JPH02263876A - Cover-up liquid - Google Patents
Cover-up liquidInfo
- Publication number
- JPH02263876A JPH02263876A JP8478689A JP8478689A JPH02263876A JP H02263876 A JPH02263876 A JP H02263876A JP 8478689 A JP8478689 A JP 8478689A JP 8478689 A JP8478689 A JP 8478689A JP H02263876 A JPH02263876 A JP H02263876A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- component
- weight
- acrylic resin
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 5
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000012463 white pigment Substances 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 239000002989 correction material Substances 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 15
- 239000000049 pigment Substances 0.000 description 12
- 239000000976 ink Substances 0.000 description 10
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethyl-hexyl Chemical group 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、１各種筆記具による筆跡、タイプライタ−に
よる印字、あるいは、乾式電子写真複写機による複写像
等を硬、べい修正するための修正液に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a method for hardening and correcting handwriting with various writing instruments, printing by a typewriter, or copied images by a dry type electrophotographic copying machine. Regarding correction fluid.
従来、万年筆、水性サインペン等の水性インキによる誤
字の修正には油性型修正液が、油性ボールペン、油性マ
ーカー等の油性インキによる誤字の修正には水性型修正
液が、また、水性、油性を問わずどのタイプのインキに
対しても修正可能な万能型の修正液が知られている。Traditionally, oil-based correction fluid was used to correct typographical errors made with water-based ink such as fountain pens and water-based felt-tip pens, while water-based correction fluid was used to correct typographical errors made with oil-based ink such as oil-based ballpoint pens and oil-based markers. A universal correction fluid that can correct any type of ink is known.
これら修正液の中で、油性および水性型修正液は消去さ
れるべきインキの種類に応じて使い分けなければならな
いという不便さがあるのに対し、万能型のものは、イン
キの種類に左右されることなく、どのタイプのインキに
対しても修正可能である点で有利である。Among these correction fluids, oil-based and water-based correction fluids have the inconvenience of having to be used depending on the type of ink to be erased, whereas universal ones are sensitive to the type of ink. It is advantageous in that it can be corrected for any type of ink without any problems.
ところで、このような修正液に要求される性能としては
、配合されている顔料の沈降や凝集がなく、また、増粘
現象が起こりにくい等経時安定性に優れていること、速
乾性を有すること、形成される修正塗膜が文字等を完全
に隠ぺいし、修正機能に優れていること等が挙（デられ
るが、従来知られている万能型修正液は、必ずしもこれ
らの要求性能の全てを十分満足し得るものであるとはい
い難い。By the way, the performance required for such a correction fluid is that there is no sedimentation or agglomeration of the pigments contained in it, that it has excellent stability over time, such as being unlikely to thicken, and that it dries quickly. The correction coating film that is formed completely hides letters, etc., and has excellent correction functions. However, conventionally known all-purpose correction fluids do not necessarily meet all of these required performances. It is difficult to say that it is completely satisfactory.
例えば、従来知られている万能型修正液としては、白色
顔料、ハロゲン化炭化水素系溶剤、および、石油系樹脂
を構成成分とするものが知られているが、この修正液は
水性インキによる文字等の修正機能には優れているもの
の、油性インキに対する修正機能に劣る傾向があり、加
えて、この（１正液に用いられている有機溶剤がハロゲ
ンを含有しているために毒性が強いという問題点を有し
ている。For example, conventional all-purpose correction fluids are known to contain white pigments, halogenated hydrocarbon solvents, and petroleum resins; Although it has an excellent correction function for oil-based inks, it tends to be inferior in correction function for oil-based inks. There are problems.
上記毒性の問題点を改善するため、ハロゲン化炭化水素
系溶剤に代えて、メチルシクロヘキサンを用いた修正液
も知られているが、メチルシクロヘキサンは石油系樹脂
に対する溶解性に優れているとはいい難く、このため、
該修正液は貯蔵中もしくは使用中に増粘したり、白色顔
料が分散不良となり、極端な場合には沈降したり凝集し
たりするなどの問題点がある。In order to improve the above-mentioned toxicity problem, a correction fluid using methylcyclohexane instead of a halogenated hydrocarbon solvent is known, but methylcyclohexane has excellent solubility in petroleum resins. For this reason, it is difficult to
The correction fluid has problems such as thickening during storage or use, poor dispersion of the white pigment, and, in extreme cases, sedimentation or agglomeration.
