JP2018021146A - Erasable colorant composition - Google Patents
Erasable colorant composition Download PDFInfo
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- JP2018021146A JP2018021146A JP2016154035A JP2016154035A JP2018021146A JP 2018021146 A JP2018021146 A JP 2018021146A JP 2016154035 A JP2016154035 A JP 2016154035A JP 2016154035 A JP2016154035 A JP 2016154035A JP 2018021146 A JP2018021146 A JP 2018021146A
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000003086 colorant Substances 0.000 title claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000000049 pigment Substances 0.000 description 41
- 239000006185 dispersion Substances 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000000740 bleeding effect Effects 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 amine salt Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004040 coloring Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 229920005732 JONCRYL® 678 Polymers 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 4
- 239000003429 antifungal agent Substances 0.000 description 4
- 229940121375 antifungal agent Drugs 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000271 synthetic detergent Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- XTVCLFHZFUWECQ-UHFFFAOYSA-O dicyclohexylazanium;nitrate Chemical compound [O-][N+]([O-])=O.C1CCCCC1[NH2+]C1CCCCC1 XTVCLFHZFUWECQ-UHFFFAOYSA-O 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- WMLKJRCNNAMELX-UHFFFAOYSA-N n-methylmethanamine;propan-2-amine Chemical compound CNC.CC(C)N WMLKJRCNNAMELX-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は消去性着色剤組成物に関する。 The present invention relates to an erasable colorant composition.
衣服等に着色剤組成物が付着しても、洗濯によって消去することが可能な顔料含有組成物は、下記特許文献１〜３に記載されているように公知である。
そして、特許文献１の実施例として記載されている組成物は、着色顔料＋分散樹脂と、アニオン性樹脂Ａ及びＢを含有し、その分散樹脂はJoncryl６７８であり、アニオン性樹脂Ａはアンモニアで中和されたJoncryl６９０又はメチルアミンで中和されたハイロスＸ−１、アニオン性樹脂Ｂはトリエタノールアミンで中和されたJoncryl６９０又はＰＶＡである。
そして、特許文献２の例えば実施例２として記載されている組成物は、黒色顔料分散体（水酸化ナトリウムで中和されたJoncryl６７８）と、エチルアミンで中和されたスチレンマレイン酸共重合体を含有している。
さらに、特許文献３の例えば実施例５として記載されている組成物は、黒色顔料分散体（水酸化ナトリウムで中和されたJoncryl６７８）と、水酸化ナトリウムで中和されたJoncryl６９０を含有している。
A pigment-containing composition that can be erased by washing even if a colorant composition adheres to clothing or the like is known as described in Patent Documents 1 to 3 below.
And the composition described as an Example of patent document 1 contains a coloring pigment + dispersion resin and anionic resins A and B, and the dispersion resin is Joncryl678, and the anionic resin A is ammonia. High-loss X-1 neutralized with Joncryl 690 or methylamine, anionic resin B is Joncryl 690 or PVA neutralized with triethanolamine.
And the composition described as Example 2 of patent document 2 contains the black pigment dispersion (Joncryl678 neutralized with sodium hydroxide) and the styrene maleic acid copolymer neutralized with ethylamine. doing.
Furthermore, the composition described in Example 5 of Patent Document 3 contains a black pigment dispersion (Joncryl 678 neutralized with sodium hydroxide) and Joncryl 690 neutralized with sodium hydroxide. .
上記の特許文献１〜３に記載の顔料含有組成物によれば、確かに洗濯消去性を有することはでき、かつ表装性や書き味にも優れるものの、洗濯消去性を有するために、専ら半紙表面のみに顔料及び樹脂が付着し、浸透する顔料及び樹脂が少ない傾向にあったので、筆記し乾燥するまでにおいて、筆記面に新聞紙や他の半紙を載せて時間が経過したときに、紙同士が付着することがあった。
また、筆記し乾燥した後において、筆記部分に水滴が付着した場合に、筆記部分が滲むことがあり、依然として、筆記した半紙の取り扱いに注意を要していた。
According to the pigment-containing compositions described in Patent Documents 1 to 3 above, although they can surely have washing erasability and are excellent in surface appearance and writing quality, they are exclusively semi-paper because they have washing erasability. There was a tendency for pigments and resins to adhere only to the surface, and less penetrated pigments and resins, so when writing and drying a newspaper or other semi-paper on the writing surface, time passed May stick.
