KR101736368B1 - manufacturing method of polyurethane elastic resin and manufacturing method of sheet for pipe protection - Google Patents
manufacturing method of polyurethane elastic resin and manufacturing method of sheet for pipe protection Download PDFInfo
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- KR101736368B1 KR101736368B1 KR1020170024564A KR20170024564A KR101736368B1 KR 101736368 B1 KR101736368 B1 KR 101736368B1 KR 1020170024564 A KR1020170024564 A KR 1020170024564A KR 20170024564 A KR20170024564 A KR 20170024564A KR 101736368 B1 KR101736368 B1 KR 101736368B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
- B29C53/16—Straightening or flattening
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
Description
본 발명은 친환경 폴리우레탄 수지 제조방법 및 이를 이용한 파이프 보호용 시트 제조방법에 관한 것으로서, 보다 구체적으로는 중금속, TVOCs, 프탈레이트 가소제 등이 없으며, 파이프, 배관, 지주강관 등의 부식이나 침식, 손상을 방지할 수 있으며, 내 충격성, 내 부식성, 부착성능, 내열성 및 내마모성이 우수한 친환경 폴리우레탄 수지 제조방법 및 이를 이용한 파이프 보호용 시트 제조방법에 관한 것이다.The present invention relates to a method for manufacturing an environmentally friendly polyurethane resin and a method for manufacturing a pipe protecting sheet using the same. More specifically, the present invention eliminates heavy metals, TVOCs, phthalate plasticizers, and prevents corrosion, erosion and damage of pipes, pipes, Which is excellent in impact resistance, corrosion resistance, adhesion performance, heat resistance and abrasion resistance, and a method for manufacturing a pipe protection sheet using the same.
종래에 사용되던 전선 및 파이프 보호관은 한국등록실용 (313,132)-케이블 보호커버, 일본공개실용 (소59-053626)-해저케이블 보호구, 한국등록실용 (223,923)-케이블 보호커버, 일본공개특허 (평8-196011)-케이블 보호장치, 한국공개실용 (1988-010767), 일본공개실용 (평2-146928) 등은 주철 혹은 주강을 소재로 된 선행된문서로 반원형으로 양분된 관체의 양측에 각각 플랜지를 일체로 형성하고 각 플랜지 사이에 볼트와 너트를 결합하여 각 반원형 관체를 원형이 되도록 조립하는 구조였다.Conventional wire and pipe protection pipes are used for Korean registration room (313,132) - Cable protection cover, Japanese public room (59-053626) - Submarine cable protection room, Korean registration room (223,923) - Cable protection cover, 8-196011), a cable protection device, a Korean public utility (1988-010767), and a Japanese public utility (Pyung 2-146928) are preliminary documents made of cast iron or cast steel, And a bolt and a nut are coupled between the flanges to assemble each of the semicircular tubes into a circular shape.
그러나 상기 보호관으로 사용되던 재료의 물성은 주철 혹은 주강으로 비중과인장강도 및 강도 등이 우수하지만 시간이 경과함에 따라 부식이 심화 되어 외부의 작은 충격에 의해 쉽게 파손될 뿐만 아니라 설치기간이 길어지면 해 수중에서 마모 안정성이 떨어져지고 부식으로 인한 보수가 어려고 변형되는 문제점이 있었다.However, the physical properties of the material used as the protective pipe are excellent in specific gravity, tensile strength and strength due to cast iron or cast steel. However, as the corrosion progresses over time, the material is easily damaged by a small external impact, There is a problem that the wear stability is deteriorated and the repair due to corrosion is deformed.
또한, 포설시 주철관의 무게로 잠수 작업자의 작업 한계가 있어 포설시 포설비용이 과다한 문제점이 있고, 보호관을 이루는 재료의 물성이 염분에 의해 약해져 보호관으로서의 기능이 약화하는 문제점이 있었다.In addition, the weight of the cast iron pipe at the time of installation has a working limit of the diving operator, which causes an excessive installation cost at the time of installation, and the property of the material constituting the protective pipe is weakened by the salt, which weakens the function as a protective pipe.
이러한 문제를 해결하기 위해 대한민국 등록특허 제10-0887890호에서는 글리콜중합체 및 디이소시아네이트로 이루어진 프리폴리머 70 내지 90 중량부, 체인 확장제 5 내지 30 중량부, 산화방지제 0.03 내지 0.06 중량부, 난연제 0.1 내지 0.5 중량부 및 자외선차단제 0.02 내지 0.1 중량부를 포함하여 이루어진 것을 특징으로 하는 전선 및 파이프 보호관이 개시되어 있다.In order to solve such a problem, Korean Patent No. 10-0887890 discloses that 70 to 90 parts by weight of a prepolymer composed of a glycol polymer and a diisocyanate, 5 to 30 parts by weight of a chain extender, 0.03 to 0.06 part by weight of an antioxidant, And 0.02 to 0.1 part by weight of an ultraviolet screening agent.
하지만 상기 등록특허에서는 파이프를 수용하는 관 형태로 성형하는 것이기 때문에 보호 대상 파이프의 크기에 따라 규격이 달라지는 문제가 있다.However, in the above-mentioned patent, since the pipe is formed in the form of a pipe for receiving the pipe, there is a problem that the standard varies depending on the size of the pipe to be protected.
