KR101174019B1 - Hotmelt adhesive composition - Google Patents
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- KR101174019B1 KR101174019B1 KR1020100023803A KR20100023803A KR101174019B1 KR 101174019 B1 KR101174019 B1 KR 101174019B1 KR 1020100023803 A KR1020100023803 A KR 1020100023803A KR 20100023803 A KR20100023803 A KR 20100023803A KR 101174019 B1 KR101174019 B1 KR 101174019B1
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/147—Copolymers of propene with monomers containing other atoms than carbon or hydrogen atoms
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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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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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
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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
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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
- 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
- C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
- C09J193/04—Rosin
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 부칠 고무(Butyl rubber) 9.9~18.5 중량%; 에틸렌 프로필렌 고무(EPDM rubber) 9.9~18.5 중량%; SIS(Styrene-Isoprene-Styrene) 고무를 포함하는 스틸렌 블록 코폴리머(Styrene block copolymer) 6.6~12.4 중량%; 무정형 폴리 올레핀(amorphous poly-alpha-olefins, APAO) 5.3~9.9 중량%; 지방족 석유수지, 로진 에스테르 및 터펜수지를 포함하는 점착 부여 수지 27~49 중량%; 폴리이소부틸렌을 포함하는 가소제 6.6~12.4 중량%; 무수말레인산-폴리프로필렌(Maleic Anhyderide Polypropylene) 0.5~7 중량%; 폐놀계 산화방지제 0.5~2 중량%; 및 UV 안정화제 0.1~0.7 중량%;를 포함하는 것을 특징으로 하는 핫멜트 접착제 조성물에 관한 것으로, 우수한 내열 크리프성 및 접착특성을 나타내기 때문에, 자동차 헤드램프 실링을 위한 핫멜트 접착제 조성물로서 유용하게 사용될 수 있다.The present invention is butyl rubber (Butyl rubber) 9.9 ~ 18.5% by weight; 9.9-18.5 wt% ethylene propylene rubber; 6.6 to 12.4 wt% of a styrene block copolymer comprising a SIS (Styrene-Isoprene-Styrene) rubber; 5.3 to 9.9 wt% of amorphous poly-alpha-olefins (APAO); 27 to 49 wt% of a tackifying resin including aliphatic petroleum resin, rosin ester, and terpene resin; 6.6-12.4 weight% of the plasticizer including polyisobutylene; Maleic anhyderide polypropylene 0.5-7 wt%; 0.5-2% by weight of spent antioxidants; And a UV stabilizer of 0.1 to 0.7 wt%; and relates to a hot melt adhesive composition, and because it shows excellent heat creep resistance and adhesive properties, it may be usefully used as a hot melt adhesive composition for automobile headlamp sealing. have.
Description
본 발명은 핫멜트 접착제 조성물에 관한 것으로, 보다 구체적으로는 자동차 헤드램프 실링용 핫멜트 접착제 조성물에 관한 것이다.
The present invention relates to a hot melt adhesive composition, and more particularly to a hot melt adhesive composition for automotive headlamp sealing.
핫멜트 접착제는 현재 산업현장에서 가장 많이 사용되는 용제형 접착제와 달리 용제를 사용치 않는 무용제형(無溶制形) 접착제로서, 작업 환경개선이 용이하고 작업공정의 인력 절감을 위한 자동화 작업이 용이하기 때문에 이에 대한 중요성이 증대되고 있다. Hot-melt adhesive is a solvent-free adhesive that does not use solvent, unlike the solvent-based adhesive that is currently used most in the industrial field, and it is easy to improve the working environment and automate work for reducing the workforce. Therefore, the importance of this is increasing.
현재 가장 보편적으로 사용되는 핫멜트 접착제의 주성분은 열가소성 수지인데, 열경화성 수지 접착제만큼 높은 접착력을 얻을 수 없고, 내열성이 약하기 때문에 큰 접착강도를 요구하지 않는 책, 종이상자, 부직포 기저귀 등의 일부 제품에 국한되어 사용되고 있을 뿐이다. The main component of the hot melt adhesive currently used is thermoplastic resin, which is limited to some products such as books, paper boxes, and nonwoven diapers, which do not require high adhesive strength due to the poor heat resistance and low heat resistance. It is just being used.
