KR100297587B1 - Rubber-based Adhesive Compositions Used in a Heat Shrinkable Sheet or Tape for the Protection of Welded Part of Gas Pipe Line - Google Patents
Rubber-based Adhesive Compositions Used in a Heat Shrinkable Sheet or Tape for the Protection of Welded Part of Gas Pipe Line Download PDFInfo
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- KR100297587B1 KR100297587B1 KR1019990011181A KR19990011181A KR100297587B1 KR 100297587 B1 KR100297587 B1 KR 100297587B1 KR 1019990011181 A KR1019990011181 A KR 1019990011181A KR 19990011181 A KR19990011181 A KR 19990011181A KR 100297587 B1 KR100297587 B1 KR 100297587B1
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- rubber
- sensitive adhesive
- gas pipe
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 title claims description 32
- 239000000853 adhesive Substances 0.000 title claims description 29
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 229920001083 polybutene Polymers 0.000 claims abstract description 7
- 239000012188 paraffin wax Substances 0.000 claims abstract description 6
- 239000010734 process oil Substances 0.000 claims abstract description 6
- 230000007797 corrosion Effects 0.000 claims description 10
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000006229 carbon black Substances 0.000 abstract description 8
- 238000003466 welding Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006355 external stress Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
-
- 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
-
- 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
- C09J121/00—Adhesives based on unspecified rubbers
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
본 발명은 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물에 관한 것으로, 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물에 있어서, 고무계 수지 100중량부에 대하여 점착부여 수지 50∼60중량부, 파라핀 프로세스 오일 15∼25중량부, 폴리부텐 45∼55중량부, 카본블랙 15∼25중량부, 탄산칼슘 20∼40중량부 및 산화아연 5∼10중량부로 구성되며, 본 발명에 따른 점착제 조성물은 4.5Kgf/25mm 이상의 박리 접착강도 및 -30℃이하의 내한성을 만족하는 고무계 점착제이며, 박리시 응집파괴가 일어난다.The present invention relates to a rubber-based pressure-sensitive adhesive composition for use in heat shrinkable sheets or tapes for anticorrosive treatment of gas pipe welding parts, and a rubber-based pressure-sensitive adhesive composition for use in heat shrinkable sheets or tapes for anti-corrosion treatment for gas pipe welds. 50 to 60 parts by weight of imparting resin, 15 to 25 parts by weight of paraffin process oil, 45 to 55 parts by weight of polybutene, 15 to 25 parts by weight of carbon black, 20 to 40 parts by weight of calcium carbonate and 5 to 10 parts by weight of zinc oxide. , The pressure-sensitive adhesive composition according to the present invention is a rubber-based pressure-sensitive adhesive that satisfies the peel adhesion strength of 4.5Kgf / 25mm or more and the cold resistance of -30 ℃ or less, the cohesive failure occurs during peeling.
Description
본 발명은 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물에 관한 것으로, 좀 더 상세하게는 우수한 박리 접착강도 및 내한성을 갖는 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물에 관한 것이다.The present invention relates to a rubber-based pressure-sensitive adhesive composition used for heat shrinkable sheets or tapes for corrosion protection of gas pipe welds, and more particularly, to rubber-based heat shrinkable sheets or tapes for anticorrosion treatment of gas pipe weldments having excellent peel adhesion strength and cold resistance. It relates to an adhesive composition.
최근 들어, 가스배관의 용접부를 방식처리(anti-corrosion)할 때 가스배관의 전체적인 안정성을 향상시킬 수 있는 열수축 시트 및 테입(heat-shrinkable sheet and tape)이 중요한 재료로서 각광받고 있다.Recently, heat-shrinkable sheets and tapes that can improve the overall stability of gas piping when anti-corrosion the welded portion of the gas piping have been spotlighted as important materials.
종래의 열수축 시트 또는 테입은 외부는 가교된 폴리에틸렌 층으로, 내부는 미가교된 점착층으로 구성되어 있다. 이러한 시트 및 테입 구성물의 성능을 결정짓는 매우 중요한 재료로서는 점착제를 들 수 있다.The conventional heat shrink sheet or tape is composed of a crosslinked polyethylene layer on the outside and an uncrosslinked adhesive layer on the inside. A very important material that determines the performance of these sheets and tape constructions is an adhesive.