본 발명은 상기한 바와 같은 종래 기술의 문제점을 해결하기 위한 것으로서,본 발명의 목적은 중금속, TVOCs, 프탈레이트 가소제 등이 없으며, 파이프, 배관, 지주강관 등의 부식이나 침식, 손상을 방지할 수 있으며, 내 충격성, 내 부식성, 부착성능, 내열성 및 내마모성이 우수한 친환경 폴리우레탄 수지 제조방법 및 이를 이용한 파이프 보호용 시트 제조방법에 관한 것이다.SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to prevent corrosion, erosion and damage of pipes, piping, holding steel pipes, etc. without heavy metals, TVOCs, phthalate plasticizers, Resistant polyurethane resin excellent in impact resistance, corrosion resistance, adhesion performance, heat resistance and abrasion resistance, and a method for manufacturing a pipe protection sheet using the same.
상기한 목적을 달성하기 위하여 본 발명에 따른 친환경 폴리우레탄 수지 제조방법은 반응기에 폴리올 55~75 중량부와, 1,6-hexane diol 0.001~0.005 중량부와, DMPA(Dimethylolpropionic Acid) 0.001~0.003 중량부를 투입하는 단계와; 상기 반응기를 80~85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15~25 중량부를 90~120분 동안 적가하면서 중합하여 isocyanate prepolymer(NCO-terminated prepolymer)를 형성시키는 단계와; 상기 isocyanate prepolymer에 dibutylamine를 적하하여 역적정하는 단계와; 상기 반응기를 50~60℃로 냉각시킨 후 아세톤 3~5중량부와, 트리에탄올아민(TEA) 0.1~0.3 중량부를 혼합하여 주입하는 단계와; 상기 반응기를 25~40℃로 재냉각한 다음 증류수를 주입하여 pre-emulsion 상태의 혼합물을 마련하는 단계와; 상기 반응기에 증류수 0.1~5중량부와 아민류의 사슬 연장제 0.1~5중량부를 첨가한 다음 1~3시간 동안 숙성시킨 혼합물을 마련하는 단계와; 상기 숙성된 혼합물에 접착성 수지 10~25중량부와, 기능성 첨가제 2~10중량부를 첨가하는 단계;를 포함하는 것을 특징으로 한다.In order to achieve the above object, the present invention provides a process for preparing an environmentally friendly polyurethane resin, which comprises reacting 55 to 75 parts by weight of a polyol, 0.001 to 0.005 parts by weight of 1,6-hexane diol, 0.001 to 0.003 parts by weight of DMPA (dimethylolpropionic acid) A step of injecting a part; Gradually increasing the temperature of the reactor to 80 to 85 ° C. and polymerizing 15 to 25 parts by weight of p-MDI (polymeric diphenylmethane diisocyanate) dropwise for 90 to 120 minutes to form an isocyanate prepolymer (NCO-terminated prepolymer); Dibutylamine is added dropwise to the isocyanate prepolymer to reverse- After the reactor is cooled to 50 to 60 ° C, 3 to 5 parts by weight of acetone and 0.1 to 0.3 parts by weight of triethanolamine (TEA) are mixed and injected. Re-cooling the reactor to 25 to 40 캜 and then injecting distilled water to prepare a pre-emulsion mixture; 0.1 to 5 parts by weight of distilled water and 0.1 to 5 parts by weight of chain extender of amines are added to the reactor, followed by aging for 1 to 3 hours; 10 to 25 parts by weight of an adhesive resin and 2 to 10 parts by weight of a functional additive are added to the aged mixture.
또한, 본 발명에 따른 친환경 폴리우레탄 수지 제조방법에 있어서, 기능성 첨가제는 TiO2, WO3 ,MoO3 중에서 적어도 하나가 선택되며 평균입경이 1~500nm인 금속산화물 분말 1~10중량부와, 용제 40~65중량부와, 분산제 10~20중량부와, 실란계 커플링제 2~5중량부와, 무기 안료 0.5~2.5중량부와, 물 2~10중량부와, UV 안정제 0.5~0.7중량부를 혼합하여 이루어지는 것을 특징으로 한다.Further, in the process for producing an environmentally friendly polyurethane resin according to the present invention, the functional additive may include TiO 2 , WO 3 1 to 10 parts by weight of a metal oxide powder having an average particle diameter of 1 to 500 nm selected from at least one of MoO 3 and MoO 3 , 40 to 65 parts by weight of a solvent, 10 to 20 parts by weight of a dispersant, 2 to 5 parts by weight of a silane coupling agent 0.5 to 2.5 parts by weight of an inorganic pigment, 2 to 10 parts by weight of water and 0.5 to 0.7 parts by weight of a UV stabilizer.
또한, 본 발명에 따른 친환경 폴리우레탄 수지 제조방법에 있어서, 분산제는 알킬암모늄염이고, 상기 용제는 이소프로폭시에탄올인 것을 특징으로 한다.Further, in the method for producing an environmentally friendly polyurethane resin according to the present invention, the dispersant is an alkylammonium salt, and the solvent is isopropoxyethanol.
또한, 본 발명에 따른 친환경 폴리우레탄 수지 제조방법에 있어서, 실란계 커플링제는 한쪽 말단에 에폭시기 또는 아민기를 가지고, 다른 말단에 실란기를 가지고 있는 것을 특징으로 한다.In the method for producing an environmentally friendly polyurethane resin according to the present invention, the silane-based coupling agent is characterized by having an epoxy group or an amine group at one end and a silane group at the other end.
또한, 본 발명에 따른 친환경 폴리우레탄 수지 제조방법에 있어서, 실란계 커플링제는 glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyltrimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane, phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane, aminoethyl aminopropyl methyltriethoxy silane 중에서 적어도 하나가 선택되는 것을 특징으로 한다.In the method for producing an environmentally friendly polyurethane resin according to the present invention, the silane-based coupling agent may be selected from glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, at least one of silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane, phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane and aminoethyl aminopropyl methyltriethoxy silane.
