KR102017064B1 - Fabrication of pmma resin with high-elastic high-instrength steel and manufacturing method thereof - Google Patents
Fabrication of pmma resin with high-elastic high-instrength steel and manufacturing method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract
Description
본 발명은 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법에 관한 것으로서, 보다 상세하게는, 상온에서 경화시킬 수 있고, 고탄성 및 고인장강도를 제공하여 국제규격에 적합한 논 슬립 방수 바닥재, 고속철도 방수재, 도로 보수재, 인테리어 칼라 디자인 방수 바닥재, 급식소 식품공장 위생 안전용 방수 바닥재 등의 다양한 제품을 제조할 수 있는 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a high-elasticity high tensile strength PMMA resin composition and a method for manufacturing the same, and more particularly, to a non-slip waterproof flooring material, high-speed rail waterproofing material, which can be cured at room temperature, providing high elasticity and high tensile strength, suitable for international standards, The present invention relates to a highly elastic high tensile strength PMMA resin composition and a method of manufacturing the same, which can manufacture various products such as road repairing materials, interior color design waterproofing flooring, and food factory hygiene safety waterproofing flooring.
일반적으로 바닥재는 주로 건물, 주택 등의 건축물의 바닥을 마감하는 용도로 사용되는 시트, 장판, 타일 등으로서, 시멘트 바닥으로부터 먼지 및 냉기를 차단하여 위생적인 공간을 제공하고, 다양한 무늬가 인쇄되어 있어 고객 취향에 따라 실내 분위기를 변경할 수 있는 등의 장식효과를 발휘할 수 있다.In general, flooring materials are sheets, floorboards, tiles, etc., which are mainly used for finishing the floor of buildings, houses, etc., and provide a sanitary space by blocking dust and cold from the cement floor, and various patterns are printed. According to the customer's taste, the decoration effect can be exerted.
통상 바닥재에 있어서, 인쇄층을 갖고 상부에 투명필름층을 갖는 경우 총휘발성유기화합물((otal Volatile Organic Compounds), 이하 "TVOCs"라 기재한다.)이 기준치 이상으로 방출되는 경우가 많다.In general, in the flooring material, total volatile organic compounds (hereinafter referred to as "TVOCs") are often released above the reference value when the printed layer has a transparent film layer on the top.
특히, 범용적으로 사용되는 PVC 타일의 경우 친환경 건축자재의 규정에 따른 TVOCs 방출량이 0.10 mg/m2h를 훨씬 넘기 때문에, TVOCs 방출량이 저감된 친환경적 바닥재에 대한 관심이 나날이 증가하고 있다.Particularly, in the case of general-purpose PVC tiles, since the TVOCs emission amount according to the regulations of eco-friendly building materials far exceeds 0.10 mg / m 2 h, there is increasing interest in environmentally friendly flooring materials with reduced TVOCs emission amount.
또한, 바닥재는 주택용 또는 상업용을 널리 사용되기 위하여 일정한 수준의 기계적 강도를 지녀야 하고, 제품의 표면 또한 일상적인 사용에 의해 스크래치 등이 발생하지 않을 정도의 경도를 보유할 필요가 있다.In addition, the flooring material must have a certain level of mechanical strength in order to be widely used for residential or commercial use, and the surface of the product also needs to have a hardness such that scratches do not occur due to daily use.
따라서 바닥재에 적용되는 투명필름층의 마모성능이 제품의 수명과 직결되는데, 투명필름층의 두께 조절만으로 바닥재의 강도를 보완하기에는 한계가 있다.Therefore, the wear performance of the transparent film layer applied to the flooring material is directly connected to the life of the product, there is a limit to supplement the strength of the flooring material only by adjusting the thickness of the transparent film layer.