상기와 같이 열가소성 수지가 주성분으로 이용되는 핫멜트 접착제는 열가소성 수지의 종류에 따라, 폴리올레핀계, 폴리에스테르계 또는 폴리아미드계의 핫멜트 접착제라 불린다. The hot melt adhesive in which the thermoplastic resin is used as a main component as described above is called a polyolefin-based, polyester-based or polyamide-based hot melt adhesive according to the type of the thermoplastic resin.
또한, 스티렌부타디엔 공중합체(SBS) 또는 스티렌이소플렌 공중합체(SIS) 등의 스티렌블록 공중합체를 주성분으로 이용한 열가소성 엘라스토머를 주성분으로 하는 핫멜트 접착제도 알려져 있다. 이 중에서, 폴리올레핀계의 핫멜트 접착제, 특히 에틸렌초산비닐 공중합체(이하, EVA라 함)에 점착 부여 수지 및 왁스를 배합한 핫멜트 접착제는 저렴하고, 주성분인 EVA의 초산비닐 함유량, 분자량, 배합 처방의 변경에 의해 광범위한 용도로 적용가능한 핫멜트 접착제를 조제할 수 있기 때문에 포장용도, 제본용도, 합판 목공 접착용도 등의 광범위한 분야에 사용되고 있다. Moreover, the hot melt adhesive which has a thermoplastic elastomer which uses styrene block copolymers, such as a styrene butadiene copolymer (SBS) or a styrene isoprene copolymer (SIS) as a main component, is also known. Among these, polyolefin-based hot melt adhesives, particularly hot melt adhesives in which tackifying resins and waxes are mixed with ethylene vinyl acetate copolymers (hereinafter referred to as EVA), are inexpensive, and the vinyl acetate content, molecular weight, and formulation of EVA It is used in a wide range of fields, such as packaging, bookbinding, plywood woodwork bonding, etc. because it can prepare a hot melt adhesive applicable to a wide range of applications by the modification.
한편, 점착 부여 수지로서 방향족 석유수지를 이용한 EVA계 핫멜트 접착제는 가열안정성과 내열접착성의 저하가 문제점으로 지적받고 있다. 가열안정성의 저하는 점착 부여 수지가 산화 열화하여 탄화 불용융 성분으로 변화되어 표면에 분리되는 「스키닝(skinning)」이 발생함으로 말미암아, 핫멜트 접착제 도포기의 노즐 막힘 등의 문제를 초래한다. 내열접착성의 저하는 여름철에 접착한 보드지 포장물이 접착층의 연화에 의해 개봉되는 문제점을 발생시킨다.On the other hand, EVA-based hot melt adhesives using aromatic petroleum resins as tackifying resins have been pointed out to have a problem of deterioration in heat stability and heat resistance. The degradation of the heat stability causes problems such as clogging of the nozzle of the hot melt adhesive applicator due to the oxidative deterioration of the tackifying resin and the formation of "skinning" which is separated from the surface and separated from the carbonized component. The lowering of the heat-resistant adhesiveness causes a problem that the cardboard package bonded in summer is opened by softening the adhesive layer.
상기 문제를 해결하기 위해, 종래에 핫멜트 조성물에 이용되는 EVA의 초산비닐량, 점착 부여 수지 및 왁스의 종류, 양 등을 최적화하는 검토가 행해졌다. 예를 들면, 초산비닐 함유량이 30 중량% 이상인 EVA 100 중량부에 대하여 방향족 성분을 함유하는 점착 부여 수지 50~200 중량부 및 파라핀왁스 2~100 중량부가 함유되는 것을 특징으로 하는 핫멜트 접착제 조성물(일본 특허공개 2001-59078호 공보)이 개시된 바 있다. 그러나, 점착 부여 수지를 최적화하는 검토는 행해져 있지 않았다.In order to solve the said problem, the examination which optimized the amount of vinyl acetate of EVA, tackifying resin, wax, etc. which are conventionally used for a hot-melt composition was done. For example, 50 to 200 parts by weight of a tackifying resin containing an aromatic component and 2 to 100 parts by weight of paraffin wax are contained with respect to 100 parts by weight of EVA having a vinyl acetate content of 30% by weight or more (Japan Patent Publication No. 2001-59078) has been disclosed. However, the examination which optimizes tackifying resin was not performed.
