KR20220040254A - Film adhesive for metal surfaces - Google Patents
Film adhesive for metal surfaces Download PDFInfo
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- KR20220040254A KR20220040254A KR1020200123217A KR20200123217A KR20220040254A KR 20220040254 A KR20220040254 A KR 20220040254A KR 1020200123217 A KR1020200123217 A KR 1020200123217A KR 20200123217 A KR20200123217 A KR 20200123217A KR 20220040254 A KR20220040254 A KR 20220040254A
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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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
- C08K5/3155—Dicyandiamide
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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
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
- C08L9/02—Copolymers with acrylonitrile
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
본 발명은 금속 표면용 필름부착 접착제에 관한 것으로, 보다 상세하게는 화성처리강판, 전기아연도금강판, 냉연강판 등의 내수성, 내열성 및 가공성 등의 물성 및 기계적 성질을 개선하기 위하여 염화비닐필름을 금속판 표면에 접착시켜 염화비닐필름 피복강판을 제조하는데 사용하는 접착제에 관한 것이다.The present invention relates to an adhesive for attaching a film to a metal surface, and more particularly, to improve physical and mechanical properties such as water resistance, heat resistance and workability of chemically treated steel sheet, electro galvanized steel sheet, cold rolled steel sheet, etc. It relates to an adhesive used to manufacture a vinyl chloride film-coated steel sheet by adhering to the surface.
금속 표면용 필름부착 접착제에 관한 종래기술로서 한국 특허공고 제78- 240호에는 메틸메타크릴레진과 에폭시레진의 비율을 1:04∼15의 범위로 조성한 레진을 도막형성제의 주성분으로 하는 용매형 및 비닐레진 성층 도착용 소착식 프라이머의 도막형성제를 조성함에 있어서 메틸메타크릴레이트레진:레솔형페놀레진=1부:02∼1부, 메틸메타크릴레진: 반응성가소제=1부:005∼03부의 비율범위로 조성하는 비닐레진 성층 도착용 프라이머가 기술되어 있고, 한국특허공고 제80-1359호에는 메틸메타크릴레이트레진과 에폭시레진의 비율을 1부:04∼15부, 메틸메타크릴레이트레진:레졸형페놀레진=1부:02∼1부, 메틸메타크릴레이트레진:반응성가소제=1부:005∼03부의 비율범위로 조성한 레진을 도막형성제의 주성분으로 하는 비닐레진필름 및 도료용 비닐레진 성층 도착용 소착식 프라이머의 도막형성제를 조성함에 있어서 메틸메타크릴레이트레진과 메틸메타크릴레이트, 에틸아크릴레이트, 아크릴산의 3원공중합체의 비율을 1부:1∼2부의 비율 범위로 조성하는 비닐레진필름 및 도료용 비닐레진 성층 도착용 프라이머가 기술되어 있다.As a prior art regarding film adhesives for metal surfaces, Korean Patent Publication No. 78-240 discloses a solvent-type resin composed of methyl methacrylic resin and epoxy resin in a ratio of 1:04 to 15 as the main component of the coating film forming agent. and methyl methacrylate resin: resol-type phenol resin = 1 part: 02 to 1 part, methyl methacrylate resin: reactive plasticizer = 1 part: 005 to 03 A primer for vinyl resin stratification is described in a ratio range of negative, and in Korean Patent Publication No. 80-1359, the ratio of methyl methacrylate resin to epoxy resin is 1:04-15 parts, methyl methacrylate resin : Resol-type phenolic resin = 1 part: 02 to 1 part, methyl methacrylate resin: Reactive plasticizer = 1 part: 005 to 03 parts Vinyl resin film and vinyl for paints composed of resin as the main component of the film forming agent In the composition of the coating film forming agent for the firing type primer for resin stratification, the ratio of methyl methacrylate resin to the terpolymer of methyl methacrylate, ethyl acrylate and acrylic acid is 1 part: 1 to 2 parts. A vinyl resin film and a primer for stratification of vinyl resin for paint are described.
