KR20180024884A - Adhesion promoter composition for acrylic foam tape having excellent adhesion strength - Google Patents
Adhesion promoter composition for acrylic foam tape having excellent adhesion strength Download PDFInfo
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- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
- C08L45/02—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers of coumarone-indene polymers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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Abstract
Description
본 발명은 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물에 관한 것으로, 보다 구체적으로는 폴리올레핀계 소재의 자동차용 부품에 아크릴 폼 테이프의 접착 시, 그 접착강도를 향상시키고, 또한 톨루엔과 같은 극성 유기용제를 함유하지 않아 작업환경을 개선시킬 수 있는 등 환경친화적인 아크릴 폼 테이프용 접착증진제 조성물에 관한 것이다.
The present invention relates to an adhesion promoter composition for an acrylic foam tape having excellent adhesion strength, and more specifically relates to a composition for improving adhesion strength of an acrylic foam tape to an automobile part of a polyolefin material, And an environmentally friendly adhesion promoting composition for an acrylic foam tape, which can improve a working environment without containing a solvent.
일반적으로 자동차용 부품의 소재인 열가소성 올레핀 플라스틱(thermoplastic olefin elastomer,TPO)계, 폴리올레핀(polyolefin)계(PE(polyethylene), PP(polypropylene) 등), 열가소성 엘라스토머(thermoplastic elastomer), 에틸렌 프로필렌 디엔 고무계(ethylene propylene diene monomer, EPDM) 또는 폴리스티렌계(polystyren, PS)는 다양한 유형의 소비재용 구조의 소재로서 사용이 꾸준히 증가하고 있다. 특히 폴리에틸렌(PE)은 비교적 불활성, 가요성, 수증기의 불침투성, 경량성, 내구성의 주요한 물성을 나타내며 비교적 저렴하게 생산될 수 있기 때문에 장난감, 용기, 포장 필름, 가정용 가전제품의 제조 및 특히 자동차 산업에서 널리 사용되고 있다.
In general, thermoplastic olefin elastomer (TPO), polyolefin (PE (polyethylene), polypropylene (PP), etc.), thermoplastic elastomer, ethylene propylene diene rubber ethylene propylene diene monomer (EPDM), or polystyrene (polystyrenes, PS) have been steadily increasing in use as materials for various types of consumer products. In particular, since polyethylene (PE) exhibits relatively inert, flexible, water impermeability, light weight, and durability, and is capable of being produced at relatively low cost, it can be used in the manufacture of toys, containers, packaging films, household appliances, Is widely used.
아울러, 상기와 같은 자동차용 부품 소재 중에서 도 1에 도시된 바와 같이, 자동차의 부품(자동차의 엔진 격실(engine compartment), 차체(body), 차내 실내공간의 인테리어 등)에 사용되고 있는 폴리올레핀계(PE, PP) 부품, 에틸렌 프로필렌 디엔 고무계(EPDM) 부품과 열가소성 올레핀 플라스틱계(TPO) 부품 등은 하이드로카본 형태로 되어 있기 때문에 표면극성이 낮아서 젖음성, 접착성, 인쇄성 등이 떨어지는 문제점이 있다.
In addition, as shown in FIG. 1, a polyolefin-based (PE) material used for parts of an automobile (an engine compartment of a vehicle, a body, and an interior of a vehicle interior) , PP) parts, ethylene propylene diene rubber (EPDM) parts and thermoplastic olefin plastics (TPO) parts are in the form of hydrocarbons, so that the surface polarity is low and the wettability, adhesiveness and printability are poor.
그리고, 상기와 같은 폴리올레핀계 자동차 부품과 접착되는 아크릴 폼 테이프의 아크릴 점착제는 극성을 가지므로 어느 정도의 접착력으로 붙을 수 있도록 표면 극성을 갖는 표면을 필요로 한다. 이에 접착증진제를 도포하여 표면의 특성을 변화시키고 있으며, 현재, 도 2에 도시된 바와 같이, 폴리올레핀계 자동차 부품(10) 등의 표면에 접착증진제(20)를 도포하여 그 표면 특성을 변화시킨 후 아크릴 폼 테이프(30)를 부착하여 자동차용 부품을 조립하고 있다.
The acrylic pressure-sensitive adhesive of the acrylic foam tape adhered to the polyolefin-based automobile parts as described above has a polarity, and thus a surface having a surface polarity is required so that it can be adhered with a certain degree of adhesion. As shown in Fig. 2, the surface of the polyolefin-based
한편, 상기 접착증진제와 관련된 선행기술로써, 특허문헌 1에서는 한가지 이상의 염소화 폴리올레핀 10~30 중량%, 톨루엔 및/또는 크실렌과 같은 방향족 용매 15~50 중량%, 한가지 이상의 유화제 1~6 중량%, 및 물 24~64 중량%를 함유하는 프라이머에 관한 것으로, 상기 특허문헌 1과 같은 종래의 프라이머는 톨루엔을 포함한 극성 유기용제를 함유하고 있는 것이 대부분으로 톨루엔을 장시간 사용할 경우 작업 환경 조건을 열악하게 하며 작업자의 인체에 악영향을 미치는 문제점이 있다.