상기 문헌 외에, (1) 특정 비점범위, 비닐톨루엔 함유율, 함유율을 갖는 석유계 탄화 수소류의 열분해에 의해 얻어지는 열분해유 증류분의 중합가능성분, (2) 특정의 테레빈유 및 (3) 페놀 화합물을 특정비율로 프리델크라프츠(Friedel-Crafts)형 촉매를 사용하여 공중합한 변성 방향족 석유수지를 점착 부여 수지로서 이용하는 것이 일본 특허공개 2002-69408호 공보, 일본 특허공개 평9-316294호 공보, 및 일본 특허공개 소55-65248호 공보에 제안되어 있으나, 시판의 석유수지에 대하여 단순히 힌더드아민 화합물을 첨가한 것만으로는 가열안정성의 개량효과는 불충분하였다. In addition to the above documents, (1) polymerizable components of pyrolysis oil distillates obtained by pyrolysis of petroleum hydrocarbons having a specific boiling range, vinyltoluene content and content, (2) specific terebin oil and (3) phenolic compounds To use a modified aromatic petroleum resin copolymerized using a Friedel-Crafts catalyst at a specific ratio as a tackifying resin, JP-A-2002-69408, JP-A-9-316294, and Although proposed in Japanese Patent Application Laid-Open No. 55-65248, the effect of improving heating stability was insufficient simply by adding a hindered amine compound to a commercial petroleum resin.
한편, 점착 부여 수지로서 수소화한 방향족 석유수지(이하, '수소 첨가 석유수지'라고 함)를 사용하여 가열안정성을 개량하는 방법(일본 특허공개 2000-103820호 공보)이 알려져 있으나, 방향족 석유수지를 더욱 수소화하여 제조하기 때문에 수소 미첨가 석유수지에 비하여 수소첨가용 설비 및 수소첨가용 원료(수소, 용매, 촉매)가 필요하여 고가의 생산비용을 초래한다.On the other hand, a method of improving heating stability by using hydrogenated aromatic petroleum resin (hereinafter referred to as hydrogenated petroleum resin) as a tackifying resin (Japanese Patent Laid-Open No. 2000-103820) is known, but aromatic petroleum resin is known. Since it is manufactured by further hydrogenation, it requires more facilities for hydrogenation and raw materials for hydrogenation (hydrogen, solvent, and catalyst) than hydrogenated petroleum resins, resulting in expensive production costs.
이에 본 발명은 내열 크리프성이 우수하여 자동차 헤드램프의 장시간 점등시에도 하우징과 렌즈의 접착성이 우수하고, 수밀성, 가스 차단성이 개선된 핫멜트 접착제 조성물을 제공하는데 그 목적이 있다.
Accordingly, an object of the present invention is to provide a hot melt adhesive composition having excellent heat creep resistance and excellent adhesion between a housing and a lens even when a car head lamp is turned on for a long time, and watertightness and gas barrier property.