그러나 상기한 종래기술들은 모두 메틸메타크릴레이트레진과 에폭시레진을 원료로하여 페놀레진과 디에틸렌트리아민을 경화제로 경화시켜 접착력을 얻는 것으로서, 이 접착제는 특히 내충격성, 내수성 및 가공성이 부족하여 염화비닐필름 피복강판을 프레스로 가공하거나 충격을 주는 분야의 제품에는 사용할 수가 없어서 건축자재나 선박용 내장재 등에만 사용되었다. 더구나 상기 프라이머는 1액형으로 저장안정성이 좋지 않고 접착온도가 240∼250℃로 높아 염화비닐필름의 무광처리에 어려움이 있는 것이다.However, all of the above prior arts use methyl methacrylate resin and epoxy resin as raw materials to obtain adhesive strength by curing phenol resin and diethylenetriamine with a curing agent. It was used only for building materials or interior materials for ships, as it could not be used for products in the field of impact processing or press processing of vinyl film-coated steel sheets. Moreover, the primer is a one-component type, has poor storage stability, and has a high adhesion temperature of 240 to 250 ° C.
또한 한국특허 제256218호에서는 메틸메타크릴레이트 1중량부에 대하여 2-하이드록시에틸메타크릴레이트 01∼02중량부, 2-에틸헥실메타크릴레이트 01∼03중량부, 아크릴로니트릴 공중합체용액 06∼10중량부 및 글리시딜메타크릴레이트 01∼02중량부로 하고 메틸에틸케톤:메틸이소부틸케톤:부틸셀로솔브:디이소부틸케톤을 1:1:1:1:1의 중량비로 하여 그라프트 중합시킨 금속 표면용 필름부착 접착제을 제안하고 있다. 그러나 이러한 접착제는 100% 중합이 불가능하고 85∼90% 정도만이 중합반응이 되고 나머지 10∼15%는 모노머 상태로 남아있기 때문에 모노머 냄새가 몹시나고 하절기에는 드럼에 보관시 2∼3개월내에 서서히 중합반응이 일어나 점도가 높아지고 겔화현상이 일어나 사용이 불가능한 상태가 되어 단시간에 소비하여야 하는 불편함이 있는 것이다. 또한 2액형 접착제이기 때문에 사용하기 직전에 B액(가교제)를 넣어 교반하여야 하는 불편과 가교제가 들어간 제품은 24시간 내에 사용하지 않으면 점도상승으로 사용이 불가능해져서 희석제로 점도를 재조정하여 사용하여야 하는 불편함이 있는 것이다.In addition, in Korean Patent No. 256218, 01 to 02 parts by weight of 2-hydroxyethyl methacrylate, 01 to 03 parts by weight of 2-ethylhexyl methacrylate, and acrylonitrile copolymer solution 06 based on 1 part by weight of methyl methacrylate ∼10 parts by weight and 01 to 02 parts by weight of glycidyl methacrylate and methyl ethyl ketone: methyl isobutyl ketone: butyl cellosolve: diisobutyl ketone in a weight ratio of 1:1:1:1:1 A film-adhesive adhesive for metal surfaces that has been polymerized is proposed. However, 100% polymerization of these adhesives is impossible, only about 85 to 90% of the polymerization reaction occurs, and the remaining 10 to 15% remains in the form of monomer, so the smell of monomer is very strong. The reaction occurs, the viscosity increases, and gelation occurs, making it impossible to use, which is inconvenient to consume in a short time. In addition, since it is a two-component adhesive, it is inconvenient to add liquid B (crosslinking agent) and stir immediately before use, and to use a product containing a crosslinking agent within 24 hours, it becomes impossible to use due to increased viscosity. there is a ham
따라서 본 발명의 목적은 1액형이면서 저장안정성이 우수하고, 접착력, 내충격성, 내비등수성, 내열성, 내구성, 가공성 등이 2액형 보다 우수하며, 낮은 접착온도에서 용이하게 접착할 수 있는 새로운 금속 표면용 필름부착 접착제를 제공하는 데에 있다.Therefore, the object of the present invention is a one-component type with excellent storage stability, superior adhesion, impact resistance, boiling water resistance, heat resistance, durability, workability, etc., better than a two-component type, and a new metal surface that can be easily adhered at a low bonding temperature It is to provide an adhesive for film adhesion.