本発明者は、上記のような現状に鑑み、経時安定性に優
れると共に、修正機能においても従来のものと同等もし
くはそれ以上の性能を有する万能型１１！正液を提供す
べく鋭意検討を行った結果、特定組成のアクリル系樹脂
が、メチルシクロヘキサンに対して良好な溶解性を示し
、その結果、顔料分散が極めて良好で、得られる修正液
に増粘現象や顔料の沈降等が全く認められないことを見
いだして本発明を完成したものである。In view of the above-mentioned current situation, the inventors of the present invention have developed a versatile model 11! which has excellent stability over time and has a correction function equivalent to or better than conventional ones! As a result of extensive research to provide a corrective solution, we found that an acrylic resin with a specific composition showed good solubility in methylcyclohexane, resulting in extremely good pigment dispersion and thickening of the resulting correction fluid. The present invention was completed by discovering that no phenomenon or precipitation of pigments was observed.
すなわち、本発明の修正液は、白色顔料、有機溶剤、及
び、下記（ａ）、（ｂ）及び（ｃ）成分を共重合して得
られるアクリル系樹脂とからなることを特徴とするもの
である。That is, the correction fluid of the present invention is characterized by comprising a white pigment, an organic solvent, and an acrylic resin obtained by copolymerizing the following components (a), (b), and (c). be.
（ａ）成分：下記一般式［Ｉ］で示される（メタ）アク
リル酸エステル ７０〜９９重量％、（ｂ）成分：下記
一般式［■］及び／又は［ＩＩＩ］で示される第３級ア
ミノ基を含むアクリルアミド系モノマー １〜３０！１
量％、
（ｃ）成分二上記（ａ）及び（ｂ）成分と共重合可能な
他のビニルモノマー ０〜２９監量％、二上１；
ｌ
ＣＨ２：Ｃ−ＣＯＯＲ２・・φ・・・・争・・［１］・
・・・・・・・・・［ｍｌ
（式中、Ｒ１は水素またはメチル基を表し、Ｒ２は炭素
数１〜１８の直鎖もしくは側鎖を有する炭化水素基、ま
たは、ナフテン環もしくは芳香環を含む炭化水素基を表
し、Ｒ３およびＲＡは同一でも異なってもよく各々メチ
ル基またはエチル基を表し、ｎ、は１〜３の整数を表す
）
本発明において用いられる白色顔料は、筆跡等を隠ぺい
するための成分であって、特に隠ぺい性の高いルチル型
、アナターゼ型等の酸化チタンを用いるのが好ましい、
使用可能な酸化チタンとしては、市場から人手容易な、
例えば、石層産業社製のタイベークＲ−５８０、同Ｒ−
５５０、同Ｒ−７８０、同Ｒ−７８０−２、同Ｒ−９３
０、同Ａ−１００，同Ａ−２２０、堺化学工業社製のタ
イトーン５Ｒ−１、同Ｒ−６５０、同Ｒ−３Ｌ。(a) Component: 70-99% by weight of (meth)acrylic acid ester represented by the following general formula [I], (b) component: Tertiary amino represented by the following general formula [■] and/or [III] Acrylamide monomer containing groups 1 to 30!1
(c) Component 2 Other vinyl monomers copolymerizable with the above (a) and (b) components 0 to 29% by weight, 2 1; l CH2:C-COOR2...φ... Conflict... [1]
・・・・・・・・・[ml (In the formula, R1 represents hydrogen or a methyl group, R2 is a hydrocarbon group having a straight chain or side chain having 1 to 18 carbon atoms, or a naphthene ring or an aromatic ring. (R3 and RA may be the same or different and each represents a methyl group or an ethyl group, and n represents an integer of 1 to 3). It is preferable to use titanium oxide such as rutile type or anatase type titanium oxide, which has a particularly high concealing property, as a component for concealing.
