KR20020090699A - Curable silicone compositon having slip property - Google Patents
Curable silicone compositon having slip property Download PDFInfo
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- KR20020090699A KR20020090699A KR1020010029685A KR20010029685A KR20020090699A KR 20020090699 A KR20020090699 A KR 20020090699A KR 1020010029685 A KR1020010029685 A KR 1020010029685A KR 20010029685 A KR20010029685 A KR 20010029685A KR 20020090699 A KR20020090699 A KR 20020090699A
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- 229920001296 polysiloxane Polymers 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 16
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims 1
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- 239000000976 ink Substances 0.000 description 35
- 239000000123 paper Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- -1 alkylbenzene sulfonates Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 150000001746 carotenes Chemical class 0.000 description 1
- 235000005473 carotenes Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
본 발명에 따르면, 아크릴로니트릴 26~32 중량%, 메틸 메타크릴레이트 12~18중량%, 메타크릴산 4~10 중량% 및 스티렌 40~58 중량%로 이루어진 단량체 혼합물을 유화중합시켜 0.3 미크론 이하의 유화중합체를 제조하고, 수득된 유화중합체를 사용하여 염료와 착색한 수성 형광 잉크 조성물이 제공된다.According to the present invention, an emulsion mixture of 26 to 32% by weight of acrylonitrile, 12 to 18% by weight of methyl methacrylate, 4 to 10% by weight of methacrylic acid and 40 to 58% by weight of styrene is emulsified to 0.3 micron or less. Emulsion polymers were prepared, and dyes and colored aqueous fluorescent ink compositions using the obtained emulsion polymers are provided.
Description
본 발명은 감열, 감압의 기록지에 특히 유용한 필기구용 수성 형광 잉크 및 그의 필기구용 수성 형광 잉크를 사용한 필기구에 관한 것이다.The present invention relates to an aqueous fluorescent ink for writing instruments and a writing instrument using the aqueous fluorescent ink for writing instruments, which are particularly useful for recording papers of heat and pressure reduction.
본 명세서의 기재에 있어서 "(메트)아크릴산"은 아크릴산 및/또는 메타크릴산을 총칭하는 용어이다.In the description of the present specification, "(meth) acrylic acid" is a term that collectively refers to acrylic acid and / or methacrylic acid.
형광펜에 충진하는 형광잉크가 구비해야 하는 성질로서는 먼저 원활하게 잉크가 유출되는 것과, 펜촉에서 잉크가 건조되지 않는 것과, 目詰가 생기지 않는 것과, 내부에서 경시변화와 같이 고화되지 않을 것 등이 권장된다. 또, 필기후의 필적에 대해서 소망되는 성질로서는 색조가 선명하고, 내수성, 내광성이 우수하고, 필구용 기재에 표리~~~ 침투하지 않고, 최근의 정보기록지 관계의 발달에 수반한 감압지, 감열지에 현색시킨 인자면에 대해 소색(消色), 변색 작용이 없어야 한다.The characteristics that the fluorescent ink filled in the highlighter should have are such that the ink flows out smoothly first, the ink does not dry out of the nib, the appearance does not occur, and the internal solid does not solidify with the change over time. do. In addition, as a property desired for the handwriting after writing, the color tone is clear, excellent in water resistance and light resistance, and does not penetrate back and forth to the base material for writing, and to pressure-sensitive paper and thermal paper with recent development of information recording paper relations. There should be no discoloration and discoloration on the printed surface.
종래에, 형광잉크는 형광도료, 염료매개물, 유기용제, 물을 주성분으로 하여 제조되었다. 이와 같은 종래의 수성 형광잉크는 색조의 선명성, 형광강도, 잉크의원활한 유출성, 저장안정성 등이 우수한 특징을 가지고 있지만, 최근 급속히 보급되고 있는 정보기록지관계의 감압지, 감열지 등의 인자에 대해서는, 소색, 변색하는 작용이 있고, 또 내수성, 내광성에 큰 결점을 가지고 있다.Conventionally, fluorescent inks have been prepared based on fluorescent paints, dye media, organic solvents and water. The conventional aqueous fluorescent ink has excellent characteristics such as color clarity, fluorescence intensity, smooth outflow of ink, storage stability, and the like. However, with respect to factors such as pressure-sensitive paper and thermal paper of information recording paper which are rapidly spreading in recent years, It has a discoloration and discoloration effect, and has a big drawback in water resistance and light resistance.