이상 설명한 바와 같이 본 발명에 따라 제조된 접착제는 1액형으로서 사용이 편리하고 겔현상이 없으며 저장안정성이 우수하고, 접착성, 내충격성, 내수성, 내열성, 가공성 및 내구성이 우수하며, 낮은 온도(190∼220℃)에서 라인속도가 빨라 생산성이 우수한 등의 장점이 있다.As described above, the adhesive prepared according to the present invention is a one-component type that is convenient to use, has no gelation, has excellent storage stability, has excellent adhesion, impact resistance, water resistance, heat resistance, processability and durability, and has excellent low temperature (190 ∼220℃), the line speed is fast and the productivity is excellent.
상기한 목적을 달성한 본 발명에 의하면 수지성분으로 폴리메틸메타크릴레이트 수지 100중량부에 대하여 아크릴로니트릴부타디엔 러버 10∼30중량부, 폴리비닐클로라이드/폴리비닐아세테이트 공중합 수지 20∼60중량부, 포화 지방족 폴리에스테르 20∼50중량부, 에폭시 수지 20∼50중량부를 함유하고; 잠재성 경화제로 디시안디아마이드를 폴리메틸메타크릴레이트 수지 100중량부에 대하여 5∼10중량부를 함유하며; 상기한 수지성분과 잠재성 경화제가 메틸이소부틸케톤, 메틸에틸케톤, 디이소부틸케톤, 톨루엔, 크실렌, 디아세톤알코올 및 부틸셀로솔부(에틸렌글리콜 모노 부틸에테르)를 함유하는 혼합유기용제시스템에 용해된 것을 특징으로 하는 금속 표면용 필름부착 접착제가 제공된다.According to the present invention that has achieved the above object, 10 to 30 parts by weight of acrylonitrile butadiene rubber, 20 to 60 parts by weight of polyvinyl chloride/polyvinyl acetate copolymer resin, 20 to 50 parts by weight of saturated aliphatic polyester and 20 to 50 parts by weight of epoxy resin; 5 to 10 parts by weight of dicyandiamide as a latent curing agent based on 100 parts by weight of polymethyl methacrylate resin; In a mixed organic solvent system containing the above resin component and the latent curing agent methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol moiety (ethylene glycol monobutyl ether) There is provided a film-attaching adhesive for a metal surface, characterized in that it is dissolved.
또한 본 발명에 의하면 상기한 혼합유기용제시스템이 메틸이소부틸케톤 : 메틸에틸케톤 : 디이소부틸케톤 : 톨루엔 : 크실렌 : 디아세톤알코올 : 부틸셀로솔부 = 08 : 03∼07 : 08 : 1 :1 : 1 : 16의 중량비로 조성된 것을 특징으로 하는 금속 표면용 필름부착 접착제가 제공된다.In addition, according to the present invention, the above-described mixed organic solvent system is methyl isobutyl ketone: methyl ethyl ketone: diisobutyl ketone: toluene: xylene: diacetone alcohol: butyl cellosol part = 08: 03 to 07: 08: 1:1 : There is provided a film-attaching adhesive for a metal surface, characterized in that it is composed in a weight ratio of 1:16.
이하, 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 금속 표면용 필름부착 접착제는 수지성분, 잠재성 경화제 및 유기용제로 주 구성되는 1액형 접착제이다.The film adhesive for metal surfaces of the present invention is a one-component adhesive mainly composed of a resin component, a latent curing agent and an organic solvent.
본 접착제는 수지 성분으로 폴리메틸메타크릴레이트 수지, 아크릴로니트릴부타디엔 러버, 폴리비닐클로라이드/폴리비닐아세테이트 공중합 수지, 포화 지방족 폴리에스테르 및 에폭시 수지를 함유한다.This adhesive contains polymethyl methacrylate resin, acrylonitrile butadiene rubber, polyvinyl chloride/polyvinyl acetate copolymer resin, saturated aliphatic polyester and epoxy resin as resin components.
본 접착제의 수지성분중 기재 수지인 폴리메틸메타크릴레이트 수지는 중량평균분자량 50,000∼150,000 정도가 적당하다.Among the resin components of this adhesive, polymethyl methacrylate resin, which is the base resin, has a suitable weight average molecular weight of about 50,000 to 150,000.