우수한 물성의 점착층을 갖는 열수축 시트 또는 테입은 배관 용접부와 점착제의 결합이 균일하고 저온에서도 취화(brittle)되지 않으며 본래의 점착 물성을 가지고 있기 때문에, 시공후 추운 환경에서도 용접부와 점착층의 탈접착을 일으킬 가능성이 낮아지며, 이로 인해 용접부 표면에서 부식이 발생할 확률은 현저히 감소하게 된다. 따라서 박리 접착강도 및 내한성과 같은 물성이 우수한 열수축 시트 또는 테입용 점착제는 가스배관 용접부의 부식을 최소화시킬 수 있을 뿐만 아니라, 더 나아가서는 배관의 가스 안전 사고를 미연에 방지할 수 있는 중요한 재료이기 때문에 현재에도 연구대상이 되고 있다.The heat shrinkable sheet or tape having an adhesive layer of excellent physical properties has a uniform bond between the pipe welded portion and the adhesive, does not brittle at low temperatures, and has inherent adhesive properties, so that the welded portion and the adhesive layer are detached even in a cold environment after construction. The likelihood of corrosion is reduced, which significantly reduces the likelihood of corrosion on the weld surface. Therefore, the heat shrinkable sheet or tape adhesive having excellent physical properties such as peeling adhesive strength and cold resistance can not only minimize corrosion of the gas pipe welding portion, but also it is an important material that can prevent gas safety accidents in the pipe in advance. It is still a research subject.
그러나, 현재 생산되고 있는 열수축 시트 관련제품들은 접착강도, 파괴거동 및 내한성과 같은 물성에 있어서 얻고자 하는 정도의 결과를 얻는데 다소 어려움이 있다. 특히 국내 생산업체에서 생산되고 있는 제품들이 접착강도 및 파괴거동이 열악하여 제품의 질이 떨어지기 때문에, 국내 열수축 시트시장은 대부분 외국제품이 점유하고 있으나, 외국제품도 국내 겨울기후의 지중매설 위치의 온도에 대한 내한성이 부족하여 여러 문제를 갖고 있어 그 개발이 시급히 요구되고 있는 실정이다.However, currently produced heat shrink sheet-related products have some difficulty in achieving the desired result in physical properties such as adhesive strength, fracture behavior and cold resistance. In particular, the products produced by domestic manufacturers have poor adhesive strength and destructive behavior, so the quality of the products is deteriorated. Therefore, the domestic heat shrink sheet market is mostly occupied by foreign products. Due to the lack of cold resistance to temperature has a number of problems, the development is urgently required.
이러한 문제점을 극복하기 위하여 본 발명자들은 광범위한 연구를 수행한 결과, 고무를 주성분으로 하는 고무계 수지에 점착부여 수지, 가소제 및 충진제를 혼입함으로써 우수한 물성을 갖는 점착제 조성물을 얻을 수 있음을 발견하였으며, 본 발명은 이에 기초하여 완성되었다.In order to overcome this problem, the present inventors have conducted extensive research and found that a pressure-sensitive adhesive composition having excellent physical properties can be obtained by incorporating a tackifying resin, a plasticizer and a filler into a rubber-based resin based on rubber. Was completed on this basis.
따라서, 본 발명의 목적은 우수한 박리 접착강도, 내한성 및 파괴거동으로 인해 가스배관 용접부의 부식을 최소화시킬 수 있으며, 배관의 가스 안전 사고를 미연에 방지할 수 있는 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to minimize the corrosion of the gas pipe welds due to the excellent peel adhesion strength, cold resistance and fracture behavior, and to prevent the gas safety accident of the pipes in advance, the heat shrinkage sheet for corrosion treatment of the gas pipe welds or It is to provide a rubber-based pressure-sensitive adhesive composition used for tape.
상기 목적을 달성하기 위한 본 발명의 조성물은 가스배관 용접부 방식처리용 열수축 시트 또는 테입에 사용되는 고무계 점착제 조성물에 있어서, 고무계 수지 100중량부에 대하여 점착부여 수지 50∼60중량부, 파라핀 프로세스 오일 15∼25중량부, 폴리부텐 45∼55중량부, 카본블랙 15∼25중량부, 탄산칼슘 20∼40중량부 및 산화아연 5∼10중량부로 이루어진다.The composition of the present invention for achieving the above object is a rubber-based pressure-sensitive adhesive composition for use in heat shrinkable sheets or tapes for corrosion protection of gas pipe welds, 50 to 60 parts by weight of the tackifying resin with respect to 100 parts by weight of the rubber resin, paraffin process oil 15 It consists of-25 weight part, polybutene 45-55 weight part, carbon black 15-25 weight part, calcium carbonate 20-40 weight part, and zinc oxide 5-10 weight part.