상기의 목적을 달성하기 위해 본 발명은 부칠 고무(Butyl rubber) 9.9~18.5 중량%; 에틸렌 프로필렌 고무(EPDM rubber) 9.9~18.5 중량%; SIS(Styrene-Isoprene-Styrene) 고무를 포함하는 스틸렌 블록 코폴리머(Styrene block copolymer) 6.6~12.4 중량%; 무정형 폴리 올레핀(APAO) 5.3~9.9 중량%; 지방족 석유수지, 로진 에스테르 및 터펜수지를 포함하는 점착 부여 수지 27~49 중량%; 폴리이소부틸렌을 포함하는 가소제 6.6~12.4 중량%; 무수말레인산-폴리프로필렌(Maleic Anhyderide Polypropylene) 0.5~7 중량%; 폐놀계 산화방지제 0.5~2 중량%; 및 UV 안정화제 0.1~0.7 중량%;를 포함하는 것을 특징으로 하는 핫멜트 접착제 조성물을 제공한다.The present invention to achieve the above object is butyl rubber (Butyl rubber) 9.9 ~ 18.5% by weight; 9.9-18.5 wt% ethylene propylene rubber; 6.6 to 12.4 wt% of a styrene block copolymer comprising a SIS (Styrene-Isoprene-Styrene) rubber; 5.3 to 9.9 wt% of amorphous polyolefin (APAO); 27 to 49 wt% of a tackifying resin including aliphatic petroleum resin, rosin ester, and terpene resin; 6.6-12.4 weight% of the plasticizer including polyisobutylene; Maleic anhyderide polypropylene 0.5-7 wt%; 0.5-2% by weight of spent antioxidants; And UV stabilizer 0.1 ~ 0.7% by weight; provides a hot melt adhesive composition comprising a.
이하, 본 발명의 과제의 해결 수단에 대해 상세히 설명하고자 한다.
Hereinafter, the means for solving the problems of the present invention will be described in detail.
본 발명의 핫멜트 접착제 조성물에 사용되는 부칠 고무(Butyl rubber)는 기후 변화에 잘 견디고, 불포화결합이 적어 열이나 오존산화제에 강하며, 전기절연성이 뛰어나고, 충격을 잘 흡수하여 충격방지제로도 사용된다. 부칠 고무는 핫멜트 접착제 조성물의 접착력 및 내한성을 증가시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 부칠 고무를 9.9~18.5 중량% 포함하는데, 9.9 중량% 미만으로 포함하는 경우에는, 본 발명에서 발휘되는 부칠 고무의 효과가 미미하고, 18.5 중량%를 초과하는 경우에는, 점도가 증가되어 작업성이 저하되는 문제점이 발생한다.Butyl rubber used in the hot-melt adhesive composition of the present invention is resistant to climate change, less unsaturated bonds, resistant to heat or ozone oxidizer, excellent in electrical insulation, absorbs shock and is also used as an anti-shock agent. . The rubber to be applied serves to increase the adhesion and cold resistance of the hot melt adhesive composition. The hot melt adhesive composition of the present invention contains 9.9 to 18.5% by weight of the rubber to be applied, but when it contains less than 9.9% by weight, the effect of the rubber applied in the present invention is insignificant, when it exceeds 18.5% by weight, There is a problem that the viscosity is increased and workability is lowered.
한편, 본 발명에 사용된 에틸렌 프로필렌 고무(EPDM rubber)는 주쇄에 이중결합이 존재하지 않는 비극성 고무재료로서, 내 노화, 내 오존, 극성액체에 대한 저항성, 전기적 성질이 양호하고, 전선피복, 자동차의 위터스트립 증기호스, 콘베어벨트 등으로 사용되고 있다. 본 발명의 핫멜트 접착제 조성물은 에틸렌 프로필렌 고무를 9.9~18.5 중량% 포함하는데, 9.9 중량% 미만으로 포함되는 경우에는, 본 발명에서 발휘되는 에틸렌 프로필렌 고무의 효과가 미미하고, 18.5 중량%를 초과하는 경우에는, 첨가량 대비 효과 증대가 미미하여 경제적이지 못하다. Meanwhile, ethylene propylene rubber (EPDM rubber) used in the present invention is a nonpolar rubber material having no double bond in the main chain, and has good resistance to aging, ozone, and polar liquids, and has excellent electrical properties. It is used as a wiper strip steam hose, a conveyor belt, and the like. The hot melt adhesive composition of the present invention includes 9.9 to 18.5% by weight of ethylene propylene rubber, but when included in less than 9.9% by weight, the effect of the ethylene propylene rubber exhibited in the present invention is insignificant, when it exceeds 18.5% by weight In addition, the effect increase compared with the addition amount is insignificant, and it is not economical.
