KR19990074181A - Adhesive resin composition - Google Patents
Adhesive resin composition Download PDFInfo
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- KR19990074181A KR19990074181A KR1019980007603A KR19980007603A KR19990074181A KR 19990074181 A KR19990074181 A KR 19990074181A KR 1019980007603 A KR1019980007603 A KR 1019980007603A KR 19980007603 A KR19980007603 A KR 19980007603A KR 19990074181 A KR19990074181 A KR 19990074181A
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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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
- C09J123/0853—Vinylacetate
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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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 필름 성형성, 내후성 및 금속과의 접착력이 우수한 에틸렌 초산 비닐계 접착성 수지 조성물을 제공하는 것으로, 이 조성물은 하기 (A)성분 40∼70중량부, (B)성분 3∼30중량부, (C)성분 5∼20중량부, (D)성분 5∼20중량부 및 (E)성분 5∼20중량부의 양으로 함유함을 특징으로 한다 :The present invention provides an ethylene vinyl acetate-based adhesive resin composition having excellent film formability, weather resistance, and adhesion to a metal, the composition comprising: 40 to 70 parts by weight of component (A) and 3 to 30 weight of component (B) And 5 to 20 parts by weight of component (C), 5 to 20 parts by weight of component (D) and 5 to 20 parts by weight of component (E).
(A)에틸렌 초산 비닐 공중합체로서, 하기 조건 ①∼②를 만족하는 것:(A) Ethylene vinyl acetate copolymer which satisfies the following conditions ① to ②:
① 초산비닐 함량 : 10∼20중량%① Vinyl acetate content: 10-20 wt%
② 용융지수(MFR(E): ASTM 1283.E) : 5∼20g/10분(190℃온도)② Melt Index (MFR (E): ASTM 1283.E): 5 ~ 20g / 10min (190 ℃)
(B)불포화카르본산 또는 그 유도체로 그라프트 변성시킨 변성 에틸렌 초산 비닐 공중합체로서, 하기의 조건 ①∼③을 만족하는 것:(B) Modified ethylene vinyl acetate copolymer graft-modified with unsaturated carboxylic acid or derivatives thereof, satisfying the following conditions ① to ③:
① 초산비닐 함량 : 3∼20중량%① Vinyl acetate content: 3 ~ 20 wt%
② 불포화카르본산 또는 그 유도체의 그라프트 변성량 : 0.1∼10중량부② Graft modification amount of unsaturated carboxylic acid or its derivatives: 0.1 to 10 parts by weight
③ 용융지수(MFR(E): ASTM 1283.E) : 0.1∼20g/10분(190℃온도)③ Melt Index (MFR (E): ASTM 1283.E): 0.1 ~ 20g / 10min (190 ℃)
(C)용융지수(MFR(G): ASTM 1283.G)가 10∼40g/10분(230℃온도)인 스티렌 단독중합체 또는 스티렌-부타디엔 이원 공중합체(C) Styrene homopolymer or styrene-butadiene binary copolymer having a melt index (MFR (G): ASTM 1283.G) of 10 to 40 g / 10 minutes (230 ° C. temperature).
(D)에틸렌 α-올레핀 공중합체로서, 하기 조건 ①∼②를 만족하는 것:(D) Ethylene α-olefin copolymer, which satisfies the following conditions ① to ②:
① 용융지수(MFR(E): ASTM 1283.E) : 1.0∼20g/10분(190℃온도)① Melt Index (MFR (E): ASTM 1283.E): 1.0 ~ 20g / 10min (190 ℃)
② 밀도 : 0.850∼0.900g/㎤② Density: 0.850 ~ 0.900g / cm3
(E)석유 수지로서, 하기 조건 ①∼②를 만족하는 것:(E) Petroleum resin which satisfies the following conditions ① to ②:
① C4계, C5계 또는 C9계로 이루어진 탄화수소 수지 및 그의 수소 첨가물① Hydrocarbon resin and its hydrogenated substance consisting of C 4 system, C 5 system or C 9 system
② 연화점(ASTM E28∼58) : 90∼120℃온도② Softening Point (ASTM E28 ~ 58): 90 ~ 120 ℃
상기한 본 발명의 조성물은 접착제 혹은 접착부여제를 처리하지 않고도 금속과의 접착력이 우수하여 건축 내외장재용 금속-플라스틱 복합 판넬 등에 사용될 수 있다.The composition of the present invention described above can be used in metal-plastic composite panels for building interior and exterior materials because it has excellent adhesion with metals without treating adhesives or tackifiers.
