일하게 실시하되 무수말레인산을 디부틸말레인산으로 치환하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.In the same manner as in Example 3, maleic anhydride was substituted with dibutyl maleic acid to prepare a polymer adhesive using high density polyethylene powder.

<실시예 5>Example 5

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 3 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 3 kGy using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<실시예 6><Example 6>

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 5 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 5 kGy electron beam using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<실시예 7><Example 7>

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 10 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a polymer adhesive using a high density polyethylene powder was prepared by irradiating a 10 kGy electron beam to a high density polyethylene powder using a direct current type high voltage electron beam accelerator (ELV-0.5 Type).

<실시예 8><Example 8>

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전 자빔 가속기(ELV-0.5 Type)를 이용하여 15 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 15 kGy using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<실시예 9>Example 9

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 20 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 20 kGy electron beam using a direct current high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

<실시예 10><Example 10>

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 25 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with a 25 kGy electron beam using a DC-type high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using high density polyethylene powder.

<실시예 11><Example 11>

실시예 1과 동일하게 진행하되 고밀도 폴리에틸렌 분말에 직류형 고전압 전자빔 가속기(ELV-0.5 Type)를 이용하여 30 kGy의 전자빔을 조사하여 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 제조하였다.Proceed in the same manner as in Example 1, a high-density polyethylene powder was irradiated with an electron beam of 30 kGy using a DC-type high voltage electron beam accelerator (ELV-0.5 Type) to prepare a polymer adhesive using a high density polyethylene powder.

실시예 1 내지 11을 통해 제조된 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 가용온도인 60 내지 70℃의 온도로 가열한 후에 접착과정을 실시하고 접착 력을 아래 표 1에 나타내었다.After the polymer adhesive using the high-density polyethylene powder prepared in Examples 1 to 11 was heated to a temperature of 60 to 70 ℃ the usable temperature, the adhesion process was performed and the adhesive strength is shown in Table 1 below.

표 1>Table 1>

Figure 112008058482751-PAT00001
Figure 112008058482751-PAT00001

위 표 1에 나타난 것처럼 압출과정과 전자빔 조사량에 따라 접착력이 향상되는 것을 알 수 있다.As shown in Table 1, it can be seen that the adhesion is improved depending on the extrusion process and the electron beam irradiation amount.

도 1은 본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조과정을 도시한 순서도.1 is a flow chart illustrating a manufacturing process of a polymer adhesive using a high density polyethylene powder according to the present invention.

도 2는 본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조과정을 나타낸 블럭도.Figure 2 is a block diagram showing the manufacturing process of the polymer adhesive using a high density polyethylene powder according to the present invention.

도 3은 본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 사용하여 폴리에틸렌 원통에 스테인리스강을 접착한 사진.Figure 3 is a photograph of bonding stainless steel to a polyethylene cylinder using a polymer adhesive using a high density polyethylene powder according to the present invention.

도 4는 본 발명에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제를 사용하여 폴리에틸렌 원통에 탄소강을 접착한 사진.Figure 4 is a photograph of bonding carbon steel to a polyethylene cylinder using a polymer adhesive using a high density polyethylene powder according to the present invention.

***도면의 주요 부분에 대한 부호의 설명****** Description of the symbols for the main parts of the drawings ***

10 ; 제 1 반응기10; First reactor

11 ; 순환기11; cycle

20 ; 제 2 반응기20; Second reactor

Claims (9)