상기한 문제점을 해결하기 위해 바닥재용 투명필름이 개발되었으며, 종래기술에 따른 투명필름은, 투명필름층, 인쇄층, 백색층 및 베이스층이 순차적으로 적층된 층을 포함하고, 투명필름층은 바닥재용 투명필름으로 형성된 것이고, 바닥재용 투명필름은 폴리염화비닐(Polyvinyl chloride) 수지, 아크릴 수지 및 고상의 열안정제를 포함하고, 폴리염화비닐 수지 100 중량부에 대하여, 아크릴 수지는 20 중량부 내지 27 중량부로 포함하고, 아크릴 수지의 ASTM1238의 조건에 따른 용융 지수(Melt Index)가 15g/10분 내지 25g/10분이고, 아크릴 수지는 폴리메틸메타아크릴레이트(PMMA) 수지이고, 폴리염화비닐 수지 100 중량부에 대하여, 고상의 열안정제는 0.1 중량부 내지 2 중량부를 포함하고, 고상의 열안정제는 Cd/Ba/Zn계, Cd/Ba계, Ba/Zn계, Na/Zn계, Sn계, Pb계, Cd계, Zn계 유기 복합 분말 안정제 및 이들의 조합으로 이루어진 군에서 선택된 적어도 하나를 포함한다.In order to solve the above problems, a transparent film for flooring has been developed, and the transparent film according to the prior art includes a layer in which a transparent film layer, a printing layer, a white layer, and a base layer are sequentially stacked, and the transparent film layer is a flooring material. It is formed of a transparent film for the floor, the transparent film for the flooring material includes a polyvinyl chloride resin, an acrylic resin and a solid heat stabilizer, with respect to 100 parts by weight of polyvinyl chloride resin, the acrylic resin is 20 to 27 parts by weight It is contained in parts by weight, the melt index (Melt Index) according to the conditions of ASTM1238 of the acrylic resin is 15g / 10 minutes to 25g / 10 minutes, the acrylic resin is a polymethyl methacrylate (PMMA) resin, 100 weight polyvinyl chloride resin To parts, the thermal stabilizer of the solid phase comprises 0.1 parts by weight to 2 parts by weight, and the thermal stabilizer of the solid phase is Cd / Ba / Zn-based, Cd / Ba-based, Ba / Zn-based, Na / Zn-based, Sn-based, or Pb. , Cd, Zn Organic Composites It includes at least one selected from the group consisting of the end of the stabilizer, and combinations thereof.
본 발명의 배경기술은 대한민국 등록특허공보 제10-1930708호(2018년 12월 20일 공고, 발명의 명칭 : 바닥재용 투명필름, 이의 제조방법 및 이를 포함하는 바닥재)에 개시되어 있다.Background art of the present invention is disclosed in Republic of Korea Patent Publication No. 10-1930708 (December 20, 2018, the name of the invention: transparent film for flooring, its manufacturing method and flooring comprising the same).
종래기술에 따른 바닥재용 수지는, 탄성 및 인장강도가 국제기준에 적합한 정도의 수치를 제공하지 못하기 때문에 해외 수출용으로 제조되는 다양한 바닥재에 사용될 수 없는 문제점이 있다.Resin for flooring according to the prior art, there is a problem that can not be used in various flooring manufactured for overseas export because the elasticity and tensile strength does not provide a value of a degree suitable for international standards.
따라서 이를 개선할 필요성이 요청된다.Therefore, there is a need for improvement.
본 발명은 상온에서 경화시킬 수 있고, 고탄성 및 고인장강도를 제공하여 국제규격에 적합한 논 슬립 방수 바닥재, 고속철도 방수재, 도로 보수재, 인테리어 칼라 디자인 방수 바닥재, 급식소 식품공장 위생 안전용 방수 바닥재 등의 다양한 제품을 제조할 수 있는 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법을 제공하는데 그 목적이 있다.The present invention can be cured at room temperature, providing high elasticity and high tensile strength, suitable for international standards, such as non-slip waterproof flooring, high-speed railway waterproofing, road repair, interior color design waterproofing flooring, food factory hygienic safety waterproof flooring, etc. It is an object of the present invention to provide a high elastic high tensile strength PMMA resin composition and a method for producing the same that can be manufactured.
본 발명은, PMMA 폴리머와, n-butyl acrylate(BA) 단량체와, methyl methacrylate 단량체와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체와, methacrylic acid(MAA) 단량체와, tripropyleneglycol diacrylate(TPGDA) 단량체를 포함하는 것을 특징으로 한다.The present invention relates to a PMMA polymer, an n-butyl acrylate (BA) monomer, a methyl methacrylate monomer, a 2-hydroxy ethyl methacrylate (2-HEMA) monomer, a methacrylic acid (MAA) monomer, and a tripropyleneglycol diacrylate (TPGDA) monomer. Characterized in that it comprises a.