또한, 본 발명에 따른 친환경 폴리우레탄 수지 제조방법에 있어서, 접착성 수지는 아크릴 수지, 에폭시 수지, 우레탄 수지, 변성 아크릴 고무계 에멀젼 및 변성 아크릴 우레탄 고무계 에멀젼 중 적어도 어느 하나가 선택되는 것을 특징으로 한다.Further, in the method for producing an environmentally friendly polyurethane resin according to the present invention, the adhesive resin is characterized in that at least one of acrylic resin, epoxy resin, urethane resin, modified acrylic rubber emulsion and modified acrylic urethane rubber emulsion is selected.
또한, 본 발명에 따른 파이프 보호용 시트 제조방법은, 탄산칼슘과 수산화나트륨을 1 : 0.3~1의 중량비로 혼합한 무기충전재를 마련하는 단계와; 상기 무기충전재 45~55중량%와, CMC(carboxymethylcellulose) 0.5~5중량%와, 잔량의 증류수를 포함하는 수용액을 마련하는 단계와; 유리섬유 원단 표면에 상기 수용액을 도포 또는 분사하여 코팅하는 단계와; 청구항 제1항의 폴리우레탄 수지에 상기 수용액으로 코팅된 유리섬유 원단을 함침하는 단계와;According to another aspect of the present invention, there is provided a method of manufacturing a pipe protecting sheet, comprising: providing an inorganic filler in which calcium carbonate and sodium hydroxide are mixed at a weight ratio of 1: 0.3 to 1; Preparing an aqueous solution containing 45 to 55% by weight of the inorganic filler, 0.5 to 5% by weight of carboxymethylcellulose (CMC), and a residual amount of distilled water; Applying or spraying the aqueous solution onto the glass fiber fabric surface; Impregnating the polyurethane resin of claim 1 with a glass fiber fabric coated with the aqueous solution;
상기 폴리우레탄 수지가 완전 경화되기 전 유리섬유 원단을 한 쌍의 롤러에 통과시켜 평탄화하는 단계;를 포함하되,Passing the glass fiber fabric through a pair of rollers before the polyurethane resin is fully cured,
상기 폴리우레탄 수지는,The above-
질소를 통과시키고 60~65℃로 가열된 분위기의 반응기에 폴리올 55~75 중량부와, 1,6-hexane diol 0.001~0.005 중량부와, DMPA(Dimethylolpropionic Acid) 0.001~0.003 중량부를 투입하는 단계와; 상기 반응기를 80~85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15~25 중량부를 90~120분 동안 적가하면서 중합하여 isocyanate prepolymer(NCO-terminated prepolymer)를 형성시키는 단계와; 상기 isocyanate prepolymer에 dibutylamine를 적하하여 역적정하는 단계와; 상기 반응기를 50~60℃로 냉각시킨 후 아세톤 3~5중량부와, 트리에탄올아민(TEA) 0.1~0.3 중량부를 혼합하여 주입하는 단계와; 상기 반응기를 25~40℃로 재냉각한 다음 증류수를 주입하여 pre-emulsion 상태의 혼합물을 마련하는 단계와; 상기 혼합물 100중량부를 기준으로 증류수 0.1~5중량부와 아민류의 사슬 연장제를 첨가한 다음 1~3시간 동안 숙성시킨 혼합물을 마련하는 단계와; 상기 숙성된 혼합물에 접착성 수지 10~25중량부와, 기능성 첨가제 2~10중량부를 첨가하는 단계;를 포함하여 얻어지는 것을 특징으로 한다.55 to 75 parts by weight of a polyol, 0.001 to 0.005 part by weight of 1,6-hexane diol and 0.001 to 0.003 part by weight of DMPA (Dimethylolpropionic Acid) are fed into a reactor having an atmosphere of nitrogen and passed through at 60 to 65 DEG C ; Gradually increasing the temperature of the reactor to 80 to 85 ° C. and polymerizing 15 to 25 parts by weight of p-MDI (polymeric diphenylmethane diisocyanate) dropwise for 90 to 120 minutes to form an isocyanate prepolymer (NCO-terminated prepolymer); Dibutylamine is added dropwise to the isocyanate prepolymer to reverse- After the reactor is cooled to 50 to 60 ° C, 3 to 5 parts by weight of acetone and 0.1 to 0.3 parts by weight of triethanolamine (TEA) are mixed and injected. Re-cooling the reactor to 25 to 40 캜 and then injecting distilled water to prepare a pre-emulsion mixture; 0.1 to 5 parts by weight of distilled water and an amine chain extender are added based on 100 parts by weight of the mixture, followed by aging for 1 to 3 hours; 10 to 25 parts by weight of an adhesive resin and 2 to 10 parts by weight of a functional additive to the aged mixture.
본 발명에서 제안하고 있는 친환경 폴리우레탄 수지 제조방법 및 이를 이용한 파이프 보호용 시트 제조방법에 의하면, 중금속, TVOCs, 프탈레이트 가소제 등이 없으며, 파이프, 배관, 지주강관 등의 부식이나 침식, 손상을 방지할 수 있으며, 내 충격성, 내 부식성, 부착성능, 내열성 및 내마모성이 우수하다.According to the method for manufacturing an environmentally friendly polyurethane resin proposed in the present invention and the method for manufacturing a pipe protecting sheet using the same, there are no heavy metals, TVOCs, phthalate plasticizers, and can prevent corrosion, erosion and damage of pipes, pipes, And is excellent in impact resistance, corrosion resistance, adhesion performance, heat resistance and abrasion resistance.