Description
본 발명은 에틸렌 초산 비닐계 접착성 수지 조성물에 관한 것으로, 더욱 상세하게는 필름 성형성, 내후성 및 금속과의 접착력이 우수하여 건축 내외장재용의 금속-플라스틱 복합 판넬 등에 사용될 수 있는 에틸렌 초산 비닐계 접착성 수지 조성물에 관한 것이다.The present invention relates to an ethylene vinyl acetate-based adhesive resin composition, and more particularly, ethylene vinyl acetate-based adhesive that can be used in metal-plastic composite panels for building interior and exterior materials due to its excellent film formability, weather resistance and adhesion to metal. It relates to a resin composition.
근래에 건축 외관의 고급스러움과 시공상의 경량화를 위하여 알루미늄 등과 같은 금속과 플라스틱을 복합시킨 금속-플라스틱 복합형 건축 내외장재가 많이 사용되고 있다. 그러나, 금속과 플라스틱은 서로에 대한 접착력이 부족하여 이를 위한 접착제가 필수적으로 요구되었다. 일반적으로, 이를 위해 사용되는 접착제로는 용제형 접착제, 비용제형 핫멜트 및 경화성 접착성 수지 등이 있으나, 용제형 접착제는 용제를 휘발하는 과정을 거치므로 작업 환경 및 생산성이 저하되는 문제점이 있고, 비용제형 핫멜트는 건축자재로 사용할 만큼 강한 내열성 및 내후성을 갖지 못하는 문제점이 있다. 또한, 경화성 접착성 수지를 사용하는 경우에는 내열성은 뛰어나지만 수지의 경화로 인하여 장기 내후성 면에서 취약한 단점을 가지고 있다.In recent years, metal-plastic composite building interior and exterior materials in which metals such as aluminum and plastics are composited are used for high-quality building appearance and light weight in construction. However, metals and plastics lack adhesion to each other, so an adhesive for this is indispensable. In general, adhesives used for this purpose include solvent type adhesives, non-type hot melts, and curable adhesive resins, but solvent type adhesives have a problem in that a working environment and productivity are lowered due to volatilization of a solvent, Formulation hot melt has a problem that does not have a strong heat resistance and weather resistance enough to use as a building material. In addition, when the curable adhesive resin is used, it has excellent heat resistance but has a disadvantage in terms of long-term weather resistance due to curing of the resin.
따라서, 이러한 단점을 극복하기 위한 연구가 많이 행하여지고 있으며, 특히, 에틸렌 초산 비닐 공중합체를 이용한 다양한 접착성 수지 조성물이 제조되어 왔는데, 그 예는 다음과 같다.Therefore, many studies have been conducted to overcome these disadvantages, and in particular, various adhesive resin compositions using ethylene vinyl acetate copolymer have been prepared, examples of which are as follows.
일본특허공개 평 7-286151호에는 에틸렌 초산 비닐 공중합체, 접착부여제 및 왁스로 이루어진 접착성 수지 조성물이 제시되어 있으나, 이는 필름 성형이 불가능하고 접착력과 내구성이 부족한 문제점이 있다.Japanese Patent Laid-Open No. 7-286151 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, an adhesive scavenger, and a wax, but this has a problem in that it is impossible to form a film and lacks adhesive strength and durability.
또한, 일본특허공개 평 8-003526호에는 에틸렌 초산 비닐 공중합체, 접착부여제 및 스티렌계 블록 공중합체로 이루어진 접착성 수지 조성물이 제시되어 있으나, 이것 역시 필름 성형이 불가능하고 접착력이 부족한 문제점이 있다.In addition, Japanese Patent Application Laid-open No. Hei 8-003526 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, an tackifier, and a styrenic block copolymer, but this also has a problem in that film molding is impossible and the adhesive strength is insufficient. .
