KR100301128B1 - Preparation of polyvinyl chloride paste resin having good blowing properties - Google Patents
Preparation of polyvinyl chloride paste resin having good blowing properties Download PDFInfo
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- KR100301128B1 KR100301128B1 KR1019990002612A KR19990002612A KR100301128B1 KR 100301128 B1 KR100301128 B1 KR 100301128B1 KR 1019990002612 A KR1019990002612 A KR 1019990002612A KR 19990002612 A KR19990002612 A KR 19990002612A KR 100301128 B1 KR100301128 B1 KR 100301128B1
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- psr
- acrylic
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- latex
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- 239000011347 resin Substances 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 229920000915 polyvinyl chloride Polymers 0.000 title description 3
- 239000004800 polyvinyl chloride Substances 0.000 title description 3
- 238000002360 preparation method Methods 0.000 title description 3
- 238000007664 blowing Methods 0.000 title 1
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 48
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 48
- 239000004816 latex Substances 0.000 claims abstract description 39
- 229920000126 latex Polymers 0.000 claims abstract description 39
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 6
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 13
- 230000002411 adverse Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 238000009408 flooring Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 238000005187 foaming Methods 0.000 description 20
- 229920001944 Plastisol Polymers 0.000 description 17
- 239000004999 plastisol Substances 0.000 description 17
- 239000006260 foam Substances 0.000 description 16
- 210000000497 foam cell Anatomy 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- KINULKKPVJYRON-PVNXHVEDSA-N n-[(e)-[10-[(e)-(4,5-dihydro-1h-imidazol-2-ylhydrazinylidene)methyl]anthracen-9-yl]methylideneamino]-4,5-dihydro-1h-imidazol-2-amine;hydron;dichloride Chemical compound Cl.Cl.N1CCN=C1N\N=C\C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1\C=N\NC1=NCCN1 KINULKKPVJYRON-PVNXHVEDSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
Abstract
본 발명은 발포성이 우수한 PVC 페이스트 수지 (PSR)의 제조방법에 관한 것으로, 좀 더 상세하게는 PSR의 제조방법에 있어서, PSR 중합 초기에 염화비닐 모노머 100 중량부에 대하여 분자량이 20,000∼100,000인 아크릴 수지 분말 0.01∼5.0 중량부를 용해시켜 첨가하거나, 유리전이온도 (Tg) 이상의 온도에서 아크릴 수지 분말을 디옥틸프탈레이트에 용해시켜 20∼70% (w/w)의 아크릴 용액을 제조한 후, 중합 완료된 PSR 라텍스에 대하여 분산제로 비이온 또는 음이온성 계면활성제 및 상기 아크릴 용액을 첨가하는 것을 특징으로 하는 발포성이 우수한 PVC 페이스트 수지의 제조방법에 관한 것으로, 본 발명의 방법에 의해 제조된 PSR은 종래의 방법에 의해 제조된 것에 비해 점도 상승의 역효과 없이 발포성 및 백색도가 개선되어 벽지, 상재, 레쟈 가공 등에 광범위하게 이용될 수 있다.The present invention relates to a method for producing a PVC paste resin (PSR) excellent in foamability, and more particularly, in the production method of PSR, acrylic acid having a molecular weight of 20,000 to 100,000 at 100 parts by weight of vinyl chloride monomer at the beginning of PSR polymerization. 0.01 to 5.0 parts by weight of the resin powder is dissolved and added, or the acrylic resin powder is dissolved in dioctylphthalate at a glass transition temperature (Tg) or higher to prepare an acrylic solution of 20 to 70% (w / w), and then polymerization is completed. A non-ionic or anionic surfactant and an acrylic solution are added to a PSR latex. The present invention relates to a method for preparing a PVC paste resin having excellent foamability. The PSR prepared by the method of the present invention is a conventional method. Compared to the one produced by the present invention, the foamability and the whiteness are improved without adverse effect of the viscosity increase, so that it is widely used for wallpaper, flooring, leather processing, It can be.
Description
본 발명은 발포성이 우수한 PVC 페이스트 수지 (Polyvinyl Chloride Paste Resin, 이하 'PSR')의 제조방법에 관한 것으로, 좀 더 상세하게는 PSR에 적절한 아크릴 수지를 첨가하여 플라스티졸 (plastisols)의 점도 상승을 초래하지 않으면서 발포성이 우수한 PSR의 제조방법에 관한 것이다.The present invention relates to a method of preparing a PVC paste resin (Polyvinyl Chloride Paste Resin, hereinafter 'PSR') having excellent foamability, and more particularly, to increase the viscosity of plastisols by adding an appropriate acrylic resin to PSR. It relates to a method for producing PSR excellent in foamability without causing.
발포 제품에서 가장 중요한 것은 발포된 제품의 표면, 발포 셀의 크기 및 셀의 균일성이며, 이러한 특성을 총칭하여 발포성이라 한다.The most important in the foam products are the surface of the foamed product, the size of the foam cells and the uniformity of the cells, and these properties are collectively called foamability.
