KR101231495B1 - Adhesive polyolefin resin composition and method of manufacturing the same - Google Patents
Adhesive polyolefin resin composition and method of manufacturing the same Download PDFInfo
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- KR101231495B1 KR101231495B1 KR1020100133765A KR20100133765A KR101231495B1 KR 101231495 B1 KR101231495 B1 KR 101231495B1 KR 1020100133765 A KR1020100133765 A KR 1020100133765A KR 20100133765 A KR20100133765 A KR 20100133765A KR 101231495 B1 KR101231495 B1 KR 101231495B1
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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Abstract
본 발명은 접착성 폴리올레핀 수지 조성물 및 그 제조방법에 관한 것으로, 올레핀계 화합물; 글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부; 및 유기 과산화물 개시제 0.001~5중량부;를 포함하되, 상기 올레핀계 화합물은, 폴리에틸렌(polyethylene) 50~100중량부, 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 50~100중량부 및 메틸아크릴레이트(methyl acrylate) 1~30중량부로 이루어지는 군에서 선택되는 1 이상인 것을 특징으로 하는 접착성 폴리올레핀 수지 조성물 및 그 제조방법을 제공하여, 폴리카보네이트, 폴리에틸렌테레프탈레이트 등 폴리에스테르 류와의 접착이 가능한 접착성 폴리올레핀 수지 조성물을 제공할 수 있고, 제조시 반응압출법을 사용하여 기존 중합법에 비하여 제조단가를 획기적으로 낮출 수 있는 접착성 폴리올레핀 수지 조성물 제조방법을 제공할 수 있다.The present invention relates to an adhesive polyolefin resin composition and a method for producing the same, an olefin compound; 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate); And 0.001 to 5 parts by weight of an organic peroxide initiator; wherein the olefin compound includes 50 to 100 parts by weight of polyethylene, 50 to 100 parts by weight of ethylene-methyl acrylate and methyl acrylate ( methyl acrylate) 1 to 30 parts by weight of the adhesive polyolefin resin composition, characterized in that at least one selected from the group consisting of, and a method for producing the same, polycarbonate, polyethylene terephthalate adhesive polyolefin capable of adhesion with polyesters, such as It is possible to provide a resin composition, it is possible to provide a method for producing an adhesive polyolefin resin composition that can significantly lower the production cost compared to the conventional polymerization method using a reaction extrusion method during the production.
Description
접착성 수지 조성물 및 그 제조방법에 관한 것으로, 보다 상세하게는 폴리에틸렌테레프탈레이트 등 폴리에스테르와의 접착이 가능한 접착성 수지 조성물 및 그 제조방법에 관한 것이다.The present invention relates to an adhesive resin composition and a method for producing the same, and more particularly, to an adhesive resin composition capable of bonding with a polyester such as polyethylene terephthalate and a method for producing the same.
폴리올레핀계 수지는 가벼운 무게, 저렴한 가격, 우수한 제반 물성을 가지고 있어 산업적 용도로 많이 사용되고 있으나, 무극성 성질을 띄고 있어 폴리에스테르와 같은 극성 소재와의 상용성 내지 접착성이 미흡하여 그 사용이 제한적인 실정이다. Polyolefin resins are used for industrial purposes because of their light weight, low price, and excellent physical properties. However, they are non-polar and have limited compatibility or adhesion with polar materials such as polyester. to be.
한편, 종래 사용되고 있는 접착성 수지로서 폴리올레핀 변성 무수말레인산(polyolefin grafted maleic anhydride; PO-g-MAH)은, 나일론, 에틸렌비닐아세테이트 공중합체(EVOH) 등과 폴리올레핀 사이에서 강한 접착력 및 상용성을 보여주지만, 폴리카보네이트(polycarbonate), 폴리에틸렌테레프탈레이트(polyethylene terephthalate) 등의 폴리에스테르(polyester) 류에는 접착력이 없는 단점이 있다. 이러한 단점을 보완하기 위해 최근 글리시딜메타크릴레이트(glycidyl methacrylate)기를 도입하여 폴리에스테르 류의 접착에 사용하고 있으나, 제조시 중합법을 이용하고 있어 제조단가의 부담이 되고 대량생산이 어려운 문제가 있다.On the other hand, polyolefin modified maleic anhydride (PO-g-MAH) as a conventionally used adhesive resin shows a strong adhesion and compatibility between nylon, ethylene vinyl acetate copolymer (EVOH) and polyolefin, Polyesters such as polycarbonate, polyethylene terephthalate, and the like have disadvantages of no adhesive strength. Recently, glycidyl methacrylate (glycidyl methacrylate) groups have been introduced to compensate for these drawbacks, and they have been used for the adhesion of polyesters. have.