이하 본 발명을 좀더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
전술한 바와 같이, 본 발명의 조성물은 고무계 수지에 점착부여 수지, 파라핀 프로세스 오일, 폴리부텐, 카본블랙, 탄산칼슘 및 산화아연을 혼입하여 이루어진다.As described above, the composition of the present invention is made by incorporating a tackifying resin, a paraffin process oil, polybutene, carbon black, calcium carbonate and zinc oxide into a rubber-based resin.
점착물성을 발현하기 위해 주 폴리머로서 고무계 수지를 사용하는데, 이 고무계 수지로서는 천연고무, 이소부틸렌-이소프렌 공중합체(IIR) 및 EVA 탄성체를 들 수 있고, 그 중 내후성 및 내화학성이 우수하고 수분 흡수 및 가스 침투성이 낮은 이소부틸렌-이소프렌 공중합체(IIR)가 가장 바람직하다.Rubber-based resins are used as main polymers to express adhesive properties, and such rubber-based resins include natural rubber, isobutylene-isoprene copolymer (IIR), and EVA elastomers, among which weather resistance and chemical resistance are excellent and moisture Most preferred is isobutylene-isoprene copolymer (IIR) with low absorption and gas permeability.
또한, 본 발명에 사용되는 점착부여 수지로는 석유계 수지, 로진 유도체, 쿠마론-인덴 수지 및 테르펜 올리고머를 들 수 있는데, 일반적으로 유리전이 온도가 고무보다 높고, 연화점 50∼150℃의 탄성체와의 상용성에 따라 점착부여 수지의 사용이 결정된다. 본 발명에서는 상기 점착부여 수지 중에서 이소부틸렌-이소프렌 공중합체와의 상용성이 우수하고, 박리 접착강도를 평가할 때 응집파괴를 유도하기 위해 피착제와 강하게 접착할 수 있도록 석유계 수지, 특히 C5/C9공중합체 석유계 수지를 사용하는 것이 바람직하며, 그 함량은 50∼60중량부가 바람직하다. 상기 함량이 50중량부 미만이면 박리 접착강도의 물성 저하를 야기시키며 60중량부를 초과하면 내한성을 급격히 저하시키므로 점착제의 물성에 좋지 않은 영향을 미치게 된다.The tackifying resins used in the present invention include petroleum resins, rosin derivatives, coumarone-indene resins, and terpene oligomers. Generally, the glass transition temperature is higher than that of rubber, and the elastomer has a softening point of 50 to 150 ° C. The compatibility of the tackifier resins determines the use of the tackifying resin. In the present invention, it is excellent in compatibility with the isobutylene-isoprene copolymer in the tackifying resin, and petroleum-based resin, in particular C 5 so as to be strongly adhered to the adhesive to induce cohesive failure when evaluating the peel adhesive strength It is preferable to use / C 9 copolymer petroleum resin, and its content is preferably 50 to 60 parts by weight. If the content is less than 50 parts by weight causes a drop in the physical properties of the peeling adhesive strength, if it exceeds 60 parts by weight sharply lowers the cold resistance has a bad effect on the physical properties of the pressure-sensitive adhesive.
한편, 가소제로서는 대표적으로 폴리부텐, 파라핀 오일, 디부틸프탈레이트 (DBP), 디옥틸프탈레이트(DOP) 등을 들 수 있는데, 일반적으로 상기 가소제는 고무에 저온 유연성을 부여하여 내한성을 향상시킬 목적으로 투입되지만, 상대적으로 박리 접착강도를 저하시키는 요인으로 작용하기도 한다. 본 발명에서는 파라핀 프로세스 오일 15∼25중량부 및 폴리부텐 45∼55중량부가 사용되었으며, 상기 사용량 이상이 될 경우에는 박리 접착강도의 저하를 유발하는 문제가 발생하고, 상기 함량에 있어서 접착력의 큰 손실이 없으면서 유동성을 최대한으로 발휘할 수 있다.On the other hand, as a plasticizer, polybutene, paraffin oil, dibutyl phthalate (DBP), dioctyl phthalate (DOP) and the like are typically used. Generally, the plasticizer is added for the purpose of improving cold resistance by providing low temperature flexibility to rubber. However, it also acts as a factor to lower the peel adhesion strength relatively. In the present invention, 15 to 25 parts by weight of paraffin process oil and 45 to 55 parts by weight of polybutene were used. When the amount is more than the amount used, a problem causing a decrease in peeling adhesive strength occurs, and a large loss of adhesion in the content is achieved. Without this, it is possible to maximize the fluidity.