PSR의 발포성을 향상시키는 기술에는 PSR 자체를 개질하는 방법과 발포배합에 사용되는 첨가제 중 발포 특성과 밀접한 관계가 있는 안정제, 발포제, 셀 (cell) 조정제 등을 최적으로 조절하는 방법이 있다. 이 중 PSR 자체를 개질하는 방법으로는 1) 중합도를 700∼1,300 정도로 조절하여 발포 조건에 적당한 용융 점도로 맞추는 법, 2) PSR 내의 작은 일차 입자 함량을 늘리는 법, 3) 발포용 PSR 중합에 사용되는 소듐 라우릴 설페이트 (Sodium Lauryl Sulfate, 이하 'SLS')와 같은 유화제의 함량을 늘리는 법, 4) 아크릴 라텍스 (acrylic latex)를 PSR 라텍스와 혼합하는 방법 등이 있으며, 발포 배합에 사용되는 첨가제를 조절하는 방법으로는 수지의 중합도에 따라 발포제, 안정제의 쌍을 변경하거나 발포 셀 조정제를 첨가하는 방법 등이 있다.Techniques for improving the foamability of the PSR include a method of modifying the PSR itself and an optimal control of stabilizers, foaming agents, cell regulators, etc., which are closely related to the foaming properties among the additives used in the foaming formulation. Among these methods, PSR itself can be modified by: 1) adjusting the degree of polymerization to about 700 to 1,300 to achieve a suitable melt viscosity for foaming conditions, 2) increasing the content of small primary particles in PSR, and 3) using PSR for foaming. Increasing the content of emulsifiers such as sodium lauryl sulfate (SLS), 4) mixing acrylic latex with PSR latex, and additives used in foam formulation. As a method of adjusting, the method of changing a pair of blowing agent and a stabilizer according to the polymerization degree of resin, or adding a foaming cell regulator etc. is mentioned.
최종 제품의 발포성에 가장 큰 영향을 주는 것은 수지 자체의 발포성이다. 따라서, 수지 자체의 발포 특성이 좋지 않다면 첨가제 조절 (또는 추가)로 발포성을 향상시키는 기술에는 한계가 있다.The biggest influence on the foamability of the final product is the foamability of the resin itself. Therefore, if the foaming property of the resin itself is not good, there is a limit to the technique of improving the foamability by adjusting (or adding) additives.
PSR 자체의 발포 특성을 개선하는 방법 중 중합도 조정 방법은 가장 손쉬운 방법이며, 용융 점도 변화로 발포 배율을 쉽게 바꿀 수 있는 장점은 있으나, 작고 균일한 발포 셀의 제품 생산을 위한 절대 요소는 아니다. 또한, PSR 내의 작은 일차 입자 함량이나 SLS와 같은 유화제 함량을 늘리는 방법은 치밀하고 균일한 발포 셀을 갖는 제품을 얻을 수 있으나, 이 PSR을 사용하여 제조한 플라스티졸의 점도가 상승하거나, 열 안정성이 약하다는 단점이 있다. 또한, 아크릴 라텍스를 PSR 라텍스에 혼합하여 건조, 분쇄하는 방법은 발포성 개선에는 효과가 있으나, 작은 입자의 수지 함량이 늘어나는 효과 때문에 플라스티졸의 제조시 점도가 상승하고 아크릴 수지가 가소제에 완전하게 용해되지 않아 발포성 개선에 한계가 있다.Among the methods for improving the foaming properties of the PSR itself, the polymerization degree adjusting method is the easiest method, and there is an advantage that the expansion ratio can be easily changed by changing the melt viscosity, but it is not an absolute factor for the production of small and uniform foam cells. In addition, a method of increasing the content of small primary particles in the PSR or an emulsifier such as SLS can give a product having a compact and uniform foamed cell, but the viscosity of the plastisol prepared using this PSR is increased or thermal stability This has the disadvantage of being weak. In addition, the method of drying and pulverizing acrylic latex by mixing with PSR latex is effective in improving foamability, but due to the effect of increasing the resin content of small particles, the viscosity increases during the preparation of plastisol and the acrylic resin is completely dissolved in the plasticizer. There is a limit to improve the foamability.
이와 같이 종래의 기술은 수지 자체의 발포성 개선에는 효과가 있으나, 이 수지를 사용한 플라스티졸의 점도가 상승하거나 열 안정성이 악화되는 문제 등이 있다.As described above, although the conventional technique is effective in improving the foamability of the resin itself, there is a problem that the viscosity of the plastisol using the resin is increased or the thermal stability is deteriorated.
이에, 본 발명자들은 광범위한 연구를 통하여, PSR에 적절한 아크릴 수지를첨가하면, 플라스티졸의 점도 상승을 초래하지 않으면서 PSR의 발포성을 개선할 수 있음을 발견하였고, 본 발명은 이에 기초하여 완성되었다.Accordingly, the inventors have found through extensive research that adding an appropriate acrylic resin to the PSR can improve the foamability of the PSR without causing an increase in the viscosity of the plastisol, and the present invention has been completed based thereon. .