On the other hand, as a prior art related to the above-mentioned adhesion promoting agent, Patent Document 1 discloses that 10 to 30% by weight of at least one chlorinated polyolefin, 15 to 50% by weight of an aromatic solvent such as toluene and / or xylene, 1 to 6% by weight of at least one emulsifier, And 24 to 64% by weight of water. Conventional primers such as the above-mentioned Patent Document 1 contain a polar organic solvent including toluene. When toluene is used for a long time, the working environment is poor, Which adversely affects the human body.
또한, 특허문헌 2에서는 하나 이상의 접착력 증진제, 하나 이상의 에틸렌형 불포화 단량체, 하나 이상의 계면활성제 및 물을 포함하는 혼합물을 전단가공(shearing)하여 미니-에멀젼(mini-emulsion)을 제조하는 단계 및, 단량체-가용성 개시제의 존재 하에 상기 미니-에멀젼을 중합시켜 수성 조성물을 제조하는 단계를 포함하여 이루어지는 접착증진제를 제안하였으나, 이 역시 톨루엔을 포함한 극성 유기용제를 함유하고 있다.
In addition, Patent Document 2 discloses a process for producing a mini-emulsion by shearing a mixture comprising at least one adhesion promoting agent, at least one ethylenically unsaturated monomer, at least one surfactant and water, - polymerizing the mini-emulsion in the presence of a solubilizing initiator to produce an aqueous composition, which also contains a polar organic solvent comprising toluene.
즉, 기존 접착증진제는 조성 중에 접착력, 젖음성 및 용해도 향상을 위해서 톨루엔을 포함하고 있으므로 장시간 사용할 경우에 작업자의 건강을 해치고 있고 또한 최근들어 휘발성 유기 물질(volatile organic compound, VOC)의 사용 규제와 같은 환경보전에 대한 요구가 증가되고 있다.
In other words, existing adhesion promoters contain toluene in order to improve adhesion, wettability and solubility in the composition. Therefore, they are detrimental to the health of workers when they are used for a long period of time, and in recent years, such as the regulation of the use of volatile organic compounds (VOC) There is a growing demand for conservation.
한편, 일반적으로 접착증진제가 사용되는 접착에서는 고체표면에 대한 액체의 젖음성이 우수한 접착을 위한 필수조건이라고 볼 수 있으며 액체의 표면장력 (surface tension)이 고체의 표면장력보다 낮을 때 젖음이 가능해진다. 고분자 고체 표면에 대한 젖음성(wettability)을 알기 위하여 고체와 액체간의 접촉각(contact angle)을 측정하게 되는데, 이 때 액체 분자들이 고체-액체 계면에 흡착되어 접촉각과 임계표면장력 (critical surface tension, γc)에 영향을 미친다. 또한 γL(액체의 표면장력)이 γc에 근접하여 어느 정도 젖음(wetting)이 이루어질 경우, 고체-액체간의 상용성이 좋을수록 접착력이 커지게 되는데 상용성은 고체와 액체의 용해도 파라미터가 유사할수록 좋아져 용해도 파라미터(solubility parameter, SP)가 접착력에 영향을 주는 또 하나의 요인이라 할 수 있으며, 이로인해 접착에 영향을 주는 이들 요인을 고려하여 적절한 분자설계를 통한 저독성 용제형 시스템의 새로운 접착증진제가 요구되고 있다.
On the other hand, in the case of bonding using an adhesion promoter, the wetting property of the liquid to the solid surface is considered to be an essential condition for adhesion, and the wetting becomes possible when the surface tension of the liquid is lower than the surface tension of the solid. In order to know the wettability of the polymer solid surface, the contact angle between the solid and the liquid is measured. At this time, the liquid molecules are adsorbed on the solid-liquid interface, and the contact angle and the critical surface tension (γ c ). Further, when γ L (surface tension of the liquid) is close to γ c and wetting is performed to some extent, the better the compatibility between the solid and the liquid, the greater the adhesive strength. The more the solubility parameters of the solid and the liquid are The solubility parameter (SP) is another factor that affects the adhesive strength. Considering these factors affecting adhesion, a new adhesion promoter of a low toxicity solvent system through appropriate molecular design Is required.