또한, 그 밖의 첨가제는 고무의 보강제로 사용되는 카본블랙, 응집력 향상을 위한 산화아연 및 가격 저하를 위한 탄산칼슘이 투입되는데, 상기 카본블랙은 입자경이 큰 FEF(N550) 15∼25중량부가 바람직하며, 25중량부를 초과하면 내한성이 급격히 저하되는 문제가 있으며, 15중량부 미만에서는 박리 접착강도가 상기 본 발명의 목적 물성을 만족시키지 못한다.In addition, other additives include carbon black used as a rubber reinforcing agent, zinc oxide for improving cohesion and calcium carbonate for lowering the price. The carbon black preferably has 15-25 parts by weight of FEF (N550) having a large particle size. If it exceeds 25 parts by weight, there is a problem that the cold resistance is sharply lowered, and if less than 15 parts by weight, the peel adhesive strength does not satisfy the object properties of the present invention.
가격 저하를 위해 증량제로서 사용하는 탄산칼슘(CaCO3)은 카본블랙과 혼입하여 투입되는 것이 바람직하며, 만약 카본블랙과 혼입되지 않으면 수지조성물의 물성에 영향을 주기 때문에 바람직하지 않은 결과를 가져올 수 있다. 또한, 투입양은 20∼40중량부로서, 40중량부 이상이 될 경우에는 분산의 어려움이 생겨 이차 분산을 해야함으로써 가격저하의 목적을 달성할 수 없고, 20중량부 미만에서는 현저한 가격저하의 효과를 얻을 수 없다.Calcium carbonate (CaCO 3 ), which is used as an extender for lowering the price, is preferably mixed with carbon black and, if not mixed with carbon black, may adversely affect the physical properties of the resin composition. . In addition, the input amount is 20 to 40 parts by weight, when more than 40 parts by weight is difficult to disperse, the secondary dispersion must be achieved to achieve the purpose of lowering the price, less than 20 parts by weight has a significant price reduction effect Can not get
또한 응집력 향상을 위해 사용하는 산화아연(Zinc oxide)은 통상적으로 5∼10중량부가 바람직하다.In addition, zinc oxide (Zinc oxide) used to improve the cohesion is usually preferably 5 to 10 parts by weight.
상기 고무계 수지에 점착부여 수지, 가교제, 및 첨가제를 혼입하여 제조되는 본 발명의 열수축 시트 또는 테입용 고무계 점착제 조성물은 토양 등의 외부응력의 임계점인 4.5Kgf/25mm 이상의 박리 접착강도를 갖고 우리나라 겨울 기후의 지중매설 위치의 온도를 고려할 때 -30℃이하의 내한성을 만족시킨다.Rubber-based pressure-sensitive adhesive composition for heat shrink sheet or tape of the present invention prepared by incorporating a tackifying resin, a crosslinking agent, and an additive in the rubber-based resin has a peel adhesion strength of 4.5Kgf / 25mm or more, which is a critical point of external stress such as soil, and winter climate in Korea. Considering the temperature of the underground burial site, the cold resistance below -30 ℃ is satisfied.
또한, 응집파괴(cohesive failure)라는 것은 피착제 표면에 점착제의 잔류물을 남기면서 박리됨을 말하는데, 이런 파괴거동은 점착제의 내부 응집력, 점착제와 피착제의 계면에서의 접착강도에 의존하게 된다.In addition, cohesive failure refers to peeling while leaving a residue of the adhesive on the surface of the adherend, which is dependent on the internal cohesion of the adhesive and the adhesive strength at the interface between the adhesive and the adhesive.