한편, 본 발명에서 사용된 SIS(Styrene-Isoprene-Styrene) 고무를 포함하는 스틸렌 블록 코폴리머(Styrene block copolymer)는 경량성 및 유연성을 향상시켜 작업시 본 발명의 취급이 용이하도록 하는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 SIS 고무를 포함하는 스틸렌 블록 코폴리머를 6.6~12.4 중량% 포함하는데, 6.6 중량% 미만으로 포함하는 경우에는, 본 발명에서 발휘되는 스틸렌 블록 코폴리머의 효과가 미미하고, 12.4 중량%를 초과하는 경우에는, 핫멜트 접착제 조성물의 흐름성 및 물성이 현저히 감소하는 문제점이 발생한다. On the other hand, the styrene block copolymer (Styrene block copolymer) containing a SIS (Styrene-Isoprene-Styrene) rubber used in the present invention serves to improve the lightness and flexibility to facilitate the handling of the present invention during operation. The hot melt adhesive composition of the present invention comprises 6.6 to 12.4 wt% of styrene block copolymer including SIS rubber, but if less than 6.6 wt%, the effect of the styrene block copolymer exhibited in the present invention is insignificant, If it exceeds 12.4% by weight, a problem occurs that the flowability and physical properties of the hot melt adhesive composition are significantly reduced.
한편, 본 발명에서 사용되는 무정형 폴리 올레핀(amorphous poly-alpha-olefins, APAO)은 본 발명의 접착력, 내열성 및 내한성을 향상시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 무정형 폴리 올레핀(APAO)을 5.3~9.9 중량% 포함하는데, 5.3 중량% 미만으로 포함되는 경우에는, 본 발명에서 발휘되는 무정형 폴리 올레핀의 첨가 효과가 미미하고, 9.9 중량%를 초과하는 경우에는, 본 핫멜트 접착제 조성물의 점도 증대로 말미암아 작업성이 저하되는 문제점이 발생한다. On the other hand, amorphous poly olefins (amorphous poly-alpha-olefins, APAO) used in the present invention serves to improve the adhesion, heat resistance and cold resistance of the present invention. The hot melt adhesive composition of the present invention contains 5.3 to 9.9% by weight of amorphous polyolefin (APAO), when included in less than 5.3% by weight, the effect of adding the amorphous polyolefin exhibited in the present invention is insignificant, 9.9% by weight When exceeding, the problem that workability falls by the viscosity increase of this hot melt adhesive composition arises.
한편, 본 발명에서 사용되는 지방족 석유수지, 로진 에스테르 및 터펜수지를 포함하는 점착 부여 수지는 상기의 부칠 고무, 에틸렌 프로필렌 고무, 스틸렌 블록 코폴리머 및 무정형 폴리 올리펜과 조합하여 본 발명 핫멜트 접착제 조성물의 접착력을 증대시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 지방족 석유수지, 로진 에스테르 및 터펜수지를 포함하는 점착 부여 수지를 27~49 중량% 포함하는데, 27 중량% 미만으로 포함하는 경우에는, 본 발명에서 발휘되는 점착 부여 수지의 효과가 미미하고, 49 중량%를 초과하는 경우에는, 조성물의 경도가 높고 접착성이 감소되는 문제점이 있다. 본 발명에서 지방족 석유수지, 로진 에스테르 및 터펜수지를 포함하는 점착 부여 수지는 바람직하게 지방족 석유수지 35~65 중량%, 로진 에스테르 15~35 중량% 및 터펜수지 15~35 중량% 로 이루어진 것이 좋다. On the other hand, the tackifying resin comprising aliphatic petroleum resin, rosin ester and terpene resin used in the present invention is a combination of the above-mentioned rubber, ethylene propylene rubber, styrene block copolymer and amorphous poly oliphen of the present invention hot melt adhesive composition It serves to increase adhesion. The hot melt adhesive composition of the present invention includes 27 to 49% by weight of a tackifying resin containing an aliphatic petroleum resin, rosin ester, and terpene resin, but when included in less than 27% by weight of the tackifying resin exhibited in the present invention. If the effect is insignificant and exceeds 49% by weight, there is a problem that the hardness of the composition is high and the adhesion is reduced. In the present invention, the tackifying resin including aliphatic petroleum resin, rosin ester and terpene resin is preferably composed of 35 to 65 wt% of aliphatic petroleum resin, 15 to 35 wt% of rosin ester and 15 to 35 wt% of terpene resin.