또한, 일본특허공개 평 3-68640호에는 에틸렌 초산 비닐 공중합체, 불포화 카르본산 또는 그 유도체로 변성시킨 폴리에틸렌, 모노비닐 방향족 탄화수소 올레핀 블록 공중합체 엘라스토머, 에틸렌 α-올레핀 공중합체로 이루어진 접착성 수지 조성물이 제시되어 있으나, 접착 발현온도가 높아 생산성이 떨어지고 접착력이 불충분한 문제점을 갖는다.In addition, Japanese Patent Application Laid-Open No. 3-68640 discloses an adhesive resin composition composed of an ethylene vinyl acetate copolymer, a polyethylene modified with an unsaturated carboxylic acid or a derivative thereof, a monovinyl aromatic hydrocarbon olefin block copolymer elastomer, and an ethylene α-olefin copolymer. Although it is presented, the adhesive expression temperature is high, there is a problem that the productivity is low and the adhesion is insufficient.
이에 본 발명자들은 상기한 문제점을 해결하기 위해서 연구를 거듭한 결과, 에틸렌 초산 비닐 공중합체에 불포화카르본산 또는 그 유도체로 그라프트 변성시킨 변성 에틸렌 초산 비닐 공중합체, 스티렌계 중합체 수지, 에틸렌 α-올레핀 공중합체 및 석유수지를 혼합함으로써 필름 성형성 및 접착내구성이 우수하며 더 낮은 온도에서도 접착 발현이 가능한 접착성 수지 조성물을 제공할 수 있음을 알고 본 발명을 완성하게 되었다.Accordingly, the present inventors have repeatedly studied to solve the above problems, and as a result, modified ethylene vinyl acetate copolymers, styrene polymer resins, and ethylene α-olefins graft-modified with unsaturated carboxylic acid or derivatives thereof. The present invention has been completed by knowing that the copolymer and the petroleum resin can provide an adhesive resin composition which is excellent in film formability and adhesive durability and capable of exhibiting adhesion even at a lower temperature.
따라서, 본 발명의 목적은 필름 성형성, 내후성 및 금속과의 접착력이 우수한 에틸렌 초산 비닐계 접착성 수지 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide an ethylene vinyl acetate-based adhesive resin composition excellent in film formability, weather resistance and adhesion to a metal.
상기한 목적을 달성하기 위하여, 본 발명에 따른 접착성 수지 조성물은 하기 (A)성분 40∼70중량부, (B)성분 3∼30중량부, (C)성분 5∼20중량부, (D)성분 5∼20중량부 및 (E)성분 5∼20중량부를 함유함을 특징으로 한다 :In order to achieve the above object, the adhesive resin composition according to the present invention comprises 40 to 70 parts by weight of the following (A) component, 3 to 30 parts by weight of (B) component, 5 to 20 parts by weight of (C) component, (D 5 to 20 parts by weight of the component and 5 to 20 parts by weight of the component (E).
(A)에틸렌 초산 비닐 공중합체로서, 하기 조건 ①∼②를 만족하는 것:(A) Ethylene vinyl acetate copolymer which satisfies the following conditions ① to ②:
① 초산비닐 함량 : 10∼20중량%① Vinyl acetate content: 10-20 wt%
② 용융지수(MFR(E): ASTM 1283.E) : 5∼20g/10분(190℃온도)② Melt Index (MFR (E): ASTM 1283.E): 5 ~ 20g / 10min (190 ℃)
(B)불포화카르본산 또는 그 유도체로 그라프트 변성시킨 변성 에틸렌 초산 비닐 공중합체로서, 하기의 조건 ①∼③을 만족하는 것:(B) Modified ethylene vinyl acetate copolymer graft-modified with unsaturated carboxylic acid or derivatives thereof, satisfying the following conditions ① to ③:
① 초산비닐 함량 : 3∼20중량%① Vinyl acetate content: 3 ~ 20 wt%
② 불포화카르본산 또는 그 유도체의 그라프트 변성량 : 0.1∼10중량부② Graft modification amount of unsaturated carboxylic acid or its derivatives: 0.1 to 10 parts by weight
③ 용융지수(MFR(E): ASTM 1283.E) : 0.1∼20g/10분(190℃온도)③ Melt Index (MFR (E): ASTM 1283.E): 0.1 ~ 20g / 10min (190 ℃)
(C)용융지수(MFR(G): ASTM 1283.G)가 10∼40g/10분(230℃온도)인 스티렌 단독중합체 또는 스티렌-부타디엔 이원 공중합체(C) Styrene homopolymer or styrene-butadiene binary copolymer having a melt index (MFR (G): ASTM 1283.G) of 10 to 40 g / 10 minutes (230 ° C. temperature).