특개소 1-268775호, 특개소 62-148580호에는, 상술한 종래의 형광잉크의 결점을 배제한 새로운 형광잉크로서 비닐계 단량체를 유화중합시켜 수득된 유화중합체를 형광염료로서 염색시켜서 된 형광잉크가 제안되어 있다. 그러나 상기 인용문헌에는, 구체적으로 가장 바람직한 수성 형광잉크의 구성 및 구체적으로 바람직하게 적용되는 필기구에 대해서는 어떠한 개시도 없다.Japanese Patent Application Laid-Open Nos. 1-268775 and 62-148580 disclose new fluorescent inks which eliminate the drawbacks of the conventional fluorescent ink described above, wherein fluorescent emulsions obtained by dyeing emulsion polymers obtained by emulsion polymerization of vinyl monomers as fluorescent dyes It is proposed. However, there is no disclosure in the citations specifically regarding the composition of the most preferred aqueous fluorescent ink and the writing instruments that are particularly preferably applied.
본 발명자들은 종래의 수성 형광잉크의 여러 가지 문제점들을 해소할 수 있는 수성 형광잉크의 구성 및 조성에 대해서 연구한 결과, 본 발명을 완성하였다.The present inventors have completed the present invention as a result of studying the constitution and composition of the aqueous fluorescent ink which can solve various problems of the conventional aqueous fluorescent ink.
본 발명의 필기구용 수성 형광잉크는, 아크릴로니트릴 26~32 중량%, 메틸 메타크릴레이트 12~18중량%, 메타크릴산 4~10 중량% 및 스티렌 40~58 중량%으로 된 단량체 혼합물을 유화중합시켜 입자경 0.3 미크론 이하로 유화중합체를 만들고, 이를 염료로 착색시킨 수성 형광잉크 조성물을 제공한다.The aqueous fluorescent ink for writing instruments of the present invention emulsifies a monomer mixture of 26 to 32% by weight of acrylonitrile, 12 to 18% by weight of methyl methacrylate, 4 to 10% by weight of methacrylic acid, and 40 to 58% by weight of styrene. The polymerization provides an emulsion polymer having a particle size of 0.3 micron or less, which is colored with a dye to provide an aqueous fluorescent ink composition.
본 발명의 하나의 바람직한 구현예에 따르면, 아크릴로니트릴 약 29 중량%, 메틸 메타크릴레이트 약 15중량%, 메타크릴산 약 7중량%, 스티렌 약 49중량%로 된 단량체 혼합물을 사용한다.According to one preferred embodiment of the invention, a monomer mixture of about 29% acrylonitrile, about 15% methyl methacrylate, about 7% methacrylic acid and about 49% styrene is used.
본 발명에서 사용되는 유화중합체는 특정한 단량체로 된 단량체 혼합믈을 유화중합하는 것에 의해 수득된 입자경 0.3 미크론 이하의 것이며, 0.25 미크론 이하의 것들이 바람직하다. 유화 중합체의 입자경이 0.3 미크론을 초과하면, 수성 형광잉크 중의 유화 중합체가 침강하여 장기간 저장안정성에 결함이 생기고, 또 수성 형광잉크가 원활하게 유동하지 않는다.The emulsion polymers used in the present invention are those having a particle size of 0.3 micron or less obtained by emulsion polymerization of monomer mixtures of specific monomers, and those having 0.25 micron or less are preferable. If the particle size of the emulsion polymer exceeds 0.3 micron, the emulsion polymer in the aqueous fluorescent ink precipitates, resulting in defects in long-term storage stability, and the aqueous fluorescent ink does not flow smoothly.
본 발명에 있어서, 유화 중합법은 계면활성제의 종류와 양 등을 목적에 따라서 적절히 선택하는 것에 의해 행해지지만, 그의 중합온도는 50~90℃가 바람직하다.In the present invention, the emulsion polymerization method is performed by appropriately selecting the type and amount of the surfactant according to the purpose, but the polymerization temperature thereof is preferably 50 to 90 ° C.