한편, 본 발명에서 사용되는 폴리이소부틸렌을 포함하는 가소제는 본 발명에 유연성을 부여하고, 사용시 접착제의 겉마름 현상을 지연시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 가소제를 6.6~12.4 중량% 포함하는데, 6.6 중량% 미만으로 포함하는 경우에는, 본 발명에서 발휘되는 가소제의 효과가 미미하고, 12.4 중량%를 초과하는 경우에는, 접착제 조성물의 흐름성이 높아지고, 접착력이 감소하는 문제점이 발생한다. On the other hand, the plasticizer containing polyisobutylene used in the present invention imparts flexibility to the present invention, and serves to retard the dryness of the adhesive when used. The hot melt adhesive composition of the present invention contains 6.6 to 12.4% by weight of a plasticizer, but when it contains less than 6.6% by weight, the effect of the plasticizer exhibited in the present invention is insignificant, and when it exceeds 12.4% by weight, the adhesive composition Problem arises that the flowability of the resin becomes high and the adhesion decreases.
한편, 본 발명은 접착력과 수밀성 및, 가스 차단성이 개선된 핫멜트 접착제 조성물을 제공하기 위해서 반드시 무수말레인산-폴리프로필렌(Maleic Anhyderide Polypropylene)을 함유하는데, 무수말레인산-폴리프로필렌(Maleic Anhyderide Polypropylene)은 폴리프로필렌 수지에 친수성 관능기의 무수말레인산(MAH)을 그라프트 중합시켜 제조된다. 무수말레인산-폴리프로필렌은 상기 본 발명을 이루는 구성 성분들이 균일하게 분산되도록 하고, 접착력을 향상시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 무수말레인산-폴리프로필렌을 0.5~7 중량% 포함하는데, 이 범위에서 내열성 및 접착강도가 높은 핫멜트 접착제 조성물 제조할 수 있는데, 이는 하기 실험예로부터 확인되었다.Meanwhile, the present invention necessarily includes maleic anhydride polypropylene in order to provide a hot melt adhesive composition having improved adhesion, watertightness, and gas barrier property, and maleic anhyderide polypropylene is poly It is produced by graft polymerization of maleic anhydride (MAH) of a hydrophilic functional group on a propylene resin. Maleic anhydride-polypropylene serves to make the constituents of the present invention uniformly dispersed and to improve adhesion. The hot melt adhesive composition of the present invention comprises 0.5 to 7% by weight of maleic anhydride-polypropylene, it is possible to prepare a hot melt adhesive composition with high heat resistance and adhesive strength in this range, which was confirmed from the following experimental example.
한편, 본 발명에서 사용되는 폐놀계 산화방지제는 본 핫멜트 접착제 조성물의 열안정성을 개선시키는 역할을 한다. 본 발명의 핫멜트 접착제 조성물은 폐놀계 산화방지제를 0.5~2 중량% 포함하는데, 0.5 중량% 미만으로 포함되는 경우에는 본 발명에서 발휘되는 산화방지제의 효과가 미미하고, 2 중량%를 초과하는 경우에는 첨가량 대비 효과증대가 미미하여 효율적이지 못하다.On the other hand, waste phenol-based antioxidant used in the present invention serves to improve the thermal stability of the hot melt adhesive composition. The hot melt adhesive composition of the present invention contains 0.5 to 2% by weight of waste-based antioxidants, when contained in less than 0.5% by weight of the antioxidant exhibited in the present invention is insignificant, when it exceeds 2% by weight It is not efficient because the effect increase is insignificant.