본 접착제의 수지 성분중 아크릴로니트릴부타디엔 러버의 함량은 폴리메틸메타크릴레이트 수지 100중량부에 대하여 10∼30중량부가 적당하다. 아크릴로니트릴부타디엔 러버의 함량의 10중량부 보다 적은 경우에는 내충격성이 불량하게 될 수 있고, 30중량부 보다 많은 경우에는 접착성 및 도포성이 불량하게 될 수 있다. 사용하기에 특히 바람직한 아크릴로니트릴부타디엔 러버는 무니점도(Mooney viscosity) 40∼90정도의 것이다.The content of acrylonitrile butadiene rubber in the resin component of the present adhesive is suitable for 10 to 30 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin. When the content of the acrylonitrile butadiene rubber is less than 10 parts by weight, the impact resistance may be poor, and when it is more than 30 parts by weight, the adhesion and applicability may be poor. A particularly preferred acrylonitrile butadiene rubber for use is one having a Mooney viscosity of about 40 to 90.
폴리비닐클로라이드/폴리비닐아세테이트 공중합 수지의 함량은 각각 폴리메틸메타크릴레이트 수지 100중량부에 대하여 20∼60중량부가 적당하다. 폴리비닐클로라이드와 폴리비닐아세테이트 공중합 수지의 함량이 20 중량부 보다 적은 경우에는 PVC 필름에 대한 접착력이 불량하게 될 수 있고, 60중량부 보다 많은 경우에는 내열성이 불량하게 될 수 있다. 사용하기에 특히 바람직한 폴리비닐클로라이드/폴리비닐아세테이트 공중합 수지는 폴리비닐클로라이드 성분 60∼85중량%와 폴리비닐아세테이트 성분 15∼40중량%의 비율로 공중합된 것이다.The content of the polyvinyl chloride/polyvinyl acetate copolymer resin is preferably 20 to 60 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin, respectively. If the content of the polyvinyl chloride and polyvinyl acetate copolymer resin is less than 20 parts by weight, the adhesion to the PVC film may be poor, and if it is more than 60 parts by weight, heat resistance may be poor. A particularly preferred polyvinyl chloride/polyvinyl acetate copolymer resin for use is copolymerized in a ratio of 60 to 85 wt % of the polyvinyl chloride component and 15 to 40 wt % of the polyvinyl acetate component.
포화 지방족 폴리에스테르의 함량은 폴리메틸메타크릴레이트 수지 100중량부에 대하여 20∼50중량부가 적당하다. 폴리에스테르의 함량이 20 중량부 보다 적은 경우에는 내충격성이 불량하게 될 수 있고, 50중량부 보다 많은 경우에는 수지 상용성이 불량하게 될 수 있다. 사용하기에 특히 바람직한 포화지방족 폴리에스테르는 중량평균분자량 10,000∼50,000 정도의 것이다.The content of the saturated aliphatic polyester is suitably 20 to 50 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin. If the content of the polyester is less than 20 parts by weight, the impact resistance may be poor, and if it is more than 50 parts by weight, the resin compatibility may be poor. Particularly preferred saturated aliphatic polyesters for use are those having a weight average molecular weight of about 10,000 to 50,000.
에폭시 수지의 함량은 폴리메틸메타크릴레이트 수지 100중량부에 대하여 20∼50중량부가 적당하다. 에폭시 수지의 함량이 20 중량부 보다 적은 경우에는 내구성이 불량하게 될 수 있고, 50중량부 보다 많은 경우에는 내충격성이 불량하게 될 수 있다. 사용하기에 특히 바람직한 에폭시 수지는 에폭시 당량 150∼250의 것이다.The content of the epoxy resin is suitable 20 to 50 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin. If the content of the epoxy resin is less than 20 parts by weight, the durability may be poor, and if it is more than 50 parts by weight, the impact resistance may be poor. Particularly preferred epoxy resins for use are those having an epoxy equivalent weight of 150 to 250.