일반적으로 가스관 용접부 방식용 열수축 시트의 경우에는 응집파괴가 요구되는데, 만약 토양등의 외부 응력으로 인해 점착층의 변형이 발생할 경우, 응집파괴가 일어난다면 점착층은 파이프와 강하게 접착하고 있으므로 파이프 표면은 부착된 점착제로 인해 부식환경으로부터 보호받을 수 있고 음극방식을 저해하지 않지만, 반대로 접착파괴가 발생한다면 파이프 표면으로부터 점착층이 탈접착되므로 부식환경에 노출되며 음극방식 효과를 저해하게 된다. 종래의 열수축 시트는 통상적으로 외부응력에 대해 접착파괴가 발생하여 방식효과가 떨어지지만, 본 발명에 따른 시트는 응집파괴가 일어남으로써 바람직한 방식효과를 얻을 수 있다.Generally, in case of heat shrink sheet for gas pipe welding part, cohesive failure is required. If the cohesive failure occurs due to external stress such as soil, if cohesive failure occurs, the cohesive layer strongly adheres to the pipe. The attached adhesive can be protected from the corrosive environment and does not inhibit the negative electrode method. However, if the adhesive breakdown occurs, the adhesive layer is debonded from the surface of the pipe and thus exposed to the corrosive environment and inhibits the negative electrode effect. Conventional heat-shrinkable sheets are generally inferior in anticorrosive effect due to adhesive breakage against external stress, but the sheet according to the present invention can obtain a desirable anticorrosive effect by cohesive failure.
이하 실시예를 통하여 본 발명의 조성물을 좀 더 구체적으로 설명하지만, 이에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the composition of the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.
실시예 1Example 1
하기 성분들을 벤치 니더(Bench Kneader)에서 혼련하여, 본 발명에 따른 열수축 시트용 고무계 점착제 조성물을 얻었다.The following components were kneaded in a bench kneader to obtain a rubber-based pressure-sensitive adhesive composition for a heat shrinkable sheet according to the present invention.
이소부틸렌-이소프렌 공중합체(Exxon butyl 268) 100 중량부100 parts by weight of isobutylene-isoprene copolymer (Exxon butyl 268)
C5/C9공중합체 석유계 수지(연화점 80℃) 50 중량부50 parts by weight of C 5 / C 9 copolymer petroleum resin (softening point 80 ° C)
파라핀 프로세스 오일 20 중량부20 parts by weight of paraffin process oil
폴리부텐 50 중량부50 parts by weight of polybutene
카본블랙 20 중량부20 parts by weight of carbon black
탄산칼슘(CaCO3) 20 중량부20 parts by weight of calcium carbonate (CaCO 3 )
산화아연(ZnO) 5 중량부5 parts by weight of zinc oxide (ZnO)
얻어진 열수축 시트용 고무계 점착제 조성물을 프레스(press)로 성형하여 두께 2mm의 시트 형태의 점착제 조성물 층을 얻었다. 상기 실시예에서 사용된 이소부틸렌-이소프렌 공중합체는 엑손(Exxon)사에서 생산되는 엑손부틸 268이고, 고유 성질은 비중 0.92, 불포화도 1.6mol%, 무늬점도(ML 1+8, 125℃)이었다.The obtained rubber-based pressure-sensitive adhesive composition for heat shrinkable sheet was molded by a press to obtain a pressure-sensitive adhesive composition layer in the form of a sheet having a thickness of 2 mm. The isobutylene-isoprene copolymer used in the above example is Exxonbutyl 268 produced by Exxon, and its specific properties are specific gravity 0.92, unsaturation 1.6mol%, pattern viscosity (ML 1 + 8, 125 ° C). It was.
실시예 2Example 2
C5/C9공중합체 석유계 수지(연화점 80℃)를 60 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 점착제 조성물 층을 얻었다.A pressure-sensitive adhesive composition layer was obtained in the same manner as in Example 1 except that 60 parts by weight of the C 5 / C 9 copolymer petroleum resin (softening point 80 ° C.) was used.
실시예 3Example 3
탄산칼슘 40 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 점착제 조성물 층을 얻었다.A pressure-sensitive adhesive composition layer was obtained in the same manner as in Example 1, except that 40 parts by weight of calcium carbonate was used.
비교예 1Comparative Example 1
이소부틸렌-이소프렌 공중합체(PIB(재생부틸고무)), 송진, 아스팔트, 탄산칼슘 및 산화아연을 이용하여 상기 실시예 1과 같은 방법으로 두께 2mm의 시트 형태의 점착제 조성물 층을 얻었다.Using an isobutylene-isoprene copolymer (PIB (regenerated butyl rubber)), rosin, asphalt, calcium carbonate and zinc oxide, a pressure-sensitive adhesive composition layer having a sheet thickness of 2 mm was obtained in the same manner as in Example 1.
상기 실시예 1, 2 , 3 및 비교예 1에 의해 제조된 점착물 조성물을 하기와 같이 성능을 평가하여 그 결과를 하기 표 1에 기재하였다.The pressure-sensitive adhesive composition prepared in Examples 1, 2, 3 and Comparative Example 1 was evaluated as follows, and the results are shown in Table 1 below.