Titanium oxide that can be used is available on the market and is easily available by hand.
For example, Thaibake R-580 manufactured by Ishiya Sangyo Co., Ltd.
550, R-780, R-780-2, R-93
0, A-100, A-220, Titone 5R-1, R-650, and R-3L manufactured by Sakai Chemical Industry Co., Ltd.
同Ｒ−３１０、同Ｒ−１１０，同Ａ−１５０、同Ｒ−５
Ｎ、 デュポン社製のタイピュアＲ−９３１、同Ｒ−
９３３、チタン工業社製のクロノスＫＲ−３１０、同Ｉ
（Ｒ−３８０、同ＫＲ−４８０、同ＫＡ−１０，同ＫＡ
−２０，同ＫＡ−３０等が挙げられ、これら酸化チタン
はそれぞれ単独でもしくは２種以上混合して用いること
ができる。Same R-310, Same R-110, Same A-150, Same R-5
N, DuPont Typure R-931, R-
933, Kronos KR-310 manufactured by Titan Kogyo Co., Ltd., I
(R-380, KR-480, KA-10, KA
-20, KA-30, etc., and these titanium oxides can be used alone or in a mixture of two or more.
なお、上記酸化チタンには、酸化チタン以外の他の白色
顔料、体質顔料等を併用しても差し支えないが、これら
白色顔料、体質顔料の併用は修正塗膜の隠ぺい性を低下
させる傾向があるので、白色顔料総量に対して酸化チタ
ン含量が５０！量％以上とするのが好ましい。Note that the above titanium oxide may be used in combination with other white pigments, extender pigments, etc. other than titanium oxide, but the combined use of these white pigments and extender pigments tends to reduce the hiding power of the correction coating. Therefore, the titanium oxide content is 50% of the total amount of white pigment! It is preferable that the amount is % or more.
本発明に用いられる有機溶剤としては、適度の乾燥速度
を有し、上記アクリル樹脂を溶解し、かつ、水性タイプ
および油性タイプの両インキによる文字の修正が行える
ものであれば、特に限定するものではないが、特に、シ
クロヘキサン、メチルシクロヘキサン、エチルシクロヘ
キサン、ジメチルシクロヘキサン等のシクロパラフィン
系溶剤、ｎ−ヘキサン、ｎ−へブタン、１ｓｏ−へブタ
ン、ｎ−オクタン、１ｓｏ−オクタン等のパラフィン系
溶剤等を用いるのが好ましい、これら有機溶剤はそれぞ
れ単独で、あるいは、２種以上混合して用いても良く、
さらには安定性を損なわない範囲で他の有機溶剤を添加
しても良い、添加し得る溶剤としては、例えば、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素系溶剤、１
，４−ジオキサン、ｎ −ブチルエーテル、トリオキサ
ン、テトラヒドロフラン等のエーテル系溶剤、メチルエ
チルケトン、メチル−ｎ−プロピルケトン、メチルイソ
ブチルケトン、シクロヘキサン等のケトン系溶剤、酢酸
エチル等のエステル系溶剤等が挙げられる。The organic solvent used in the present invention is not particularly limited as long as it has an appropriate drying speed, dissolves the acrylic resin, and can correct characters with both water-based and oil-based inks. However, in particular, cycloparaffinic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, paraffinic solvents such as n-hexane, n-hebutane, 1so-hebutane, n-octane, 1so-octane, etc. It is preferable to use these organic solvents, each of which may be used alone or in combination of two or more,
Furthermore, other organic solvents may be added within a range that does not impair stability. Examples of solvents that can be added include aromatic hydrocarbon solvents such as benzene, toluene, and xylene;
, 4-dioxane, n-butyl ether, trioxane, and tetrahydrofuran, ketone solvents such as methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, and cyclohexane, and ester solvents such as ethyl acetate.