또한, 본 발명의 상기 조성물은, n,n-dimethyl-p-toluidine(DMPT)로 이루어지는 경화촉진제와 혼합되는 것을 특징으로 한다.In addition, the composition of the present invention is characterized in that it is mixed with a curing accelerator consisting of n, n-dimethyl-p-toluidine (DMPT).
또한, 본 발명의 상기 조성물은, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함하는 것을 특징으로 한다.In addition, the composition of the present invention, 30 to 50% by weight PMMA polymer, 20 to 40% by weight n-butyl acrylate (BA) monomer, 10 to 30% by weight methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2 -HEMA) 5 to 10% by weight of monomer, 2 to 5% by weight of methacrylic acid (MAA) monomer, and 2 to 5% by weight of tripropyleneglycol diacrylate (TPGDA) monomer.
또한, 본 발명의 상기 조성물은, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지는 경화촉진제와 혼합되는 것을 특징으로 한다.In addition, the composition of the present invention is characterized in that it is mixed with a curing accelerator comprising 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT).
또한, 본 발명의 n,n-dimethyl-p-toluidine(DMPT)가 혼합되어 이루어지는 상기 조성물에 dibenzoyl peroxide(BPO) 1~2중량%가 혼합되는 것을 특징으로 한다.In addition, 1, 2% by weight of dibenzoyl peroxide (BPO) is mixed with the composition of n, n-dimethyl-p-toluidine (DMPT) of the present invention.
또한, 본 발명은, (a) PMMA 폴리머와, n-butyl acrylate(BA) 단량체와, methyl methacrylate 단량체와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체와, methacrylic acid(MAA) 단량체와, tripropyleneglycol diacrylate(TPGDA) 단량체를 혼합하여 60~70℃로 가열하는 단계; (b) 상기 조성물을 40~50℃로 냉각시킨 후에 n,n-dimethyl-p-toluidine(DMPT)를 혼합하는 단계; 및 (c) 상기 n,n-dimethyl-p-toluidine(DMPT)가 혼합되는 조성물을 상온으로 냉각시킨 후에 dibenzoyl peroxide(BPO)를 혼합하여 경화시키는 단계를 포함하는 것을 특징으로 한다.The present invention also relates to (a) PMMA polymer, n-butyl acrylate (BA) monomer, methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA) monomer, methacrylic acid (MAA) monomer, tripropyleneglycol mixing diacrylate (TPGDA) monomer and heating to 60 ~ 70 ℃; (b) mixing n, n-dimethyl-p-toluidine (DMPT) after cooling the composition to 40-50 ° C .; And (c) cooling the composition to which n, n-dimethyl-p-toluidine (DMPT) is mixed to room temperature, followed by curing by mixing dibenzoyl peroxide (BPO).
또한, 본 발명의 상기 (a)단계는, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함하여 이루어지는 것을 특징으로 한다.In addition, the step (a) of the present invention, 30-50% by weight of the PMMA polymer, 20-40% by weight of the n-butyl acrylate (BA) monomer, 10-30% by weight of the methyl methacrylate monomer, 2-hydroxy ethyl 5 to 10% by weight of methacrylate (2-HEMA) monomer, 2 to 5% by weight of methacrylic acid (MAA) monomer, and 2 to 5% by weight of tripropyleneglycol diacrylate (TPGDA) monomer.
또한, 본 발명의 상기 (b)단계는, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지는 경화촉진제와 혼합되어 이루어지는 것을 특징으로 한다.In addition, the step (b) of the present invention is characterized in that it is mixed with a curing accelerator comprising 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT).
또한, 본 발명의 상기 (c)단계는, dibenzoyl peroxide(BPO) 1~2중량%가 혼합되어 이루어지는 것을 특징으로 한다.In addition, the step (c) of the present invention is characterized in that 1 to 2% by weight of dibenzoyl peroxide (BPO) is mixed.