따라서, 본 발명의 목적은 플라스티졸의 점도 상승효과가 없는 발포성이 우수한 PSR의 제조방법을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a method for producing PSR excellent in foamability without increasing the viscosity of the plastisol.
상기 목적을 달성하기 위한 본 발명의 PSR 제조방법은 PSR의 제조방법에 있어서, 염화비닐 모노머 (vinyl chloride monomer, 이하 'VCM') 100 중량부에 대하여 분자량이 20,000∼100,000인 아크릴 수지 분말 (알킬 메타크릴릭 모노머 및 아크릴릭 모노머의 코폴리머) 0.01∼5.0 중량부를 PSR 중합 초기에 용해시켜 첨가시키는 것으로 이루어진다.PSR production method of the present invention for achieving the above object is an acrylic resin powder (alkyl meta) of 20,000 to 100,000 molecular weight per 100 parts by weight of a vinyl chloride monomer (VCM) in the production method of PSR Copolymer of Krylic Monomer and Acrylic Monomer) 0.01 to 5.0 parts by weight of the PSR polymerization is dissolved and added.
상기 목적을 달성하기 위한 본 발명의 또 다른 PSR 제조방법은 PSR의 제조방법에 있어서, 유리전이온도 (Tg) 이상의 온도에서 아크릴 수지 분말을 디옥틸프탈레이트 (dioctyl phthalate, 이하 'DOP')에 용해시켜 20∼70% (w/w)의 아크릴 용액을 제조하는 단계, PSR 라텍스를 중합하는 단계 및 PSR 라텍스 100 중량부에 대하여 분산제로 비이온 또는 음이온성 계면활성제 0.01∼0.5 중량부 및 상기 아크릴 용액 0.006∼10 중량부를 첨가하는 것으로 이루어진다.Another PSR manufacturing method of the present invention for achieving the above object is a method of producing a PSR, by dissolving the acrylic resin powder in dioctyl phthalate (DOP) below the glass transition temperature (Tg) Preparing an acrylic solution of 20 to 70% (w / w), polymerizing PSR latex and 0.01 to 0.5 parts by weight of a nonionic or anionic surfactant as a dispersant based on 100 parts by weight of PSR latex and 0.006 parts of the acrylic solution It consists of adding -10 weight part.
이하, 본 발명을 좀 더 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 발포성이 우수한 PSR의 제조방법에 관한 것으로, 종래 기술의 문제점으로 제시된 플라스티졸의 점도 상승을 초래하지 않으면서 발포성이 우수한 PSR은 다음과 같은 방법으로 제조된다.The present invention relates to a method for producing PSR excellent in foamability, PSR excellent in foamability without causing an increase in the viscosity of the plastisol presented as a problem of the prior art is prepared by the following method.
PSR 자체의 발포성을 개선할 때 발생되는 문제점을 해결하기 위하여 본 발명에서는 PSR의 제조방법에 있어서, 염화비닐 모노머 100 중량부에 대하여 분자량이 20,000∼100,000인 아크릴 수지 분말 (알킬 메타크릴릭 모노머 및 아크릴릭 모노머의 코폴리머) 0.01∼5.0 중량부를 PSR 중합 초기에 용해시켜 첨가시켜 PSR을 제조하거나, 유리전이온도 (Tg) 이상의 온도에서 상기 아크릴 수지 분말을 디옥틸프탈레이트에 용해시켜 20∼70% (중량/중량)의 아크릴 용액을 제조하고, PSR 라텍스를 중합시킨 후, 상기 PSR 라텍스 100 중량부에 분산제로 비이온성 또는 음이온성 계면활성제 0.01∼0.5 중량부 및 상기 아크릴 용액 0.006∼10 중량부를 첨가하여 PSR을 제조하였다. 이렇게 제조된 PSR의 분자량은 69,000∼100,000이다.In order to solve the problems caused when improving the foamability of the PSR itself, in the present invention, in the production method of the PSR, an acrylic resin powder (alkyl methacryl monomer and acrylic) having a molecular weight of 20,000 to 100,000 with respect to 100 parts by weight of the vinyl chloride monomer. Copolymer of monomer) 0.01-5.0 parts by weight of the PSR polymerization is dissolved and added at the beginning to prepare PSR, or the acrylic resin powder is dissolved in dioctylphthalate at a temperature of glass transition temperature (Tg) or higher and 20 to 70% (weight / Weight) to prepare an acrylic solution, polymerize PSR latex, and add 0.01 to 0.5 parts by weight of a nonionic or anionic surfactant and 0.006 to 10 parts by weight of the acrylic solution to 100 parts by weight of the PSR latex as a dispersant. Prepared. The molecular weight of the PSR thus prepared is 69,000 to 100,000.