本発明に用いられるアクリル系樹脂は、上記有機溶剤に
溶解して白色顔料の分散性を向上させると共に、形成さ
れる修正塗膜に適度の強度を付与するための重要成分で
あり、上記（ａ）成分７０〜９９１量％、（ｂ）成分１
〜３０重量％、および、（ｃ）成分０〜２９！量％を共
重合してなるものである。The acrylic resin used in the present invention is an important component for dissolving in the organic solvent to improve the dispersibility of the white pigment and imparting appropriate strength to the correction coating film formed. ) component 70-991% by weight, (b) component 1
~30% by weight, and component (c) 0~29! % by copolymerization.
上記アクリル系樹脂を構成する（ａ）成分は、上記一般
式［Ｉ］で示される（メタ）アクリル酸エステルであり
、その具体例としては、メチル（メタ）アクリレート、
エチルくメタ）アクリレート、プロピル（メタ）アクリ
レート、１ｓｏ−プロピル（メタ）アクリレート、・ｎ
−ブチル（メタ）アクリレート、１ｓｏ−ブチル（メタ
）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレー
ト、２−エチル−ヘキシル（メタ）アクリレート、オク
チル（メタ）アクリレート、ラウリル（メタ）アクリレ
ート、セチル（メタ）アクリレート、ステアリル（メタ
）アクリレート、オレイル（メタ）アクリレート、シク
ロヘキシル（メタ）アクリレート、ベンジル（メタ）ア
クリレート等が挙げられ、これら（メタ）アクリル酸エ
ステルは、それぞれ単独で用いても良いが、修正塗膜の
強度向上を考慮しつつ２種、もしくは、それ以上の、組
み合わせで用いるのが有利である。Component (a) constituting the acrylic resin is a (meth)acrylic acid ester represented by the general formula [I], and specific examples thereof include methyl (meth)acrylate,
Ethyl (meth)acrylate, propyl (meth)acrylate, 1so-propyl (meth)acrylate, ・n
-Butyl (meth)acrylate, 1so-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate , stearyl (meth)acrylate, oleyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, etc., and these (meth)acrylic acid esters may be used alone, but they can also be used for correction coatings. It is advantageous to use two or more types in combination, taking into consideration the improvement in strength.
上記（ａ）の（メタ）アクリル酸エステルは、アクノル
系樹脂中７０〜９９重量％含有することが必要であり、
含有量が７０重量％より少ないと有機溶剤に対するアク
リル樹脂の溶解性が悪くなり、９９重量％を超えると顔
料の分散性が悪くなる。The (meth)acrylic acid ester in (a) above needs to be contained in an amount of 70 to 99% by weight in the Acnol resin,
If the content is less than 70% by weight, the solubility of the acrylic resin in organic solvents will be poor, and if it exceeds 99% by weight, the dispersibility of the pigment will be poor.
上記アクリル系樹脂の構成成分である（ｂ）成分として
は、上記一般式［■］または［■］で示される第３級ア
ミノ基を含むアクリルアミド系モノマーであり、その具
体例としては、Ｎ、 Ｎ−ジメチル（メタ）アクリル
アミド、Ｎ、 Ｎ−ジエチル（メタ〉アクリルアミド
、Ｎ、 Ｎ−ジメチルアミノエチル（メタ）アクリル
アミド、Ｎ、Ｎ−ジエチルアミノエチル（メタ）アクリ
ルアミド、Ｎ、Ｎ−ジメチルアミノプロピル（メタ）ア
クリルアミド、Ｎ、Ｎ−ジエチルアミノプロピル（メタ
）アクリルアミド等である。Component (b), which is a constituent component of the acrylic resin, is an acrylamide monomer containing a tertiary amino group represented by the general formula [■] or [■], and specific examples thereof include N, N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide ) acrylamide, N,N-diethylaminopropyl (meth)acrylamide, and the like.