본 발명에 따른 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법은, PMMA 폴리머, n-butyl acrylate, methyl methacrylate, 2-hydroxy ethyl methacrylate, methacrylic acid, tripropyleneglycol diacrylate 및 n,n-dimethyl-p-toluidine로 이루어지는 경화촉진제가 포함되어 이루어지므로 신장률 100% 이상, 인장강도 10MPa 이상을 유지하는 바닥재를 제조할 수 있어 국제기준에 적합한 다양한 바닥재를 제공할 수 있는 이점이 있다.The high modulus high tensile strength PMMA resin composition and its preparation method according to the present invention are PMMA polymer, n-butyl acrylate, methyl methacrylate, 2-hydroxy ethyl methacrylate, methacrylic acid, tripropyleneglycol diacrylate and n, n-dimethyl-p-toluidine Since the curing accelerator is formed to be included, it is possible to manufacture a flooring material that maintains 100% or more of elongation and 10MPa or more of tensile strength, thereby providing various flooring materials suitable for international standards.
이하, 첨부된 도면들을 참조하여 본 발명에 따른 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법의 일 실시예를 설명한다.Hereinafter, with reference to the accompanying drawings will be described an embodiment of a high elastic high tensile strength PMMA resin composition and a method for manufacturing the same.
이러한 과정에서 도면에 도시된 선들의 두께나 구성요소의 크기 등은 설명의 명료성과 편의상 과장되게 도시되어 있을 수 있다.In this process, the thickness of the lines or the size of the components shown in the drawings may be exaggerated for clarity and convenience of description.
또한, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로써, 이는 사용자, 운용자의 의도 또는 관례에 따라 달라질 수 있다.In addition, terms to be described later are terms defined in consideration of functions in the present invention, which may vary according to a user's or operator's intention or custom.
그러므로 이러한 용어들에 대한 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.Therefore, the definitions of these terms should be made based on the contents throughout the specification.
본 발명의 일 실시예에 따른 고탄성 고인장강도 PMMA수지 조성물은, PMMA 폴리머와, n-butyl acrylate(BA) 단량체와, methyl methacrylate 단량체와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체와, methacrylic acid(MAA) 단량체와, tripropyleneglycol diacrylate(TPGDA) 단량체를 포함한다.Highly elastic high tensile strength PMMA resin composition according to an embodiment of the present invention, PMMA polymer, n-butyl acrylate (BA) monomer, methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA) monomer, methacrylic acid (MAA) monomers and tripropyleneglycol diacrylate (TPGDA) monomers.
PMMA수지는 메틸메타크릴레이트 단량체를 주성분으로 하는 수지를 말하며, 인간의 일상 생활에 널리 사용되는 소재로서, 콘택트렌즈, 인공 관절, 뼈 등으로 사용되고 있으며, PMMA수지를 이용하여 제조되는 바닥재 및 보수재로도 널리 사용되고 있다.PMMA resin is a resin mainly composed of methyl methacrylate monomer, and is widely used in human daily life. It is used as contact lens, artificial joint, bone, etc. Also widely used.
PMMA수지는 규칙적인 결합체로 구성되어 있어 미반응 물질로 인한 환경오염이 적고 작업 및 화재 시에 유독가스가 발생되지 않아 친환경적이며, 인체에 안전하다.PMMA resin is composed of regular binder, so it is less environmental pollution due to unreacted substances and it is eco-friendly and safe for human body because no toxic gas is generated during work and fire.
또한, PMMA수지는 빠른 건조 성능으로 인하여 바닥재로 사용되는 경우에 영하 30℃까지 작업이 가능하며, 마감공정 후 1시간 이내에 차량통행이 가능하여 도로 보수공사에 적합하고, 도막이 단단하고 내구성능이 좋아 내구수명이 긴 장점이 있다.In addition, PMMA resin can work up to minus 30 ℃ when used as a flooring material due to its fast drying performance, and it is suitable for road repair work within 1 hour after finishing process, and is suitable for road repair work. It has the advantage of long life.
본 실시예는, 상기한 바와 같은 PMMA 폴리머에 1관능성 단량체인 2-hydroxy ethyl methacrylate(2-HEMA)와, methacrylic acid(MAA)와, 2관능성 단량체인 tripropyleneglycol diacrylate(TPGDA)의 혼합하여 바닥재의 탄성 및 인장강도를 향상시킨 것이다.In this embodiment, a flooring material is prepared by mixing a monofunctional monomer, 2-hydroxy ethyl methacrylate (2-HEMA), methacrylic acid (MAA), and tripropyleneglycol diacrylate (TPGDA), which is a bifunctional monomer. The elasticity and tensile strength of the will be improved.