국제공개특허출원 제WO2007/135340호는, 기존 폴리에틸렌 변성 무수말레인산 수지와 달리, 알킬아크릴레이트(alkyl acrylate) 및 글리시딜메타크릴레이트(glycidyl methacrylate)를 공중합하여 3량체(terpolymer)를 제조함으로써 폴리에스테르에 직접 접착할 수 있는 수지를 제공하고자 하였다. 그러나, 역시 중합법을 사용하여 3량체를 제조하는 방법으로 제조단가에 부담이 되는 한계가 있다.International Patent Application No. WO2007 / 135340, unlike conventional polyethylene modified maleic anhydride resin, copolymerizes alkyl acrylate and glycidyl methacrylate to prepare a terpolymer. An attempt was made to provide a resin that could be directly bonded to the ester. However, there is a limit that the manufacturing cost is burdened by the method of producing the trimer using the polymerization method.
따라서, 본 발명은 상기 문제점을 해결하고자 안출된 것으로, 폴리에스테르와의 접착력이 우수한 성분을 함유하고 있는 접착성 수지 조성물을 제공하고자 한다.Accordingly, the present invention has been made to solve the above problems, and to provide an adhesive resin composition containing a component having excellent adhesion to polyester.
또한, 본 발명은 제조단가 측면에서 경쟁력 있는 접착성 수지 조성물 제조방법을 제공하고자 한다.In addition, the present invention is to provide a method for producing an adhesive resin composition competitive in terms of manufacturing cost.
상기 과제를 해결하기 위하여 본 발명은,According to an aspect of the present invention,
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(5) 용융흐름지수(melt flow index)가 1~20g/10min이고, 메틸아크릴레이트 함량이 1~50중량%인 에틸렌메틸아크릴레이트(ethylene-methyl acrylate)로 이루어진 공중합체 50~100중량부; 글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부; 및 과산화물을 1~20중량% 함유한 폴리프로필렌과 과산화물의 혼합물 0.001~5중량부;로 구성된 반응물이 용융압출되어, 상기 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 사슬에 상기 글리시딜메타크릴레이트(glycidyl methacrylate)가 그라프트되어 형성된 접착성 수지 조성물을 제공한다.(5) 50 to 100 parts by weight of a copolymer made of ethylene-methyl acrylate having a melt flow index of 1 to 20 g / 10 min and a methyl acrylate content of 1 to 50 wt%; 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate); And 0.001 to 5 parts by weight of a mixture of polypropylene and peroxide containing 1 to 20% by weight of a peroxide; the reactant is melt-extruded to form the glycidyl meta on the ethylene-methyl acrylate copolymer chain. Glycidyl methacrylate is grafted to provide an adhesive resin composition formed.
(6) 상기 (5)에 있어서, 상기 접착성 수지 조성물은 폴리에틸렌테레프탈레이트에 대한 접착강도가 2~3kgf/㎠인 것을 특징으로 하는 접착성 수지 조성물을 제공한다.(6) In the above (5), the adhesive resin composition provides an adhesive resin composition, characterized in that the adhesive strength to polyethylene terephthalate is 2 ~ 3kgf / ㎠.