또한 본 접착제에는 잠재성 경화제로서 디시안디아마이드가 함유된다. 잠재성 경화제인 디시안디아마이드가 함유되어 1액형으로 되는 본 접착제는 상온에서 반응이 일어나지 않고 150℃ 이상의 온도로 가열시에 경화반응이 일어나므로 저장안정성이 우수하다. 본 접착제 중 디시안디아마이드의 함량은 수지성분들의 함량에 의존하는 것으로서, 바람직하게는 폴리메틸메타크릴레이트 수지 100중량부에 대하여 5∼10중량부가 적당하다.In addition, the present adhesive contains dicyandiamide as a latent curing agent. This one-component adhesive containing dicyandiamide, a latent curing agent, does not react at room temperature, but has excellent storage stability because the curing reaction occurs when heated to a temperature of 150° C. or higher. The content of dicyandiamide in the present adhesive depends on the content of the resin components, and preferably 5 to 10 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin is appropriate.
본 접착제는 에폭시 수지와 열경화성 잠재성 경화제인 디시안디아마이드의 도입으로 우수한 내부식성을 나타내며, 아크릴로니트릴부타디엔 러버의 도입으로 우수한 내열성 및 내충격성을 나타낸다.This adhesive exhibits excellent corrosion resistance by introducing epoxy resin and dicyandiamide, a thermosetting latent curing agent, and exhibits excellent heat resistance and impact resistance by introducing acrylonitrile butadiene rubber.
본 접착제에 함유되는 잠재성 경화제와 수지성분들을 용해시키는데에는 특별히 설계된 유기용제시스템이 필요하다. 본 접착제에 사용되는 유기용제시스템에는 유기용제들인 메틸이소부틸케톤, 메틸에틸케톤, 디이소부틸케톤, 톨루엔, 크실렌, 디아세톤알코올 및 부틸셀로솔부인 혼합되어 있다. 각각의 유기용제의 배합비는 용해시키고자하는 잠재성 경화제와 수지 성분들의 배합비에 좌우되는 것으로, 바람직한 배합비는 대체로 메틸이소부틸케톤 : 메틸에틸케톤 : 디이소부틸케톤 : 톨루엔 : 크실렌 : 디아세톤알코올 : 부틸셀로솔부 = 08 : 03∼07 : 08 : 1 :1 : 1 : 16의 중량비 정도가 적당하다.A specially designed organic solvent system is required to dissolve the latent curing agent and resin components contained in this adhesive. In the organic solvent system used for this adhesive, the organic solvents methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, toluene, xylene, diacetone alcohol and butyl cellosol are mixed. The mixing ratio of each organic solvent depends on the mixing ratio of the latent curing agent and the resin components to be dissolved, and the preferred mixing ratio is generally methyl isobutyl ketone: methyl ethyl ketone: diisobutyl ketone: toluene: xylene: diacetone alcohol: Butyl cellosol part = 08: 03 to 07: 08: 1:1: A weight ratio of 1: 16 is suitable.
또한 본 접착제에는 상기한 성분이외에도 기타 통상의 첨가제를 본 발명의 목적을 벗어나지 않는 범위내에서 적정량으로 함유시킬 수 있다. 이러한 기타 첨가제의 예로는 산화방지제, 안정제, 가소제 등이 있다.In addition, in addition to the above components, the present adhesive may contain other conventional additives in an appropriate amount within the scope not departing from the purpose of the present invention. Examples of such other additives include antioxidants, stabilizers, plasticizers, and the like.
이하, 본 발명의 실시예의 방법으로 설명하기로 한다. 단, 본 발명이 하기 실시예로 제한되는 것은 아니다.Hereinafter, the method of the embodiment of the present invention will be described. However, the present invention is not limited to the following examples.