본 발명에 있어서 바람직하게 사용되는 계면활성제는 알킬벤젠술폰산염, 알킬페놀술폰산염, 알킬디페닐 고리를 갖는 술폰산염, 알킬아릴술폰산염의 포르말린 축합물, 알킬아릴술폰산염의 케톤화합물, 수포숙신산 에스테르염, 폴리옥시에틸렌알킬술포네이트염, 폴리옥시에틸렌알킬아릴술포네이트염 등의 음이온 계면활성제 및 지방산과 글리센린, 글리콜, 펜타에리트리톨, 소르비탄, 혹은 만니탄 등의 에스테르류, 또는 폴리에틸렌옥사이드과 고급 지방산, 고급 알콜, 고급 알킬아민, 혹은 알킬페놀인산 등과의 축합물류 등의 비이온 계면활성제가 있으며, 음이온 계면활성제만을 사용하는 경우 혹은 비이온 계면활성제를 병용하는 경우등이 있다.Surfactants preferably used in the present invention are alkylbenzene sulfonates, alkylphenol sulfonates, sulfonates having alkyl diphenyl rings, formalin condensates of alkylaryl sulfonates, ketone compounds of alkylaryl sulfonates, water succinic ester salts, Anionic surfactants and fatty acids such as polyoxyethylene alkylsulfonate salts and polyoxyethylene alkylarylsulfonate salts and esters such as glycerin, glycol, pentaerythritol, sorbitan, or mannitanium, polyethylene oxide and higher fatty acids, There are nonionic surfactants such as condensation products with higher alcohols, higher alkylamines, or alkylphenol phosphoric acids, and the like, in which only anionic surfactants are used or in combination with nonionic surfactants.
또 중합 개시제로서는 암모늄 퍼술페이트, 칼륨 퍼술페이트, 과산화수소 등을 사용할 수 있으며, 혹은 필요에 따라서 환원제를 병용할 수도 있다.Moreover, as a polymerization initiator, ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. can be used, or a reducing agent can also be used together as needed.
본 발명에 있어서 형광염료로서는 특별히 한정되지 않으며, 염기염료 (카로틴 염료를 포함), 분산염료, 유용성 염료, 형광증백 염료 등 각종 염료 군에서 선택하여 이용할 수 있다. 특히 일광 형광염료의 일종 및 2종 이상과 일광 형광염료와 보통염료 (형광성이 없는 염료) 또는 안료를 함께 사용할 수 있다.It does not specifically limit as fluorescent dye in this invention, It can select from various dye groups, such as a base dye (including a carotene dye), a disperse dye, an oil-soluble dye, and a fluorescent whitening dye. In particular, one or two or more types of daylight fluorescent dyes and daylight fluorescent dyes and ordinary dyes (dyes without fluorescence) or pigments may be used together.
이러한 염료에 따른 착색은 유화 중합시 또는 중합 후에 각각 행해질 수 있다. 이의 조건에 관해서는 교반 상태에서 대기압 이하가 아닌 가압하에 40~110℃, 1~5 시간이 바람직하며, 염료의 사용량은 유화 중합체 (고형분) 100중량부에 대해서 0.01~10 중량뿌가 바람직하며, 0.1~50중량부가 더욱 바람직하다.Coloring with such dyes can be done either during emulsion polymerization or after polymerization, respectively. Regarding the conditions thereof, 40 to 110 ° C. for 1 to 5 hours is preferable under a pressurization condition not under atmospheric pressure, and the amount of dye used is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the emulsion polymer (solid content). 0.1-50 weight part is more preferable.
염료에 따른 착색은 통상적인 방법에 따라 행해질 수 있지만, 계면활성제를 사용하여 행하는 것이 바람직하며, 유화 중합가 음이온성 또는 비이온성인 경우에는 염료의 종류에는 관계 없지만, 계면활성제는 음이온성 또는 비이온성의 것이 바람직하다. 유화 중합체, 염료 및 계면활성제의 극성은 목적에 따라서 적절히 선택된다.The coloring according to the dye may be carried out according to a conventional method, but is preferably performed using a surfactant, and in the case where the emulsion polymerization is anionic or nonionic, regardless of the type of dye, the surfactant may be anionic or nonionic. It is preferable. The polarity of the emulsion polymer, the dye and the surfactant is appropriately selected according to the purpose.