상기 또 다른 과제 해결을 위하여 본 발명은,The present invention for solving the another problem,
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(8) 용융흐름지수(melt flow index)가 1~20g/10min이고, 메틸아크릴레이트 함량이 1~50중량%인 에틸렌메틸아크릴레이트(ethylene-methyl acrylate)로 이루어진 공중합체 50~100중량부; 및 과산화물을 1~20중량% 함유한 폴리프로필렌과 과산화물의 혼합물 0.001~5중량부;를 내부 혼합기(internal mixer)에 투입하여 혼합하는 단계; 상기 혼합된 반응물을 2축 압출기(twin screw extruder)로 이송하여 반응온도 160~220℃에서 용융압출하는 단계; 및 글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부를 상기 2축 압출기에 구비된 side feeder에 투입하는 단계;를 포함하여, 상기 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 사슬에 상기 글리시딜메타크릴레이트(glycidyl methacrylate)가 그라프트되어 형성된 접착성 수지 조성물을 제조하는 방법을 제공한다.(8) 50 to 100 parts by weight of a copolymer made of ethylene-methyl acrylate having a melt flow index of 1 to 20 g / 10 min and a methyl acrylate content of 1 to 50 wt%; And 0.001 to 5 parts by weight of a mixture of polypropylene and peroxide containing 1 to 20% by weight of a peroxide; injecting the mixture into an internal mixer; Transferring the mixed reactant to a twin screw extruder to melt extrusion at a reaction temperature of 160 to 220 ° C .; And 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate) into a side feeder provided in the twin screw extruder; including, the ethylene methyl acrylate (ethylene-methyl acrylate) copolymer chain It provides a method for producing an adhesive resin composition formed by grafting glycidyl methacrylate (glycidyl methacrylate).
이러한 본 발명에 따른 접착성 수지 조성물 및 그 제조방법에 따르면, 폴리카보네이트, 폴리에틸렌테레프탈레이트 등 폴리에스테르 류와의 접착이 가능한 접착성 수지 조성물을 제공할 수 있고, 제조시 반응압출법을 사용하여 기존 중합법에 비하여 제조단가를 획기적으로 낮출 수 있는 접착성 수지 조성물 제조방법을 제공할 수 있다.According to such an adhesive resin composition according to the present invention and a method for manufacturing the same, it is possible to provide an adhesive resin composition capable of bonding with polyesters such as polycarbonate, polyethylene terephthalate, and the like by using a reaction extrusion method during manufacturing. Compared with the polymerization method, it is possible to provide a method for producing an adhesive resin composition that can significantly lower the production cost.
이하 바람직한 실시예를 통하여 본 발명을 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.따라서, 본 명세서에 기재된 실시예의 구성은 본 발명의 가장 바람직한 일실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.
Hereinafter, the present invention will be described in detail with reference to preferred embodiments. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims and their equivalents. It is to be understood that various equivalents and modifications may be substituted for those at the time of the present application.
먼저, 본 발명에 따른 접착성 수지 조성물의 각 구성 성분에 대하여 상세히 설명한다.First, each component of the adhesive resin composition which concerns on this invention is demonstrated in detail.
본 발명에 따른 접착성 수지 조성물은, 폴리에틸렌(polyethylene) 50~100중량부, 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 50~100중량부 및 메틸아크릴레이트(methyl acrylate) 공중합체 1~30중량부로 이루어지는 군에서 선택되는 1 이상인 화합물; 글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부; 및 폴리프로필렌과 과산화물의 혼합물 0.001~5중량부;를 포함한다.Adhesive resin composition according to the present invention, 50 to 100 parts by weight of polyethylene, 50 to 100 parts by weight of ethylene-methyl acrylate copolymer and methyl acrylate (methyl acrylate) copolymer 1 to 30 One or more compounds selected from the group consisting of parts by weight; 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate); And 0.001-5 parts by weight of a mixture of polypropylene and peroxide.
상기 폴리에틸렌은, 폴리올레핀 필름층, 예를 들면, 폴리에틸렌 필름층과의 접착시 친화력을 갖도록 하는 것으로, 50~100중량부 포함된다. 상기 폴리에틸렌 함량이 50중량부 미만일 경우 미반응 글리시딜메타크릴레이트가 많아질 수 있고, 100중량부를 초과하는 경우 접착력이 저하될 수 있다. The polyethylene is to have affinity during adhesion with a polyolefin film layer, for example, a polyethylene film layer, 50 to 100 parts by weight is included. When the polyethylene content is less than 50 parts by weight, unreacted glycidyl methacrylate may increase, and when it exceeds 100 parts by weight, the adhesion may be lowered.