이때, 아크릴 수지 분말을 중합반응 초기에 용해시켜 첨가하는 방법에 있어서, 상기 아크릴 수지 분말의 사용량이 상기 VCM 100 중량부에 대하여 0.01 중량부 미만이면, 발포성 개선 효과가 거의 없는 문제가 있고, 5.0 중량부를 초과하면, 추가 첨가에도 불구하고 더 이상의 발포성 개선 효과를 기대할 수 없다. 상기 아크릴 수지 분말의 입자 크기는 1000 ㎛ 이하가 바람직하며, 상기 크기가 1000 ㎛를 초과하면, 용해시간이 길어지는 문제가 있다.At this time, in the method of dissolving and adding the acrylic resin powder in the initial stage of the polymerization reaction, if the amount of the acrylic resin powder is less than 0.01 parts by weight based on 100 parts by weight of the VCM, there is a problem that there is almost no foaming improvement effect, 5.0 weight When the amount is exceeded, no further foaming effect can be expected despite the addition. The particle size of the acrylic resin powder is preferably 1000 μm or less, and when the size exceeds 1000 μm, there is a problem in that the dissolution time is long.
또한, 본 발명의 아크릴 용액을 중합 완료된 PSR 라텍스에 후-첨가하는 방법에 있어서, 상기 아크릴 용액의 함량이 0.006 중량부 미만이면, 발포성 개선 효과가 거의 없는 문제가 있고, 10 중량부를 초과하면, 추가 첨가에 따른 발포성 개선 효과가 거의 없고, 건조 공정에서 응집 문제를 유발할 가능성이 있다.In addition, in the method of post-adding the acrylic solution of the present invention to the polymerized PSR latex, when the content of the acrylic solution is less than 0.006 parts by weight, there is little problem of improving the foamability, and when it exceeds 10 parts by weight, There is little effect of improving the foamability by addition, and there is a possibility of causing aggregation problem in the drying process.
상기 아크릴 용액은 친유성이 강하므로 이온교환수가 주성분인 PSR 라텍스에첨가하면 이온교환수와의 상용성이 떨어지기 때문에 분산이 잘 되지 않은 상태인 아크릴 용액 응집체로 존재하게 된다. 상기 응집체는 라텍스 내의 PSR 일차 입자의 응집을 일으키거나 라텍스 이송 또는 건조시 시브 (sieve)나 건조기 벽면에 붙게 되어 정상적인 수지 생산을 방해한다. 이러한 문제를 해결하기 위해, 본 발명에서는 아크릴 용액에 계면활성제를 첨가하였다. 본 발명의 계면활성제는 비이온성 또는 음이온성 계면활성제로, 폴리옥시에틸렌 (polyoxyethylene), 폴리옥시프로필렌 블록 폴리머 (polyoxypropylene block polymer), 폴리옥시에틸렌 노닐페닐 에테르 (polyoxyethylene nonylphenyl ether) 및 소듐 라우릴 설페이트 (SLS)로 이루어진 군으로부터 선택되며, 바람직하기로는 폴리옥시에틸렌 노닐페닐 에테르이다. 상기 계면활성제의 사용량은 PSR 라텍스 100 중량부에 대하여 0.01∼0.5 중량부가 바람직하며, 만일 상기 계면활성제의 사용량이 0.01 중량부 미만이면, 아크릴 용액의 분산이 잘 되지 않는 문제가 발생하며, 0.5 중량부를 초과하면, PSR의 열 안정성 악화 및 원가 상승 문제가 있다.Since the acrylic solution has a high lipophilic property, when ion exchanged water is added to PSR latex, which is a main component, compatibility with ion exchanged water is inferior, so that the acrylic solution is present as an acrylic solution aggregate that is not well dispersed. The agglomerates cause agglomeration of PSR primary particles in the latex, or adhere to sieves or dryer walls during latex transfer or drying, preventing normal resin production. In order to solve this problem, in the present invention, a surfactant was added to the acrylic solution. Surfactants of the present invention are nonionic or anionic surfactants, which include polyoxyethylene, polyoxypropylene block polymer, polyoxyethylene nonylphenyl ether and sodium lauryl sulfate ( SLS), preferably polyoxyethylene nonylphenyl ether. The amount of the surfactant is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the PSR latex, and if the amount of the surfactant is less than 0.01 parts by weight, the acrylic solution may not be easily dispersed, and 0.5 parts by weight. If exceeded, there is a problem of deterioration of thermal stability and cost increase of PSR.
이와 같은 방법으로 제조된 아크릴 수지가 첨가된 PSR 라텍스를 휠 타입 분무 건조기 (wheel type spray dryer)에서 건조·분쇄하여 PSR을 제조한 후, 아조디카본아미드 (azodicarbonamide, ADCA)계 발포제 2∼3 중량부, 가소제 60∼80 중량부, Ba/Zn계 안정제 2∼3 중량부, 탄산칼슘 0∼100 중량부, 백색 무기 안료 0∼20 중량부를 첨가한 상태에서 혼합하여 플라스티졸을 제조하였다. 상기 플라스티졸을 종이 (백상지)에 0.05∼0.3 ㎜ 두께로 코팅한 후, 200∼230℃의 발포 오븐에서 2∼3배로 발포시켜 발포 쉬트 (sheet)를 제작하였다.The PSR latex containing the acrylic resin prepared in this manner was dried and pulverized in a wheel type spray dryer to prepare PSR, and then 2 to 3 weights of azodicarbonamide-based foaming agent. A plastisol was prepared by mixing with 60 parts by weight, a plasticizer of 60 to 80 parts by weight, 2 to 3 parts by weight of a Ba / Zn-based stabilizer, 0 to 100 parts by weight of calcium carbonate, and 0 to 20 parts by weight of a white inorganic pigment. The plastisol was coated on paper (white paper) to a thickness of 0.05 to 0.3 mm, and then foamed two to three times in a foam oven at 200 to 230 ° C. to prepare a foam sheet.