1) 박리 접착 강도 평가1) Peel Adhesion Strength Evaluation
표준 시편을 SUS 302 강판에 부착시키고, 고무롤러를 사용하여 저속으로 8회 왕복 압착하고 상온에서 24시간 방치한 후, 인스트론(Instron) 4301을 사용하여 50mm/min의 박리속도로 180°박리를 실시하여 박리 접착 강도를 평가하였다.Standard specimens were attached to the SUS 302 steel plate, reciprocally crimped eight times at low speed using a rubber roller and left at room temperature for 24 hours, followed by peeling of 180 ° at 50 mm / min using an Instron 4301. It carried out and evaluated the peeling adhesive strength.
2) 내한성 평가2) cold resistance evaluation
우에시마(Ueshima)사의 No. 920455인 취화온도 측정기를 사용하였으며, KS M 6676에 명시된 시험조건과 계산식에 따라 내한성을 평가하였다.No. of Ueshima Corporation An embrittlement temperature gauge of 920455 was used and cold resistance was evaluated according to the test conditions and calculation formula specified in KS M 6676.
상기 박리 접착 강도 시편 제조시 사용되는 백킹(backing)재로는 인조피혁이 사용될 수 있으며, 내한성 시편 제조시 사용되는 이형 필름은 폴리에틸렌테레프탈레이트(PET) 이형 필름이 사용될 수 있다. 이형성이 나쁜 필름은 시편 제조 후 점착제와 필름의 박리가 깨끗하지 못하여 물성평가시 악영향으로 작용하며, 박리 접착 강도 평가시 피착제로는 100×25×1mm의 SUS 302 강판과 100×25×2mm의 폴리에틸렌판이 사용된다.Artificial backing material may be used as a backing material used in preparing the peel strength test specimen, and a release film used in the manufacture of cold resistant specimens may use a polyethylene terephthalate (PET) release film. Films with poor releasing properties do not clean the adhesive and the film after the specimen is produced, which adversely affects the evaluation of physical properties.As the adhesive is evaluated when the adhesive strength is measured, 100 x 25 x 1 mm SUS 302 steel sheet and 100 x 25 x 2 mm polyethylene Plates are used.
상기 실시예 및 비교예의 결과를 비교한 표 1에서도 알 수 있는 바와 같이, 본 발명의 따른 점착제 조성물은 4.5Kgf/25mm 이상의 박리 접착강도, -30℃이하의 내한성 및 응집파괴의 파괴거동을 만족함으로써 이러한 점착층을 갖는 열수축 시트 또는 테입은 시공 후에 배관 용접부와 점착제의 결합이 균일하고, 저온에서도 취화되지 않으면서 본래의 점착 물성을 가지고 있기 때문에 추운 환경에서도 용접부와 점착층의 탈접착을 일으킬 가능성이 낮아져 가스배관 용접부의 부식을 최소화시킬 수 있고, 더 나아가서는 배관의 가스 안전 사고를 방지할 수 있다.As can be seen from Table 1 comparing the results of the Examples and Comparative Examples, the pressure-sensitive adhesive composition according to the present invention satisfies the peel adhesive strength of 4.5Kgf / 25mm or more, cold resistance of -30 ℃ or less and the fracture behavior of cohesive fracture Since the heat shrinkable sheet or tape having such an adhesive layer has a uniform bond between the pipe welded portion and the adhesive after construction, and has inherent adhesive properties without embrittlement even at low temperatures, there is a possibility of debonding the welded portion and the adhesive layer even in a cold environment. It can be lowered to minimize corrosion of the gas pipe welds, and further prevent gas safety accidents in the pipe.
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| KR1019990011181A KR100297587B1 (en) | 1999-03-31 | 1999-03-31 | Rubber-based Adhesive Compositions Used in a Heat Shrinkable Sheet or Tape for the Protection of Welded Part of Gas Pipe Line |
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| KR101283112B1 (en) * | 2010-06-28 | 2013-07-05 | 이봉규 | A One Pot Type Water-Soluble Adhesive and A One Pot Type Water-Soluble Adhesive Manufacturing method Using Synthetic Latex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100376004B1 (en) * | 2000-12-27 | 2003-03-15 | 진호문 | accouplement Adhesive tapes for pipe arrangement |
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| Publication number | Publication date |
|---|---|
| KR20000061818A (en) | 2000-10-25 |
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