여기서, 상기 폴리에틸렌은 본 발명이 속하는 분야에서 통상적으로 사용되는 것을 사용할 수 있으나, 용융흐름지수(melt flow index)가 1~20g/10min이고, 중량평균분자량이 10,000~200,000인 것이 바람직하다. 상기 용융흐름지수가 1g/10min 미만이거나 20g/10min을 초과하는 경우 가공성이 좋지 않을 수 있다. 또한, 상기 중량평균분자량이 10,000 미만일 경우는 기계적 물성이 저하될 수 있고, 200,000을 초과하는 경우 제품 가공성이 좋지 않을 수 있다. Here, the polyethylene may be used in the field to which the present invention belongs, but melt flow index (melt flow index) is 1 ~ 20g / 10min, the weight average molecular weight is preferably 10,000 ~ 200,000. If the melt flow index is less than 1g / 10min or more than 20g / 10min, workability may not be good. In addition, when the weight average molecular weight is less than 10,000, mechanical properties may be lowered, and when the weight average molecular weight is more than 200,000, product processability may not be good.
상기 에틸렌메틸아크릴레이트 공중합체는 폴리에틸렌 필름층과 친화력을 갖도록 함과 동시에 접착능력을 향상시키는 역할을 하는 것으로, 50~100중량부 포함된다. 상기 에틸렌메틸아크릴레이트 공중합체 함량이 50중량부 미만일 경우 미반응 글리시딜메타크릴레이트가 많아질 수 있고, 100중량부를 초과하는 경우 접착력이 떨어질 수 있다.The ethylene methyl acrylate copolymer has affinity with the polyethylene film layer and at the same time serves to improve the adhesive ability, it contains 50 to 100 parts by weight. When the content of the ethylene methyl acrylate copolymer is less than 50 parts by weight, unreacted glycidyl methacrylate may increase, and when it exceeds 100 parts by weight, the adhesion may be reduced.
여기서, 상기 에틸렌메틸아크릴레이트 공중합체는 용융흐름지수(melt flow index)가 1~20g/10min이고, 상기 에틸렌메틸아크릴레이트 공중합체 총 중량에 대하여 메틸아크릴레이트 1~50중량%를 포함하는 것이 바람직하다. 상기 용융흐름지수가 1g/10min 미만이거나, 20g/10min을 초과하는 경우 가공성이 좋지 않을 수 있다. 또한, 상기 메틸아크릴레이트 함량이 1중량% 미만일 경우는 접착력이 저하될 수 있고, 50중량%를 초과하는 경우 폴리에틸렌 필름층과의 친화력이 감소할 수 있다.Here, the ethylene methyl acrylate copolymer has a melt flow index (melt flow index) of 1 ~ 20g / 10min, preferably containing 1 to 50% by weight of methyl acrylate relative to the total weight of the ethylene methyl acrylate copolymer. Do. If the melt flow index is less than 1g / 10min or more than 20g / 10min, workability may not be good. In addition, when the methyl acrylate content is less than 1% by weight, the adhesion may be lowered, and when the methylacrylate content is greater than 50% by weight, the affinity with the polyethylene film layer may be reduced.
본 발명에 따른 접착성 수지 조성물에 함유되는 상기 메틸아크릴레이트 공중합체는 폴리에스테르에 대한 접착력을 향상시키는 역할을 하는 것으로, 1~30중량부 포함된다. 상기 메틸아크릴레이트 공중합체 함량이 1중량부 미만일 경우 접착력이 저하될 수 있고, 30중량부를 초과하는 경우 미반응물이 생성될 수 있다. 또한, 상기 글리시딜메타크릴레이트는 폴리에스테르에 대한 접착력을 부여하는 역할을 하는 것으로, 1~50중량부 포함된다. 상기 글리시딜메타크릴레이트 함량이 1중량부 미만일 경우 접착력이 저하될 수 있고, 50중량부를 초과하는 경우 미반응물이 생성될 수 있다. The methyl acrylate copolymer contained in the adhesive resin composition according to the present invention serves to improve the adhesive force to the polyester, it contains 1 to 30 parts by weight. When the methyl acrylate copolymer content is less than 1 part by weight, the adhesion may be lowered, and when it exceeds 30 parts by weight, unreacted material may be produced. In addition, the glycidyl methacrylate is to serve to give the adhesive force to the polyester, 1 to 50 parts by weight is included. If the glycidyl methacrylate content is less than 1 part by weight, the adhesion may be lowered, and if it exceeds 50 parts by weight, unreacted material may be produced.