따라서 본 실시예의 바닥재는, 인장강도를 향상시켜 고진동이나 큰 힘을 받는 고속철도와 같은 특수 부위에 사용할 수 있는 바닥재를 제공할 수 있고, 바닥재에 크랙이 발생되는 것을 방지할 수 있게 된다.Therefore, the flooring material of the present embodiment can provide a flooring material which can be used for a special part such as high-speed railway under high vibration or large force by improving tensile strength, thereby preventing cracks from occurring in the flooring material.
본 실시예의 조성물은, n,n-dimethyl-p-toluidine(DMPT)로 이루어지는 경화촉진제와 혼합되고, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함한다.The composition of this embodiment is mixed with a curing accelerator consisting of n, n-dimethyl-p-toluidine (DMPT), 30-50 wt% of PMMA polymer, 20-40 wt% of n-butyl acrylate (BA) monomer, 10-30 wt% of methyl methacrylate monomer, 5-10 wt% of 2-hydroxy ethyl methacrylate (2-HEMA) monomer, 2-5 wt% of methacrylic acid (MAA) monomer, tripropyleneglycol diacrylate (TPGDA) monomer 2-5 Contains weight percent.
또하, 본 실시예의 조성물은, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지고, n,n-dimethyl-p-toluidine(DMPT)가 혼합되어 이루어지는 조성물에 dibenzoyl peroxide(BPO) 1~2중량%가 혼합되어 이루어진다.In addition, the composition of the present embodiment, containing 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT), and dibenzoyl in a composition in which n, n-dimethyl-p-toluidine (DMPT) is mixed Peroxide (BPO) 1 to 2% by weight is mixed.
상기와 같이 구성된 본 발명의 일 실시예에 따른 고탄성 고인장강도 PMMA수지 조성물의 제조방법을 살펴보면 다음과 같다.Looking at the manufacturing method of high elastic high tensile strength PMMA resin composition according to an embodiment of the present invention configured as described above are as follows.
본 발명의 일 실시예에 따른 고탄성 고인장강도 PMMA수지 조성물의 제조방법은, PMMA 폴리머와, n-butyl acrylate(BA) 단량체와, methyl methacrylate 단량체와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체와, methacrylic acid(MAA) 단량체와, tripropyleneglycol diacrylate(TPGDA) 단량체를 혼합하여 60~70℃로 가열하는 단계와, 조성물을 40~50℃로 냉각시킨 후에 n,n-dimethyl-p-toluidine(DMPT)를 혼합하는 단계와, n,n-dimethyl-p-toluidine(DMPT)가 혼합되는 조성물을 상온으로 냉각시킨 후에 dibenzoyl peroxide(BPO)를 혼합하여 경화시키는 단계를 포함한다.Method for producing a high elastic high tensile strength PMMA resin composition according to an embodiment of the present invention, PMMA polymer, n-butyl acrylate (BA) monomer, methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA) monomer And, mixing the methacrylic acid (MAA) monomer and the tripropyleneglycol diacrylate (TPGDA) monomer and heating them at 60 to 70 ° C., and cooling the composition to 40 to 50 ° C., followed by n, n-dimethyl-p-toluidine (DMPT). ) And a step of cooling the composition to which n, n-dimethyl-p-toluidine (DMPT) is mixed at room temperature, followed by mixing and curing dibenzoyl peroxide (BPO).
본 실시예의 가열단계는, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함하여 이루어진다.The heating step of this embodiment, 30-50% by weight PMMA polymer, 20-40% by weight n-butyl acrylate (BA) monomer, 10-30% by weight methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA ) 5 to 10% by weight of monomer, 2 to 5% by weight of methacrylic acid (MAA) monomer, and 2 to 5% by weight of tripropyleneglycol diacrylate (TPGDA) monomer.
또한, 본 실시예의 경화촉진제 혼합단계는, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지는 경화촉진제와 혼합되어 이루어지고, 경화제 혼합단계는, dibenzoyl peroxide(BPO) 1~2중량%가 혼합되어 이루어진다.In addition, the curing accelerator mixing step of the present embodiment is mixed with a curing accelerator comprising 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT), the curing agent mixing step, dibenzoyl peroxide (BPO) It is made by mixing 1 to 2% by weight.