(D)에틸렌 α-올레핀 공중합체로서, 하기 조건 ①∼②를 만족하는 것:(D) Ethylene α-olefin copolymer, which satisfies the following conditions ① to ②:
① 용융지수(MFR(E): ASTM 1283.E) : 1.0∼20g/10분(190℃온도)① Melt Index (MFR (E): ASTM 1283.E): 1.0 ~ 20g / 10min (190 ℃)
② 밀도 : 0.850∼0.900g/㎤② Density: 0.850 ~ 0.900g / cm3
(E)석유 수지로서, 하기 조건 ①∼②를 만족하는 것:(E) Petroleum resin which satisfies the following conditions ① to ②:
① C4계, C5계 또는 C9계로 이루어진 탄화수소 수지 및 그의 수소 첨가물① Hydrocarbon resin and its hydrogenated substance consisting of C 4 system, C 5 system or C 9 system
② 연화점(ASTM E28∼58) : 90∼120℃온도② Softening Point (ASTM E28 ~ 58): 90 ~ 120 ℃
본 발명의 다른 목적 및 적용은 하기 발명의 구성 및 작용으로부터 당업자들에게 명백해질 것이다.Other objects and applications of the present invention will become apparent to those skilled in the art from the construction and function of the following invention.
이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 접착성 수지 조성물은 필름 성형성이 우수하여 생산성이 좋으며, 접착력, 내구성 및 저온 접착력이 우수하므로 건축 내외장용의 금속-플라스틱 복합 판넬 등에 사용될 수 있다.Since the adhesive resin composition of the present invention has excellent film formability and good productivity, the adhesive resin composition may be used in metal-plastic composite panels for building interior and exterior since it has excellent adhesive strength, durability, and low temperature adhesive strength.
본 발명의 접착성 수지 조성물에 있어서, 성분(A)는 초산비닐의 함량이 10∼20중량%이고, ASTM 1283.E 방법으로 측정한 용융지수(MFR(E))가 5∼20g/10분(190℃온도)인 에틸렌 초산 비닐 공중합체로서, 조성물 총 중량에 대하여 40∼70중량부의 양으로 함유된다. (A)성분의 용융지수가 5g/10분 이하일 경우에는 접착력이 부족하고, 20g/10분 이상일 경우에는 본 발명에 사용되는 타성분과의 혼련성이 떨어진다. 또한, 초산비닐의 함량이 10중량%미만일 경우에는 접착력이 부족하고 20중량%를 초과할 경우에는 내열성 및 필름 성형성이 부족하다. 또한, 조성물 총 중량에 대하여 (A)성분의 함량이 40중량부 이하이거나 70중량부 이상일 경우에는 충분한 접착력을 주지 못 한다.In the adhesive resin composition of the present invention, the component (A) has a vinyl acetate content of 10 to 20% by weight, and a melt index (MFR (E)) measured by the ASTM 1283.E method is 5 to 20 g / 10 minutes. Ethylene vinyl acetate copolymer, which is (190 DEG C), is contained in an amount of 40 to 70 parts by weight based on the total weight of the composition. When the melt index of the component (A) is 5 g / 10 min or less, the adhesive strength is insufficient, and when it is 20 g / 10 min or more, the kneading property with other components used in the present invention is poor. In addition, when the content of vinyl acetate is less than 10% by weight, the adhesive strength is insufficient, and when the content exceeds 20% by weight, heat resistance and film formability are insufficient. In addition, when the content of the component (A) is 40 parts by weight or less or 70 parts by weight or more with respect to the total weight of the composition, it does not give sufficient adhesive force.