한편, 상기 메틸아크릴레이트 공중합체 및 상기 글리시딜메타크릴레이트는 그 순도가 90% 이상인 것이 바람직하다. 상기 메틸아크릴레이트 공중합체 순도가 90% 미만일 경우 부반응이 발생할 가능성이 높고, 상기 글리시딜메타크릴레이트 순도가 90% 미만일 경우 역시 부반응이 발생할 가능성이 높다.On the other hand, the methyl acrylate copolymer and the glycidyl methacrylate is preferably at least 90% purity. When the methyl acrylate copolymer purity is less than 90%, there is a high possibility of side reactions, and when the glycidyl methacrylate purity is less than 90%, there is a high possibility of side reactions.
상기 폴리프로필렌과 과산화물의 혼합물은 상기 글리시딜메타크릴레이트를 폴리에틸렌(polyethylene), 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 또는 메틸아크릴레이트(methyl acrylate) 공중합체 사슬에 붙이는 역할을 하는 것으로, 0.001~5중량부 포함된다. 상기 폴리프로필렌과 과산화물의 혼합물 함량이 0.001중량부 미만일 경우 미반응물이 과도하게 발생할 수 있고, 5중량부를 초과하는 경우 가교 또는 β-Scission 현상이 발생해 물성이 저하될 수 있다.The mixture of polypropylene and peroxide serves to attach the glycidyl methacrylate to a chain of polyethylene, ethylene-methyl acrylate or methyl acrylate copolymer. , 0.001 to 5 parts by weight. When the mixture content of the polypropylene and the peroxide is less than 0.001 parts by weight, unreacted materials may be excessively generated, and when the content of the mixture is more than 5 parts by weight, crosslinking or β-Scission may occur, thereby deteriorating physical properties.
여기서, 상기 폴리프로필렌은 폴리올레핀 필름층, 예를 들면, 폴리프로필렌 필름층과 친화력을 갖게 하는 역할을 하며, 상기 과산화물은 반응의 개시제 역할을 한다. 이때, 상기 과산화물 함량은 상기 폴리프로필렌과 과산화물의 혼합물 총 중량에 대하여 1~20중량%인 것이 바람직하다. 상기 과산화물 함량이 1중량% 미만일 경우 미반응물이 생성되고 접착력이 저하될 수 있고, 20중량%를 초과하는 경우 가교 또는 β-Scission 현상이 발생해 물성이 저하될 수 있다.Here, the polypropylene serves to have affinity with the polyolefin film layer, for example, the polypropylene film layer, and the peroxide serves as an initiator of the reaction. In this case, the peroxide content is preferably 1 to 20% by weight based on the total weight of the mixture of the polypropylene and the peroxide. When the peroxide content is less than 1% by weight, unreacted matter may be generated and the adhesion may be lowered. When the peroxide content is greater than 20% by weight, crosslinking or β-Scission may occur, thereby deteriorating physical properties.
이상 설명한 바와 같은 본 발명에 따른 접착성 수지 조성물은 폴리카보네이트, 폴리에틸렌테레프탈레이트 등의 폴리에스테르 류에 우수한 접착성 및 상용성을 보이게 되며, 상기 폴리에틸렌테레프탈레이트에 대한 접착강도의 경우 1~3kgf/㎠로서 우수한 접착성을 나타낼 수 있다.As described above, the adhesive resin composition according to the present invention shows excellent adhesion and compatibility to polyesters such as polycarbonate and polyethylene terephthalate, and in the case of adhesive strength to the polyethylene terephthalate, 1 to 3 kgf / cm 2 As a result, excellent adhesion can be exhibited.
이하, 본 발명에 따른 접착성 수지 조성물 제조방법에 대하여 상세히 설명한다.
Hereinafter, the adhesive resin composition manufacturing method which concerns on this invention is demonstrated in detail.