In addition, after writing and drying, when water droplets adhere to the written part, the written part may bleed, and the handling of the written half paper was still required.
本発明者らは、上記課題を解決すべく鋭意検討を行った結果、分散安定性に優れると共に、滲み等の問題が無く、洗濯消去性を備えた上で、筆記し乾燥するまでにおいて他の紙に着色剤組成物が付着しても紙同士が付着することがなく、乾燥後において表装性に優れるとともに、水滴が付着しても筆記部分が滲まない消去性着色剤組成物を得ることができた。
具体的には以下の通りである。
１．共重合体Ａ（重量平均分子量が１２０００〜２００００である、スチレンアクリル酸共重合体Ａ）及び共重合体Ｂ（重量平均分子量が７０００〜１１０００である、スチレンアクリル酸共重合体Ｂ）、のアルカリ金属との塩及び／又はアンモニアとの塩を含有し、樹脂固形分中の共重合体Ｂのアンモニアの塩の含有比率は４２．０重量％以上であり、
さらにｐＨが６以上のカーボンブラック、水
を含有する消去性着色剤組成物。
２．共重合体Ａの含有量は共重合体Ｂの含有量よりも少ない１に記載の消去性着色剤組成物。
３．スチレンアクリル酸共重合体Ａのアルカリ金属との塩を含有する１又は２記載の消去性着色剤組成物。
４．スチレンアクリル酸共重合体Ａ及びスチレンアクリル酸共重合体Ｂは、共にそれらの酸価が１５０〜３００である１〜３のいずれかに記載の消去性着色剤組成物。
５．消去性着色剤組成物中の、カーボンブラックの含有量／（共重合体Ａの含有量と共重合体Ｂの含有量の和）が１／１〜１／３０である１〜４のいずれかに記載の消去性着色剤組成物。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have excellent dispersion stability, no problem of bleeding, etc., and have washing erasability, before writing and drying. Even if the colorant composition adheres to the paper, the papers do not adhere to each other, and it is excellent in surface appearance after drying, and it is possible to obtain an erasable colorant composition in which the writing part does not blur even if water droplets adhere. did it.
Specifically, it is as follows.
1. Alkali of copolymer A (styrene acrylic acid copolymer A having a weight average molecular weight of 12,000 to 20,000) and copolymer B (styrene acrylic acid copolymer B having a weight average molecular weight of 7,000 to 11,000) Containing a salt with a metal and / or a salt with ammonia, the content ratio of the salt of ammonia of the copolymer B in the resin solid content is 42.0% by weight or more,
Further, an erasable colorant composition containing carbon black having a pH of 6 or more and water.
2. 2. The erasable colorant composition according to 1, wherein the content of the copolymer A is less than the content of the copolymer B.
3. 3. The erasable colorant composition according to 1 or 2, comprising a salt of the styrene acrylic acid copolymer A with an alkali metal.
4). The erasable colorant composition according to any one of 1 to 3, wherein the styrene acrylic acid copolymer A and the styrene acrylic acid copolymer B both have an acid value of 150 to 300.
5. Any of 1 to 4 in which the content of carbon black in the erasable colorant composition / (the sum of the content of copolymer A and the content of copolymer B) is 1/1 to 1/30. The erasable colorant composition described in 1.