따라서, 본 발명은 상술한 문제점을 해결하기 위하여 폴리올레핀계 소재의 자동차용 부품에 아크릴 폼 테이프의 접착 시, 그 접착강도를 향상시시킬 뿐만 아니라 특히 톨루엔과 같은 극성 유기용제를 함유하지 않아 작압환경을 개선시킬 수 있는 등 환경친화적인 아크릴 폼 테이프용 접착증진제 조성물을 제공함을 과제로 한다.
Accordingly, in order to solve the above-described problems, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a polyolefin- The present invention also provides an adhesion promoting composition for an acrylic foam tape.
본 발명은 접착증진제 조성물에 있어서, 폴리아미드(polyamide) 수지 1 ~ 3 중량%, CPO(chlorinated polyolefin) 수지 2 ~ 6 중량%, 열가소성 폴리우레탄(thermo plastic polyurethane) 수지 0.5 ~ 1.5 중량%, 점착부여제 0.5 ~ 1.5 중량% 및 용제 88 ~ 96 중량%로 이루어지는 것을 특징으로 하는, 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물을 과제의 해결 수단으로 한다.
The present invention relates to an adhesion promoter composition comprising 1 to 3 wt% of a polyamide resin, 2 to 6 wt% of a chlorinated polyolefin (CPO) resin, 0.5 to 1.5 wt% of a thermoplastic polyurethane resin, And 0.5 to 1.5% by weight of a binder, and 88 to 96% by weight of a solvent. The adhesion promoter composition for an acrylic foam tape having excellent adhesion strength is a solution to the problem.
여기서, 상기 폴리아미드 수지는, 다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 150 ~ 200 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 100 ~ 150 중량부로 이루어지는 것이 바람직하다.
The polyamide resin may include 150-200 parts by weight of soyabean oil (SOFA) and 100-150 parts by weight of tetraethylenepentamine (TEPA) relative to 100 parts by weight of dimer acid desirable.
그리고, 상기 점착부여제는, 석유수지, 알킬페놀(alkylphenol)수지, 로진(rosin), 로진에스테르(rosin ester)수지 또는 쿠마론인덴(Coumaroneindene)수지 중에서 단독 또는 2종 이상 병용하여 사용하는 것이 바람직하다.
It is preferable that the tackifier is used alone or in combination of two or more among petroleum resins, alkylphenol resins, rosin, rosin ester resins or coumaroneindene resins Do.
아울러, 상기 용제는, 메틸에틸케톤(methylethylketone), 에틸아세테이트(ethylacetate), 싸이클로헥산(cyclohexane), 아세톤(Acetone), 이소프로필알콜(isopropylalcohol) 또는 메틸싸이클로헥산(methylcyclohexane)으로 이루어진 군에서 3종 이상 병용하여 사용하는 것이 바람직하다.
The solvent may be at least one selected from the group consisting of methylethylketone, ethylacetate, cyclohexane, acetone, isopropylalcohol, and methylcyclohexane. It is preferable to use them in combination.
본 발명은 접착증진제와 아크릴 폼 테이프와의 상호작용을 고려한 분자설계로부터 조성물의 종류와 조성비를 선정하여 접착 개선효과를 구현하고, 특히 톨루엔과 같은 극성용제를 제외한 용제를 사용하여 작업환경을 개선시키고 환경친화적인 접착증진제를 제공하면서도 피착재(폴리올레핀계 소재의 자동차용 부품 등) 및 아크릴 폼 테이프와의 상용성 개선시킬 뿐만 아니라 피착재의 표면 및 난접착재질 표면과 아크릴 폼 테이프와의 젖음성을 개선하여 접착력을 향상시킬 수 있는 효과가 있다.
The present invention improves adhesion by selecting the kind and composition ratio of the composition from the molecular design considering the interaction between the adhesion promoter and the acrylic foam tape and improves the working environment by using a solvent other than a polar solvent such as toluene (Such as automobile parts of polyolefin material) and acrylic foam tape while improving the wettability between the surface of the adherend material and the surface of the adhesive material and the acrylic foam tape while providing an environmentally friendly adhesion promoter The adhesive strength can be improved.
아울러, 기존 외산 제품에 의존하고 있는 자동차 부품용 접착증진제를 국선화시킴으로써 지속적인 기술 경쟁력 확보와 시장 점유를 유지할 수 있는 토대를 마련할 수 있을 것으로 판단되며, 본 발명을 통해 자동차용 부품 뿐만 아니라 다양한 재료의 접착에 적용할 수 있어 외산 제품과 비교하여 원가경쟁력을 보유함은 물론 사업화를 할 때에 부가가치 또한 높은 효과를 구현한다. 아울러, 휘발성 유기 물질에 관한 환경규제가 EU 국가 뿐 아니라, 미국, 중국도 규제 확대에 가세하고 있는 추세에 따라 국내는 물론 전 세계적으로 규제가 일반화될 경우에 시장규모가 크게 증가할 것으로 예상되며 아울러 전량 수입에 의존하는 접착증진제의 수입 대체 및 그에 따른 수출증대, 무역역조 개선 등의 파급효과가 기대된다.