이렇게 제조된 발포 쉬트는 아크릴 수지가 첨가되지 않은 PSR로 제작된 발포 쉬트보다 발포 셀, 발포 표면, 백색도가 우수하였다. 또한, 아크릴 수지가 첨가된 PSR로 제조된 플라스티졸과 비교시 점도는 아크릴 수지가 첨가되지 않은 PSR로 제조된 플라스티졸보다 오히려 낮았다.The foam sheet thus prepared was superior to the foam cell, foam surface, and whiteness of the foam sheet made of PSR to which no acrylic resin was added. In addition, the viscosity was lower than that of plastisols prepared with PSRs without added acrylic resins as compared to plastisols made with PSRs added with acrylic resins.
실시예Example
이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만 하기 실시예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
하기 실시예에 사용된 물성 측정방법을 간략하면 다음과 같다.The physical property measurement method used in the following examples is briefly described as follows.
1) 라텍스 입도 분포 측정1) Latex particle size distribution measurement
PSR 라텍스는 이온교환수 (Deionized water)에 0.1∼수 ㎛의 PSR의 일차 입자가 분산되어 있는 형태이며, 상기 라텍스 상의 일차 입자 입도 분포는 최종 제품의 점도와 발포성을 결정하는 주요 인자이며, 중합 이상 여부를 판단할 수 있는 자료가 된다.PSR latex is a form in which primary particles of 0.1 to several μm of PSR are dispersed in deionized water, and the primary particle size distribution on the latex is a major factor in determining the viscosity and foamability of the final product. It becomes the data to judge whether or not.
라텍스 상의 일차 입자 입도 분포는 Malvern사의 Malvern Master Sizer를 이용하여 측정하였다.Primary particle size distribution on latex was measured using Malvern Master Sizer from Malvern.
2) 플라스티졸의 제조2) Preparation of Plastisol
PSR 100 g에 DOP 70 중량부, LFX705B (Ba/Zn계 안정제) 3 중량부, AC5000 (ADCA계 발포제) 3 중량부, 탄산칼슘 40 중량부, TiO210 중량부를 첨가한 후, Ishikawa사의 Raikaiki 혼합기의 진공 상태에서 15분간 혼합하여 플라스티졸을 제조하였다.After adding 70 parts by weight of DOP, 3 parts by weight of LFX705B (Ba / Zn-based stabilizer), 3 parts by weight of AC5000 (ADCA-based blowing agent), 40 parts by weight of calcium carbonate, and 10 parts by weight of TiO 2 , a Raikaiki mixer from Ishikawa Plastisol was prepared by mixing in a vacuum state for 15 minutes.
3) 점도 측정3) viscosity measurement
상기 제조된 플라스티졸을 25℃ 항온 오븐에서 1시간 숙성 (aging)시킨 후, 브룩필드 (Brookfield) 점도계 (spindle＃6.20 rpm)를 이용하여 점도를 측정하였다.The plastisol prepared above was aged for 1 hour in a 25 ° C. constant temperature oven, and then the viscosity was measured using a Brookfield viscometer (spindle ＃ 6.20 rpm).
4) 발포 표면 및 발포 셀 측정4) Foam surface and foam cell measurement
플라스티졸을 0.4 ㎜ 어플리케이터 (applicator)로 종이 위에 코팅한 후, 230℃ 오븐에서 발포시켜 발포 쉬트를 제작하였다. 이렇게 제작된 발포 쉬트의 표면 상태는 육안 관찰을 통해, 발포 셀은 전자현미경을 이용하여 촬영, 관찰하였다.The plastisol was coated on paper with a 0.4 mm applicator and then foamed in a 230 ° C. oven to prepare a foam sheet. The surface state of the thus prepared foam sheet was visually observed, and the foaming cell was photographed and observed using an electron microscope.
관찰을 통해 얻은 결과는 다음과 같은 기호로 표시하였다.The results obtained through observation are indicated by the following symbols.
◎ 매우우수◎ Very good
○ 우수○ excellent
△ 불량△ bad
5) 백색도 측정5) Whiteness Measurement
발포 쉬트의 백색도는 조색 공정에서 색상의 선명도 등에 영향을 주므로 매우 중요하다. 백색도는 비색계 (colorimeter)를 이용하여 측정한 후, 수치화하였다.The whiteness of the foam sheet is very important because it affects the clarity of color in the coloration process. Whiteness was measured using a colorimeter and then quantified.