本発明によれば、分散安定性に優れると共に滲みなどの問題がなく、洗濯消去性に優れ、半紙等に筆記し、乾燥するまでの間において筆記面に新聞紙や他の半紙を重ねて経時後においても、紙同士が付着することがないという効果、乾燥後において表装性、耐水滴滴下にも優れるという効果を発揮する。 According to the present invention, the dispersion stability is excellent and there is no problem such as bleeding, the washing erasability is excellent, writing on a half paper, etc. In this case, the effect that the papers do not adhere to each other, and the effect that the surface property and the water-resistant dripping resistance are excellent after drying are exhibited.
本発明の消去性着色剤組成物は、衣類等に付着し乾燥した後であっても、通常の洗濯を行うことによって洗い落とすことができるという洗濯消去性に優れた性質を有する。
加えて、半紙等の紙に対して筆記した場合であっても、滲みの問題がなく、表装性に優れるために、清書用の筆記用組成物として使用することができる。また、筆記後完全に乾燥していない状態であっても、紙同士が付着することがなく、さらに乾燥後に水滴が付着しても筆記部分が滲まない。
The erasable colorant composition of the present invention has a property excellent in washing erasability such that it can be washed off by performing ordinary washing even after it is attached to clothes and dried.
In addition, even when writing on a paper such as a semi-paper, there is no problem of bleeding and excellent surface appearance, so that it can be used as a writing composition for clear writing. Further, even when the paper is not completely dried after writing, the papers do not adhere to each other, and even if water droplets adhere after drying, the written part does not bleed.
以下に本発明の消去性着色剤組成物の具体的組成について説明する。
＜顔料＞
本発明において使用できる着色顔料としては、スチレンアクリル酸共重合体Ａ及びスチレンアクリル酸共重合体Ｂのアルカリ金属との塩及び／又はアンモニア塩によって、水性媒体中に安定的に分散させることができるものである。
このような顔料として、カーボンブラック、銅フタロシアニン系顔料、スレン系顔料、アゾ系顔料、キナクリドン系顔料、アンスラキノン系顔料、ジオキサン系顔料、インジゴ系顔料、チオインジゴ系顔料、ペリノン系顔料、ペリレン系顔料、インドレノン系顔料、アゾメチン系顔料などの公知の有機顔料を使用することができる。
本発明の消去性着色剤組成物を黒色の墨汁組成物として使用する場合には、これらの顔料の中からｐＨ６以上のカーボンブラックを選択して使用することができる。
本発明中の消去性着色剤組成物１００重量部中の着色顔料の含有量としては、２．０〜８．０重量部が好ましい。２．０重量部未満であると、着色効果が弱く、８．０重量部を超えると、粘度が高くなりすぎたり、着色顔料が沈殿して消去性着色剤組成物の保存安定性に劣ったりする可能性がある。
また、消去性着色剤組成物中の、着色顔料の含有量／（共重合体Ａの含有量と共重合体Ｂの含有量の和）が１／１〜１／３０であることが好ましい。着色顔料の含有量が１／３０未満であると着色効果が弱く、１／１を超えると、粘度が高くなりすぎたり、着色顔料が沈殿して消去性着色剤組成物の保存安定性に劣る可能性がある。
The specific composition of the erasable colorant composition of the present invention will be described below.
<Pigment>
The coloring pigment that can be used in the present invention can be stably dispersed in an aqueous medium by a salt of styrene acrylic acid copolymer A and styrene acrylic acid copolymer B with an alkali metal and / or an ammonia salt. Is.
Examples of such pigments include carbon black, copper phthalocyanine pigment, selenium pigment, azo pigment, quinacridone pigment, anthraquinone pigment, dioxane pigment, indigo pigment, thioindigo pigment, perinone pigment, and perylene pigment. Known organic pigments such as indolenone pigments and azomethine pigments can be used.
When the erasable colorant composition of the present invention is used as a black ink composition, carbon black having a pH of 6 or more can be selected from these pigments.