In addition, it will be possible to establish a basis for securing continuous technological competitiveness and maintaining market share by curbing adhesion promoting agent for automobile parts which relies on existing foreign products. Through this invention, not only automobile parts but also various materials It is not only cost competitiveness compared to foreign products, but also has a high added value when commercialized. In addition, as the environmental regulations on volatile organic substances are increasingly being extended not only by EU countries but also by the United States and China, the market size is expected to increase significantly when the regulations are generalized both domestically and globally. It is expected to have a ripple effect such as import substitution of importing agent which depends on imports all over the world, increase in exports and improvement of trade inverse.
도 1은 아크릴 폼 테이프의 자동차 적용 사례를 나타낸 도면
도 2는 접착증진제를 매개로 한 폴리올레핀계 자동차 부품과 아크릴 폼 테이프의 접착구조를 나타낸 모식도1 is a view showing an application example of an acrylic foam tape to an automobile
Fig. 2 is a schematic view showing a bonding structure of a polyolefin automobile part and an acrylic foam tape through an adhesion promoter
이하, 본 발명의 바람직한 실시 예를 상세히 설명하며, 상세한 설명에서 일반적인 코팅제 조성물 제조분야의 종사자들이 용이하게 알 수 있는 구성 및 작용에 대한 언급은 간략히 하거나 생략하였다.
Hereinafter, preferred embodiments of the present invention will be described in detail. In the detailed description, the construction and operation of the coating composition composition of the present invention will be briefly described or omitted.
본 발명에 따른 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물은 폴리아미드(polyamide) 수지 1 ~ 3 중량%, CPO(chlorinated polyolefin) 수지 2 ~ 6 중량%, 열가소성 폴리우레탄(thermo plastic polyurethane) 수지 0.5 ~ 1.5 중량%, 점착부여제 0.5 ~ 1.5 중량% 및 용제 88 ~ 96 중량%로 이루어지는 것을 특징으로 하며, 고형분이 10 중량% 이하가 되도록 하는 것이 바람직하지만 여기에 한정되는 것은 아니다.
The adhesion promoter composition for an acrylic foam tape having excellent adhesion strength according to the present invention comprises 1 to 3% by weight of a polyamide resin, 2 to 6% by weight of a chlorinated polyolefin (CPO) resin, 0.5 to 10% by weight of a thermoplastic polyurethane resin By weight to 1.5% by weight, a tackifier of 0.5 to 1.5% by weight, and a solvent of 88 to 96% by weight. The solid content is preferably 10% by weight or less, but is not limited thereto.
상기 폴리아미드 수지는 내열성, 내약품성 및 내마모성 등이 뛰어난 폴리아미드로 된 열가소성 수지로써 본 발명에서는 다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 150 ~ 200 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 100 ~ 150 중량부로 폴리아미드 수지를 제조한다.
The polyamide resin is a polyamide thermoplastic resin having excellent heat resistance, chemical resistance and abrasion resistance. In the present invention, 150 to 200 parts by weight of soyabean oil (SOFA) is added to 100 parts by weight of dimer acid, A polyamide resin is prepared with 100 to 150 parts by weight of tetraethylenepentamine (TEPA).
보다 구체적으로 상기 폴리아미드 수지는 반응기(파샬콘덴서와 수직콘덴서를 구비하고, 상하단측에 열매를 보유한 이미 공지된 통상의 반응기(제조사 : DURAN사 / 제품명 : PYREX))에 질소기류하에 상기 다이머산, 대두유 지방산 및 테트라에틸렌펜타민을 투입후 서서히 교반하고, 열매(熱媒)를 이용하여 150℃로 승온시킨다. 이때 승온 중 150℃ 전후에서 탈수반응이 진행되고 탈수반응 진행 후 160℃에서 1시간을 유지한다(이때 반응기 파샬콘덴서의 Top온도는 100 ~ 104℃로 유지되도록 승온속도를 조정한다.). 그리고 160℃에서 200℃로 승온이 2시간동안 되도록 조정한다. 아울러 200℃에서 반응기의 상단 열매를 차단하고 하단 열매로 220℃로 승온하되 215℃되었을때 산가 및 아민가를 체크(AV(acid value)=2↓, AMV(amin value)= 285~305)한 후, 최종 220℃로 승온되었을 때, 수직콘덴서로 교체하고 탈수량을 체크(320±10㎏)한다. 그리고 220℃에서 진공압력을 700~720mmHg로 높이고 30분 동안 미반응물을 회수(160±5㎏)한 후 질소를 투입하여 진공을 해제하여 반응물을 수득하고 산가, 아민가 및 점도가 규격에 맞는지 측정(점도 - 1800±500 cps/25℃, 산가(AV) - 7 KOHmg/g)↓, 아민가(AMV) - 300±30)한 후 80℃이하로 냉각하여 제조한다.