본 발명에 따른 접착성 수지 조성물 제조방법은, 폴리에틸렌(polyethylene) 50~100중량부, 용융흐름지수(melt flow index)가 1~20g/10min이고, 메틸아크릴레이트 함량이 1~50중량%인 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 50~100중량부 및 메틸아크릴레이트(methyl acrylate) 공중합체 1~30중량부로 이루어지는 군에서 선택되는 1 이상인 화합물; 및 과산화물을 1~20중량% 함유한 폴리프로필렌과 과산화물의 혼합물 0.001~5중량부;를 내부 혼합기(internal mixer)에 투입하여 혼합하는 단계; 상기 혼합된 반응물을 2축 압출기(twin screw extruder)로 이송하여 반응온도 160~220℃에서 용융압출하는 단계; 및 글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부를 상기 2축 압출기에 구비된 side feeder에 투입하는 단계;를 포함하여, 상기 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 사슬에 상기 글리시딜메타크릴레이트(glycidyl methacrylate)가 그라프트되어 형성된 접착성 수지 조성물을 제조하는 것을 특징으로 한다.Adhesive resin composition manufacturing method according to the invention, 50 to 100 parts by weight of polyethylene, melt flow index (melt flow index) of 1 to 20g / 10min, methyl acrylate content of 1 to 50% by weight of ethylene 50 to 100 parts by weight of a methyl acrylate (ethylene-methyl acrylate) copolymer and 1 to 30 parts by weight of a methyl acrylate (methyl acrylate) copolymer; And 0.001 to 5 parts by weight of a mixture of polypropylene and peroxide containing 1 to 20% by weight of a peroxide; injecting the mixture into an internal mixer; Transferring the mixed reactant to a twin screw extruder to melt extrusion at a reaction temperature of 160 to 220 ° C .; And 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate) into a side feeder provided in the twin screw extruder; including, the ethylene methyl acrylate (ethylene-methyl acrylate) copolymer chain Glycidyl methacrylate (glycidyl methacrylate) is characterized in that to prepare an adhesive resin composition formed by grafting.
본 발명에 따른 접착성 수지 조성물 제조방법은 종래 폴리에스테르 류와 폴리올레핀 류와의 접착성을 위해 중합법을 이용하여 제조하는 것과 달리, 반응압출법(reactive extrusion process)을 이용하여, 공정을 단순화하고 원가를 획기적으로 절감하면서도 폴리에스테르 류에 우수한 접착성을 갖는 접착성 수지 조성물을 제조할 수 있음을 발견하였다.The adhesive resin composition manufacturing method according to the present invention, unlike the conventional manufacturing method using a polymerization method for adhesion between polyesters and polyolefins, using a reactive extrusion process, to simplify the process It has been found that an adhesive resin composition having excellent adhesion to polyesters can be produced while significantly reducing costs.
상기 반응압출법에 따라 접착성 수지 조성물을 제조하기 위해, 내부 혼합기 및 압출기(extruder)가 사용된다. In order to manufacture the adhesive resin composition according to the reaction extrusion method, an internal mixer and an extruder are used.
상기 내부 혼합기에 폴리에틸렌, 에틸렌메틸아크릴레이트 공중합체 또는 메틸아크릴레이트 공중합체 및 폴리프로필렌과 과산화물의 혼합물을 투입하여 혼합한 후 압출기로 이송한 후, 상기 압출기에 글리시딜메타크릴레이트를 추가 투입하고 용융압출하는 공정을 거쳐 본 발명에 따른 접착성 수지 조성물을 제조하게 된다. 이때, 상기 내부 혼합기는 밴버리 믹서(banbury mixer) 또는 니더 믹서(kneader mixer)가 사용될 수 있다. 또한, 상기 압출기는 충분한 혼합 및 반응을 위해 L/D가 32 이상인 2축 압출기(twin screw extruder)가 사용된다. 이때, 상기 2축 압출기의 L/D가 32 미만일 경우 미반응된 반응물이 존재할 수 있다.The polyethylene, ethylene methyl acrylate copolymer or methyl acrylate copolymer and a mixture of polypropylene and peroxide were added to the internal mixer, mixed, transferred to an extruder, and then glycidyl methacrylate was further added to the extruder. Through the process of melt extrusion, to prepare an adhesive resin composition according to the present invention. In this case, the internal mixer may be a Banbury mixer or kneader mixer. In addition, the extruder is used a twin screw extruder (L / D 32 or more) for sufficient mixing and reaction. In this case, when the L / D of the twin screw extruder is less than 32, an unreacted reactant may be present.
또한 본 발명에 따른 접착성 수지 조성물 제조방법에서는, 상기 혼합 및 용융압출이 160~220℃의 반응온도에서 수행되어진다. 상기 반응온도가 160℃ 미만일 경우 반응율이 저하될 수 있고, 220℃를 초과하는 경우 수지열화 현상이 발생할 수 있다.In addition, in the method for producing an adhesive resin composition according to the present invention, the mixing and melt extrusion are performed at a reaction temperature of 160 to 220 ° C. If the reaction temperature is less than 160 ℃ reaction rate can be lowered, if it exceeds 220 ℃ resin degradation may occur.