[실시예 1][Example 1]
접착제 총중량기준으로 수지성분으로서 폴리메틸메타크릴레이트 수지(Paraloid A-11) 110중량%, 아크릴로니트릴부타디엔 러버(Mooney viscosity 60) 20중량%, 폴리비닐클로라이트/폴리비닐아세테이트 공중합 수지(Wacker 제품 H40/50) 55중량%, 포화 지방족 폴리에스테르(ES-300; 분자량 26000) 32중량% 및 에폭시 수지(에폭시당량 200) 36중량%와; 열경화성 잠재성 경화제로서 디시안디아마이드 08중량%와; 유기용제시스템으로서 메틸이소부틸케톤 86중량%, 메틸에틸케톤 43중량%, 디이소부틸케톤 86 중량%, 톨루엔 114 중량%, 크실렌 114중량%, 디아세톤알코올 114 중량% 및 부틸셀로솔부 178 중량%와; 기타 첨가제로서 산화방지제 01중량%, 안정제 01 중량% 및 가소제 02 중량%로 이루어진 금속 표면용 필름부착 접착제를 제조하였다.As a resin component based on the total weight of the adhesive, 110 wt% of polymethyl methacrylate resin (Paraloid A-11), 20 wt% of acrylonitrile butadiene rubber (Mooney viscosity 60), polyvinylchlorite/polyvinyl acetate copolymer resin (Wacker product) H40/50) 55% by weight, saturated aliphatic polyester (ES-300; molecular weight 26000) 32% by weight and epoxy resin (epoxy equivalent 200) 36% by weight; 08 wt% of dicyandiamide as a thermosetting latent curing agent; As an organic solvent system, methyl isobutyl ketone 86 wt%, methyl ethyl ketone 43 wt%, diisobutyl ketone 86 wt%, toluene 114 wt%, xylene 114 wt%, diacetone alcohol 114 wt%, and butyl cellosol part 178 wt% %Wow; As other additives, a film-adhesive adhesive for metal surfaces consisting of 01% by weight of antioxidant, 01% by weight of stabilizer, and 02% by weight of plasticizer was prepared.
제조된 접착제를 사용하여 한국품질표준규격 KS M3343에 따라 각각 시편을 3개씩 제작하여 하기의 방법으로 박리시험, 에릭슨시험, 충격시험, 굴곡시험, 내한성시험, 내비등수성시험, 내식성시험을 실시하였다. 시험결과는 표 2에 제시된다. 각 시험결과는 3개의 시편에 대한 평균 성적부호로 나타내며, 성적부호 +++는 가장양호한 것, ++는 양호한 것, +는 보통인 것을 의미한다.Using the prepared adhesive, three specimens were prepared in accordance with the Korean Quality Standards KS M3343, and peel test, Ericsson test, impact test, bending test, cold resistance test, boiling water resistance test, and corrosion resistance test were performed by the following methods. . The test results are presented in Table 2. Each test result is expressed as the average grade code for three specimens, and the grade code +++ means the best, ++ means good, and + means average.
* 박리시험* Peel test
시편제작: 너비 20㎜, 길이 150㎜Specimen production: width 20㎜, length 150㎜
시험편은 한쪽 끝에서 90㎜ 정도 비닐층을 떼어낸 다음 비닐층을 180°구부린다. 장치 및 기구는 인장강도시험기를 사용하고 매분 50㎜의 속도로 인장하중을 가하여 박리시의 최대 하중을 측정하고 비닐층이 파탄되었을 때는 파탄시의 하중을 취한다.Remove the vinyl layer by about 90 mm from one end of the test piece, and then bend the vinyl layer by 180°. Apparatus and apparatus use a tensile strength tester and apply a tensile load at a rate of 50 mm per minute to measure the maximum load at the time of peeling. When the vinyl layer breaks, the load at break is taken.
* 에릭슨시험* Ericsson test
시편제작: 가로 90㎜, 세로 90㎜Specimen production: Width 90㎜, Length 90㎜
시험편은 중심선에서 양쪽 25㎜ 거리에 길이 50㎜되게 가로와 세로에 각각 2개의 선을 예리한 칼로 비닐층을 절단한다.For the specimen, cut the vinyl layer with a sharp knife at a distance of 25 mm from the center line and a length of 50 mm on both sides of two lines, each horizontally and vertically.
에릭슨시험기는 KS B 5529(에릭슨시험기)에 규정한 기구를 사용한다. 조작은 시험편의 중심이 다이스 중심에 일치하도록 하고 펀치의 속도는 5∼20㎜/min로 반지름이 6㎜되도록 염화비닐필름 피복강판을 팽출시켜 PVC필름이 박리되는 시험을 한다. 이 때 팽출된 중심에서 크로스 컷트한 PVC필름이 끊어지는 상태를 관찰한다.The Ericsson tester uses the equipment specified in KS B 5529 (Ericsson tester). For the operation, make the center of the test piece coincide with the center of the die, and the speed of the punch is 5-20 mm/min, and the PVC film is peeled off by expanding the vinyl chloride film-coated steel sheet to have a radius of 6 mm. At this time, observe the state in which the cross-cut PVC film is broken at the swollen center.