상기 친수성 유기 용제로서는 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜, 디프로킬렌글리콜, 글리세린으로부터 선택되는 1종 또는 2종 이상을 함유할 수 있다. 이러한 친수성 유기용제를 반응시에 또는 반응 후에 혼합사용하는 것에 의해 형광잉크의 유출성, 색조의 선명성, 펜촉에서 건조도의 조정, 보온성, 점도의 조정, 필기특성의 개선 등에 사용된다. 이외에도, 에틸렌글리콜은 감압지에 대해서, 글리세린은 감열지에 대해서 특히 유용한 용제이고, 디에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜은 샘조의 선명성을 개선하는데 유용한 용제이다. 이러한 친수성 유기용제의 배합량은 5중량% 미만에서는 펜촉의 건조가 현저해져 필구불능이 되며, 35 중량%를 초과하면 펜촉에서 건조성은 양호하지만 잉크의 누출, 감압지, 감열지의 인자에 대해 소색, 변색하는 경우도 있다.As said hydrophilic organic solvent, 1 type (s) or 2 or more types chosen from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and glycerol can be contained. By mixing and using such a hydrophilic organic solvent at the time of reaction or after reaction, it is used for the outflow property of fluorescent ink, the clarity of a color tone, adjustment of the dryness in a nib, heat insulation, adjustment of a viscosity, improvement of writing characteristics, etc. In addition, ethylene glycol is a particularly useful solvent for pressure-sensitive paper, glycerin is a thermal paper, and diethylene glycol, propylene glycol, and dipropylene glycol are useful solvents for improving the sharpness of a spring bath. If the amount of the hydrophilic organic solvent is less than 5% by weight, the tip of the pen becomes dry and becomes unnecessary. If the amount of the hydrophilic organic solvent exceeds 35% by weight, the tip of the hydrophilic organic solvent has good dryness but discolors and discolors the ink leakage, pressure-sensitive paper, and thermal paper. In some cases.
또, 본 발명의 수성형광 잉크를 사용한 필기구로는, 예를 들면, 중면으로는폴리에스테르계 섬유를 사용하고, 펜촉으로는 폴리에스테르계 장섬유를 묶은 것을 사용한 것을 들 수 있다. 중면은 원통체에 내장되어 잉크를 머금도록 되어 있으며, 펜촉은 한쪽 말단이 전술한 중면에 접촉하고 다른 쪽 말단은 반대쪽으로 돌출되어 필기구의 사용시에 종이 등의 표면에 접촉하여 잉크를 유출시켜 인자하도록 되어 있다.Moreover, as writing utensils using the aqueous fluorescent ink of the present invention, for example, a polyester fiber may be used as the middle surface and a polyester bundle fiber may be used as the nib. The middle surface is embedded in the cylindrical body to contain the ink, and the pen tip is in contact with the above-described middle surface and the other end is protruded to the opposite side, so that when the writing utensil is used, the ink comes out by contacting the surface of paper or the like. It is.
본 발명에 따른 수성 형광잉크는, 이를 구성하는 라텍스가 0.3 미크론 이하의 크기를 갖고 있기 때문에, 잉크의 유출성 및 필기감이 우수하며, 색조가 균질하다.In the aqueous fluorescent ink according to the present invention, since the latex constituting the same has a size of 0.3 micron or less, it is excellent in ink spillability and writing feeling, and the color tone is uniform.
수성 형광잉크 조성은 전술한 성분 이외에 비이온성 활성제, 음이온 활성와 같은 계면활성제, 염료용해제, 균염제, 방부제, 가스퇴색방지제, 이온봉쇄제, 산화방지제, 자외선흡수제, 소포제 등을 포함할 수 있으며, 이들의 상호간의 물리, 화학 작용에 따른 상승효과가 점도, 표면장력의 조정, 잉크의 내열성, 일광견뢰도 등의 향상, 필기 특성의 개선을 할 수 있는 효과를 줄 수 있다.The aqueous fluorescent ink composition may include, in addition to the aforementioned components, nonionic active agents, surfactants such as anionic activities, dye dissolving agents, leveling agents, preservatives, gas fading agents, ion blocking agents, antioxidants, ultraviolet absorbers, antifoaming agents, and the like. The synergistic effect of the physical and chemical interactions can have the effect of adjusting the viscosity, surface tension, heat resistance of the ink, fastness of daylight and the like, and improving the writing characteristics.
실시예Example
이하에 본 발명의 실시예를 들어 설명한다.EMBODIMENT OF THE INVENTION Below, the Example of this invention is given and described.