한편, 액상 성분인 상기 글리시딜메타크릴레이트 투입은, 투입시 작업성 향상을 위해 다른 원료와 함께 믹서에 혼합시키지 않고, 압출기에서 추가 투입된다. 따라서, 본 발명의 일실시예에 따르면, 상기 2축 압출기에 1 이상의 side feeder를 구비하여 상기 글리시딜메타크릴레이트를 상기 side feeder에 투입할 수 있다.
On the other hand, the glycidyl methacrylate is added as a liquid component in the extruder, without mixing in the mixer with other raw materials to improve the workability during the addition. Therefore, according to one embodiment of the present invention, the biaxial extruder may include at least one side feeder to inject the glycidyl methacrylate into the side feeder.
실시예Example 1 One
에틸렌메틸아크릴레이트 공중합체 93중량부(메틸아크릴레이트 함량 24중량%) 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 6중량부를 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
93 parts by weight of the ethylene methyl acrylate copolymer (24% by weight of methyl acrylate) and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 6 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
실시예Example 2 2
에틸렌메틸아크릴레이트 공중합체 90중량부(메틸아크릴레이트 함량 24중량%) 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 9중량부를 을 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
90 parts by weight of the ethylene methyl acrylate copolymer (24% by weight of methyl acrylate) and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 9 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
실시예Example 3 3
에틸렌메틸아크릴레이트 공중합체 88중량부(메틸아크릴레이트 함량 24중량%) 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 11중량부를 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
88 parts by weight of the ethylene methyl acrylate copolymer (24% by weight of methyl acrylate) and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 11 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
실시예Example 4 4
폴리에틸렌 83중량부, 메틸아크릴레이트 공중합체 8중량부 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 8중량부를 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
83 parts by weight of polyethylene, 8 parts by weight of methyl acrylate copolymer and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 8 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
실시예Example 5 5
폴리에틸렌 79중량부, 메틸아크릴레이트 공중합체 12중량부 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 8중량부를 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
79 parts by weight of polyethylene, 12 parts by weight of methyl acrylate copolymer, and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 8 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
실시예Example 6 6
폴리에틸렌 76중량부, 메틸아크릴레이트 공중합체 15중량부 및 폴리프로필렌과 과산화물의 혼합물(상기 과산화물 함량이 10중량%) 1중량부를 밴버리 믹서에 투입하여 혼합한다. 상기 혼합된 반응물을 L/D=40인 2축 압출기로 이송하여 180~200℃의 반응온도에서 용융압출 시킨다. 이후, 글리시딜메타크릴레이트 8중량부를 side feeder에 투입한다. 제조된 수지 조성물로 하기 방법으로 시편을 제작하여 접착력을 측정하고 그 결과를 하기 표 1에 나타내었다.
76 parts by weight of polyethylene, 15 parts by weight of methyl acrylate copolymer, and 1 part by weight of a mixture of polypropylene and peroxide (the content of the peroxide is 10% by weight) are added to a Banbury mixer and mixed. The mixed reactants are transferred to a twin screw extruder having L / D = 40 and melt-extruded at a reaction temperature of 180 to 200 ° C. Then, 8 parts by weight of glycidyl methacrylate is added to the side feeder. The prepared resin composition was prepared in the following method to measure the adhesive strength and the results are shown in Table 1 below.
물성 측정 방법How to measure property
1) 시편 제작1) Specimen Fabrication
용융압출된 수지 조성물을 압축기로 고온(140~210℃)에서 압력(50~200bar)을 가해 폴리에틸렌테레프탈레이트 필름에 접착하여 시편을 제작하였다.The melt-extruded resin composition was applied to a polyethylene terephthalate film by applying a pressure (50 to 200 bar) at a high temperature (140 to 210 ° C.) using a compressor to prepare a specimen.
2) 접착강도 측정2) Adhesion strength measurement
제작된 시편을 2㎝×10㎝ 크기로 잘라서 만능인장시험기를 사용하여 부하(load)값을 측정하였다.The prepared specimens were cut into 2 cm × 10 cm size and the load value was measured using a universal tensile tester.