실시예 1∼4 및 비교예 1Examples 1-4 and Comparative Example 1
200ℓ 분산조에 하기 표 1에 나타난 조성과 같이 이온교환수, SLS, AIBN (azobisisobutyronitrile), ABVN (azobis(2,4-dimethylvaleronitrile)), CA (cetylalcohol) 및 아크릴 수지 분말을 첨가한 후, 감압 상태에서 VCM을 사입하고, 270 rpm에서 30분간 교반을 하여 아크릴 수지가 녹아 있는 VCM 액적을 형성하였다. 이를 분산 펌프를 이용하여 200ℓ의 중합기에 이송한 후, 58℃로 승온하여 중합을 실시하였다. 약 6시간 후, 0.5 ㎏/㎠의 압력 강하가 일어나면, 중합을 정지한 후 미반응 VCM을 제거하면 아크릴 수지를 함유한 PSR 라텍스를 얻게 된다. 상기 라텍스를 휠 타입 분무 건조기 (입구온도 150℃, 출구온도 55℃)로 건조한 후, 분쇄기로 분쇄하여 아크릴 수지를 함유한 PSR을 얻었다 (실시예 1∼4). 비교예 1은 아크릴 수지를 첨가하지 않은 PSR이다.After adding ion-exchanged water, SLS, AIBN (azobisisobutyronitrile), ABVN (azobis (2,4-dimethylvaleronitrile)), CA (cetylalcohol) and acrylic resin powder to the 200-L dispersion tank as shown in Table 1 below, VCM was injected and stirred at 270 rpm for 30 minutes to form VCM droplets in which acrylic resin was dissolved. This was transferred to a 200 L polymerizer using a dispersion pump, and then heated to 58 ° C to carry out polymerization. After about 6 hours, if a pressure drop of 0.5 kg / cm 2 occurs, the PSR latex containing the acrylic resin is obtained by removing the unreacted VCM after stopping the polymerization. The latex was dried in a wheel type spray dryer (inlet temperature 150 ° C., outlet temperature 55 ° C.) and then pulverized with a grinder to obtain a PSR containing acrylic resin (Examples 1 to 4). Comparative Example 1 is PSR to which no acrylic resin is added.
상기 수지를 이용하여 발포용 플라스티졸을 제조하여 점도를 측정하고 발포성, 백색도를 평가한 결과는 하기 표 2에 나타내었다.Using the resin to prepare a foamed plastisol to measure the viscosity and to evaluate the foamability, whiteness are shown in Table 2 below.
상기 표 2에서 라텍스의 입자 크기 결과를 보면, 아크릴 수지가 첨가된 PSR (실시예 (1∼4)) 및 첨가되지 않은 PSR (비교예 1) 모두 거의 유사한 평균 입자 크기를 보였다. 상기 결과로부터, 아크릴 수지 분말을 중합 초기에 VCM에 용해하여 첨가하더라도 PSR 중합에는 문제가 없음을 알 수 있다.In the particle size results of the latex in Table 2, both the PSR with the acrylic resin (Examples (1-4)) and the PSR without the addition (Comparative Example 1) showed almost similar average particle sizes. From the above results, it can be seen that there is no problem in PSR polymerization even if the acrylic resin powder is dissolved and added to VCM at the initial stage of polymerization.
또한, 실시예 1∼4의 초기 점도는 비교예 1과 비교시 동등 이하의 값을 보였다. 즉, 아크릴 수지를 VCM에 용해하여 첨가한 결과 점도 상승은 거의 없음을 알수 있다. 아크릴 수지 첨가에 따른 발포 특성을 보면, VCM 100 중량부에 대하여 0.25 중량부의 아크릴 수지를 첨가시 (실시예 1) 약간 발포 특성이 개선되었으며, 0.5∼2.0 중량부 (실시예 2∼4)에서는 매우 우수한 결과를 보였다. 또한, 발포 쉬트의 백색도도 발포 특성 개선과 함께 향상되는 결과를 보였다. 이러한 발포 특성의 개선은 아크릴 수지가 PSR에 첨가됨으로써 발포 영역 (170∼200℃)에서의 PSR의 용융 탄성력이 향상되었기 때문에 나타나는 현상이다.In addition, the initial viscosity of Examples 1-4 showed the below equivalent value when compared with the comparative example 1. That is, it can be seen that there is almost no increase in viscosity as a result of dissolving acrylic resin in VCM. In view of the foaming properties according to the addition of acrylic resin, the foaming properties were slightly improved when 0.25 parts by weight of acrylic resin was added (Example 1) to 100 parts by weight of VCM, and in 0.5 to 2.0 parts by weight (Examples 2 to 4), Excellent results were shown. In addition, the whiteness of the foam sheet also improved with the foaming properties. This improvement in foaming properties is a phenomenon which occurs because the melt elastic force of PSR in the foaming region (170 to 200 ° C) is improved by adding an acrylic resin to the PSR.