The content of the color pigment in 100 parts by weight of the erasable colorant composition in the present invention is preferably 2.0 to 8.0 parts by weight. If it is less than 2.0 parts by weight, the coloring effect is weak, and if it exceeds 8.0 parts by weight, the viscosity becomes too high, or the coloring pigment precipitates and the erasable colorant composition has poor storage stability. there's a possibility that.
Further, the content of the color pigment / (sum of the content of the copolymer A and the content of the copolymer B) in the erasable colorant composition is preferably 1/1 to 1/30. When the content of the color pigment is less than 1/30, the coloring effect is weak, and when it exceeds 1/1, the viscosity becomes too high or the color pigment precipitates and the storage stability of the erasable colorant composition is poor. there is a possibility.
カーボンブラックを使用する場合は、ｐＨが６以上であることが望ましい。
ｐＨが６未満であると本発明の消去性着色剤組成物の分散安定性が悪くなる。
When carbon black is used, the pH is desirably 6 or more.
When the pH is less than 6, the dispersion stability of the erasable colorant composition of the present invention is deteriorated.
＜共重合体Ａ及びＢ＞
本発明の消去性着色剤組成物に含有されているスチレンアクリル酸共重合体としては、公知の共重合体を使用することができる。
これらの共重合体Ａ及びＢは、重量平均分子量が１２０００〜２００００である共重合体Ａ（スチレンアクリル酸共重合体Ａ）と、重量平均分子量が７０００〜１１０００である共重合体Ｂ（スチレンアクリル酸共重合体Ｂ）を使用でき、さらに、共重合体Ａの含有量は共重合体Ｂの含有量以下である。
また、塗膜形成またはビヒクルとして、このような共重合体Ａ及びＢ以外の樹脂を含有しないほうが、耐水滴滴下、非新聞付着、及び表装性の各性質をバランス良く備えやすくなる。
<Copolymers A and B>
As the styrene acrylic acid copolymer contained in the erasable colorant composition of the present invention, a known copolymer can be used.
These copolymers A and B are copolymer A (styrene acrylic acid copolymer A) having a weight average molecular weight of 12,000 to 20,000, and copolymer B (styrene acrylic) having a weight average molecular weight of 7,000 to 11,000. Acid copolymer B) can be used, and the content of copolymer A is less than or equal to the content of copolymer B.
In addition, it is easier to provide each of the properties of water-resistant dripping, non-newspaper adhesion, and coverability in a well-balanced manner when the coating film formation or vehicle does not contain any resin other than the copolymers A and B.
＜共重合体Ａ＞
本発明の消去性着色剤組成物に含有され得る共重合体Ａとしては、酸価が１５０〜３００が好ましい。
酸価が１５０未満又は３００を超えると、着色顔料の分散安定性及び滲み防止の効果を両立できない可能性がある。
また重量平均分子量は上記のように１２０００〜２００００であり、好ましくは１４０００〜１８０００、さらに好ましくは、１５０００〜１７０００である。
重量平均分子量が１２０００未満であると、滲み防止効果を損なう可能性があり、２００００を超えると、筆記性に劣る可能性がある。
本発明中の消去性着色剤組成物１００重量部中の共重合体Ａの含有量としては、共重合体Ｂの含有量のよりも少なく、さらに共重合体Ｂの４０．０重量％以下、好ましくは３０．０重量％以下、より好ましくは２０．０重量％以下、さらに好ましくは１０．０重量％以下であることがよい。
共重合体Ａの含有量が共重合体Ｂの含有量よりと同じかそれ以上である場合には、半紙に筆記したあとに水滴を垂らすと滲みが発生する可能性がある。
また共重合体Ａの含有量は共重合体Ｂの含有量よりも少ないことが好ましく、この場合には耐水滴滴下、非新聞付着、及び表装性の各性質をバランス良く備えやすくなる。
<Copolymer A>
The copolymer A that can be contained in the erasable colorant composition of the present invention preferably has an acid value of 150 to 300.
When the acid value is less than 150 or more than 300, there is a possibility that both the dispersion stability of the color pigment and the effect of preventing bleeding are not compatible.