또한, 본 발명에서 사용한 변성 에틸렌 초산 비닐 공중합체(B)는 초산비닐의 함량이 3∼20중량%인 에틸렌 초산 비닐 공중합체를 불포화카르본산 또는 그 유도체로 그라프트 반응시켜 얻어진 것으로, 불포화카르본산 또는 그 유도체의 그라프트 변성량은 0.1∼10중량부이다. 에틸렌 초산 비닐 공중합체와 불포화카르본산 또는 그 유도체와의 반응은 촉매의 존재 또는 비존재하에 라디칼 개시제를 사용하여 단순 가온을 행하는 것이 일반적이다. 본 발명에서 에틸렌 초산 비닐을 그라프트 변성시키는데 사용한 불포화카르본산 또는 그의 유도체는 구체적으로 무수말레인산, 무수시트라콘산, 아크릴산메틸, 메타크리산메틸, 아크릴산에틸, 메타크릴산에틸, 아크릴산부틸, 메타크릴산부틸, 아크릴산그리시딜, 메타크릴산그리시딜, 말레인산모노에틸에스테르, 말레인산디에틸에스테르, 프말산디메틸에스테르, 이타콘산모노메틸에스테르, 프말산디메틸에스테르, 이타콘산모노메틸에스테르, 이타폰산에틸에스테르, 아크릴산아미드, 메타아크릴아미드, 메타크릴아미드, 말레인산모노아미드, 말레인산디아미드, 말레인산-N-모노에틸아미드, 말레인산-N-N-디에틸아미드, 말레인산-N-모노부틸아미드, 말레인산-N,N-디부틸아미드, 프말산-N-모노에틸아미드, 프말산-N,N-디부틸아미드, 말레이미드, N-부틸말레이미드, N-페닐말레이미드 등이 있다.The modified ethylene vinyl acetate copolymer (B) used in the present invention is obtained by graft reaction of an ethylene vinyl acetate copolymer having a vinyl acetate content of 3 to 20% by weight with an unsaturated carboxylic acid or a derivative thereof. Or the graft modification amount of the derivative is 0.1-10 weight part. The reaction between the ethylene vinyl acetate copolymer and the unsaturated carboxylic acid or derivatives thereof is generally performed by simple heating using a radical initiator in the presence or absence of a catalyst. In the present invention, the unsaturated carboxylic acid or derivative thereof used for graft modification of ethylene vinyl acetate is specifically maleic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methacrylic. Butyl acid, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleic acid, dimethyl ester of maleic acid, monomethyl ester of itaconic acid, dimethyl ester of itaconic acid, monomethyl ester of itaconic acid, monomethyl ester of itaconic acid, Acrylic acid amide, methacrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-NN-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-di Butylamide, Fmaric acid-N-monoethylamide, Fmaric acid-N, N-dibutylamide, maleimide, N-butylmale Imides, N-phenylmaleimide, and the like.
또한, (B)성분의 용융지수는 0.1∼20g/10분(190℃온도), 바람직하게는 5∼15g/10분 이고, 조성물 총 중량에 대하여 3∼30중량부의 양으로 함유되는데, (B)성분의 함량이 3중량부 미만일 경우에는 접착력이 발현되지 않고 30중량부를 초과하는 경우에는 접착력이 향상되지 않는다.Further, the melt index of component (B) is 0.1 to 20 g / 10 minutes (190 ° C. temperature), preferably 5 to 15 g / 10 minutes, and is contained in an amount of 3 to 30 parts by weight based on the total weight of the composition. ) When the content of the component is less than 3 parts by weight, the adhesive strength is not expressed and when the content exceeds 30 parts by weight, the adhesive strength does not improve.
상기 (A)와 (B)성분 이외에 본 발명에 따른 조성물은 (C)성분인 스티렌 단독중합체 또는 스티렌-부타디엔 이원 공중합체를 5∼20중량부의 양으로 함유한다. (C)성분은 ASTM 1283.G 방법으로 측정한 용융지수가 10∼40g/10분, 바람직하게는 10∼20g/10분이다. (C)성분의 용융지수가 10g/10분 이하이거나 40g/10분 이상일 경우에는 타성분과의 용융혼련성이 좋지 않으며, (C)성분의 함량이 5중량부 미만일 경우에 내후성이 부족하고 20중량부를 초과하는 경우에는 접착력이 저하된다.In addition to the components (A) and (B), the composition according to the present invention contains styrene homopolymer or styrene-butadiene binary copolymer as component (C) in an amount of 5 to 20 parts by weight. The component (C) has a melt index of 10 to 40 g / 10 minutes, preferably 10 to 20 g / 10 minutes, measured by the ASTM 1283.G method. If the melt index of component (C) is less than 10g / 10 minutes or more than 40g / 10 minutes, melt kneading with other components is not good, and if the content of component (C) is less than 5 parts by weight, the weather resistance is insufficient and 20% When it exceeds a part, adhesive force falls.