도 1은 본 발명에 따른 파이프 보호용 시트 제조방법의 각 단계를 도시하는 공정도이다.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process diagram showing each step of a method for manufacturing a pipe protecting sheet according to the present invention. Fig.
이하 본 발명의 바람직한 실시예에 대하여 구체적으로 설명한다.Hereinafter, preferred embodiments of the present invention will be described in detail.
본 발명을 설명함에 있어서, 관련된 공지기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명은 생략한다. 또한, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 판례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, the terms described below are defined in consideration of the functions of the present invention, and these may vary depending on the intention of the user, the operator, or the precedent. Therefore, the definition should be based on the contents throughout this specification.
도 1은 본 발명에 따른 파이프 보호용 시트 제조방법의 각 단계를 도시하는 공정도이다.BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process diagram showing each step of a method for manufacturing a pipe protecting sheet according to the present invention. Fig.
도 1을 참조하면, 본 발명에 따른 파이프 보호용 시트는 중금속, TVOCs, 프탈레이트 가소제 등이 없으며, 파이프, 배관, 지주강관 등의 부식이나 침식, 손상을 방지할 수 있으며, 내 충격성, 내 부식성, 부착성능, 내열성 및 내마모성이 우수한 친환경 폴리우레탄 수지를 이용하여 제조되는 것을 특징으로 한다.1, the pipe protecting sheet according to the present invention is free from heavy metals, TVOCs, and phthalate plasticizers, and can prevent corrosion, erosion and damage of pipes, pipes, holding steel pipes, etc., and is excellent in impact resistance, And is produced using an environmentally friendly polyurethane resin having excellent performance, heat resistance and abrasion resistance.
구체적으로, 본 발명에 따른 파이프 보호용 시트 제조방법은 탄산칼슘과 수산화나트륨을 1 : 0.3~1의 중량비로 혼합한 무기충전재를 마련하는 S1단계와, 상기 무기충전재 45~55중량%와, CMC(carboxymethylcellulose) 0.5~5중량%와, 잔량의 증류수를 포함하는 수용액을 마련하는 S2단계와, 유리섬유 원단 표면에 상기 수용액을 도포 또는 분사하여 코팅하는 S3단계와, 친환경 폴리우레탄 수지에 상기 수용액으로 코팅된 유리섬유 원단을 함침하는 S4단계와, 상기 폴리우레탄 수지에 함침된 원단을 꺼낸 다음, 폴리우레탄 수지가 완전 경화되기 전 유리섬유 원단을 한 쌍의 롤러에 통과시켜 압착하여 평탄화하는 S5단계를 포함하여 이루어진다. 여기서, 유리섬유 원단은 유리섬유로 직조된 원단인 것을 예시할 수 있다.Specifically, the method for producing a pipe protecting sheet according to the present invention comprises a step S1 of providing an inorganic filler in which calcium carbonate and sodium hydroxide are mixed at a weight ratio of 1: 0.3 to 1, 45 to 55 weight% of the inorganic filler, carboxymethylcellulose, 0.5 to 5% by weight, and a residual amount of distilled water; Step S3: coating or spraying the aqueous solution onto the surface of the glass fiber fabric surface, and coating the environmentally-friendly polyurethane resin with the aqueous solution A step S4 of infiltrating the glass fiber fabric into the polyurethane resin, and a step S5 of taking the fabric impregnated in the polyurethane resin before the polyurethane resin is completely cured, passing the glass fiber cloth through a pair of rollers, . Here, the glass fiber fabric may be a fabric that is woven with glass fiber.
본 발명에 따른 파이프 보호용 시트는 폴리우레탄 수지가 완전 경화되기 전에 파이프 등에 직접 부착할 수도 있고, 별도의 접착제를 시트 일면에 도포한 다음 파이프에 부착할 수도 있다.The pipe protecting sheet according to the present invention may be directly attached to a pipe or the like before the polyurethane resin is completely cured, or may be applied to one side of the sheet after attaching another adhesive to the pipe.
상기 S4단계의 친환경 폴리우레탄 수지는 크게 S4-1단계 내지 S4-7단계를 순차적으로 수행하여 제조되는 것을 예시할 수 있다.The eco-friendly polyurethane resin in step S4 may be prepared by sequentially performing steps S4-1 to S4-7.
상기 S4-1단계에서는 질소를 통과시키고 60~65℃로 가열된 분위기의 반응기에 폴리올 55~75 중량부와, 1,6-hexane diol 0.001~0.005 중량부와, DMPA(Dimethylolpropionic Acid) 0.001~0.003 중량부를 투입한다.In the step S4-1, 55 to 75 parts by weight of a polyol, 0.001 to 0.005 part by weight of 1,6-hexane diol, 0.001 to 0.003 parts by weight of DMPA (Dimethylolpropionic Acid) Weight part is put in.
여기서, 폴리올은 폴리에스테르 폴리올, 폴리에테르 폴리올 또는 폴리카보네이트 폴리올 중 선택된 어느 하나인 것을 예시할 수 있다.Here, the polyol may be any one selected from a polyester polyol, a polyether polyol or a polycarbonate polyol.
상기 S4-2단계에서는 상기 반응기를 80~85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15~25 중량부를 90~120분 동안 적가하면서 중합하여 isocyanate prepolymer(NCO-terminated prepolymer)를 형성시킨다.In step S4-2, the reactor is gradually heated to 80 to 85 ° C., and 15 to 25 parts by weight of polymeric diphenylmethane diisocyanate (p-MDI) is added dropwise for 90 to 120 minutes to form an isocyanate prepolymer (NCO-terminated prepolymer) .