Moreover, a weight average molecular weight is 12000-20000 as mentioned above, Preferably it is 14000-18000, More preferably, it is 15000-17000.
If the weight average molecular weight is less than 12000, the effect of preventing bleeding may be impaired, and if it exceeds 20000, the writing property may be inferior.
The content of the copolymer A in 100 parts by weight of the erasable colorant composition in the present invention is less than the content of the copolymer B, and further 40.0% by weight or less of the copolymer B, The content is preferably 30.0% by weight or less, more preferably 20.0% by weight or less, and still more preferably 10.0% by weight or less.
When the content of the copolymer A is equal to or higher than the content of the copolymer B, bleeding may occur when a water droplet is dropped after writing on a half paper.
Further, the content of the copolymer A is preferably less than the content of the copolymer B. In this case, it becomes easy to provide each of the properties of water-resistant dripping, non-newspaper adhesion, and surface covering with a good balance.
＜共重合体Ｂ＞
本発明の消去性着色剤組成物に含有されている共重合体Ｂとしては、酸価が１５０〜３００が好ましい。このような共重合体Ｂを使用することによって、さらに、筆記後乾燥するまでに筆記面に新聞紙や他の半紙を重ねて置いた場合であっても、紙同士が付着することもない。
酸価が１５０未満又は３００を超えると、着色顔料の分散安定性及び滲み防止の効果を両立できない可能性がある。また重量平均分子量は上記のように７０００〜１１０００であり、好ましくは８０００〜１００００、さらに好ましくは、８２００〜９０００である。
また重量平均分子量が７０００未満であると、滲み防止効果を損ない、１１０００を超えると、筆記性に劣ることになる。
本発明の消去性着色剤組成物の樹脂固形分中の共重合体Ｂのアンモニア塩の含有比率は４２．０重量％以上であることが必要であり、４２．０重量％未満であると、耐水滴滴下、非新聞付着、及び表装性の各性質をバランス良く備えることが困難になる。
また、樹脂固形分中の共重合体Ｂの含有量としては、５５．０重量％以上、好ましくは、６５．０重量％以上であり、またその上限は、９０．０重量％以下、さらに８０．０重量％以下、よりさらには７０．０重量％以下が好ましい。５５．０重量％以上とすることによって、耐水滴滴下、非新聞付着、及び表装性の各性質をバランス良く備えやすくなる。
なお、本発明中の消去性着色剤組成物中の共重合体Ｂのアミン塩の含有量としては、７．４〜１５．０重量％が好ましく、さらに好ましくは７．４〜１２．０重量％である。共重合体Ｂのアミン塩の含有量としては、７．４〜１５．０重量％であると、半紙に筆記したあとに水滴を垂らしても滲みが発生することがない。
<Copolymer B>
The copolymer B contained in the erasable colorant composition of the present invention preferably has an acid value of 150 to 300. By using such a copolymer B, papers do not adhere to each other even when newspaper paper or other semi-paper is placed on the writing surface before drying after writing.
When the acid value is less than 150 or more than 300, there is a possibility that both the dispersion stability of the color pigment and the effect of preventing bleeding are not compatible. Moreover, a weight average molecular weight is 7000-11000 as mentioned above, Preferably it is 8000-10000, More preferably, it is 8200-9000.
Further, if the weight average molecular weight is less than 7000, the effect of preventing bleeding is impaired, and if it exceeds 11,000, the writing property is inferior.
The content ratio of the ammonia salt of copolymer B in the resin solid content of the erasable colorant composition of the present invention needs to be 42.0% by weight or more, and is less than 42.0% by weight, It becomes difficult to provide each of the properties of water-resistant dripping, non-newspaper adhesion, and coverability in a well-balanced manner.