실시예 5∼8 및 비교예 2∼4Examples 5-8 and Comparative Examples 2-4
실시예 5∼8은 실시예 1∼4와 달리 아크릴 수지 용액을 비교예 1의 방법으로 중합 완료된 PSR 라텍스에 후-첨가하는 방법이다. 60∼100℃에서 플라스티졸의 배합에 사용되는 가소제인 DOP 67g에 아크릴 수지 33g을 첨가한 후 용해시켜 33% (w/w) 아크릴 용액을 제조한다. 비교예 1의 방법으로 중합 완료된 PSR 라텍스 (고체 함량: 40%) 3000 g에 상기 아크릴 용액을 하기 표 3에 나타난 바와 같이 첨가량을 달리하여 첨가하고, 계면활성제로 0.8 g의 폴리옥시에틸렌 노닐페닐 에테르를 첨가하였다. 상기 아크릴 용액 및 계면활성제가 첨가된 라텍스를 실시예 1∼4와 같은 방법으로 건조·분쇄하여 아크릴 수지가 첨가된 PSR을 제조하였다. 비교예 2는 아크릴 수지를 첨가하지 않고, 비이온 계면활성제인 폴리옥시에틸렌 노닐페닐 에테르만을 첨가한 것이며, 비교예 3은 건조된 1∼700 ㎛ 크기의 아크릴 수지 분말을 PSR 라텍스에 직접 첨가한 것이다. 또한, 비교예 4는 아크릴 수지 첨가 효과와 유화제 중량 효과를 비교하기 위하여 발포용 수지에 주로 사용되는 유화제인 SLS를 수지 대비 5,000 ppm으로 라텍스에 첨가한 것이다. 상기 라텍스들도 실시예 1∼4와 같은 방법으로 건조·분쇄하여 PSR을 얻었다.In Examples 5 to 8, unlike Examples 1 to 4, the acrylic resin solution is post-added to the PSR latex polymerized by the method of Comparative Example 1. A 33% (w / w) acrylic solution is prepared by adding 33 g of acrylic resin to 67 g of DOP, a plasticizer used for compounding plastisol at 60 to 100 ° C., and then dissolving it. To 3000 g of PSR latex (solid content: 40%) polymerized by Comparative Example 1, the acrylic solution was added in different amounts as shown in Table 3 below, and 0.8 g of polyoxyethylene nonylphenyl ether was used as a surfactant. Was added. The latex to which the acrylic solution and the surfactant were added was dried and pulverized in the same manner as in Examples 1 to 4 to prepare a PSR to which an acrylic resin was added. In Comparative Example 2, only the polyoxyethylene nonylphenyl ether, which is a nonionic surfactant, was added without adding the acrylic resin. In Comparative Example 3, the dried acrylic resin powder having a size of 1 to 700 µm was added directly to the PSR latex. . In addition, in Comparative Example 4, in order to compare the acrylic resin addition effect and the emulsifier weight effect, SLS, an emulsifier mainly used in foaming resin, was added to the latex at 5,000 ppm relative to the resin. The latexes were also dried and pulverized in the same manner as in Examples 1 to 4 to obtain PSR.
하기 표 4는 하기 표3의 조성에 따라 제조된 PSR에 대한 평가 결과를 나타낸 것이다.Table 4 below shows the evaluation results for PSR prepared according to the composition of Table 3.
상기 표 4에서 아크릴 수지를 첨가하지 않은 PSR (비교예 2)에 비해 아크릴 수지를 첨가하여 제조한 수지는 점도가 상승하지 않은 상태에서 발포성이 크게 개선되었다. 특히, 33% (w/w)의 아크릴 용액 20 g 이상 첨가시 매우 우수한 발포성(발포 표면, 발포 셀)을 얻었다. 또한, 백색도도 발포 특성에 비례해서 향상되었다. 그러나, 비교예 3과 같이 아크릴 수지 분말을 PSR 라텍스에 직접 첨가하여 제조한 PSR의 발포성은 아크릴 수지를 첨가하지 않은 PSR의 발포성과 거의 유사하였다. 즉, 아크릴 수지가 용해되지 않은 상태에서는 발포성 개선 효과가 없다는 것을 알 수 있었다. 또한, 이 경우에는 백색도 개선 효과도 없었다. 상기 비교예 4의 결과에서 유화제를 후-첨가함으로서 발포 셀은 후-첨가하지 않은 경우보다 현저히 개선될 수는 있으나, 발포 표면은 아크릴 수지를 첨가한 수지에 비해서는 열세이다. 또한, 유화제 후-첨가 제품은 비교예 2와 비교시 점도가 크게 상승하는 단점이 있었다.Compared to PSR (Comparative Example 2) without adding an acrylic resin in Table 4, the resin prepared by adding an acrylic resin was greatly improved in foamability in a state where the viscosity was not increased. In particular, very good foamability (foamed surface, foam cells) was obtained when 20 g or more of 33% (w / w) acrylic solution was added. In addition, the whiteness also improved in proportion to the foaming properties. However, the foamability of PSR prepared by adding acrylic resin powder directly to PSR latex as in Comparative Example 3 was almost similar to that of PSR without addition of acrylic resin. That is, it turned out that there is no foaming improvement effect in the state which acrylic resin did not melt | dissolve. Moreover, in this case, there was also no whiteness improvement effect. By post-adding the emulsifier in the results of Comparative Example 4, the foamed cell may be significantly improved than without the post-added, but the foamed surface is inferior to the resin to which the acrylic resin is added. In addition, the emulsifier after-added products had a disadvantage in that the viscosity is significantly increased in comparison with Comparative Example 2.