More specifically, the polyamide resin is prepared by reacting a polyamide resin in a reactor (a well-known conventional reactor having a partial condenser and a vertical condenser and having a heat storage at the upper and lower ends) (manufactured by DURAN Co., Ltd. under the trade name of PYREX) Soybean oil fatty acid and tetraethylenepentamine are added and stirred slowly, and the mixture is heated to 150 ° C using a heat medium. At this time, the dehydration reaction proceeds at around 150 ° C. during the temperature rise, and after the dehydration reaction proceeds, the temperature is maintained at 160 ° C. for 1 hour. (At this time, the temperature of the reactor is adjusted so that the top temperature of the partial condenser of the reactor is maintained at 100~104 ° C.). And the temperature is raised from 160 ° C to 200 ° C for 2 hours. The upper end of the reactor was blocked at 200 ° C. and the temperature was raised to 220 ° C. as the bottom product. At 215 ° C., the acid value and amine value were checked (AV value = 2 ↓, AMV value = 285~305) When the temperature is finally raised to 220 ° C, replace with a vertical condenser and check the amount of dehydration (320 ± 10 kg). Then, the vacuum pressure was increased to 700~720 mmHg at 220 ° C., and the unreacted material was recovered (160 ± 5 kg) for 30 minutes. Then, the vacuum was released by introducing nitrogen to obtain a reaction product and the acid value, amine value and viscosity were measured Viscosity - 1800 ± 500 cps / 25 ℃, acid value (AV) - 7 KOHmg / g) ↓, amine value (AMV) - 300 ± 30) and cooled to below 80 ℃.
한편, 상기 폴리아미드 수지의 제조방법은 이미 공지된 제조방법으로써 상기 방법 이외에 이미 공지된 다양한 방법을 적용할 수 있다.
On the other hand, the polyamide resin can be produced by a well known method other than the method described above.
그리고, 상기 다이머산, 대두유 지방산 및 테트라에틸렌펜타민의 함량이 상기 범위를 벗어날 경우 폴리아미드가 제대로 제조되지 않을 우려가 있으며, 상기와 같이 제조된 폴리아미드 수지의 함량이 1 중량% 미만으로 첨가될 경우 접착강도의 향상효과가 미비해질 우려가 있으며, 3 중량%를 초과할 경우 접착증진제에 대한 용해도가 저하될 우려가 있다.
If the content of the dimer acid, soybean oil fatty acid and tetraethylene pentamine is out of the above range, the polyamide may not be produced properly. If the content of the polyamide resin is less than 1% by weight There is a possibility that the effect of improving the bonding strength is insufficient. When the amount exceeds 3% by weight, the solubility in the adhesion promoting agent may be lowered.
상기 CPO 수지 및 열가소성 폴리우레탄 수지는 접착증진제에 대한 접착력을 부여하기 위한 것으로, CPO 수지의 경우 2 ~ 6 중량%가 사용되는데 그 사용량이 2 중량% 미만일 경우 접착력 향상효과가 미비해질 우려가 있으며 6 중량%를 초과할 경우 점도가 상승하여 작업성이 저하될 우려가 있다. 아울러 열가소성 폴리우레탄 수지의 경우 0.5 ~ 1.5 중량%가 사용되는데 이 역시 0.5 중량% 미만일 경우 접착력 향상효과가 미비해질 우려가 있으며 1.5 중량%를 초과할 경우 점도가 상승하여 작업성이 저하될 우려가 있다.
The CPO resin and the thermoplastic polyurethane resin are used for imparting an adhesive strength to the adhesion promoter. When the amount of the CPO resin is less than 2% by weight, the adhesion improving effect may be insufficient. If the amount is more than 10% by weight, the viscosity may increase and the workability may be deteriorated. In addition, in the case of the thermoplastic polyurethane resin, 0.5 to 1.5% by weight is used. If it is less than 0.5% by weight, the effect of improving the adhesive strength may be insufficient. If it exceeds 1.5% by weight, the viscosity may increase, .
한편, 상기 CPO 수지의 경우 염소화폴리올레핀 수지로써 HARDLEN® CY-9124P(toyo kasei kogyo 사) 또는 SUPERCHLON® 930S(nippon paper chemicals 사) 등을 병용(예를들면 HARDLEN® CY-9124P 1 ~ 3 중량% + SUPERCHLON® 930S 1 ~ 3 중량%)하여 사용할 수도 있지만 여기에 한정되는 것은 아니고 이미 공지된 다양한 CPO 수지를 적용할 수 있다.