한편, 본 발명에서 사용되는 UV 안정제는 본 발명이 자외선에 의한 변색 및 물성의 변화 등이 일어나지 않도록 한다. 본 발명의 핫멜트 접착제 조성물은 UV 안정제를 0.1~0.7 중량% 포함하는데, 0.1중량% 미만으로 포함되는 경우에는 본 발명에서 발휘되는 산화방지제의 효과가 미미하고, 0.7 중량%를 초과하는 경우에는 첨가량 대비 효과증대가 미미하여 효율적이지 못하다.Meanwhile, the UV stabilizer used in the present invention prevents the present invention from discoloring and changing physical properties due to ultraviolet rays. The hot melt adhesive composition of the present invention contains 0.1 to 0.7% by weight of UV stabilizer, when included in less than 0.1% by weight of the antioxidant exhibited in the present invention is insignificant, when it exceeds 0.7% by weight compared to the added amount The effect increase is insignificant and inefficient.
한편, 본 발명의 핫멜트 접착제 조성물은 일예로, 자동차 헤드램프 실링용으로 사용될 수 있다.
On the other hand, the hot melt adhesive composition of the present invention, for example, can be used for automotive headlamp sealing.
상기에서 살펴본 바와 같이 본 발명의 핫멜트 접착제 조성물은 우수한 내열 크리프성 및 접착특성을 나타냄으로, 자동차 헤드램프 실링을 위한 핫멜트 접착제 조성물로서 유용하게 사용될 수 있다.
As described above, the hot melt adhesive composition of the present invention exhibits excellent heat creep resistance and adhesive properties, and thus may be usefully used as a hot melt adhesive composition for automobile headlamp sealing.
이하, 본 발명의 내용에 대해 하기 실시예에서 더욱 상세히 설명하지만, 본 발명의 권리범위가 하기 실시예에만 한정되는 것은 아니고, 이와 등가의 기술적 사상의 변형까지를 포함한다.
Hereinafter, the content of the present invention will be described in more detail in the following examples, but the scope of the present invention is not limited only to the following examples, and includes modifications of equivalent technical ideas.
실시예Example 1 내지 7: 1 to 7: 핫멜트Hot melt 접착제 조성물의 제조 Preparation of Adhesive Composition
하기 표 1에 나타낸 바와 같은 조성으로 통상의 방법에 따라 핫멜트 접착제 조성물을 제조하였다. 표 1은 핫멜트 접착제 조성물을 100중량%로 하여 각각 성분의 중량% 환산한 후, 나타낸 표이다To prepare a hot melt adhesive composition according to a conventional method with a composition as shown in Table 1 below. Table 1 shows the tables after converting the weight percent of each component to 100 wt% of the hot melt adhesive composition.
실험예Experimental Example 1: 내열 1: heat resistant 크리프성Creep Castle 및 접착특성 측정 And adhesion properties
본 실험예 1에서는 상기 실시예 1 내지 7에서 제조된 핫멜트 접착체의 내열 크리프성 및 접착특성을 측정하였다. In Experimental Example 1, the heat creep resistance and adhesion characteristics of the hot melt adhesives prepared in Examples 1 to 7 were measured.
내열 크리프성은 실시예 1 내지 실시예 7을 각각 이용하여 PC/PP 접착시킨 후, 지정온도에서 1시간 이상 방치한 다음, 200g 무게의 추를 매달고 추가 떨어질 때까지의 시간을 측정함으로써 확인하였다. Heat creep resistance was confirmed by PC / PP bonding using Examples 1 to 7, respectively, and then left at a designated temperature for at least 1 hour, and then hanging a weight of 200 g and measuring the time until further dropping.
접착특성은 실시예 1 내지 실시예 7 각각으로 접착된 PC/PP 접착 시편을 지정온도에서 1시간 이상 방치한 후, UTM으로 접착강도 및 박리율을 측정함으로써 확인하였다.Adhesion properties were confirmed by measuring the bonding strength and peeling rate by UTM after leaving the PC / PP bonded specimen bonded to each of Examples 1 to 7 at a specified temperature for 1 hour or more.
Evaluation items
200g(min)Heat Resistant Creep
200 g (min)
○: 비교적 우수한 접착 특성을 나타냄.
△: 비교적 약한 접착특성을 보임(Double-circle): It shows the outstanding adhesive characteristic.
(Circle): It shows comparatively outstanding adhesive property.