상기 S4-3단계는 반응기에 수용된 isocyanate prepolymer에 dibutylamine 0.1~10중량부를 10~30분 동안 적하하여 이루어진다.In step S4-3, 0.1 to 10 parts by weight of dibutylamine is added dropwise to the isocyanate prepolymer contained in the reactor for 10 to 30 minutes.
상기 S4-4단계에서는 반응기를 50~60℃로 냉각시킨 후 아세톤 3~5중량부와, 트리에탄올아민(TEA) 0.1~0.3 중량부를 혼합하여 주입한다.In step S4-4, the reactor is cooled to 50 to 60 DEG C, and 3 to 5 parts by weight of acetone and 0.1 to 0.3 part by weight of triethanolamine (TEA) are mixed and injected.
상기 S4-5단계에서는 반응기를 25~40℃로 재냉각한 다음 증류수를 주입하여 pre-emulsion 상태의 혼합물을 마련한다.In step S4-5, the reactor is re-cooled to 25 to 40 DEG C, and distilled water is injected to prepare a pre-emulsion mixture.
상기 S4-6단계에서는 상기 S4-5단계의 혼합물이 수용된 반응기에 증류수 0.1~5중량부와 아민류의 사슬 연장제 0.01~1중량부를 첨가한 다음 1~3시간 동안 숙성시킨 혼합물을 마련한다.In step S4-6, 0.1 to 5 parts by weight of distilled water and 0.01 to 1 part by weight of an amine chain extender are added to the reactor containing the mixture of step S4-5 and then aged for 1 to 3 hours.
여기서, 아민류 사슬 연장제는 헥사메틸렌디아민( Hexamethylenediamine) 또는 m-페닐렌디아민(m-Phenylenediamine)인 것을 예시할 수 있다.Here, the amine chain extending agent may be exemplified by hexamethylenediamine or m-phenylenediamine.
상기 S4-7단계에서는 S4-6단계의 숙성된 혼합물이 수용된 반응기에 접착성 수지 10~25중량부와, 기능성 첨가제 2~10중량부를 혼합하여 친환경 폴리우레탄 수지 제조를 완료하게 된다.In the step S4-7, 10 to 25 parts by weight of the adhesive resin and 2 to 10 parts by weight of the functional additive are mixed in the reactor containing the aged mixture of step S4-6 to complete the production of the environmentally friendly polyurethane resin.
상기 접착성 수지는 아크릴 수지, 에폭시 수지, 우레탄 수지, 변성 아크릴 고무계 에멀젼 수지 및 변성 아크릴 우레탄 고무계 에멀젼 수지 중 적어도 어느 하나가 선택되는 것을 예시할 수 있다.The adhesive resin may be at least one selected from acrylic resin, epoxy resin, urethane resin, modified acrylic rubber emulsion resin and modified acrylic urethane rubber emulsion resin.
여기서, 변성 아크릴 고무계 에멀젼 수지는 아크릴 수지를 고무계 에멀젼 수지에 혼합하여 이루어진 것이다.Here, the modified acrylic rubber emulsion resin is formed by mixing an acrylic resin with a rubber emulsion resin.
상기 기능성 첨가제는 금속산화물 분말 1~10중량부와, 용제 40~65중량부와, 분산제 10~20중량부와, 실란계 커플링제 2~5중량부와, 무기 안료 0.5~2.5중량부와, 물 2~10중량부와, UV 안정제 0.5~0.7중량부를 혼합하여 이루어지는 것을 예시할 수 있다.Wherein the functional additive comprises 1 to 10 parts by weight of a metal oxide powder, 40 to 65 parts by weight of a solvent, 10 to 20 parts by weight of a dispersant, 2 to 5 parts by weight of a silane coupling agent, 0.5 to 2.5 parts by weight of an inorganic pigment, 2 to 10 parts by weight of water, and 0.5 to 0.7 parts by weight of a UV stabilizer.
여기서, 금속산화물 분말은 TiO2, WO3 ,MoO3 중에서 적어도 하나가 선택되며, 그 평균입경이 1~500nm인 것을 예시할 수 있다.Here, the metal oxide powder may be TiO 2 , WO 3 , And MoO 3 , and has an average particle diameter of 1 to 500 nm.
상기 용제는 이소프로폭시에탄올, 에톡시에탄올, 메틸에틸케톤 및 메톡시에탄올 중에서 선택될 수 있고, 분산제는 알킬암모늄염인 것을 예시할 수 있다.The solvent may be selected from isopropoxy ethanol, ethoxy ethanol, methyl ethyl ketone and methoxy ethanol, and the dispersing agent may be an alkyl ammonium salt.
상기 실란계 커플링제는 한쪽 말단에 에폭시기를 가지고, 다른 말단에 실란기를 가지고 있는 것, 또는 한쪽 말단에 아민기를 가지고 다른 말단에 실란기를 가지고 있는 두 종류의 커플링제 사용이 가능하다.The silane-based coupling agent can use two kinds of coupling agents having an epoxy group at one end and a silane group at the other end, or an amine group at one end and a silane group at the other end.
이러한 구조를 가진 실란계 커플링제는 glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyltrimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane, phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane, aminoethyl aminopropyl methyltriethoxy silane 등을 예시할 수 있다. 이러한 실란 커플링제는 결합력 내지 접착력을 크게 향상시키는 역할을 한다.The silane-based coupling agent having such a structure may be selected from glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane, phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane, and aminoethyl aminopropyl methyltriethoxy silane. Such a silane coupling agent plays a role of greatly enhancing bonding force or adhesion force.