On the other hand, a combination of the case of a CPO resin HARDLEN ® CY-9124P (toyo kasei kogyo Co.) or SUPERCHLON ® 930S (nippon paper chemicals Inc.) as a chlorinated polyolefin resin, and the like (e.g. HARDLEN ® CY-9124P 1 ~ 3% by weight + SUPERCHLON ® 930S 1 to 3% by weight). However, the present invention is not limited thereto, and various well known CPO resins may be used.
상기 점착부여제는 피착재에 대한 표면 젖음성 및 접착성 증가를 위해 첨가되는 것으로, 석유수지, 알킬페놀(alkylphenol)수지, 로진(rosin), 로진에스테르(rosin ester)수지 또는 쿠마론인덴(Coumaroneindene)수지 중에서 단독 또는 2종 이상 병용하여 사용한다. 한편, 상기 점착부여제의 함량이 0.5 중량% 미만일 경우 표면 젖음성의 증가효과를 얻기 어려우며, 1.5 중량%를 초과할 경우 저장안정성이 저하될 우려가 있다.
The tackifier is added for increasing the surface wettability and adhesiveness to the adherend, and it can be a petroleum resin, alkylphenol resin, rosin, rosin ester resin or coumaroneindene, These resins are used alone or in combination of two or more. On the other hand, when the content of the tackifier is less than 0.5% by weight, it is difficult to obtain the effect of increasing the surface wettability. When the content exceeds 1.5% by weight, the storage stability may be deteriorated.
상기 용제는 접착증진제의 고형분이 10 중량% 이하가 되도록 점도를 조절하기 위해 첨가되는 것으로 용제의 함량이 상기 범위를 벗어날 경우 접착증진제로써의 기능이 미비하거나 작업성이 저하될 우려가 있다. 이때, 본 발명에서는 톨루엔을 함유하지 않기 때문에 그 용해도가 현저히 떨어지므로 용제를 3종 이상 사용하는 것이 바람직하며, 일예로 메틸에틸케톤(methylethylketone), 에틸아세테이트(ethylacetate), 싸이클로헥산(cyclohexane), 아세톤(Acetone), 이소프로필알콜(isopropylalcohol) 또는 메틸싸이클로헥산(methylcyclohexane)으로 이루어진 군에서 3종 이상 병용하여 사용할 수 있다.
The solvent is added to adjust the viscosity so that the solid content of the adhesion promoter is 10 wt% or less. When the content of the solvent is out of the above range, the function as the adhesion promoter may be insufficient or the workability may be deteriorated. At this time, since the present invention does not contain toluene, its solubility is significantly lowered. Therefore, it is preferable to use three or more kinds of solvents. For example, methyl ethyl ketone, ethylacetate, cyclohexane, (Acetone), isopropylalcohol, or methylcyclohexane, may be used in combination of three or more.
이하, 본 발명을 실시예를 들면서 상세히 설명하는바 본 발명이 다음의 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
1. 접착증진제의 제조
1. Preparation of Adhesion Enhancer
(실시예 1)(Example 1)
온도조절과 속도조절이 가능한 혼합용기에 폴리아미드 수지 3 중량%, CPO 수지 6 중량%, 열가소성 폴리우레탄 수지 1.5 중량%, 점착부여제 1.5 중량% 및 용제 88 중량%를 투입하고, 50℃의 온도에서 8시간 교반, 용해시켜 접착증진제를 제조하였다. 3% by weight of a polyamide resin, 6% by weight of a CPO resin, 1.5% by weight of a thermoplastic polyurethane resin, 1.5% by weight of a tackifier and 88% by weight of a solvent were fed into a mixing container capable of controlling temperature and speed, For 8 hours to prepare an adhesion promoting agent.
여기서 상기 폴리아미드 수지는 다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 150 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 100 중량부로 폴리아미드 수지를 제조하였고, 상기 CPO 수지는 CPO-1(HARDLEN® CY-9124P) 3 중량% 및 CPO-2 930S(SUPERCHLON® 930S) 3 중량%를 혼용하여 사용하였으며, 상기 점착부여제는 석유수지인 SU-120(코오롱인더스트리 사)를 사용하였다. 그리고 상기 용제는 메틸에틸케톤, 에틸아세테이트 및 사이클로헥산을 1.5 : 1 : 2.5 중량비로 병용한 용제를 사용하였다.
The polyamide resin was prepared by preparing 150 parts by weight of soyabean oil (SOFA) and 100 parts by weight of tetraethylenepentamine (TEPA) based on 100 parts by weight of dimer acid, 3% by weight of CPO-1 (HARDLEN 占 CY-9124P) and 3% by weight of CPO-2 930S (SUPERCHLON 占 930S) were used in combination. The tackifier was a petroleum resin SU-120 (manufactured by Kolon Industries, ) Was used. A solvent in which methyl ethyl ketone, ethyl acetate and cyclohexane were used together at a weight ratio of 1.5: 1: 2.5 was used as the solvent.