The content of the copolymer B in the resin solid content is 55.0% by weight or more, preferably 65.0% by weight or more, and the upper limit is 90.0% by weight or less, and further 80 It is preferably 0.0% by weight or less, and more preferably 70.0% by weight or less. By setting the content to 55.0% by weight or more, it becomes easy to provide each of the properties of water-resistant dripping, non-newspaper adhesion, and coverability with a good balance.
In addition, as content of the amine salt of the copolymer B in the erasable colorant composition in this invention, 7.4 to 15.0 weight% is preferable, More preferably, 7.4 to 12.0 weight% %. If the content of the amine salt of the copolymer B is 7.4 to 15.0% by weight, bleeding does not occur even if a water droplet is dropped after writing on a half paper.
＜共重合体Ａ及びＢのアンモニア塩、及びアルカリ金属塩＞
共重合体Ａ及びＢのアルカリ金属の塩としては、カリウム及び／又はナトリウムを使用することができ、共重合体Ａ及びＢに対して、アルカリ金属の水酸化物として使用される。
また共重合体Ａ及びＢのアンモニアの塩としては、共重合体Ａ及びＢに対してアンモニウム塩として形成されるものである。
<Ammonia salt of copolymer A and B, and alkali metal salt>
As the alkali metal salt of the copolymers A and B, potassium and / or sodium can be used, and the alkali metal hydroxide is used for the copolymers A and B.
Further, the ammonia salts of the copolymers A and B are formed as ammonium salts with respect to the copolymers A and B.
＜その他の塩＞
共重合体Ａ及びＢを中和するその他の塩としては、トリエタノールアミン、モノエチルアミン、イソプロピルアミンジメチルアミン、ジエチルアミン、モノエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、エチレンジアミン、プロピレンジアミン等の塩を用いることができる。
共重合体Ｂのその他の塩を採用する際には、アンモニアの塩よりも少量になるようにする。
<Other salts>
Other salts that neutralize the copolymers A and B include triethanolamine, monoethylamine, isopropylamine dimethylamine, diethylamine, monoethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, propylenediamine Etc. can be used.
When the other salt of copolymer B is employed, the amount is smaller than that of ammonia.
＜その他添加剤＞
その他必要に応じて、グリセリン、プロピレングリコール、エチレングリコール等の多価アルコールや、防錆剤（例えば、ベンゾトリアゾール、トリルトリアゾール、ジシクロヘキシルアンモニウムナイトレートなど）、防腐防黴剤（例えば、ベンゾイソチアゾリン系防腐防黴剤、ペンタクロロフェノール系防腐防黴剤、クレゾール系防腐防黴剤など）、界面活性剤、湿潤剤、消泡剤、レベリング剤、凝集防止剤、ｐＨ調整剤、擬塑性付与剤、香料等の慣用の添加剤を添加することができる。
<Other additives>
Other polyhydric alcohols such as glycerin, propylene glycol and ethylene glycol, rust preventives (for example, benzotriazole, tolyltriazole, dicyclohexylammonium nitrate), antiseptic / antifungal agents (for example, benzoisothiazoline-based antiseptics) Antifungal agents, pentachlorophenol antiseptic / antifungal agents, cresol antiseptic / antifungal agents, etc.), surfactants, wetting agents, antifoaming agents, leveling agents, anti-aggregation agents, pH adjusters, pseudoplasticity imparting agents, perfumes Conventional additives such as can be added.
＜製造方法＞
本発明の消去性着色剤組成物の製造方法においては、まず着色顔料及び共重合体Ｂのアルカリ金属塩、水、必要に応じて顔料濡れ剤を配合したものを分散し、顔料分散体を作製する。次に当該水性顔料分散体に共重合体Ａや共重合体Ｂのアンモニウム塩、アルカリ金属塩、アミン塩を添加し、さらに各種の添加剤を添加し、均一になるまで撹拌することにより、水性インキ組成物を得た。
上記水性顔料分散体製造時の分散工程においては公知の分散機や撹拌機を用いることができる。具体的にはビーズミル、ボールミル、サンドミル、ロールミル、ニーダー等の分散機、またターボミキサーなどの撹拌機などが挙げられる。
<Manufacturing method>
In the method for producing an erasable colorant composition of the present invention, first, a pigment pigment is prepared by dispersing a coloring pigment and an alkali metal salt of copolymer B, water, and a pigment wetting agent as necessary. To do. Next, by adding the ammonium salt, alkali metal salt, or amine salt of copolymer A or copolymer B to the aqueous pigment dispersion, adding various additives, and stirring until uniform, An ink composition was obtained.