PMMA 폴리머 합성PMMA Polymer Synthesis
Methyl methacrylate acid(MAA) 단량체 40중량%와, n-butyl methacrylate(BMA) 단량체 59중량%와, methacrylic acid(MAA) 단량체 1중량%를 혼합한 단량체 100중량부에 대하여, 반응개시제 AIBN(azobisisobutyronitrile) 0.2중량부와, 이온교환수 200중량부와, 분산제 5% polyvinyl alcohol 수용액(Kuraray사 POVAL PVA117) 1중량부와, 보호콜로이드 인산수소나트륨 0.01중량부와, 분자량조절제 n-도데실메르캅탄(n-dodecylmercaptan) 0.4중량부를 혼합하고, 반응온도 85℃로 2시간 동안 현탁중합 반응을 시키고, 잔류 미반응 단량체를 제거하기 위해 120℃로 반응온도를 상승시켜 20분 동안 추가 반응시킨다.Reaction initiator AIBN (azobisisobutyronitrile) based on 100 parts by weight of a mixture of 40% by weight of methyl methacrylate acid (MAA) monomer, 59% by weight of n-butyl methacrylate (BMA) monomer and 1% by weight of methacrylic acid (MAA) monomer. 0.2 part by weight, 200 parts by weight of ion-exchanged water, 1 part by weight of a 5% polyvinyl alcohol aqueous solution (Kuraray Corporation POVAL PVA117), 0.01 part by weight of protective colloidal sodium hydrogen phosphate, and a molecular weight regulator n-dodecyl mercaptan (n -dodecylmercaptan) 0.4 parts by weight are mixed, the reaction is subjected to suspension polymerization for 2 hours at a reaction temperature of 85 ℃, further reaction for 20 minutes by raising the reaction temperature to 120 ℃ to remove residual unreacted monomer.
상기한 작업에 의해 중합된 PMMA 폴리머를 탈수기에 수납하여 세척하고, 유동층 건조기에서 20시간 건조시켜 중량평균 분자량 70000, 유리전이온도 50℃, 산가 6.0mgKOH/g인 PMMA 폴리머를 제조한다.The PMMA polymer polymerized by the above operation is stored in a dehydrator, washed, and dried in a fluidized bed dryer for 20 hours to prepare a PMMA polymer having a weight average molecular weight of 70000, a glass transition temperature of 50 ° C., and an acid value of 6.0 mgKOH / g.
본 실시예에 따른 고탄성 및 고인장강도 PMMA수지 조성물의 실시예1과, 비교예1 내지 비교예6을 표 1에 기재하였으며, 실시예1은 제1단계에서 1관능성 단량체인 2-hyroxy ethyl methacrylate(2-HEMA) 7중량%와, methacrylate(MMA) 3중량%와, 2관능성 단량체인 tripropyleneglycol diacrylate(TPGDA) 3중량%를 사용한 것이고, 비교예1 내지 비교예3은, 관능성 단량체를 1가지만 사용한 것이며, 비교예4 내지 비교예6은 관능성 단량체를 2가지 사용한 것이다.Example 1 and Comparative Examples 1 to 6 of the high-elasticity and high tensile strength PMMA resin composition according to this embodiment are described in Table 1, and Example 1 is 2-hyroxy ethyl which is a monofunctional monomer in the first step. 7% by weight of methacrylate (2-HEMA), 3% by weight of methacrylate (MMA), and 3% by weight of tripropyleneglycol diacrylate (TPGDA), which is a bifunctional monomer, are used in Comparative Examples 1 to 3. Only one is used, and Comparative Examples 4 to 6 use two functional monomers.
상기한 바와 같이 실시예1 및 비교예1 내지 비교예6의 인장강도 및 신장률 시험을 진행하였으며, 인장강도 및 신장률 시험은, "SPS-KTS.1102-1890:2017"에 따라 5개의 시편을 20℃, 재령 7일 측정한 평균값을 표 2에 나타내었다.As described above, the tensile strength and elongation tests of Example 1 and Comparative Examples 1 to 6 were carried out, and the tensile strength and elongation tests were performed according to "SPS-KTS.1102-1890: 2017". Table 2 shows the average values measured at 7 ° C and age 7 days.