또한, 본 발명에 따른 조성물은 (D)성분으로서 ASTM 1283.E 방법으로 측정한 용융지수가 0.1∼20g/10분(190℃온도), 바람직하게는 1∼10g/10분이고, 밀도가 0.850∼0.900g/㎤, 바람직하게는 0.87∼0.88g/㎤인 에틸렌 α-올레핀 공중합체를 조성물 총 중량에 대하여 5∼20중량부의 양으로 함유한다. (D)성분의 함량이 5중량부 미만일 경우에는 접착력이 충분하지 않고 20중량부를 초과하는 경우 내열성이 저하되고 필름 성형성이 좋지 않게 된다. (D)성분의 에틸렌-α-올레핀 공중합체에 함유되는 α-올레핀으로는 탄소수 3∼20의 α-올레핀을 사용할 수 있으며, 구체적으로는 프로필렌, 1-부텐, 4-메틸-1-펜텐, 1-헥센, 1-옥텐, 1-데센, 1-테트라센 등이 사용될 수 있고, 이러한 α-올레핀은 단독 혹은 2종 이상의 혼합물로서 사용될 수 있다.Further, the composition according to the present invention has a melt index of 0.1 to 20 g / 10 minutes (190 DEG C), preferably 1 to 10 g / 10 minutes, and a density of 0.850 to The ethylene α-olefin copolymer, which is 0.900 g / cm 3 and preferably 0.87-0.88 g / cm 3, is contained in an amount of 5 to 20 parts by weight based on the total weight of the composition. When content of (D) component is less than 5 weight part, adhesive force is not enough, and when it exceeds 20 weight part, heat resistance will fall and film formability will become bad. As an alpha olefin contained in the ethylene- alpha -olefin copolymer of (D) component, C3-C20 alpha olefin can be used, Specifically, propylene, 1-butene, 4-methyl-1- pentene, 1-hexene, 1-octene, 1-decene, 1-tetracene and the like can be used, and such α-olefins can be used alone or as a mixture of two or more thereof.
또한, 본 발명에 따른 조성물은 (E)성분으로서 ASTM E28∼58 방법으로 측정한 연화점이 90∼120℃이고 C4계, C5계 또는 C9계로 이루어진 탄화수소 수지 또는 그의 수소 첨가물의 석유수지를 조성물 총 중량에 대해 5∼20중량부로 함유한다. (E)성분의 함량이 5중량부 미만일 경우 접착력이 불충분하고 20중량부를 초과하는 경우에는 블로킹이 일어나기 쉬우므로 취급상에 문제가 있다.In addition, the composition according to the present invention is a petroleum resin of a hydrocarbon resin or a hydrogenated substance thereof having a softening point of 90 to 120 ° C. and a C 4 system, C 5 system or C 9 system measured by ASTM E28 to 58 as the component (E). 5 to 20 parts by weight, based on the total weight of the composition. When the content of the component (E) is less than 5 parts by weight, the adhesive strength is insufficient, and when the content of the component (E) exceeds 20 parts by weight, blocking is likely to occur, which causes problems in handling.
또한, 본 발명의 접착성 수지 조성물에 있어서, 상기 (A)∼(E)성분 이외에도 필요에 따라 당업계에 주지된 각종의 산화방지제, 자외선 흡수제, 광보호제, 활제, 대전방지제, 무기 또는 유기 충진제를 당업자가 어려움없이 적의 선정하여 배합할 수 있다.Further, in the adhesive resin composition of the present invention, in addition to the components (A) to (E), various antioxidants, ultraviolet absorbers, photoprotective agents, lubricants, antistatic agents, inorganic or organic fillers well known in the art as needed. Can be suitably selected and blended by those skilled in the art without difficulty.
이하, 실시예를 통하여 본 발명을 구체화시키고자 한다.Hereinafter, the present invention will be embodied through the examples.
하기의 실시예 및 비교예에 사용된 각종 물성의 평가방법은 다음의 시험법에 의해 행하였다.Evaluation methods of various physical properties used in the following Examples and Comparative Examples were carried out by the following test methods.
(1) 필름 성형성 :(1) Film formability:
3등급으로 평가하였다.It was evaluated by three grades.