A known disperser or stirrer can be used in the dispersion step when the aqueous pigment dispersion is produced. Specific examples include a disperser such as a bead mill, a ball mill, a sand mill, a roll mill, and a kneader, and a stirrer such as a turbo mixer.
下記表１の組成になるように、着色顔料と、Ｊ６７８（スチレンアクリル酸共重合体（重量平均分子量８５００）の水酸化カリウムによる中和物）と、ＰＧ（プロピレングリコール）を水で分散し、顔料分散体を得た。次いで水溶性樹脂を添加して均一に分散して、例１〜１８を得た。水溶性樹脂の欄の（２０％）は、水溶性樹脂を２０％の濃度の溶液として、表中の量を使用したことを意味する。
Ｊ６９０：ジョンクリル６９０（重量平均分子量１６５００）共重合体Ａ
Ｊ６７８：ジョンクリル６７８（重量平均分子量８５００） 共重合体Ｂ
（ＫＯＨ）、（ＮＨ３）はそれぞれ、水酸化カリウム、アンモニアによる中和物であることを示す。
表１において顔料分散体１４．０重量部には、Ｊ６７８（ＫＯＨ）が０．７重量部含有されている。
Color pigment, J678 (neutralized product of styrene acrylic acid copolymer (weight average molecular weight 8500) with potassium hydroxide) and PG (propylene glycol) were dispersed with water so as to have the composition shown in Table 1 below. A pigment dispersion was obtained. Subsequently, water-soluble resin was added and it disperse | distributed uniformly and obtained Examples 1-18. (20%) in the column of the water-soluble resin means that the amount in the table was used with the water-soluble resin as a solution having a concentration of 20%.
J690: Jonkrill 690 (weight average molecular weight 16500) copolymer A
J678: Joncryl 678 (weight average molecular weight 8500) Copolymer B
(KOH) and (NH 3) indicate neutralized products of potassium hydroxide and ammonia, respectively.
In Table 1, 14.0 parts by weight of the pigment dispersion contains 0.7 part by weight of J678 (KOH).
（消去性試験）
・試験サンプルの作製
綿ブロード（晒）の試験布に水を含まない画筆（平筆４号）を用いて、作製した墨汁又はインキを塗布し、室温で指触乾燥するまで放置した。
・洗濯
乾燥後の試験サンプルを弱アルカリ性合成洗剤を使用して（０．４重量％量）２時間漬け置きし、３分間手でもみ洗いした。
その後、洗濯機で弱アルカリ性合成洗剤を使用して（０．１重量％量）２０℃で１５分間洗濯し、１５分間水洗した。
乾燥後に試験サンプルと綿ブロード(晒)の色差ΔＥを測定し、以下の基準により評価した。
・消去性評価基準
○：ΔＥが１０．０未満
△：ΔＥが１０．０以上２０．０未満
×：ΔＥが２０．０以上
(Eraseability test)
-Preparation of test sample The prepared ink or ink was applied to a cotton broad (bleached) test cloth without using water (flat brush No. 4), and left to dry at the room temperature.
-Laundry The test sample after drying was immersed in a weak alkaline synthetic detergent (0.4 wt% amount) for 2 hours, and then washed by hand for 3 minutes.
Then, it was washed for 15 minutes at 20 ° C. using a weak alkaline synthetic detergent (0.1 wt% amount) in a washing machine, and washed with water for 15 minutes.