上記（ｂ）成分はアクリル系樹脂中１〜３０重量％含有
することが重要であり、含有量が１重量％より少ないと
白色顔料に対する吸着が弱いため白色駅料の分散性が悪
くなり、含有量が３０ｉｉ量％を超えると、もう一方の
共重合成分（ａ）の種類によっては有機溶剤に対するア
クリル系樹脂の溶解性が悪くなることがある。It is important to contain the above component (b) in an amount of 1 to 30% by weight in the acrylic resin. If the content is less than 1% by weight, the adsorption to the white pigment will be weak, resulting in poor dispersibility of the white pigment, If the amount exceeds 30% by weight, the solubility of the acrylic resin in the organic solvent may deteriorate depending on the type of the other copolymer component (a).
本発明に用いられるアクリル系樹脂においては、必要に
応じてさらに（ｃ）成分が用いられる。使用可能な（ｃ
）成分としては、上記（ａ）及び（ｂ）成分と共重合可
能なその他のビニルモノマーであり、該ビニルモノマー
としては水酸基、カルボキシル基等の官能基を有する（
メタ）アクリル酸エステル、酢酸ビニル、スチレン、ビ
ニルトルエン等が挙げられ、また、（メタ）アクリルア
ミド、Ｎ−メチロール（メタ）アクリルアミド等も挙げ
られ、これらビニルモノマーはアクリル系樹脂９０〜２
９重量％含有することができ、含有量が２９重量％を超
えると有機溶剤に対するアクリル系樹脂の溶解性が悪く
なる。In the acrylic resin used in the present invention, component (c) may be further used as necessary. Usable (c
The component ) is another vinyl monomer copolymerizable with the above components (a) and (b), and the vinyl monomer has a functional group such as a hydroxyl group or a carboxyl group (
Examples include meth)acrylic acid ester, vinyl acetate, styrene, vinyltoluene, etc., and also (meth)acrylamide, N-methylol(meth)acrylamide, etc., and these vinyl monomers are used for acrylic resins 90-2
The content can be 9% by weight, and if the content exceeds 29% by weight, the solubility of the acrylic resin in organic solvents will deteriorate.
本発明に用いられるアクリル系樹脂を製造するのに、何
等特殊な方法を必要とするものではなく、公知の重合法
によって製造することができる。−例としては、上記に
例示した修正液用有機溶剤中で、（ａ）〜（ｃ）成分の
重合反応を行う溶液重合法によって製造するのが好まし
い、また、その場合のアクリル共重合体の分子量につい
ての特別な限定がないが、１０，０００〜３００，００
０の範囲とするの好ましく、分子量がこの範囲を外れて
小さいと修正塗膜が柔らかくなり過ぎたり、筆記面から
剥がれ易くなる等の欠点が生じる傾向があり、反対に分
子量が上記範囲を外れて大きいと修正液の粘度が上昇し
て流動性に乏しくなり、修正時の塗布性が悪くなる傾向
がある。No special method is required to produce the acrylic resin used in the present invention, and it can be produced by any known polymerization method. - For example, it is preferable to manufacture by a solution polymerization method in which components (a) to (c) are polymerized in the organic solvent for correction fluid exemplified above, and in that case, the acrylic copolymer There is no special limitation on the molecular weight, but it is between 10,000 and 300,000.
It is preferable that the molecular weight be within the range of 0.If the molecular weight is outside this range and it is small, the correction coating will tend to be too soft and will tend to peel off easily from the writing surface. If it is too large, the viscosity of the correction fluid increases, resulting in poor fluidity, which tends to result in poor applicability during correction.
本発明の修正液は、上述した各成分を適宜の混合分散機
、例えば、ボールミル、アトライターコロイドミル、サ
ンドグラインダー等で温合分散することによって調製す
ることができる。なお、その際、白色ｌＩ料の分散安定
性をさらに高めるために分散剤や沈降防止剤を、粘度調
整のために増粘剤を、修正塗膜の表面状態を良好にする
ためにレベリング剤を、適宜小量添加しても良く、また
、修正塗膜上に再筆記した場合の筆跡の色沈みを防止す
るために液状ゴム成分を、紙等の筆記面と色調を合わせ
るために着色顔料や体質顔料を適宜に加えても良い。The correction fluid of the present invention can be prepared by heating and dispersing the above-mentioned components using an appropriate mixing and dispersing machine, such as a ball mill, an attritor colloid mill, and a sand grinder. In addition, at this time, a dispersant and an anti-settling agent are used to further improve the dispersion stability of the white II material, a thickener is used to adjust the viscosity, and a leveling agent is used to improve the surface condition of the correction coating. In addition, a liquid rubber component may be added in small amounts as appropriate to prevent discoloration of the handwriting when rewritten on the correction coating, and a coloring pigment or Extender pigments may be added as appropriate.