재령 7일(20℃)Tensile Strength (MPa)
7 days (20 ℃)
재령 7일(20℃)Elongation (%)
7 days (20 ℃)
표 2에 나타난 바와 같이 본 발명의 실시예1은, 1관능성 단량체인 2-hydroxy ethyl methacrylate(2-HEMA) 7중량%와, methacrylic acid(MAA) 3중량%와, 2관능성 단량체인 tripropyleneglycol diacrylate(TPGEA) 3중량% 사용한 것으로 인장강도 및 신장률이 우수한 결과를 확인하였다.As shown in Table 2, Example 1 of the present invention, 7% by weight of 2-hydroxy ethyl methacrylate (2-HEMA) monofunctional monomer, 3% by weight of methacrylic acid (MAA), tripropyleneglycol is a bifunctional monomer 3% by weight of diacrylate (TPGEA) was used to confirm the excellent tensile strength and elongation.
비교예1 내지 비교예3는, 관능성 단량체를 1가지만 사용한 것으로 인장강도가 불량하였고, 비교예4 내지 비교예6은, 관능성 단량체를 2가지 사용한 경우로 인장강도는 다소 증가하였지만 신장률이 미흡함을 알 수 있다.In Comparative Examples 1 to 3, only one functional monomer was used, resulting in poor tensile strength. In Comparative Examples 4 to 6, when the two functional monomers were used, tensile strength was slightly increased, but the elongation was insufficient. It can be seen.
이로써, 상온에서 경화시킬 수 있고, 고탄성 및 고인장강도를 제공하여 국제규격에 적합한 논 슬립 방수 바닥재, 고속철도 방수재, 도로 보수재, 인테리어 칼라 디자인 방수 바닥재, 급식소 식품공장 위생 안전용 방수 바닥재 등의 다양한 제품을 제조할 수 있는 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법을 제공할 수 있게 된다.As a result, it can be cured at room temperature and provides high elasticity and high tensile strength to meet international standards, such as non-slip waterproof flooring, high-speed railway waterproofing, road repairing, interior color design waterproofing flooring, food factory sanitary safety waterproofing flooring, etc. It is possible to provide a high elastic high tensile strength PMMA resin composition and a method for producing the same.
본 발명은 도면에 도시되는 일 실시예를 참고로 하여 설명되었으나, 이는 예시적인 것에 불과하며, 당해 기술이 속하는 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 것이다.Although the present invention has been described with reference to one embodiment shown in the drawings, this is merely exemplary, and various modifications and equivalent other embodiments are possible to those skilled in the art. Will understand.
또한, 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법을 예로 들어 설명하였으나, 이는 예시적인 것에 불과하며, 고탄성 고인장강도 PMMA수지 조성물 및 이의 제조방법이 아닌 다른 제품에도 본 발명의 조성물 및 이의 제조방법이 사용될 수 있다.In addition, the high-elasticity high tensile strength PMMA resin composition and its manufacturing method have been described as an example, but this is merely exemplary, and the composition of the present invention and a method for producing the same in other products other than the high-elasticity high tensile strength PMMA resin composition and method for producing the same. This can be used.
따라서 본 발명의 진정한 기술적 보호범위는 아래의 특허청구범위에 의해서 정하여져야 할 것이다.Therefore, the true technical protection scope of the present invention will be defined by the claims below.
Claims (9)
Containing PMMA polymers, n-butyl acrylate (BA) monomers, methyl methacrylate monomers, 2-hydroxy ethyl methacrylate (2-HEMA) monomers, methacrylic acid (MAA) monomers, and tripropyleneglycol diacrylate (TPGDA) monomers. A highly elastic high tensile strength PMMA resin composition.
상기 조성물은, n,n-dimethyl-p-toluidine(DMPT)로 이루어지는 경화촉진제와 혼합되는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물.
The method of claim 1,
The composition is a high elastic high tensile strength PMMA resin composition, characterized in that it is mixed with a curing accelerator consisting of n, n-dimethyl-p-toluidine (DMPT).
상기 조성물은, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함하는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물.
The method of claim 1,
The composition is 30 to 50% by weight PMMA polymer, 20 to 40% by weight n-butyl acrylate (BA) monomer, 10 to 30% by weight methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA) monomer 5 A high modulus high tensile strength PMMA resin composition comprising ~ 10% by weight, 2-5% by weight of methacrylic acid (MAA) monomer, and 2-5% by weight of tripropyleneglycol diacrylate (TPGDA) monomer.