(실시예 2)(Example 2)
온도조절과 속도조절이 가능한 혼합용기에 폴리아미드 수지 2 중량%, CPO 수지 6 중량%, 열가소성 폴리우레탄 수지 1.0 중량%, 점착부여제 1.0 중량% 및 용제 90 중량%를 투입하고, 50℃의 온도에서 8시간 교반, 용해시켜 접착증진제를 제조하였다. 2% by weight of a polyamide resin, 6% by weight of a CPO resin, 1.0% by weight of a thermoplastic polyurethane resin, 1.0% by weight of a tackifier and 90% by weight of a solvent were introduced into a mixing vessel capable of controlling temperature and speed, For 8 hours to prepare an adhesion promoting agent.
여기서 상기 폴리아미드 수지는 다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 176 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 142 중량부로 폴리아미드 수지를 제조하였고, 상기 CPO 수지는 CPO-1(HARDLEN® CY-9124P) 3 중량% 및 CPO-2 930S(SUPERCHLON® 930S) 3 중량%를 혼용하여 사용하였으며, 상기 점착부여제는 석유수지인 SU-120(코오롱인더스트리 사)를 사용하였다. 그리고 상기 용제는 메틸에틸케톤, 에틸아세테이트 및 사이클로헥산을 1.5 : 1 : 2.5 중량비로 병용한 용제를 사용하였다.
The polyamide resin was prepared from polyamide resin with 176 parts by weight of soyabean oil (SOFA) and 142 parts by weight of tetraethylenepentamine (TEPA) based on 100 parts by weight of dimer acid, 3% by weight of CPO-1 (HARDLEN 占 CY-9124P) and 3% by weight of CPO-2 930S (SUPERCHLON 占 930S) were used in combination. The tackifier was a petroleum resin SU-120 (manufactured by Kolon Industries, ) Was used. A solvent in which methyl ethyl ketone, ethyl acetate and cyclohexane were used together at a weight ratio of 1.5: 1: 2.5 was used as the solvent.
(실시예 3)(Example 3)
온도조절과 속도조절이 가능한 혼합용기에 폴리아미드 수지 1 중량%, CPO 수지 2 중량%, 열가소성 폴리우레탄 수지 0.5 중량%, 점착부여제 0.5 중량% 및 용제 96 중량%를 투입하고, 50℃의 온도에서 8시간 교반, 용해시켜 접착증진제를 제조하였다. 1% by weight of a polyamide resin, 2% by weight of a CPO resin, 0.5% by weight of a thermoplastic polyurethane resin, 0.5% by weight of a tackifier and 96% by weight of a solvent were fed into a mixing container capable of controlling temperature and speed, For 8 hours to prepare an adhesion promoting agent.
여기서 상기 폴리아미드 수지는 다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 200 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 50 중량부로 폴리아미드 수지를 제조하였고, 상기 CPO 수지는 CPO-1(HARDLEN® CY-9124P) 1 중량% 및 CPO-2 930S(SUPERCHLON® 930S) 1 중량%를 혼용하여 사용하였으며, 상기 점착부여제는 석유수지인 SU-120(코오롱인더스트리 사)를 사용하였다. 그리고 상기 용제는 메틸에틸케톤, 에틸아세테이트 및 사이클로헥산을 1.5 : 1 : 2.5 중량비로 병용한 용제를 사용하였다.
The polyamide resin was prepared by preparing polyamide resin with 200 parts by weight of soybean oil (SOFA) and 50 parts by weight of tetraethylenepentamine (TEPA) per 100 parts by weight of dimer acid, CPO resin CPO-1 (HARDLEN ® CY- 9124P) 1 wt% and CPO-2 930S (SUPERCHLON ® 930S ) was used by mixing 1 wt%, the tackifier is a SU-120 petroleum resin (Kolon Industries Inc. ) Was used. A solvent in which methyl ethyl ketone, ethyl acetate and cyclohexane were used together at a weight ratio of 1.5: 1: 2.5 was used as the solvent.
(비교예 1)(Comparative Example 1)
3M 사에서 제조 및 판매되고 있는 K-520K 제품을 사용하였다.
The K-520K manufactured and sold by 3M Company was used.
2. 접착증진제의 평가
2. Evaluation of adhesion promoter
상기 실시예 1 내지 3 및 비교예 1에 따른 접착증진제에 대한 불휘발분(wt%), 점도(cps), 접착강도(N/25mm), 톨루엔 함량(mg/kg) 및 저장안정성(day)을 평가하였으며, 시험규격 및 결과는 아래 [표 1]에 나타내었다.
(Wt%), viscosity (cps), adhesive strength (N / 25 mm), toluene content (mg / kg) and storage stability (day) of the adhesion promoter according to Examples 1 to 3 and Comparative Example 1 The test specifications and results are shown in [Table 1] below.