以下、実施例に基づいて本発明の詳細な説明する。なお
、実施例中の各成分の配合量は重量部で示した。Hereinafter, the present invention will be described in detail based on Examples. The amounts of each component in the examples are shown in parts by weight.
Ｘ−嵐−ｌ
攪拌機、温度計、還流コンデンサーを付設した１０００
ｄの反応容器に、メタククリル酸ブチル３０部、メタク
リル酸−２−エチルヘキシル３０部、アクリル酸ブチル
１５部、スチレン５祁、ジメチルアクリルアミド２０部
、及び、メチルシクロヘキサン１５０部を配合し、重合
開始剤としてアゾビスイソブチロニトリル１部を加え、
窒素ガス気流下、８０℃で８時閏溶液重合を行ってアク
リル系樹脂の有機溶剤溶液を得た（樹脂濃度４０ｍ［量
％）。X-Arashi-l 1000 equipped with stirrer, thermometer, and reflux condenser
30 parts of butyl methacrylate, 30 parts of 2-ethylhexyl methacrylate, 15 parts of butyl acrylate, 5 parts of styrene, 20 parts of dimethylacrylamide, and 150 parts of methylcyclohexane were added to the reaction vessel of d, and as a polymerization initiator. Add 1 part of azobisisobutyronitrile,
An organic solvent solution of an acrylic resin was obtained by carrying out a superfluous solution polymerization at 80° C. for 8 hours under a nitrogen gas flow (resin concentration: 40 m [% by weight)].
上記アクリル系樹脂溶液を用い、下記処方に従フて各成
分をボールミルに加え、２４時間湛合分散して修正液を
製造した。Using the above acrylic resin solution, each component was added to a ball mill according to the following recipe, and the mixture was soaked and dispersed for 24 hours to produce a correction fluid.
・アクリル系共重合体溶液 ３０ｖ３・ルチル
型酸化チタン（石屋産業
社製、タイベークＲ−５５０） ８０＃・メチルシ
クロヘキサン ５０部・微細シリカ（水沢化
学工業社製、
ミズカシル、Ｐ−８０１） ２部以上のよ
うにして得られた（１正液について、その３０艷を容ｊ
１５０ｄの密栓付きガラス瓶に採り、１力月間室温に放
置後、白色顔料の沈降伏態によって分散安定性を評価し
た。評価結果を、該修正液製造直後の顔料の沈降伏態と
併せて後記表−１に示した。・Acrylic copolymer solution 30v3 ・Rutile type titanium oxide (manufactured by Ishiya Sangyo Co., Ltd., Tybake R-550) 80# ・Methylcyclohexane 50 parts ・Fine silica (manufactured by Mizusawa Chemical Industry Co., Ltd., Mizukasil, P-801) 2 parts or more Obtained as follows (for 1 positive solution, 30 liters of it were
The mixture was placed in a 150 d glass bottle with a sealed stopper, and after being left at room temperature for one month, the dispersion stability was evaluated based on the precipitation behavior of the white pigment. The evaluation results are shown in Table 1 below, together with the sedimentation behavior of the pigment immediately after producing the correction fluid.