(중량%)GMA Graft Rate
(weight%)
(kgf/㎠)Adhesive strength
(kgf / cm2)
- EMA: 에틸렌메틸아크릴레이트 공중합체
- PE: 폴리에틸렌
- MA: 메틸아크릴레이트 공중합체
- GMA: 글리시딜메타크릴레이트* Note
EMA: ethylene methyl acrylate copolymer
PE: polyethylene
MA: methyl acrylate copolymer
GMA: glycidyl methacrylate
상기 표 1을 참조하면, 본 발명의 실시예에 따른 접착성 수지 조성물은 기존 상용 접착성 수지에 비해 폴리에틸렌테레프탈레이트와 같은 폴리에스테르 류에 대한 접착력이 향상됨을 알 수 있다. 또한, 실시예 1 내지 3, 실시예 5 및 6의 경우 접착강도가 1~3kgf/㎠로 우수하여, 기존 접착성 수지에서의 무수말레인산과 달리 극성기를 글리시딜메타크릴레이트로 도입하고 경제적인 제조방법을 사용하면서도, 폴리에스테르 류에 대한 접착력이 뛰어난 접착성 수지 조성물을 제공할 수 있음을 알 수 있다.Referring to Table 1, it can be seen that the adhesive resin composition according to the embodiment of the present invention has improved adhesion to polyesters such as polyethylene terephthalate as compared to conventional commercial adhesive resins. In addition, in Examples 1 to 3, Examples 5 and 6, the adhesive strength is excellent at 1 to 3 kgf / cm 2, and unlike the maleic anhydride in the conventional adhesive resin, the polar group is introduced as glycidyl methacrylate and economical. It can be seen that an adhesive resin composition having excellent adhesion to polyesters can be provided while using the production method.
Claims (8)
상기 혼합된 반응물을 2축 압출기(twin screw extruder)로 이송하여 반응온도 160~220℃에서 용융압출하는 단계; 및
글리시딜메타크릴레이트(glycidyl methacrylate) 1~50중량부를 상기 2축 압출기에 구비된 side feeder에 투입하는 단계;
를 포함하여, 상기 에틸렌메틸아크릴레이트(ethylene-methyl acrylate) 공중합체 사슬에 상기 글리시딜메타크릴레이트(glycidyl methacrylate)가 그라프트되어 형성된 접착성 수지 조성물을 제조하는 방법.50-100 parts by weight of a copolymer made of ethylene-methyl acrylate having a melt flow index of 1 to 20 g / 10 min and a methyl acrylate content of 1 to 50 wt%; And 0.001 to 5 parts by weight of a mixture of polypropylene and peroxide containing 1 to 20% by weight of a peroxide; injecting the mixture into an internal mixer;
Transferring the mixed reactant to a twin screw extruder to melt extrusion at a reaction temperature of 160 to 220 ° C .; And
Injecting 1 to 50 parts by weight of glycidyl methacrylate (glycidyl methacrylate) to the side feeder provided in the twin screw extruder;
Including, Glycidyl methacrylate (glycidyl methacrylate) is formed on the ethylene methyl acrylate (chain) copolymer chain to prepare an adhesive resin composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR940018428A (en) * | 1993-01-20 | 1994-08-18 | 김항덕 | Heat Adhesive Polyolefin Resin Composition |
| KR0127292B1 (en) * | 1991-08-01 | 1998-04-01 | 김항덕 | Polyolefin composition and its preparation containing reactivelow molecular weght compound |
| KR20010041901A (en) * | 1998-03-19 | 2001-05-25 | 고사이 아끼오 | Adhesive composition, adhesive laminate, process for producing adhesive laminate, and multilayered laminate |
| KR100638293B1 (en) * | 2002-03-18 | 2006-10-26 | 미쯔이가가꾸가부시끼가이샤 | Adhesive resin and adhesive resin composition for liquid crystalline polymer |
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| KR0127292B1 (en) * | 1991-08-01 | 1998-04-01 | 김항덕 | Polyolefin composition and its preparation containing reactivelow molecular weght compound |
| KR940018428A (en) * | 1993-01-20 | 1994-08-18 | 김항덕 | Heat Adhesive Polyolefin Resin Composition |
| KR20010041901A (en) * | 1998-03-19 | 2001-05-25 | 고사이 아끼오 | Adhesive composition, adhesive laminate, process for producing adhesive laminate, and multilayered laminate |
| KR100638293B1 (en) * | 2002-03-18 | 2006-10-26 | 미쯔이가가꾸가부시끼가이샤 | Adhesive resin and adhesive resin composition for liquid crystalline polymer |
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