After drying, the color difference ΔE between the test sample and cotton broad (bleached) was measured and evaluated according to the following criteria.
Erasability evaluation criteria ○: ΔE is less than 10.0 Δ: ΔE is 10.0 or more and less than 20.0 ×: ΔE is 20.0 or more
（表装性試験）
書道用紙に毛筆を用いて書写し、室温で１週間放置した。その後、ベニヤ板の上に裏返して置き霧吹きで水を噴霧し、顔料の流れ出しを以下の基準により評価した。
・表装性評価基準
○：流れない
△：若干流れ出す
×：筆跡がわからない程流れ出す
(Appearance test)
The calligraphy paper was copied using a brush and left at room temperature for a week. Then, it was turned over on a plywood board, sprayed with water with a spray, and the flow of the pigment was evaluated according to the following criteria.
・ Appearance evaluation criteria ○: Not flowing △: Flowing slightly ×: Flowing to the extent that the handwriting is not understood
（水滴滴下試験）
書道用紙に毛筆を用いて書写し、室温で１週間放置した。その後、ベニヤ板の上に表向きにして置き水滴を滴下し、顔料の流れ出しを以下の基準により評価した。
・水滴滴下評価基準
○：流れない
△：若干流れ出す
×：筆跡がわからない程流れ出す
(Water drop test)
The calligraphy paper was copied using a brush and left at room temperature for a week. Thereafter, water drops were placed face up on a plywood board, and the flow of the pigment was evaluated according to the following criteria.
・ Drop drop evaluation criteria ○: Not flowing △: Slightly flowing out ×: Flowing out so that the handwriting is not understood
（新聞付着性試験）
書道用紙に毛筆を用いて書写し、すぐに新聞紙に挟んで室温で放置した。乾燥後に新聞紙が書道用紙の筆跡に付着しているか以下の基準により評価した。
・新聞付着性評価基準
○：付着なし
△：付着するがはがせる
×：付着して書道用紙に新聞紙が残る
(Newspaper adhesion test)
The calligraphy paper was copied using a brush and immediately sandwiched between newspapers and left at room temperature. Whether or not the newspaper was attached to the calligraphy paper after drying was evaluated according to the following criteria.
-Newspaper adhesion evaluation criteria ○: No adhesion △: Adhered but peelable ×: Adhered and newspaper remains on calligraphy paper
表１の比較例１〜５は、共重合体Ｂのアンモニウム塩の含有量が少ない例であり、その結果、半紙に筆記されて乾燥した着色剤組成物が水滴滴下で滲むものであった。また比較例６及び７は、酸性のカーボンブラックを使用したので、分散安定性に劣る結果となった。
これらに対して、実施例１〜１８は、本発明に沿った例であるため、十分な消去性、新聞付着性、表装性に優れ、さらに水滴滴下による滲みを発生しないという性質をバランス良く備えていた。
Comparative Examples 1 to 5 in Table 1 are examples in which the content of the ammonium salt of the copolymer B is small, and as a result, the colorant composition written on a half-paper and dried bleeds when dropped. In Comparative Examples 6 and 7, since acidic carbon black was used, the dispersion stability was inferior.
On the other hand, since Examples 1 to 18 are examples according to the present invention, they are excellent in sufficient erasability, newspaper adhesion, and coverability, and have the property of not causing bleeding due to water droplet dropping in a well-balanced manner. It was.
Claims (5)
さらにｐＨが６以上のカーボンブラック、水
を含有する消去性着色剤組成物。 Alkali of copolymer A (styrene acrylic acid copolymer A having a weight average molecular weight of 12,000 to 20,000) and copolymer B (styrene acrylic acid copolymer B having a weight average molecular weight of 7,000 to 11,000) Containing a salt with a metal and / or a salt with ammonia, the content ratio of the salt of ammonia of the copolymer B in the resin solid content is 42.0% by weight or more,
Further, an erasable colorant composition containing carbon black having a pH of 6 or more and water.
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