고밀도폴리에틸렌 분말에 전자빔을 조사하여 라디칼을 생성시키는 라디칼생성단계;Radical generation step of generating a radical by irradiating the electron beam to the high-density polyethylene powder; 상기 라디칼생성단계를 거친 고밀도폴리에틸렌 분말을 제 1 반응기로 투입하는 폴리에틸렌투입단계;A polyethylene input step of introducing the high density polyethylene powder, which has undergone the radical generation step, into a first reactor; 상기 폴리에틸렌투입단계를 거친 고밀도폴리에틸렌 분말을 70 내지 80℃의 온도로 가열하는 제 1 가열단계;A first heating step of heating the high-density polyethylene powder passed through the polyethylene injection step at a temperature of 70 to 80 ° C .; 상기 제 1 반응기에 첨가제 0.2 내지 55 중량부를 분무하는 분무단계;Spraying step of spraying 0.2 to 55 parts by weight of the additive in the first reactor; 상기 분무단계를 계속 진행하면서 고밀도폴리에틸렌 분말은 순환기를 이용하여 순환시키는 순환단계; 및A circulation step of circulating the high density polyethylene powder using a circulator while continuing the spraying step; And 상기 순환단계를 거친 고밀도폴리에틸렌 분말을 제 2 반응기로 이송하여 100 내지 200℃의 온도로 가열하는 제 2 가열단계;를 포함하여 이루어지는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.And a second heating step of transferring the high-density polyethylene powder passed through the circulation step to a second reactor and heating it to a temperature of 100 to 200 ° C. 2. 청구항 1에 있어서,The method according to claim 1, 상기 라디칼생성단계에서 전자빔의 조사 범위는 3 내지 30 kGy(kilogray)인 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The irradiation range of the electron beam in the radical generation step is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that 3 to 30 kGy (kilogray). 청구항 1에 있어서,The method according to claim 1, 상기 고밀도폴리에틸렌 분말의 입자크기는 200 마이크론 이하인 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The particle size of the high density polyethylene powder is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that less than 200 microns. 청구항 1에 있어서,The method according to claim 1, 상기 첨가제는 단량체 0.1 내지 40 중량부 및 분산제 0.1 내지 15 중량부를 포함하여 이루어지는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The additive is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that it comprises 0.1 to 40 parts by weight of monomer and 0.1 to 15 parts by weight of dispersant. 청구항 4에 있어서,The method according to claim 4, 상기 단량체는 디부틸말레인산 및 무수말레인산으로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The monomer is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that it comprises at least one selected from the group consisting of dibutyl maleic acid and maleic anhydride. 청구항 4에 있어서,The method according to claim 4, 상기 분산제는 아세톤 및 자일렌으로 이루어진 그룹으로부터 선택된 하나 이 상을 포함하여 이루어지는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The dispersant is a method for producing a polymer adhesive using a high density polyethylene powder, characterized in that it comprises at least one selected from the group consisting of acetone and xylene. 청구항 4에 있어서The method according to claim 4 상기 첨가제에는 개시제 1 내지 10 중량부가 더 포함되며,The additive further comprises 1 to 10 parts by weight of initiator, 상기 개시제는 디부틸퍼옥사이드, 벤조일퍼옥사이드 및 2,2-아조비스이소부틸로니트릴로 이루어진 그룹으로부터 선택된 하나 이상을 포함하여 이루어지는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.Wherein said initiator comprises at least one selected from the group consisting of dibutyl peroxide, benzoyl peroxide and 2,2-azobisisobutylonitrile. 청구항 1에 있어서,The method according to claim 1, 상기 순환단계는 25 내지 35분 동안 이루어지며, 상기 분무단계 실시하는 동안 순환기를 이용하여 고밀도폴리에틸렌 분말의 3 내지 8중량%를 순환시키는 것을 특징으로 하는 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법.The circulation step is made for 25 to 35 minutes, during the spraying step of the polymer adhesive using a high density polyethylene powder, characterized in that for circulating 3 to 8% by weight of the high density polyethylene powder using a circulator. 청구항 1 내지 청구항 8중 어느 하나의 항에 따른 고밀도폴리에틸렌 분말을 이용한 고분자 접착제의 제조방법으로 제조된 접착제.Adhesive prepared by the method for producing a polymer adhesive using a high-density polyethylene powder according to any one of claims 1 to 8.
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