一一笠−１
争メタククリル酸ブチル ３５部・メタクリ
ル酸−２−エチルヘキシル３５部−アクリル酸ブチル
２０部−スチレン
１０部・メチルシクロヘキサン １５０部
・アゾビスイソブチロニトリル １部の組成から
なるモノマー 有機溶剤混合物で上記実施例と同様にし
てアクリル樹脂溶液を得、次いで修正液を製造し、同様
に白色顔料の沈降伏態で分散安定性を評価した。評価結
果を下記表−１に示した。Ichikasa-1 Butyl methacrylate 35 parts 2-ethylhexyl methacrylate 35 parts - Butyl acrylate
20 parts - styrene
An acrylic resin solution was obtained in the same manner as in the above example using a monomer organic solvent mixture consisting of 10 parts of methylcyclohexane, 150 parts of azobisisobutyronitrile, and then a correction fluid was prepared. Dispersion stability was evaluated by sedimentation state. The evaluation results are shown in Table 1 below.
表 −ｌ
上記表−１の結果から明らかなように、本発明の実施に
相当する実施例の修正液は、第３級アミノ基を含むアク
リルアミド系モノマーを共重合成分としたアクリル系樹
脂を用いているので、長門間にわたって良好な分散が得
られ、経時安定性に優れたたものであったが、共重合成
分としてアクリルアミド系モノマーを含まないアクリル
系樹脂を用いた比較例の修正液は、１力月の貯蔵により
堅い沈積物が生じ、使用に適さない状態のものであった
。Table 1 As is clear from the results in Table 1 above, the correction fluid of the example corresponding to the implementation of the present invention uses an acrylic resin containing an acrylamide monomer containing a tertiary amino group as a copolymer component. As a result, good dispersion was obtained over a long period of time, and the stability over time was excellent. After one month of storage, hard deposits formed and the product was in an unusable condition.
本発明の修正液は、上記したように、第３級アミノ基を
含むアクリルアミド系モノマーを共重合成分とするアク
リル系樹脂を用でいるので、白色顔料の分散性を長期間
にわたって良好に維持することができ、また、水性及び
油性の種類を問わすどのタイプのインキによる筆跡に対
しても１１正可能である等、実用性に優れた修正液であ
る。As mentioned above, the correction fluid of the present invention uses an acrylic resin whose copolymerization component is an acrylamide monomer containing a tertiary amino group, and therefore maintains the dispersibility of the white pigment well over a long period of time. It is a highly practical correction fluid that can correct handwriting made with any type of ink, both water-based and oil-based.
Claims (1)
ｃ）成分を共重合して得られるアクリル系樹脂とからな
る修正液。 （ａ）成分：下記一般式［ I ］で示される（メタ）ア
クリル酸エステル７０〜９９重量％、 （ｂ）成分：下記一般式［II］および／または［III］
で示される第３級アミノ基を含むアクリルアミド系モノ
マー１〜３０重量％、 （ｃ）成分：上記（ａ）および（ｂ）成分と共重合可能
な他のビニルモノマー０〜２９重量％、 一般式： ▲数式、化学式、表等があります▼・・・・・・・・・
・［I］ ▲数式、化学式、表等があります▼・・・・・・・・・
・［II］ ▲数式、化学式、表等があります▼・・・・・・・・・
・［III］ （式中、Ｒ＿１は水素またはメチル基を表し、Ｒ＿２は
炭素数１〜１８の直鎖もしくは側鎖を有する炭化水素基
、または、ナフテン環もしくは芳香環を含む炭化水素基
を表し、 Ｒ＿３およびＲ＿４は同一でも異なってもよく各々メチ
ル基またはエチル基を表し、ｎは１〜３の整数を表す）[Claims] A white pigment, an organic solvent, and the following (a), (b) and (
c) A correction liquid consisting of an acrylic resin obtained by copolymerizing components. (a) Component: 70-99% by weight of (meth)acrylic acid ester represented by the following general formula [I], (b) component: the following general formula [II] and/or [III]
1 to 30% by weight of an acrylamide monomer containing a tertiary amino group represented by Component (c): 0 to 29% by weight of another vinyl monomer copolymerizable with the above components (a) and (b), general formula : ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・［I］ ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・［II］ ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・[III] (In the formula, R_1 represents hydrogen or a methyl group, and R_2 represents a hydrocarbon group having a straight chain or side chain having 1 to 18 carbon atoms, or a hydrocarbon group containing a naphthene ring or an aromatic ring. , R_3 and R_4 may be the same or different and each represents a methyl group or an ethyl group, and n represents an integer of 1 to 3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478689A JP2662599B2 (en) | 1989-04-05 | 1989-04-05 | Correction fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8478689A JP2662599B2 (en) | 1989-04-05 | 1989-04-05 | Correction fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02263876A true JPH02263876A (en) | 1990-10-26 |
