KR100616192B1 - Adhesive Treating Agent Composition for Polyester Deep Cord Production - Google Patents
Adhesive Treating Agent Composition for Polyester Deep Cord Production Download PDFInfo
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- KR100616192B1 KR100616192B1 KR1020000009716A KR20000009716A KR100616192B1 KR 100616192 B1 KR100616192 B1 KR 100616192B1 KR 1020000009716 A KR1020000009716 A KR 1020000009716A KR 20000009716 A KR20000009716 A KR 20000009716A KR 100616192 B1 KR100616192 B1 KR 100616192B1
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- polyester
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- epoxy compound
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- isocyanate
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- 229920000728 polyester Polymers 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000000853 adhesive Substances 0.000 title claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 25
- -1 isocyanate compound Chemical class 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229920000126 latex Polymers 0.000 claims abstract description 12
- 239000004816 latex Substances 0.000 claims abstract description 9
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 21
- 239000005060 rubber Substances 0.000 abstract description 21
- 230000002787 reinforcement Effects 0.000 abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000011221 initial treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- CETVPVOSOKJLKX-UHFFFAOYSA-N 1-methoxynaphthalen-2-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C(OC)=C([NH3+])C=CC2=C1 CETVPVOSOKJLKX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04H—BUILDINGS OR LIKE STRUCTURES FOR PARTICULAR PURPOSES; SWIMMING OR SPLASH BATHS OR POOLS; MASTS; FENCING; TENTS OR CANOPIES, IN GENERAL
- E04H13/00—Monuments; Tombs; Burial vaults; Columbaria
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
본 발명은 에폭시화합물, 이소시아네이트 화합물, 수산화나트륨, 레소시놀-포르말린 축합물 및 라텍스를 함유하는 폴리에스테르 디프코드 제조용 접착처리제 조성물에 있어서, 이소시아네이트 화합물과 에폭시 화합물의 합량이 조성물의 총건조중량 기준으로 20 중량% 이상이고, 건조중량기준으로 상기 에폭시 화합물의 혼합비율이 이소시아네이트의 혼합비율과 같거나 또는 보다 높은 것을 특징으로 하며, 이러한 본 발명의 조성물은 높은 접착력과 낮은 스티프니스를 동시에 만족하는 고무 보강용 폴리에스테르 디프 코드를 제조할 수 있게 되고 그 결과 고 품질의 보강고무제품의 제조를 가능하게 한다.The present invention relates to an adhesive treatment composition for preparing a polyester diff cord containing an epoxy compound, an isocyanate compound, sodium hydroxide, a resorcinol-formalin condensate, and a latex, wherein the total amount of the isocyanate compound and the epoxy compound is based on the total dry weight of the composition. It is 20% by weight or more, and on a dry weight basis, the mixing ratio of the epoxy compound is equal to or higher than that of isocyanate, and the composition of the present invention is used for rubber reinforcement that satisfies high adhesion and low stiffness simultaneously. It is possible to produce polyester deep cords, which results in the production of high quality reinforced rubber products.
Description
본 발명은 고무와 보강용 폴리에스테르 코드간의 접착성을 부여하기 위한 접착처리제 조성물에 관한 것으로서, 특히 고무에 대한 접착력이 높고 스티프니스(stiffness)가 낮은 고무보강용 폴리에스테르 디프코드(dipped cord)를 제조하기 위한 접착처리제 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive treatment composition for imparting adhesion between rubber and reinforcing polyester cords. In particular, the present invention provides a polyester reinforced cord for rubber reinforcement having high adhesion to rubber and low stiffness. It relates to an adhesive treatment composition for.
래디얼 타이어의 출현에 따라 고탄성을 갖는 보강섬유에 대한 요구가 증대되면서 폴리에틸렌테레프탈레이트 섬유로 대표되는 폴리에스테르의 수요가 늘어나고 이에 따라 폴리에스테르 코드의 고무에 대한 접착력을 향상시키기 위한 접착처리제에 대한 연구가 많이 이루어지고 있다. With the advent of radial tires, the demand for reinforcing fibers with high elasticity has increased, and the demand for polyesters represented by polyethylene terephthalate fibers has increased. Accordingly, research on adhesive treatment agents for improving adhesion of rubber to polyester cords has been conducted. A lot is done.
폴리에스테르는 레조시놀-포름알데히드 축합물(이하, 'RF 수지"라 약칭한다.)과의 친화성이 낮기 때문에 종래의 레조시놀-포름알데히드-라텍스(이하, "RFL"이라 약칭한다.) 시스템으로는 충분한 접착력을 얻을 수 없었으므로, 폴리에스테르 코드와 고무와의 접착력을 개량하는 것이 개발초기의 과제가 되었다.Polyester is abbreviated as conventional resorcinol-formaldehyde-latex (hereinafter referred to as "RFL") because of its low affinity with resorcinol-formaldehyde condensate (hereinafter referred to as "RF resin"). Since sufficient adhesive strength could not be obtained with the system, improving the adhesive strength between the polyester cord and the rubber became a problem in the early stage of development.
폴리에스테르와 고무와의 결합력을 증대시키기 위한 방법은 폴리에스테르 코드를 폴리에폭시 화합물, 블로킹된(blocked) 이소시아네이트 화합물 등을 함유하는 약제로 처리하는 것에 의해서 접착활성을 부여하는 방법과, 할로겐화페놀 화합물(그 대표적인 물질로서 펙슐이 있다.)과 같이 폴리에스테르와의 친화성이 높은 물질을 혼합한 처리액으로 처리하는 것에 의해서 접착력을 부여하는 방법으로 대별된다. Methods for increasing the bonding strength between polyester and rubber include a method of imparting adhesive activity by treating a polyester cord with a drug containing a polyepoxy compound, a blocked isocyanate compound, and the like, and a halogenated phenol compound ( As a representative material thereof, there is a patch), which is roughly classified into a method of imparting adhesive strength by treating a material having a high affinity with polyester as a mixed solution.
이 분야의 선행기술을 살펴보면, 먼저 미국 특허 제 3,234,067호에는 카프로락탐 혹은 페놀을 사용하여 블로킹된 디이소시아네이트와 에폭시화합물의 혼합액으로 이루어진 1차 처리액으로 폴리에스테르 섬유를 처리하고 뒤이어 레소시놀과 포름알데히드의 초기축합물 및 고무라텍스로 이루어진 2차 처리액으로 처리하는 방법이 개시되어 있다. 그러나 이러한 방법으로 처리하는 경우 디이소시아네이트의 분산 안정성이 좋지 못하고, 섬유에 피복시 열을 가하면 블로킹 화합물인 페놀 혹은 카프로락탐의 발생으로 환경에 유해한 문제가 있다.Looking at the prior art in this field, U.S. Patent No. 3,234,067 discloses a polyester fiber with a primary treatment solution consisting of a mixed solution of diisocyanate and epoxy compound blocked using caprolactam or phenol followed by resorcinol and form A method of treating with a secondary treatment liquid consisting of an initial condensate of aldehyde and a rubber latex is disclosed. However, when treated in this way, the dispersion stability of the diisocyanate is not good, and when heat is applied to the fibers, there is a problem that is harmful to the environment due to the generation of a blocking compound phenol or caprolactam.
일본 특공소46-11251호에는 레소시놀과 포름알데히드의 초기축합물 및 고무라텍스 등으로 이루어진 RFL액에 2,6-비스(2',4'-디히드록시페닐메틸)-4-클로로페닐과 같은 할로겐화 페놀과 레소시놀-포름알데히드의 반응 생성물을 혼합한 것이 폴리에스테르에 대한 대표적인 처리액으로 개시되어 있다. 그러나 이러한 조성의 처리액을 사용하는 경우 충분한 접착력(인발력)을 얻기 위해서는 폴리에스테르 섬유에 대한 처리제의 부착량이 상당히 많아야 하며, 그 결과 디프코드의 스티프니스가 지나치게 높게 되어 타이어와 같은 고무제품을 보강하는데 어려움이 있으며 또 한 품질의 균일화를 달성하는데에도 문제가 있는 것이다. Japanese Patent Application No. 46-11251 discloses 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenyl in an RFL solution composed of an initial condensate of resorcinol and formaldehyde and rubber latex. Mixing of reaction products of halogenated phenols such as resorcinol-formaldehyde is disclosed as a representative treatment solution for polyester. However, when using a treatment liquid of such a composition, in order to obtain sufficient adhesive force (pulling force), the amount of adhesion of the treatment agent to the polyester fiber must be considerably high. As a result, the stiffness of the diff cord is too high, which makes it difficult to reinforce rubber products such as tires. There is also a problem in achieving quality uniformity.
또한, 최근에는 물, 레소시놀, 포르말린, 고무라텍스, 펙슐(Pexul)로 이루어진 1차 처리액으로 처리한후, RFL로 이루어진 2차처리액으로 처리하는 방법도 알려져 있다. 그러나 상기한 조성의 1차 처리액으로 폴리에스테르 섬유를 처리하는 것은 펙슐이 암모니아수를 70% 이상을 함유하고 있으므로 환경공해 및 작업성을 불량하게 할 뿐만 아니라, 함침 처리후 레소시놀과 포르말린 및 펙슐에 의해 함침 먼지 종류인 작은 겔이 발생하여 최종적으로 타이어 생산시 불량율이 높아지고, 또한 처리된 폴리에스테르 섬유의 단위 중량이 높아 생산자의 원가 부담이 늘어나는 단점이 있다.In addition, recently, a method of treating with a primary treatment liquid consisting of water, resorcinol, formalin, rubber latex, and capsules (Pexul) and then treating with a secondary treatment liquid composed of RFL is also known. However, treating the polyester fiber with the above-mentioned primary treatment liquid does not only degrade the environmental pollution and workability since the capsules contain more than 70% of ammonia water, but also resorcinol, formalin and patch after the impregnation treatment. Due to the small impregnation of the gel, which is a type of impregnated dust, the defect rate is finally increased during tire production, and the unit weight of the treated polyester fiber is high, which increases the cost burden of the producer.
따라서 본 발명은 고 품질의 타이어 제조에 적합한 높은 접착력과 낮은 스티프니스를 갖는 폴리에스테르 디프코드를 제공하는 것을 목적으로 한다. It is therefore an object of the present invention to provide a polyester deep cord with high adhesion and low stiffness suitable for the manufacture of high quality tires.
또한 본 발명은 고 품질의 타이어 제조에 적합한 고강력과 저스티프니스를 갖는 폴리에스테르 디프코드의 제조를 가능하게 하고 암모니아의 사용을 배제함으로써 보다 안전한 작업 환경을 보장하는 새로운 1차 처리액 조성물을 제공하는 것을 목적으로 한다.The present invention also provides a new primary treatment liquid composition which enables the production of polyester deep cords having high strength and low stiffness suitable for the manufacture of high quality tires and which eliminates the use of ammonia to ensure a safer working environment. For the purpose of
상기한 목적을 달성하기 위한 본 발명자의 연구에서 에폭시화합물, 이소시아네이트 화합물, 수산화나트륨, 레소시놀-포르말린 축합물 및 라텍스를 함유하는 폴리에스테르 디프코드 제조용 접착처리제 조성물에서 에폭시화합물과 이소시아네이 트 화합물의 함유량 및 이들간의 비율을 특별히 제한된 범위로 사용하면 제조되는 폴리에스테르 디프코드가 접착력이 높으면서 스티프니스가 낮아 고 품질의 타이어 제조에 적합하게 되고, 또한 암모니아의 사용을 배제함으로써 보다 안전한 작업환경에서 폴리에스테르 디프코드를 제조할 수 있게 된다는 사실을 알게 되어 본 발명을 완성하게 된 것이다.
Epoxy compound and isocyanate compound in the adhesive treatment composition for preparing polyester deep cord containing epoxy compound, isocyanate compound, sodium hydroxide, resorcinol-formalin condensate and latex When the content of and the ratio between these are used in a particularly limited range, the polyester diff cords produced are suitable for the manufacture of high-quality tires with high adhesion and low stiffness, and also eliminate the use of ammonia to make polyester in a safer working environment. The present invention has been completed by knowing that it is possible to manufacture a diff code.
그러므로 본 발명에 의하면 에폭시화합물, 이소시아네이트 화합물, 수산화나트륨, 레소시놀-포르말린 축합물 및 라텍스를 함유하는 폴리에스테르 디프코드 제조용 접착처리제 조성물에 있어서, 이소시아네이트 화합물과 에폭시 화합물의 합량이 조성물의 총건조중량 기준으로 20 중량% 이상이고, 건조중량기준으로 에폭시 화합물의 혼합비율이 이소시아네이트의 혼합비율과 같거나 또는 보다 높은 것을 특징으로 하는 폴리에스테르 디프코드 제조용 접착처리제 조성물이 제공된다.Therefore, according to the present invention, in the adhesive treatment composition for preparing polyester diff cord containing epoxy compound, isocyanate compound, sodium hydroxide, resorcinol-formalin condensate and latex, the total dry weight of the composition is the total amount of isocyanate compound and epoxy compound. It is 20% by weight or more on the basis of the dry weight basis, there is provided an adhesive treatment composition for producing a polyester deep cord, characterized in that the mixing ratio of the epoxy compound is equal to or higher than the mixing ratio of the isocyanate.
또한 본 발명에 의하면 상기한 접착처리제 조성물로 처리하여 제조된 것을 특징으로 하는 폴리에스테르 디프 코드가 제공된다.According to the present invention, there is provided a polyester deep cord, which is prepared by treating with the adhesive agent composition described above.
이하 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 고무 보강용 폴리에스테르 디프 코드 제조용 접착처리제 조성물은 에폭시 화합물과 이소시아네이트 화합물의 합량(sum)이 조성물의 총건조중량 기준으로 20중량% 이상, 바람직하게 20 내지 30 중량%이고, 건조중량기준으로 에폭시 화합물의 혼합비율이 이소시아네이트의 혼합비율과 같거나 또는 보다 높게, 바람직 하게 이소시아네이트 화합물 대 에폭시 화합물의 혼합비율이 건조중량기준으로 1:1 ∼ 1:4, 보다 바람직하게 1:2∼1:3인 것을 요지로 한다.In the adhesive treatment composition for preparing a polyester deep cord for rubber reinforcement of the present invention, the sum of the epoxy compound and the isocyanate compound is 20% by weight or more, preferably 20-30% by weight, based on the total dry weight of the composition, Therefore, the mixing ratio of the epoxy compound is equal to or higher than the mixing ratio of the isocyanate, preferably the mixing ratio of the isocyanate compound to the epoxy compound is 1: 1 to 1: 4 on a dry weight basis, more preferably 1: 2 to 1: 1. We assume three things.
본 조성물중 이소시아네이트 화합물과 에폭시 화합물의 합량이 조성물의 총건조중량 기준으로 20 중량% 보다 적으면 제조되는 폴리에스테르 디프코드의 접착력이 불량하게 되고, 30 중량% 보다 많으면 접착력이 더 이상 향상되지 않고 디프코드의 가격상승을 초래하므로 바람직하지 못하다. If the total amount of the isocyanate compound and the epoxy compound in the present composition is less than 20% by weight based on the total dry weight of the composition, the adhesive force of the produced polyester deep cord becomes poor, and when more than 30% by weight, the adhesive force no longer improves and deep This is undesirable because it leads to a price increase in the code.
또한 본 조성물은 상기 이소시아네이트 화합물과 에폭시 화합물의 혼합비율에서 에폭시 화합물의 비율을 이소시아네이트 화합물의 비율과 같게 하던지 보다 높게 하는데, 만일 이소시아네이트 화합물의 비율을 에폭시 화합물의 비율 보다 높게 하면 제조되는 디프코드의 스티프니스가 지나치게 높게 되어 결국 균일한 품질의 고무제품을 제조하는 것이 곤란하게 된다. 이와 같이 에폭시 화합물의 비율을 높게 하면 낮은 스티프니스와 높은 접착력을 달성할 수 있으나, 에폭시 화합물은 이소시아네이트 화합물 보다 고가이고 또한 에폭시 화합물의 양을 이소시아네이트의 양보다 4배 이상으로 높게 하면 더 이상 접착력의 향상을 기대할 수 없으므로 이소시아네이트 화합물 대 에폭시 화합물의 혼합비율을 1:1∼1:4, 보다 바람직하게 1:2∼1:3으로 하는 것이 유리하다. In addition, the present composition has a ratio of the epoxy compound in the mixing ratio of the isocyanate compound and the epoxy compound equal to or higher than that of the isocyanate compound, but if the ratio of the isocyanate compound is higher than that of the epoxy compound, the stiffness of the produced diff code is It becomes so high that it becomes difficult to manufacture rubber products of uniform quality. In this way, when the ratio of the epoxy compound is increased, low stiffness and high adhesion can be achieved. However, when the epoxy compound is more expensive than the isocyanate compound and the amount of the epoxy compound is more than four times the amount of the isocyanate, the adhesion is no longer improved. Since it cannot be expected, it is advantageous to make the mixing ratio of an isocyanate compound to an epoxy compound 1: 1 to 1: 4, more preferably 1: 2 to 1: 3.
본 조성물에는 또한 물, 수산화나트륨, 레소시놀-포르말린 축합물, 라텍스 등이 함유되며, 또한 접착처리제 조성물에 통상적으로 첨가할 수 있는 기타의 첨가제가 함유될 수 있다. 폴리에스테르 디프코드 제조용 접착처리제 조성물에서 상기한 성분들의 배합비율은 잘 알려져있으며, 본 조성물에서 이들의 배합비율은 특별 히 제한되지 않으며 공지의 배합비율로 첨가하되, 단 이소시아네이트와 에폭시 화합물의 함량 및 이들간의 비율을 상기한 범위내로 구성하게 되면 소망하는 효과를 달성할 수 있게 된다.The composition also contains water, sodium hydroxide, resorcinol-formalin condensate, latex, and the like, and may also contain other additives that can typically be added to the adhesive agent composition. The blending ratio of the above-mentioned ingredients in the adhesive treatment agent composition for preparing polyester deep cord is well known, and the blending ratio thereof in the present composition is not particularly limited and is added in a known blending ratio, provided that the content of isocyanate and epoxy compound and these If the ratio of liver is comprised within the above range, the desired effect can be achieved.
본 발명에서 고무와 폴리에스테르 섬유간의 접착성을 부여하기 위하여 사용되는 1차 처리액의 작용은 다음과 같다. 폴리에스테르 섬유에 이소시아네이트와 에폭시가 우선 분자결합을 하고 레소시놀과 포르말린이 이소시아네이트와 에폭시에 공유결합을 한 후, 여기에 라텍스가 결합되어 후에 고무구조물과의 가교역할을 하게 된다.In the present invention, the action of the primary treatment liquid used to impart the adhesiveness between the rubber and the polyester fiber is as follows. Isocyanate and epoxy are first bonded to polyester fibers, and resorcinol and formalin are covalently bonded to isocyanate and epoxy, and latex is then bonded to the rubber structure.
본 발명의 접착처리제 조성물로 폴리에스테르 코드를 처리하여 디프코드를 제조하는 방법으로는 본 조성물만으로 처리하는 1단계(one-step) 방법을 적용할 수도 있고, 본 조성물로 1차 처리하고나서 통상의 RFL액으로 2차처리하는 2단계(two-step) 방법을 적용할 수도 있다. 이중에서 특히 2단계 방법이 바람직하다. As a method for producing a dip cord by treating the polyester cord with the adhesive treatment agent composition of the present invention, a one-step method of treating only the present composition may be applied, and after the first treatment with the present composition, A two-step method of secondary processing with RFL solution may be applied. Of these, two-step methods are particularly preferred.
2단계 방법으로 폴리에스테르 디프코드를 제조하는 방법의 일예를 들어 설명하면 다음과 같다. 먼저 폴리에스테르 코드을 본 조성물에 1차 디핑한 후 꺼내서 70∼150℃에서 건조한 후 200∼255℃에서 열처리를 실시한다. 이것은 침지, 도포 및 분무의 방법에 따라 부여되는데, 이때의 장력은 통상 0.05∼0.20g/d 정도이고, 부착량은 고형분 환산으로 1.0∼2.0중량% 정도가 적당하다. 이어서 RFL액에 2차 디핑한 후 꺼내서 1차 디핑처리와 유사하게 70∼150℃에서 건조한 후 200∼255℃에서 열처리를 실시하여 제조한다.An example of a method of manufacturing a polyester deep cord by a two-step method will be described below. First, the polyester cord is first dipped into the present composition, taken out, dried at 70 to 150 ° C., and then heat treated at 200 to 255 ° C. This is given by the method of immersion, application | coating, and spraying, At this time, tension is about 0.05-0.20g / d normally, and adhesion amount is suitable about 1.0-2.0 weight% in conversion of solid content. Subsequently, after dipping into the RFL solution, it is taken out, dried at 70 to 150 ° C., and heat-treated at 200 to 255 ° C., similarly to the first dipping treatment.
이상 설명한 바와 같은 본 발명의 특징 및 기타의 장점들은 후술되는 실시예 로부터 보다 명백하게 될 것이다. 단, 본 발명이 이에 한정되는 것은 아니다.Features and other advantages of the present invention as described above will become more apparent from the following examples. However, the present invention is not limited thereto.
〈실시예 1∼2 및 비교예 1∼2〉<Examples 1-2 and Comparative Examples 1-2>
폴리에스테르 섬유 1,000데니어/2합으로 된 코드를 물 76중량%와 표 1의 조성물 24중량%로 이루어진 수성 접착처리제 조성물이 들어 있는 욕조를 분당 60m의 속도로 통과시키고 90℃에서 2분 건조시킨후 230℃에서 2분간 열처리하여 1차 디핑처리하였다. A cord containing 1,000 denier / 2 sum of polyester fibers was passed through a bath containing an aqueous adhesive treatment composition consisting of 76% by weight of water and 24% by weight of the composition of Table 1 at 60 m / min, and dried at 90 ° C. for 2 minutes. First dipping was performed by heat treatment at 230 ° C. for 2 minutes.
이어서 1차 디핑처리된 코드를 물 100중량부 기준으로 레소시놀 8.8중량부, 포르말린 4.76중량부, 수산화나트륨 10중량부, 스타이렌/부타디엔/비닐피리딘(15/70/15) 고무 28중량부 및 스타이렌/부타디엔(50/50) 고무 28중량부를 함유하는 통상의 RFL 조성의 2차 처리액에서 1차 처리액과 동일한 방법으로 디핑처리하여 폴리에스테르 디프코드를 제조하였다. Subsequently, the primary dipping cord was subjected to 8.8 parts by weight of resorcinol, 4.76 parts by weight of formalin, 10 parts by weight of sodium hydroxide, and 28 parts by weight of styrene / butadiene / vinylpyridine (15/70/15) rubber based on 100 parts by weight of water. And a dipping treatment in the same manner as the primary treatment liquid in a secondary treatment liquid having a conventional RFL composition containing 28 parts by weight of styrene / butadiene (50/50) rubber to prepare a polyester deep cord.
제조된 디프코드의 고무에 대한 접착력, 스티프니스 및 고무픽업율(Rubber pick-up: RPU)을 다음과 같은 방법으로 측정하였다. 측정결과는 표 3에 제시된다.Adhesion, stiffness and rubber pick-up ratio (RPU) of the prepared deep cord rubber were measured by the following method. The measurement results are shown in Table 3.
* 접착력 : 천연고무 100중량부를 기준으로 산화아연 3.0중량부, 카본블랙 29.5중량부, 스테아릭산 2.0중량부, 핀타아르(pine tar) 7.0중량부, 머캅토벤조티아졸 1.25중량부, 황 3.0중량부, 디페닐구아니딘 0.15중량부, 페닐베타나프탈아민 1.0중량부의 조성으로로 된 고무에 디프 코드를 매설하되, 디프코드와 고무와의 접착면의 길이가 1/4인치가 되도록 한 후 204℃에서 4분간 가황(vulcanization)하고, 가황된 시료를 가지고 접착력을 측정하였다 (ASTM D 4776-88 H-Test 및 ASTM D 4777-88 U-Test).* Adhesion: 3.0 parts by weight of zinc oxide, 29.5 parts by weight of carbon black, 2.0 parts by weight of stearic acid, 7.0 parts by weight of pin tar, 1.25 parts by weight of mercaptobenzothiazole, and 3.0 parts by weight of sulfur. Subsequently, the deep cord was embedded in a rubber having a composition of 0.15 parts by weight of diphenylguanidine and 1.0 part by weight of phenylbetanaphthalamine, and the length of the adhesive surface between the deep cord and the rubber was 1/4 inch. It was vulcanized for 4 minutes at, and the adhesion was measured with the vulcanized sample (ASTM D 4776-88 H-Test and ASTM D 4777-88 U-Test).
* 스티프니스 : 구어레이(Gurley)사의 스티프니스 측정기(모델명 4171-ET)를 사용하여, 시료길이 = 1.5인치, 웨이트 위치 = 2" 위치, 하중 = 5g의 조건하에 3개의 시료에 대해서 좌,우 평균값을 측정하여 나타냄.* Stiffness: Using Gurley's stiffness measuring instrument (model name 4171-ET), the left and right average values were measured for three samples under the conditions of sample length = 1.5 inches, weight position = 2 "position, and load = 5 g. Measured and indicated.
* RPU : 디프 코드의 무게를 측정하고, 트리플루오르아세트산(TFA) 또는 트리클로로아세트산(TCA)에 디프 코드를 녹이고 남은 수지의 무게를 측정한후 두 무게의 비율을 퍼센트로 나타낸다. RPU: Measure the weight of the diff code, dissolve the diff code in trifluoroacetic acid (TFA) or trichloroacetic acid (TCA), and measure the weight of the remaining resin.
상기한 실험결과로부터 명백하게 되는 바와 같이, 본 발명에 따르는 접착처리제 조성물을 사용하면 높은 접착력과 낮은 스티프니스를 동시에 만족하는 고무 보강용 폴리에스테르 디프 코드를 제조할 수 있게 되고 그 결과 그 결과 고 품질의 보강고무제품의 제조를 가능하게 한다.As will be apparent from the above experimental results, the use of the adhesive treatment agent composition according to the present invention makes it possible to produce a polyester deep cord for reinforcing rubber that satisfies both high adhesion and low stiffness at the same time, and as a result, high quality reinforcement. It enables the manufacture of rubber products.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5624765A (en) * | 1994-08-01 | 1997-04-29 | Toray Industries, Inc. | Adhesive compositions for adhering rubber and fiber, rubber-reinforcing synthetic fibers, and fiber-reinforced rubber structures |
| KR100238336B1 (en) * | 1997-11-26 | 2000-01-15 | 구광시 | Deep fiber for fiber-reinforced rubber structures with excellent heat resistance and manufacturing method |
| KR20000026308A (en) * | 1998-10-20 | 2000-05-15 | 구광시 | Adhesive composition for rubber reinforced fiber and dipped cord for reinforcing rubber and dipped cord cloth |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199878A (en) * | 2011-04-12 | 2011-09-28 | 可隆（南京）特种纺织品有限公司 | Primary dip solution and dipping treatment method of polyester cord fabrics |
| CN102199878B (en) * | 2011-04-12 | 2013-01-09 | 可隆（南京）特种纺织品有限公司 | Primary dip solution and dipping treatment method of polyester cord fabrics |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010084565A (en) | 2001-09-06 |
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