상기 조성물은, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지는 경화촉진제와 혼합되는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물.
The method of claim 3,
The composition is a high elastic high tensile strength PMMA resin composition, characterized in that it is mixed with a curing accelerator comprising 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT).
n,n-dimethyl-p-toluidine(DMPT)가 혼합되어 이루어지는 상기 조성물에 dibenzoyl peroxide(BPO) 1~2중량%가 혼합되는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물.
The method of claim 4, wherein
A high elastic high tensile strength PMMA resin composition, characterized in that 1 to 2% by weight of dibenzoyl peroxide (BPO) is mixed with the composition comprising n, n-dimethyl-p-toluidine (DMPT).
(b) 상기 조성물을 40~50℃로 냉각시킨 후에 n,n-dimethyl-p-toluidine(DMPT)를 혼합하는 단계; 및
(c) 상기 n,n-dimethyl-p-toluidine(DMPT)가 혼합되는 조성물을 상온으로 냉각시킨 후에 dibenzoyl peroxide(BPO)를 혼합하여 경화시키는 단계를 포함하는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물 제조방법.
(a) PMMA polymer, n-butyl acrylate (BA) monomer, methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA) monomer, methacrylic acid (MAA) monomer, tripropyleneglycol diacrylate (TPGDA) monomer Mixing to heat to 60 ~ 70 ℃;
(b) mixing n, n-dimethyl-p-toluidine (DMPT) after cooling the composition to 40-50 ° C .; And
(c) a high modulus high tensile strength PMMA resin, comprising the step of curing dibenzoyl peroxide (BPO) after cooling the composition at which n, n-dimethyl-p-toluidine (DMPT) is mixed to room temperature Method for preparing the composition.
상기 (a)단계는, PMMA 폴리머 30~50중량%와, n-butyl acrylate(BA) 단량체 20~40중량%와, methyl methacrylate 단량체 10~30중량%와, 2-hydroxy ethyl methacrylate(2-HEMA) 단량체 5~10중량%와, methacrylic acid(MAA) 단량체 2~5중량%와, tripropyleneglycol diacrylate(TPGDA) 단량체 2~5중량%를 포함하여 이루어지는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물 제조방법.
The method of claim 6,
The step (a), 30-50% by weight PMMA polymer, 20-40% by weight n-butyl acrylate (BA) monomer, 10-30% by weight methyl methacrylate monomer, 2-hydroxy ethyl methacrylate (2-HEMA 5 to 10% by weight of monomer, 2 to 5% by weight of methacrylic acid (MAA) monomer, and 2 to 5% by weight of tripropyleneglycol diacrylate (TPGDA) monomer. .
상기 (b)단계는, n,n-dimethyl-p-toluidine(DMPT) 0.1~1.0중량%를 포함하여 이루어지는 경화촉진제와 혼합되어 이루어지는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물 제조방법.
The method of claim 6,
The step (b) is a high elastic high tensile strength PMMA resin composition, characterized in that the mixture is made with a curing accelerator comprising 0.1 to 1.0% by weight of n, n-dimethyl-p-toluidine (DMPT).
상기 (c)단계는, dibenzoyl peroxide(BPO) 1~2중량%가 혼합되어 이루어지는 것을 특징으로 하는 고탄성 고인장강도 PMMA수지 조성물 제조방법.The method of claim 6,
The step (c) is a method for producing a high elastic high tensile strength PMMA resin composition, characterized in that 1 to 2% by weight of dibenzoyl peroxide (BPO) is mixed.
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| JP2016524667A (en) * | 2013-07-11 | 2016-08-18 | エルジー・ハウシス・リミテッド | Cushion flooring and manufacturing method thereof |
| KR101767252B1 (en) * | 2017-04-11 | 2017-08-10 | 한라케미칼(주) | flame retardant and coating floor composition |
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| KR20100071506A (en) * | 2008-12-19 | 2010-06-29 | 진도화성주식회사 | Flooring with acrylic resin |
| JP2016524667A (en) * | 2013-07-11 | 2016-08-18 | エルジー・ハウシス・リミテッド | Cushion flooring and manufacturing method thereof |
| KR101767252B1 (en) * | 2017-04-11 | 2017-08-10 | 한라케미칼(주) | flame retardant and coating floor composition |
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