이하에서는 본 발명에 따른 친환경 폴리우레탄 수지 제조방법의 바람직한 실시예를 통해 보다 상세하게 설명한다.Hereinafter, a method of manufacturing an environmentally friendly polyurethane resin according to the present invention will be described in more detail with reference to preferred embodiments.
친환경 폴리우레탄 수지 제조Eco-friendly polyurethane resin manufacturing
먼저, 질소 분위기이며 65℃로 가열된 반응기에 폴리올 55~75 중량부와, 1,6-hexane diol 0.001~0.005 중량부와, DMPA(Dimethylolpropionic Acid) 0.001~0.003 중량부를 투입한다.First, 55 to 75 parts by weight of polyol, 0.001 to 0.005 part by weight of 1,6-hexane diol, and 0.001 to 0.003 part by weight of DMPA (Dimethylolpropionic Acid) are introduced into a reactor heated to 65 DEG C in a nitrogen atmosphere.
다음으로, 반응기를 85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15 중량부를 90분 동안 적가한 다음, dibutylamine 1중량부를 10분 동안 적하한다.Next, the reactor was gradually heated to 85 DEG C, 15 parts by weight of p-MDI (polymeric diphenylmethane diisocyanate) was added dropwise for 90 minutes, and 1 part by weight of dibutylamine was added dropwise over 10 minutes.
그 다음으로, 반응기를 50℃로 냉각시킨 후 아세톤 3중량부와, 트리에탄올아민(TEA) 0.1 중량부를 주입한 다음 10분 동안 교반한다.Next, the reactor was cooled to 50 DEG C, 3 parts by weight of acetone and 0.1 part by weight of triethanolamine (TEA) were added, followed by stirring for 10 minutes.
그 다음으로, 반응기를 25~40℃로 재냉각한 다음 증류수 5중량부와, m-페닐렌디아민 0.1중량부를 첨가한 다음 1시간 동안 교반한다.Next, the reactor is re-cooled to 25 to 40 DEG C, and then 5 parts by weight of distilled water and 0.1 part by weight of m-phenylenediamine are added, followed by stirring for 1 hour.
그 다음으로, 반응기에 아크릴 수지를 고무계 에멀젼 수지에 혼합하여 이루어진 변성 아크릴 고무계 에멀젼 수지 10중량부와, 기능성 첨가제 5중량부를 첨가한다.Next, 10 parts by weight of a modified acryl rubber emulsion resin obtained by mixing an acrylic resin in a rubber emulsion resin with a reactor, and 5 parts by weight of a functional additive were added.
여기서, 기능성 첨가제는 TiO2 분말 5중량부와, 이소프로폭시에탄올 40중량부와, 알킬암모늄염 10중량부와, glycidyloxypropyl trimethoxy silane 2중량부와, 무기 안료 2중량부와, 물 10중량부와, UV 안정제 0.5중량부를 혼합하여 얻었다.5 parts by weight of TiO 2 powder, 40 parts by weight of isopropoxy ethanol, 10 parts by weight of an alkylammonium salt, 2 parts by weight of glycidyloxypropyl trimethoxy silane, 2 parts by weight of an inorganic pigment, 10 parts by weight of water, And 0.5 parts by weight of a UV stabilizer.
[비교예 1][Comparative Example 1]
실시예 1에서 기능성 첨가제를 사용하지 않은 것을 제외하고 동일한 방법으로 폴리우레탄 수지를 제조하였다.A polyurethane resin was prepared in the same manner as in Example 1, except that the functional additive was not used.
상기 실시예 1 및 비교예 1의 폴리우레탄 수지를 450× 350× 2mm(인장강도 및 신장률 시험용), 40× 40× 2mm(접착강도 시험용)의 몰드에 다진 후 성형하여 만든 시편을 대상으로 KS F 4919(시멘트 혼입 폴리머계 방수재)에 준하여 인장강도 및 접착강도 시험을 수행하였고, KS F 4919(시멘트 혼입 폴리머계 방수재)에 준하여 신장률을 측정하였고, 그 결과를 아래 표 1에 나타내었다.The specimens obtained by molding the polyurethane resin of Example 1 and Comparative Example 1 in a mold of 450 × 350 × 2 mm (for tensile strength and elongation test) and 40 × 40 × 2 mm (for bonding strength test) 4919 (cement-incorporated polymer-based waterproofing material), and the elongation percentage was measured according to KS F 4919 (cement-incorporated polymer-based waterproofing material). The results are shown in Table 1 below.
위 표 1에서 확인할 수 있듯이 기능성 첨가제를 사용한 실시예 1의 물성이 우수하다는 것을 확인할 수 있었다.As shown in Table 1, it was confirmed that the physical properties of Example 1 using the functional additive were excellent.
파이프 보호용 시트 제조Manufacture of pipe protection sheet
탄산칼슘과 수산화나트륨을 1 : 0.5의 중량비로 혼합한 무기충전재를 마련한 다.An inorganic filler is prepared by mixing calcium carbonate and sodium hydroxide in a weight ratio of 1: 0.5.
무기충전재 45중량%와, CMC(carboxymethylcellulose) 1중량%와, 잔량의 증류수로 이루어지는 수용액을 마련한 다음, 유리섬유 원단 표면에 도포한다.45% by weight of an inorganic filler, 1% by weight of carboxymethylcellulose (CMC) and distilled water of a remaining amount is prepared and then coated on the surface of the glass fiber fabric.