실시예 1Example 1
(1) 단량체 혼합물 및 개시제 용액의 제조(1) Preparation of monomer mixture and initiator solution
아세트니트릴(AN) 140 ㎏, 스티렌 단량체 236.4 ㎏, 메틸 메타크릴레이트 (MMA) 72.2 ㎏ 및 메타크릴산(MAA) 33.8 ㎏으로 구성된 단량체 혼합물을 제조하고, 개시제 3.24 ㎏을 물 60 ㎏에 완전히 용해시켜 개시제 용액을 제조한다.A monomer mixture consisting of 140 kg of acetonitrile (AN), 236.4 kg of styrene monomer, 72.2 kg of methyl methacrylate (MMA) and 33.8 kg of methacrylic acid (MAA) was prepared, and 3.24 kg of initiator was completely dissolved in 60 kg of water. Prepare the initiator solution.
(2) 라텍스 중합(2) latex polymerization
반응기에 물 630 ㎏을 투입하고 유화제 45.2 ㎏을 계량하여 투입한다. 물 30 ㎏로 유화제 계량시에 사용된 용기를 세척하여 투입하여, 교반하에 스팀으로써 약 50℃까지 승온시킨다.630 kg of water was added to the reactor, and 45.2 kg of emulsifier was weighed out. The vessel used at the time of emulsifier metering with 30 kg of water was washed and put in, and it heated up to about 50 degreeC with steam under stirring.
상기 제조된 단량체 혼합물 중의 72 ㎏을 질소 기류하에 먼저 반응기 내로 교반하에 투입하고 온도를 상승시킨다. 반응물 온도가 78℃ 정도가 되면 스팀을 닫고, 반응물의 온도가 80℃가 되면 위에서 제조된 개시제 용액 중에서 12 ㎏을 신속하게 투입한다.72 kg of the monomer mixture prepared above are first introduced into the reactor under nitrogen stream under stirring and the temperature is raised. When the temperature of the reactant is about 78 ℃ steam is closed, when the temperature of the reactant is 80 ℃ 12 kg in the initiator solution prepared above is rapidly added.
온도가 87℃ 이상 상승되면, 단량체 혼합물의 잔량 및 개시제 용액 잔량을 함께 교반하에 적가한다. 냉각수를 순환시키면서 반응물의 온도가 60℃ 부근까지 저하될 때까지 교반한 후, 다음날까지 교반을 계속하여 실온으로 냉각되게 한다.When the temperature rises above 87 ° C., the remaining amount of the monomer mixture and the remaining amount of the initiator solution are added dropwise together under stirring. Stir until the temperature of the reactant drops to around 60 ° C. while circulating the cooling water, and then continue stirring until the next day to allow to cool to room temperature.
약 1200 ㎏의 라텍스를 수득하였으며, 이를 다음 착색 단계에서 사용할 수 있게 준비한다.About 1200 kg of latex was obtained, which was prepared for use in the next coloring step.
(3) 착색공정(3) coloring process
물 86 ㎏을 분산조에 투입하고, 교반하에 B.Y.40 18.6 ㎏, NP10 24 ㎏, EG 24㎏, TEA 6㎏, 및 이온교환수 11 ㎏을 차례로 투입하고, 상온에서 1시간 동안 교반하에 분산시킨다.86 kg of water was added to the dispersing tank, and 18.6 kg of B.Y.40, 24 kg of NP10, 24 kg of EG, 6 kg of TEA, and 11 kg of ion-exchanged water were sequentially added, followed by dispersion at room temperature under stirring for 1 hour.
상기 단계 (2)에서 제조된 라텍스 1200 ㎏을 상기 분산조에 투입하고, 염료 분산액을 신속하게 적가하고, 곧바로 스팀으로 승온시킨다. 온도가 84℃ 정도가 되면 스팀을 닫고, 냉각수를 투입하여 교반하면서 상온까지 뇽각하고 침전조로 보낸다.1200 kg of the latex prepared in the step (2) is added to the dispersion tank, the dye dispersion is added dropwise quickly, and immediately heated up by steam. When the temperature is about 84 ℃ close the steam, adding cooling water and stirring to room temperature while stirring and sent to the settling tank.
1차 여과작업을 거친 후에, 420 메쉬로 2차로 여과하여, 소망하는 수성 형광잉크를 수득한다.After the first filtration operation, the filtration was performed secondly with 420 mesh to obtain the desired aqueous fluorescent ink.
상기 실시예에서 제조된 수성 형광 잉크 및 이를 사용하여 제조된 필기구의 물성 등을 하기에 따라 시험하였다.The physical properties of the aqueous fluorescent ink prepared in the above Example and the writing instrument prepared using the same were tested as follows.