○: 안정적인 성형가능○: Stable molding
△: 필름 셩형은 되나 안정적인 성형이 불량(자주 터지거나 단속됨)(Triangle | delta): Although it is a film-shaped film | membrane, stable shaping | molding is bad (frequently bursts or interrupts)
▲: 성형자체가 불가능▲: molding itself is impossible
(2) Fish eye 갯수(2) Fish eye number
600㎠당 Fish eye의 갯수를 측정하였다.The number of fish eyes per 600 cm 2 was measured.
(3) 접착력(1) :(3) Adhesive force (1):
200㎛ 알루미늄/50㎛ 접착성수지 필름/2㎜ 폴리에틸렌 시트로 구성되고, 길이는 15㎝, 너비는 15㎜인 시험편을 준비한 후, 압출기를 이용하여 150℃의 온도, 5㎏/㎠의 압력하에서 2분간 접착시키고 급냉한 다음 만능인장기에서 박리속도 200m/분으로 180℃에서 박리하여 그 시험편의 15㎜당의 LOAD값(단위: ㎏/15㎜)을 측정하였다.A test piece composed of 200 μm aluminum / 50 μm adhesive resin film / 2 mm polyethylene sheet, having a length of 15 cm and a width of 15 mm was prepared, and then extruder was used at a temperature of 150 ° C. under a pressure of 5 kg / cm 2. After bonding for 2 minutes and quenching, peeling was carried out at 180 ° C. at a peel rate of 200 m / min in a universal tensile machine, and the LOAD value (unit: kg / 15 mm) per 15 mm of the test piece was measured.
(4) 접착력(2) :(4) adhesive strength (2):
WEATHER-O-METER(제논 아크)에 ASTM D2565 방법으로 63℃의 온도, 50%의 습도하에서, 340㎚ 파장의 자외선 0.35wt/㎡로 1000시간 동안 에이징(aging)한 후 접착력을 측정하였다.Adhesion was measured after aging for 1000 hours at a temperature of 63 ° C. and a humidity of 50% in a WEATHER-O-METER (Xenon arc) at a temperature of 63 ° C. and a humidity of 50%.
(5) 접착 발현온도 :(5) adhesion expression temperature:
상기 접착력(1)의 시험방법과 동일한 시험편을 준비한 후, 압출기를 이용하여 온도별로 성형하여 접착력이 발현되기 시작하는 온도를 측정하였다.After preparing the same test piece as the test method of the adhesive force (1), by molding for each temperature using an extruder was measured the temperature at which the adhesive force begins to express.
[실시예 1]EXAMPLE 1
(A)에틸렌-비닐-아세테이트(EVA) 40중량부에 (B)무수말레인산 변성 에틸렌-비닐-아세테이트(M-EVA) 20중량부, (C)스티렌계 중합체 수지(PS) 15중량부, (D)에틸렌-프로필렌 공중합체(EPR) 10중량부 및 (E)석유수지 5.0중량부의 양으로 첨가하고, 헨셀 믹서로 각 성분들을 혼합한 후, L/D 26이며 직경 40㎜인 단축 압출기를 이용하여 용융·혼련시켜 제립한 후 컨벡션 오븐에서 건조하고 다이직경 50㎜ 상향식 인플레이션 필름 성형기를 이용하여 두께 50㎛의 필름을 성형하였다. 얻어진 성형물의 각종 물성을 상기 기술한 방법에 따라 측정하고, 그 결과를 하기 표 1에 나타내었다.(A) 40 parts by weight of ethylene-vinyl acetate (EVA) (B) 20 parts by weight of (B) maleic anhydride modified ethylene-vinyl-acetate (M-EVA), (C) 15 parts by weight of styrene-based polymer resin (PS), ( D) Add 10 parts by weight of ethylene-propylene copolymer (EPR) and 5.0 parts by weight of (E) petroleum resin, mix each component with Henschel mixer, and use L / D 26, 40 mm diameter single screw extruder. After melting, kneading and granulation, the resultant was dried in a convection oven, and a film having a thickness of 50 μm was formed using a die diameter 50 mm upward inflation film molding machine. Various physical properties of the obtained moldings were measured in accordance with the method described above, and the results are shown in Table 1 below.