유리섬유 원단에 실시예 1의 폴리우레탄 수지를 함침한 다음, 한 쌍의 압착롤러에 통과시켜 파이프 보호용 시트를 제조한다.The glass fiber fabric was impregnated with the polyurethane resin of Example 1 and then passed through a pair of compression rollers to produce a pipe protection sheet.
[비교예 2][Comparative Example 2]
실시예 2에서 실시예 1의 폴리우레탄 수지 대신 비교예 1의 폴리우레탄 수지를 사용한 것을 제외하고 동일한 방법으로 파이프 보호용 시트를 제조하였다.A pipe protecting sheet was prepared in the same manner as in Example 2, except that the polyurethane resin of Comparative Example 1 was used instead of the polyurethane resin of Example 1.
실시예 2 및 비교예 2의 파이프 보호용 시트에 대하여 인장강도(kgf/50mm) 및 테이퍼 마모시험 시험을 하였으며, 그 결과는 아래 표 2와 같다.Tensile strength (kgf / 50 mm) and taper abrasion test test were conducted on the pipe protection sheets of Example 2 and Comparative Example 2, and the results are shown in Table 2 below.
위 표 2에서 확인할 수 있듯이 기능성 첨가제를 사용한 실시예 2의 인장강도 및 내 마모성이 우수하다는 것을 확인할 수 있었다.As shown in Table 2, it was confirmed that the tensile strength and abrasion resistance of Example 2 using the functional additive were excellent.
이상에서 설명된 본 발명은 예시적인 것에 불과하며, 본 발명이 속한 기술분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 잘 알 수 있을 것이다. 그러므로 본 발명은 상기의 상세한 설명에서 언급되는 형태로만 한정되는 것은 아님을 잘 이해할 수 있을 것이다. 따라서 본 발명의 진정한 기술적 보호 범위는 첨부된 특허청구범위의 기술적 사상에 의해 정해져야 할 것이다. 또한, 본 발명은 첨부된 청구범위에 의해 정의되는 본 발명의 정신과 그 범위 내에 있는 모든 변형물과 균등물 및 대체물을 포함하는 것으로 이해되어야 한다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Therefore, it is to be understood that the present invention is not limited to the above-described embodiments. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims. It is also to be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (7)
상기 반응기를 80~85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15~25 중량부를 90~120분 동안 적가하면서 중합하여 isocyanate prepolymer(NCO-terminated prepolymer)를 형성시키는 단계와;
상기 isocyanate prepolymer에 dibutylamine를 적하하여 역적정하는 단계와;
상기 반응기를 50~60℃로 냉각시킨 후 아세톤 3~5중량부와, 트리에탄올아민(TEA) 0.1~0.3 중량부를 혼합하여 주입하는 단계와;
상기 반응기를 25~40℃로 재냉각한 다음 증류수를 주입하여 pre-emulsion 상태의 혼합물을 마련하는 단계와;
상기 반응기에 증류수 0.1~5중량부와 아민류의 사슬 연장제 0.1~5중량부를 첨가한 다음 1~3시간 동안 숙성시킨 혼합물을 마련하는 단계와;
상기 숙성된 혼합물에 접착성 수지 10~25중량부와, 기능성 첨가제 2~10중량부를 첨가하는 단계;
를 포함하는 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
55 to 75 parts by weight of a polyol, 0.001 to 0.005 part by weight of 1,6-hexane diol, and 0.001 to 0.003 part by weight of DMPA (Dimethylolpropionic Acid) are fed into a reactor.
Gradually increasing the temperature of the reactor to 80 to 85 ° C. and polymerizing 15 to 25 parts by weight of p-MDI (polymeric diphenylmethane diisocyanate) dropwise for 90 to 120 minutes to form an isocyanate prepolymer (NCO-terminated prepolymer);
Dibutylamine is added dropwise to the isocyanate prepolymer to reverse-
After the reactor is cooled to 50 to 60 ° C, 3 to 5 parts by weight of acetone and 0.1 to 0.3 parts by weight of triethanolamine (TEA) are mixed and injected.
Re-cooling the reactor to 25 to 40 캜 and then injecting distilled water to prepare a pre-emulsion mixture;
0.1 to 5 parts by weight of distilled water and 0.1 to 5 parts by weight of chain extender of amines are added to the reactor, followed by aging for 1 to 3 hours;
Adding 10 to 25 parts by weight of an adhesive resin and 2 to 10 parts by weight of a functional additive to the aged mixture;
Based on the weight of the polyurethane resin.
상기 기능성 첨가제는,
TiO2, WO3 ,MoO3 중에서 적어도 하나가 선택되며 평균입경이 1~500nm인 금속산화물 분말 1~10중량부와, 용제 40~65중량부와, 분산제 10~20중량부와, 실란계 커플링제 2~5중량부와, 무기 안료 0.5~2.5중량부와, 물 2~10중량부와, UV 안정제 0.5~0.7중량부를 혼합하여 이루어지는 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
The method according to claim 1,
The above-
TiO 2 , WO 3 1 to 10 parts by weight of a metal oxide powder having an average particle diameter of 1 to 500 nm selected from at least one of MoO 3 and MoO 3 , 40 to 65 parts by weight of a solvent, 10 to 20 parts by weight of a dispersant, 2 to 5 parts by weight of a silane coupling agent 0.5 to 2.5 parts by weight of an inorganic pigment, 2 to 10 parts by weight of water, and 0.5 to 0.7 parts by weight of a UV stabilizer.