비교예 5Comparative Example 5
본 비교예는 0.1∼수 ㎛의 아크릴 폴리머가 이온교환수에 분산된 아크릴 라텍스 (고체 함량: 33%)를 비교예 1에서 얻은 PSR 라텍스에 후-첨가한 것이다. 상기 라텍스들도 실시예 1∼4와 같은 방법으로 건조·분쇄하여 PSR을 얻었다 (표 5). 이렇게 제조된 PSR을 실시예 8의 PSR과 비교하였다.In this comparative example, an acrylic latex (solid content: 33%) in which an acrylic polymer of 0.1 to several micrometers was dispersed in ion-exchanged water was post-added to the PSR latex obtained in Comparative Example 1. The latexes were also dried and pulverized in the same manner as in Examples 1 to 4 to obtain PSR (Table 5). The PSR thus prepared was compared with that of Example 8.
하기 표 5의 조성에 따라 제조한 PSR의 평가 결과는 하기 표 6에 나타내었다.Evaluation results of the PSR prepared according to the composition of Table 5 are shown in Table 6 below.
디옥틸프탈레이트에 아크릴 수지를 용해시켜 제조된 33% (w/w)의 아크릴 용액을 첨가하여 제조한 PSR (실시예 8)은 아크릴 수지 라텍스를 첨가하여 얻은 PSR(비교예 5)에 비해 플라스티졸의 점도는 낮으면서 발포 특성은 우수하였다. 즉, 아크릴 수지 라텍스를 직접 첨가하는 방법은 아크릴 수지 자체의 입자 효과에 의해 점도는 상승되고, 발포성 개선 효과에서는 용액상태 첨가 방법에 비해 약간 떨어진다.PSR (Example 8) prepared by adding 33% (w / w) acrylic solution prepared by dissolving acrylic resin in dioctylphthalate was compared to PSR (Comparative Example 5) obtained by adding acrylic resin latex. Although the viscosity of the sol was low, the foaming property was excellent. That is, in the method of directly adding the acrylic resin latex, the viscosity is increased by the particle effect of the acrylic resin itself, and the foaming improvement effect is slightly inferior to the solution state addition method.
상기 결과로부터 알 수 있는 바와 같이, PSR의 종래 제조방법은 발포성이 개선되면 점도가 상승하는 역효과가 있었으나, 본 방법에서는 이러한 역 효과 없이 발포성을 종래 기술보다 크게 개선할 수 있었다. 즉, 아크릴 수지를 중합 초기에 염화비닐 모노머에 용해시켜 첨가하거나, 디옥틸프탈레이트에 용해시켜 계면활성제와 함께 중합 후의 PSR 라텍스에 첨가하여 제조한 수지의 발포성은 이를 사용하지 않은 수지에 비해 매우 우수하였으며, 점도 상승도 나타나지 않았다. 또한, 이러한 발포 셀과 발포 표면 향상으로 백색도가 개선되는 효과가 있었다. 따라서, 본 발명에 따라 제조된 PSR는 발포성과 백색도가 매우 중요한 벽지, 상재, 레쟈 가공등에 광범위하게 이용될 수 있다.As can be seen from the above results, the conventional manufacturing method of the PSR had an adverse effect of increasing the viscosity when the foamability was improved, but the present method was able to greatly improve the foamability without the adverse effect. That is, the foamability of the resin prepared by dissolving the acrylic resin in the vinyl chloride monomer at the beginning of polymerization or adding it to the PSR latex after polymerization by dissolving in dioctylphthalate was very excellent compared to the resin without using the resin. There was no increase in viscosity. In addition, there was an effect that the whiteness is improved by the foam cell and the foam surface improvement. Therefore, the PSR prepared according to the present invention can be widely used for wallpaper, material, leather processing, etc. where foamability and whiteness are very important.
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| KR19990062671A (en) * | 1997-12-04 | 1999-07-26 | 가네가 베르기 엔.브이 | Vinyl Chloride Resin Composition |
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| KR830002456A (en) * | 1980-02-22 | 1983-05-28 | 리 바스킨드 데이비드 | Variable control power equalization circuit |
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| WO2014065570A1 (en) * | 2012-10-26 | 2014-05-01 | 한화케미칼 주식회사 | Polyvinyl chloride-based paste resin, and preparation method therefor |
| KR101530335B1 (en) * | 2012-10-26 | 2015-06-22 | 한화케미칼 주식회사 | Polyvinyl chloride paste resin and Method for preparing the same |
| CN104837918A (en) * | 2012-10-26 | 2015-08-12 | 韩化石油化学株式会社 | Polyvinyl chloride-based paste resin, and preparation method therefor |
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