(시료수)Test Specification
(sample water)
(5개)KS M 3705
(5)
(5개)KS M 3708
(5)
(5개)KS T 1028
(5)
(5개)KS M 1993
(5)
점도평가Visual and
Viscosity evaluation
상기 [표 1]에서와 같이 본 발명의 실시예 1 내지 3에 따른 접착증진제는 비교예 1에 따른 접착증진제에 비하여 불휘발분(wt%), 점도(cps), 접착강도(N/25mm), 톨루엔 함량(mg/kg) 및 저장안정성(day)이 모두 우수함을 알 수 있으며, 이로 인해 폴리올레핀계 소재의 자동차용 부품에 아크릴 폼 테이프의 접착 시, 그 접착강도를 향상시시킬 뿐만 아니라 특히 톨루엔과 같은 극성 유기용제를 함유하지 않아 작압환경을 개선시킬 수 있는 등 환경친화적임을 알 수 있다.
As shown in Table 1, the adhesion promoting agents according to Examples 1 to 3 of the present invention had non-volatile matter (wt%), viscosity (cps), adhesion strength (N / 25 mm) It can be seen that the toluene content (mg / kg) and the storage stability (day) are both excellent, thereby improving not only the adhesion strength of the acrylic foam tape to automobile parts of polyolefin materials, It is possible to improve the environment in which the pressure is suppressed because it does not contain the same polar organic solvent.
상술한 바와 같은, 본 발명의 바람직한 실시 예에 따른 접착강도가 우수한 아크릴 폼 테이프용 접착증진제을 설명하였지만, 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.
While the present invention has been described in connection with the preferred embodiments thereof with reference to the accompanying drawings, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the appended claims. It will be appreciated by those of ordinary skill in the art that this is possible.
10 : 폴리올레핀계 자동차 부품
20 : 접착증진제
30 : 아크릴 폼 테이프10: Polyolefin-based automobile parts
20: Adhesion enhancer
30: Acrylic foam tape
Claims (4)
폴리아미드(polyamide) 수지 1 ~ 3 중량%, CPO(chlorinated polyolefin) 수지 2 ~ 6 중량%, 열가소성 폴리우레탄(thermo plastic polyurethane) 수지 0.5 ~ 1.5 중량%, 점착부여제 0.5 ~ 1.5 중량% 및 용제 88 ~ 96 중량%로 이루어지는 것을 특징으로 하는, 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물.
In the adhesion promoter composition,
1 to 3 wt% of a polyamide resin, 2 to 6 wt% of a chlorinated polyolefin (CPO) resin, 0.5 to 1.5 wt% of a thermoplastic polyurethane resin, 0.5 to 1.5 wt% of a tackifier, By weight to 96% by weight based on the total weight of the composition.
상기 폴리아미드 수지는,
다이머산(dimer acid) 100 중량부에 대하여, 대두유 지방산(soyabean oil, SOFA) 150 ~ 200 중량부 및 테트라에틸렌펜타민(tetraethylenepentamine, TEPA) 100 ~ 150 중량부로 이루어지는 것을 특징으로 하는, 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물.
The method according to claim 1,
In the polyamide resin,
Characterized in that it comprises 150 to 200 parts by weight of soyabean oil (SOFA) and 100 to 150 parts by weight of tetraethylenepentamine (TEPA) per 100 parts by weight of dimer acid. Adhesion promoter composition for acrylic foam tapes.
상기 점착부여제는,
석유수지, 알킬페놀(alkylphenol)수지, 로진(rosin), 로진에스테르(rosin ester)수지 또는 쿠마론인덴(Coumaroneindene)수지 중에서 단독 또는 2종 이상 병용하여 사용하는 것을 특징으로 하는, 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물.
The method according to claim 1,
The tackifier,
(1), which is characterized in that it is used singly or in combination of two or more selected from the group consisting of petroleum resins, alkylphenol resins, rosin, rosin ester resins and coumaroneindene resins, Adhesion promoter composition for foam tapes.
상기 용제는,
메틸에틸케톤(methylethylketone), 에틸아세테이트(ethylacetate), 싸이클로헥산(cyclohexane), 아세톤(Acetone), 이소프로필알콜(isopropylalcohol) 또는 메틸싸이클로헥산(methylcyclohexane)으로 이루어진 군에서 3종 이상 병용하여 사용하는 것을 특징으로 하는, 접착강도가 우수한 아크릴 폼 테이프용 접착증진제 조성물.The method according to claim 1,
The solvent,
It is preferably used in combination with at least three of the group consisting of methylethylketone, ethylacetate, cyclohexane, acetone, isopropylalcohol or methylcyclohexane. By weight based on the total weight of the composition.
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