상기 분산제는 알킬암모늄염이고,
상기 용제는 이소프로폭시에탄올인 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
3. The method of claim 2,
The dispersant is an alkylammonium salt,
Wherein the solvent is isopropoxyethanol. ≪ RTI ID = 0.0 > 8. < / RTI >
상기 실란계 커플링제는 한쪽 말단에 에폭시기 또는 아민기를 가지고, 다른 말단에 실란기를 가지고 있는 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
3. The method of claim 2,
Wherein the silane-based coupling agent has an epoxy group or an amine group at one end and a silane group at the other end.
상기 실란계 커플링제는,
glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyltrimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane, phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane, aminoethyl aminopropyl methyltriethoxy silane 중에서 적어도 하나가 선택되는 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
The method of claim 3,
The silane-
glycidyloxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, glycidoxypropyl methyldiethoxy silane, glycidoxypropyl methyldimethoxy silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane, aminoethyl aminopropyl triethoxy silane, aminoethyl aminopropyl methyldimethoxy silane , phenyl aminopropyl trimethoxy silane, aminopropyl methyldimethoxy silane, aminopropyl methyldimethoxy silane and aminoethyl aminopropyl methyltriethoxy silane.
상기 접착성 수지는,
아크릴 수지, 에폭시 수지, 우레탄 수지, 변성 아크릴 고무계 에멀젼 및 변성 아크릴 우레탄 고무계 에멀젼 중 적어도 어느 하나가 선택되는 것을 특징으로 하는 친환경 폴리우레탄 수지 제조방법.
The method according to claim 1,
In the adhesive resin,
Wherein at least one of an acrylic resin, an epoxy resin, a urethane resin, a modified acrylic rubber emulsion and a modified acrylic urethane rubber emulsion is selected.
상기 무기충전재 45~55중량%와, CMC(carboxymethylcellulose) 0.5~5중량%와, 잔량의 증류수를 포함하는 수용액을 마련하는 단계와;
유리섬유 원단 표면에 상기 수용액을 도포 또는 분사하여 코팅하는 단계와;
청구항 제1항의 폴리우레탄 수지에 상기 수용액으로 코팅된 유리섬유 원단을 함침하는 단계와;
상기 폴리우레탄 수지가 완전 경화되기 전 유리섬유 원단을 한 쌍의 롤러에 통과시켜 평탄화하는 단계;를 포함하되,
상기 폴리우레탄 수지는,
질소를 통과시키고 60~65℃로 가열된 분위기의 반응기에 폴리올 55~75 중량부와, 1,6-hexane diol 0.001~0.005 중량부와, DMPA(Dimethylolpropionic Acid) 0.001~0.003 중량부를 투입하는 단계와;
상기 반응기를 80~85℃까지 서서히 승온시킨 후 p-MDI(polymeric diphenylmethane diisocyanate) 15~25 중량부를 90~120분 동안 적가하면서 중합하여 isocyanate prepolymer(NCO-terminated prepolymer)를 형성시키는 단계와;
상기 isocyanate prepolymer에 dibutylamine를 적하하여 역적정하는 단계와;
상기 반응기를 50~60℃로 냉각시킨 후 아세톤 3~5중량부와, 트리에탄올아민(TEA) 0.1~0.3 중량부를 혼합하여 주입하는 단계와;
상기 반응기를 25~40℃로 재냉각한 다음 증류수를 주입하여 pre-emulsion 상태의 혼합물을 마련하는 단계와;
상기 혼합물 100중량부를 기준으로 증류수 0.1~5중량부와 아민류의 사슬 연장제를 첨가한 다음 1~3시간 동안 숙성시킨 혼합물을 마련하는 단계와;
상기 숙성된 혼합물에 접착성 수지 10~25중량부와, 기능성 첨가제 2~10중량부를 첨가하는 단계;를 포함하여 얻어지는 것을 특징으로 하는 파이프 보호용 시트 제조방법.Providing an inorganic filler in which calcium carbonate and sodium hydroxide are mixed at a weight ratio of 1: 0.3 to 1;
Preparing an aqueous solution containing 45 to 55% by weight of the inorganic filler, 0.5 to 5% by weight of carboxymethylcellulose (CMC), and a residual amount of distilled water;
Applying or spraying the aqueous solution onto the glass fiber fabric surface;
Impregnating the polyurethane resin of claim 1 with a glass fiber fabric coated with the aqueous solution;
Passing the glass fiber fabric through a pair of rollers before the polyurethane resin is fully cured,
The above-
55 to 75 parts by weight of a polyol, 0.001 to 0.005 part by weight of 1,6-hexane diol and 0.001 to 0.003 part by weight of DMPA (Dimethylolpropionic Acid) are fed into a reactor having an atmosphere of nitrogen and passed through at 60 to 65 DEG C ;
Gradually increasing the temperature of the reactor to 80 to 85 ° C. and polymerizing 15 to 25 parts by weight of p-MDI (polymeric diphenylmethane diisocyanate) dropwise for 90 to 120 minutes to form an isocyanate prepolymer (NCO-terminated prepolymer);
Dibutylamine is added dropwise to the isocyanate prepolymer to reverse-
After the reactor is cooled to 50 to 60 ° C, 3 to 5 parts by weight of acetone and 0.1 to 0.3 parts by weight of triethanolamine (TEA) are mixed and injected.
Re-cooling the reactor to 25 to 40 캜 and then injecting distilled water to prepare a pre-emulsion mixture;
0.1 to 5 parts by weight of distilled water and an amine chain extender are added based on 100 parts by weight of the mixture, followed by aging for 1 to 3 hours;
10 to 25 parts by weight of an adhesive resin and 2 to 10 parts by weight of a functional additive are added to the aged mixture.
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