저장안정성Storage stability
형광펜을 45℃의 항온조에 위치시켜 필기불능으로 될 때까지의 일수를 측정하였다. 본 발명에 따른 수성 형광잉크를 사용하여 제조된 형광펜은 180일간 이상이 없었다.The highlighter was placed in a 45 ° C. thermostat and the number of days until it became unwritable was measured. The highlighter prepared using the aqueous fluorescent ink according to the present invention did not have more than 180 days.
색조의 선명성Hue sharpness
본 발명에 따른 수성 형광잉크를 사용하여 제조된 형광펜으로 종이위에 인자(印字)하고 형광분광광도계로 측정하였을 때, 높은 정도의 선명성을 나타내었다.A fluorescent pen prepared using an aqueous fluorescent ink according to the present invention showed a high degree of sharpness when printed on paper and measured with a fluorescence spectrophotometer.
내광성 시험Light resistance test
본 발명에 따른 수성 형광잉크를 사용하여 제조된 형광펜으로 종이위에 인자(印字)하고 10시간 조사하여 측정하였을 때, 색조 소멸이나 변색이 관찰되지 않았다.When a fluorescent pen prepared using an aqueous fluorescent ink according to the present invention was printed on paper and irradiated for 10 hours, no hue disappearance or discoloration was observed.
내수성 시험Water resistance test
본 발명에 따른 수성 형광잉크를 사용하여 제조된 형광펜으로 종이위에 인자(印字)하고, 종이를 1시간 물에 침지하여 필적의 흐트러짐을 육안으로 관찰하였다. 글자체의 흐르러짐이 관찰되지 않았다.Printing was carried out on a paper with a highlighter prepared using an aqueous fluorescent ink according to the present invention, and the paper was immersed in water for 1 hour to observe the handwriting disorder. No flowing font was observed.
본 발명에 따른 형광펜의 감압지에 적용Application to the pressure-sensitive paper of the highlighter according to the present invention
본 발명에 따른 수성 형광잉크를 사용하여 제조된 형광펜으로 시판되는 감압지에 위에 인자(印字)하고 3분 후에 글자체의 흐트러짐 및 선명성을 육안으로 관찰하였다. 글자체의 흐트러짐 및 선명성에 나쁜 영향이 없었다.Printing was carried out on a pressure-sensitive paper commercially available with a fluorescent pen prepared using an aqueous fluorescent ink according to the present invention, and after 3 minutes, the discoloration and sharpness of the font were visually observed. There was no adverse effect on the distorting and sharpness of the font.
본 발명에 따른 수성 형광 잉크 조성물은 색조의 선명성, 형광강도, 잉크의 원활한 유출성, 저장안정성 등이 우수하였으며, 기존의 필기용 종이 외에 감압지와 같은 용지에도 우수하게 적용될 수 있고, 색조의 소멸, 변색에 대해 내성이 높고, 내구성, 내광성 등이 우수하다.The aqueous fluorescent ink composition according to the present invention was excellent in color clarity, fluorescence intensity, smooth outflow of ink, storage stability, and the like, and can be applied to papers such as pressure-sensitive paper in addition to the existing writing paper, and the color disappears. It is resistant to discoloration, and has excellent durability and light resistance.
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| KR1020010029685A KR20020090699A (en) | 2001-05-29 | 2001-05-29 | Curable silicone compositon having slip property |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304163A (en) * | 1988-06-02 | 1989-12-07 | Nippon Keikou Kagaku Kk | Water-base fluorescent ink for writing utensil |
| US5131916A (en) * | 1990-03-01 | 1992-07-21 | Bayer Aktiengesellschaft | Colored fluorescent polymer emulsions for marker pens: graft copolymers and fluorescent dyes in aqueous phase |
| KR960034335A (en) * | 1995-03-09 | 1996-10-22 | 송삼석 | Fluorescent Ink Composition for Aqueous Ballpoint Pen |
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2001
- 2001-05-29 KR KR1020010029685A patent/KR20020090699A/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304163A (en) * | 1988-06-02 | 1989-12-07 | Nippon Keikou Kagaku Kk | Water-base fluorescent ink for writing utensil |
| US5131916A (en) * | 1990-03-01 | 1992-07-21 | Bayer Aktiengesellschaft | Colored fluorescent polymer emulsions for marker pens: graft copolymers and fluorescent dyes in aqueous phase |
| KR960034335A (en) * | 1995-03-09 | 1996-10-22 | 송삼석 | Fluorescent Ink Composition for Aqueous Ballpoint Pen |
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