Δ: relatively weak adhesion
측정결과(표 2), 실시예 1 내지 실시예 7은 무수말레인산-폴리프로필렌의 첨가량이 증가할수록 내열 크리프성 및 접착특성이 증가하는 것을 확인할 수 있었고, 대체적으로 우수한 내열 크리프성 및 접착특성을 나타냄을 확인할 수 있었다.
As a result of the measurement (Table 2), Examples 1 to 7 showed that heat creep resistance and adhesive properties increased as the amount of maleic anhydride-polypropylene increased. Could confirm.
본 발명의 핫멜트 접착제 조성물은 우수한 내열 크리프성 및 접착특성을 가져 자동차 헤드램프의 장시간 점등시에 하우징과 렌즈의 접착성이 우수하여 수밀성 및 가스 차단성이 개선되는데, 자동차 헤드램프 실링을 위한 핫멜트 접착제 조성물로서 유용하게 사용될 수 있다.The hot melt adhesive composition of the present invention has excellent heat creep resistance and adhesive properties, and has excellent adhesiveness between the housing and the lens when the automobile headlamp is turned on for a long time, thereby improving watertightness and gas barrier property. It can be usefully used as a composition.
Claims (3)
Butyl rubber 14.5-14.7 weight%; Ethylene propylene rubber (EPDM rubber) 14.5-14.7 wt%; 9.6 to 9.8 wt% of a styrene block copolymer comprising styrene (Isoprene-Styrene) rubber; 7.7 to 7.9% by weight of amorphous poly-alpha-olefins (APAO); Aliphatic petroleum resin 19.4 to 19.7 wt% as a tackifying resin; 9.6 to 9.9 wt% rosin ester as a tackifying resin; Terpene resin 9.6 to 9.9 wt% as the tackifying resin; 9.6 to 9.9 weight percent of a plasticizer including polyisobutylene; Maleic anhyderide polypropylene 2 to 4 wt%; Phenolic antioxidant 0.5 to 1% by weight; And UV stabilizer 0.1 ~ 0.5% by weight; Hot melt adhesive composition comprising a.
핫멜트 접착제 조성물은,
자동차 헤드램프 실링용인 것을 특징으로 하는 핫멜트 접착제 조성물.The method of claim 1,
Hot melt adhesive composition,
Hot melt adhesive composition for automotive headlamp sealing.
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| KR1020100023803A KR101174019B1 (en) | 2010-03-17 | 2010-03-17 | Hotmelt adhesive composition |
| JP2010068365A JP2011195797A (en) | 2010-03-17 | 2010-03-24 | Hot melt adhesive composition |
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| KR1020100023803A KR101174019B1 (en) | 2010-03-17 | 2010-03-17 | Hotmelt adhesive composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019004675A1 (en) | 2017-06-30 | 2019-01-03 | 코오롱인더스트리 주식회사 | Curable petroleum resin, preparation method therefor, and use thereof |
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| US11655398B2 (en) | 2016-06-30 | 2023-05-23 | Kolon Industries, Inc. | Curable petroleum resin, preparation method therefor, and use thereof |
| US10954420B2 (en) | 2016-09-27 | 2021-03-23 | Kolon Industries, Inc. | Curable modified petroleum resin, and preparation method and use thereof |
| WO2019004675A1 (en) | 2017-06-30 | 2019-01-03 | 코오롱인더스트리 주식회사 | Curable petroleum resin, preparation method therefor, and use thereof |
| US11499068B2 (en) | 2017-06-30 | 2022-11-15 | Kolon Industries, Inc. | Curable petroleum resin, preparation method thereof, and use thereof |
| KR101965382B1 (en) | 2018-06-05 | 2019-04-03 | (주)포브코리아 | Hot melt adhesive film for transcription and manufacturing method thereof and goods using thereof |
| KR20230096423A (en) | 2021-12-23 | 2023-06-30 | 단국대학교 산학협력단 | Low density polyolefin resin adhesive composition and encapsulant film for photovoltaic module using the composition |
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| Publication number | Publication date |
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| KR20110104732A (en) | 2011-09-23 |
| JP2011195797A (en) | 2011-10-06 |
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