* 굴곡시험* Flexural test
시편제작: 가로 50㎜, 세로 150㎜Specimen production: Width 50㎜, Length 150㎜
KS B 0804(금속재료 굴곡시험방법)에 따르며 25±5℃에서 180°로 시험편을 접었을 때 PVC필름이 끊어지지 않아야 한다.According to KS B 0804 (Method for bending test for metal materials), the PVC film should not break when the specimen is folded at 180° at 25±5℃.
* 내한성시험* Cold resistance test
굴곡시험시의 시편과 같으며 시험편을 0±1℃에서 1시간이상 유지하고 다시 굴곡시험과 똑같은 방법으로 한다.It is the same as the specimen in the bending test. Keep the specimen at 0±1℃ for 1 hour or more, and then perform the same procedure as in the bending test.
* 내비등수성시험* Boiling water resistance test
시편제작: 가로 20㎜, 세로 100㎜Specimen production: width 20 mm, length 100 mm
200㎖이상되는 비이커에 자기의 작은 파편 2∼3개를 넣고 깨끗한 물을 깊이가 130㎜되게 넣고 가열한다. 0 기포가 매초 2∼3개 정도 발생하도록 끓인다. 60분후에 꺼내서 냉수에 5분간 넣어 냉각시킨후 건조시킨다. 이 때 PVC필름이 박리되는지 확인한다.Put 2-3 small pieces of porcelain in a beaker of 200 ml or more, add clean water to a depth of 130 mm, and heat it. 0 Boil so that 2 to 3 bubbles are generated every second. After 60 minutes, take it out and place it in cold water for 5 minutes to cool and dry it. At this time, check if the PVC film is peeled off.
* 내식성시험* Corrosion resistance test
시편제작: 가로 50㎜, 세로 100㎜Specimen production: Width 50㎜, Length 100㎜
시험편의 절단부분을 5㎜정도 투명테이프로 감싸서 부착하고 KS D 9502(염수분무 시험방법)에 따라 시험한다. 시험시간은 1000시간으로 한다.Wrap the cut part of the test piece with about 5 mm transparent tape and attach it, and test according to KS D 9502 (salt spray test method). The test time is 1000 hours.
[실시예 2∼5][Examples 2 to 5]
표 1에 나타낸 바와 같이 조성성분의 함량을 변경한 것을 제외하고는 실시예 1과 동일한 절차를 반복하여 접착제 조성물을 제조하고, 제조된 조성물의 특성을 실시예 1과 동일한 방법으로 평가하였다. 그 결과는 표 2에 제시된다.As shown in Table 1, an adhesive composition was prepared by repeating the same procedure as in Example 1 except for changing the content of the component, and the properties of the prepared composition were evaluated in the same manner as in Example 1. The results are presented in Table 2.
[표 1][Table 1]
[비교예 1][Comparative Example 1]
접착제 총중량기준으로 메틸메타크릴레이트 85중량%, 2-하이드록시에틸메타크릴레이트 08중량%, 2-에틸헥실메타크릴레이트 08중량%, 아클리로니트릴공중합체 51 중량%, 글리시딜메타크릴레이트 08 중량%, 메틸에틸케톤 155중량%, 메틸이소부틸케톤 165 중량%, 디이소부틸케톤 18중량%, 톨루엔 165중량% 및 부틸셀로솔브 165 중량%를 함유하는 접착제를 제조하고, 얻어진 접착제를 실시예 1과 동일한 방법으로 평가하였다. 평가결과는 표 2에 제시된다.Based on the total weight of the adhesive, methyl methacrylate 85% by weight, 2-hydroxyethyl methacrylate 08% by weight, 2-ethylhexyl methacrylate 08% by weight, acrylonitrile copolymer 51% by weight, glycidyl methacrylic Adhesives obtained by preparing an adhesive containing 08% by weight of rate, 155% by weight of methylethylketone, 165% by weight of methylisobutylketone, 18% by weight of diisobutylketone, 165% by weight of toluene and 165% by weight of butylcellosolve was evaluated in the same manner as in Example 1. The evaluation results are presented in Table 2.
[표 2][Table 2]
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|---|---|
| KR (1) | KR20220040254A (en) |
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2020
- 2020-09-23 KR KR1020200123217A patent/KR20220040254A/en unknown
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