[실시예 2∼5][Examples 2 to 5]
하기 표 1에 기재된 함량으로 (A)∼(E)성분을 함유한다는 것을 제외하고는 실시예 1과 동일하게 실시하여 성형물을 얻고, 그 물성을 측정한 결과를 하기 표 1에 나타내었다.Except for containing the components (A) to (E) in the content shown in Table 1, to carry out in the same manner as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.
[비교예 1∼2][Comparative Examples 1 and 2]
하기 표 1에 기재된 함량으로 (A)∼(E)성분을 함유하는 것을 제외하고는 실시예 1과 동일하게 실시하여 성형물을 얻었고, 그 물성을 측정한 결과를 하기 표 1에 나타내었다.Except for containing the components (A) to (E) in the amounts shown in Table 1, and was carried out in the same manner as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.
[비교예 3][Comparative Example 3]
무수말레인산 변성 에틸렌-비닐-아세테이트(B) 대신에 무수말레인산 변성 고밀도폴리에틸렌(M-PE)을 조성물 총 중량에 대하여 20중량부 함유하는 것을 제외하고는 실시예 1과 동일하게 실시하여 성형물을 얻었고, 그 물성을 측정한 결과를 하기 표 1에 나타내었다.A molded product was obtained in the same manner as in Example 1 except for containing 20 parts by weight of maleic anhydride-modified high density polyethylene (M-PE) based on the total weight of the composition instead of maleic anhydride-modified ethylene-vinyl-acetate (B). The results of measuring the physical properties are shown in Table 1 below.
[비교예 4][Comparative example 4]
(A)∼(E)성분 중 (A), (C), (D)성분만을 하기 표 1에 기재된 함량으로 첨가하며 무수말레인산 변성 고밀도폴리에틸렌(M-PE)을 조성물 총 중량에 대하여 10중량부, 쉘 스타이렌-에틸렌-부타디엔-스타이렌 삼원 블록 공중합체(SEBS)를 5중량부 더 함유하는 것을 제외하고는 실시예 1과 동일하게 실시하여 성형물을 얻었고, 그 물성을 측정한 결과를 하기 표 1에 나타내었다.Of the components (A) to (E), only (A), (C) and (D) components are added in the amounts shown in Table 1 below, and maleic anhydride-modified high density polyethylene (M-PE) is 10 parts by weight based on the total weight of the composition. , Except that the shell styrene-ethylene-butadiene-styrene terpolymer block copolymer (SEBS) containing 5 parts by weight of the same as in Example 1 to obtain a molded article, the results of measuring the physical properties are shown in the following table 1 is shown.
[비교예 5][Comparative Example 5]
(A)∼(E)성분 중 (A)와 (E)성분만을 하기 표 1에 기재된 양만큼 첨가하며, 왁스를 조성물 총 중량에 대하여 20중량부 더 함유하는 것을 제외하고는 실시예 1과 동일하게 실시하여 성형물을 얻었고, 그 물성을 측정한 결과를 하기 표 1에 나타내었다.Same as Example 1 except adding only the components (A) and (E) in the amounts shown in Table 1 among the components (A) to (E), and further containing 20 parts by weight based on the total weight of the composition. It was carried out to obtain a molded article, the results of measuring the physical properties are shown in Table 1 below.
이상의 설명에서 알 수 있는 바와 같이, 본 발명의 에틸렌 초산 비닐계 접착성 수지 조성물은 에틸렌-비닐-아세테이트(A)에 무수 말레인산 변성 에틸렌-비닐-아세테이트(B), 스티렌계 중합체 수지(C), 에틸렌-프로필렌 공중합체(D) 및 석유수지(E)를 첨가하여 제조됨으로써 우수한 필름 성형성, 내후성 및 금속과의 접착력을 가지므로 접착제 혹은 접착부여제를 처리함이 없이 건축 내외장재용 금속-플라스틱 복합 판넬 등에 사용될 수 있다.As can be seen from the above description, the ethylene vinyl acetate-based adhesive resin composition of the present invention is a maleic anhydride-modified ethylene-vinyl-acetate (B), styrene-based polymer resin (C), in ethylene-vinyl-acetate (A), It is manufactured by adding ethylene-propylene copolymer (D) and petroleum resin (E) to have excellent film formability, weather resistance, and adhesion to metal. Therefore, it is a metal-plastic composite for building interior and exterior materials without treating adhesives or tackifiers. It can be used for panels.
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