| JP2662599B2 JP2662599B2 (en) | 1997-10-15 |
Family
ID=13840383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8478689A Expired - Fee Related JP2662599B2 (en) | 1989-04-05 | 1989-04-05 | Correction fluid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2662599B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993025626A1 (en) * | 1992-06-17 | 1993-12-23 | Mitsubishi Pencil Kabushiki Kaisha | Liquid eraser composition |
| US5594045A (en) * | 1992-06-03 | 1997-01-14 | Alexiou; Michael | Correction fluids |
| US5922400A (en) * | 1997-01-09 | 1999-07-13 | The Gillette Company | Correction fluid |
| US5925693A (en) * | 1994-07-08 | 1999-07-20 | The Gillette Company | Aqueous correction fluids |
| JP2010186172A (en) * | 2009-01-16 | 2010-08-26 | Mitsubishi Rayon Co Ltd | Plastic optical fiber cable |
-
1989
- 1989-04-05 JP JP8478689A patent/JP2662599B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5594045A (en) * | 1992-06-03 | 1997-01-14 | Alexiou; Michael | Correction fluids |
| US5726221A (en) * | 1992-06-03 | 1998-03-10 | The Gillette Company | Correction fluids |
| WO1993025626A1 (en) * | 1992-06-17 | 1993-12-23 | Mitsubishi Pencil Kabushiki Kaisha | Liquid eraser composition |
| US5500455A (en) * | 1992-06-17 | 1996-03-19 | Mitsubishi Pencil Kabushiki Kaisha | Correction fluid composition containing acrylic resin |
| US5925693A (en) * | 1994-07-08 | 1999-07-20 | The Gillette Company | Aqueous correction fluids |
| US6331579B1 (en) | 1994-07-08 | 2001-12-18 | The Gillette Company | Aqueous correction fluids |
| US5922400A (en) * | 1997-01-09 | 1999-07-13 | The Gillette Company | Correction fluid |
| JP2010186172A (en) * | 2009-01-16 | 2010-08-26 | Mitsubishi Rayon Co Ltd | Plastic optical fiber cable |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2662599B2 (en) | 1997-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02263876A (en) | Cover-up liquid | |
| US5500455A (en) | Correction fluid composition containing acrylic resin | |
| JPH0159308B2 (en) | ||
| JPH02169678A (en) | Erasing liquid | |
| JP2921011B2 (en) | High hiding liquid composition | |
| JP4110609B2 (en) | High hiding liquid composition | |
| RU2154080C2 (en) | Ozone-saving correcting liquid having improved rubbing power | |
| JP2893411B2 (en) | Correction fluid | |
| JP4870267B2 (en) | Correction fluid and correction tool using the same | |
| JPS608376A (en) | Eraser solution | |
| JP3304296B2 (en) | Correction fluid | |
| JP5103756B2 (en) | Correction fluid and method for producing the same | |
| JP3354854B2 (en) | Correction fluid | |
| JPH04332776A (en) | Erasable ink composition | |
| JPH0256379B2 (en) | ||
| JPH0139695B2 (en) | ||
| JPS58141254A (en) | Correcting ink | |
| JPH0331375A (en) | Cover-up liquid | |
| JPS582363A (en) | Liquid paper | |
| JPH01170671A (en) | Erasing solution | |
| JP2012036250A (en) | Oily correction fluid composition | |
| JP2002012824A (en) | Covering-up liquid for reclaimed paper | |
| JPH11100536A (en) | Highly-hiding liquid composition | |
| JPH0411665A (en) | Liquid composition | |
| JPS58152069A (en) | Water-based ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |