JP6154157B2 - Marking pen - Google Patents
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- JP6154157B2 JP6154157B2 JP2013039280A JP2013039280A JP6154157B2 JP 6154157 B2 JP6154157 B2 JP 6154157B2 JP 2013039280 A JP2013039280 A JP 2013039280A JP 2013039280 A JP2013039280 A JP 2013039280A JP 6154157 B2 JP6154157 B2 JP 6154157B2
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- 239000000203 mixture Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229930006000 Sucrose Natural products 0.000 claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 239000005720 sucrose Substances 0.000 claims description 24
- -1 sucrose fatty acid ester Chemical class 0.000 claims description 24
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- 239000004033 plastic Substances 0.000 claims description 4
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- 229920005989 resin Polymers 0.000 description 24
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- 230000000052 comparative effect Effects 0.000 description 9
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- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 3
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- 150000007942 carboxylates Chemical group 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229960000901 mepacrine Drugs 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000010452 phosphate Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GPKJTRJOBQGKQK-UHFFFAOYSA-N quinacrine Chemical compound C1=C(OC)C=C2C(NC(C)CCCN(CC)CC)=C(C=CC(Cl)=C3)C3=NC2=C1 GPKJTRJOBQGKQK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229940031439 squalene Drugs 0.000 description 1
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
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- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明はインキ組成物及びマーキングペンに関する。 The present invention relates to an ink composition and a marking pen.
従来より、水で濡れたティッシュ又は布等で擦ることにより、非浸透面上の筆記線を消去できるマーキングペンが知られている（特許文献１〜３）。 2. Description of the Related Art Conventionally, there is known a marking pen that can erase a writing line on a non-penetrating surface by rubbing with a tissue or cloth wet with water (Patent Documents 1 to 3).
しかしながら、特許文献１に記載されている水消去性油性インキは浸透性が高く、表面に微細な傷を有する非浸透面上に筆記した際の筆記線の消去が困難であった。 However, the water-erasable oil-based ink described in Patent Document 1 has high penetrability, and it has been difficult to erase writing lines when writing on a non-penetrating surface having fine scratches on the surface.
また、特許文献２及び３に記載されている水消去性水性インキ組成物では、非浸透面、特に皮脂が付着した非浸透面に筆記した際の筆記線が、非浸透面上ではじかれて、筆跡が途切れるという問題があった。
Moreover, in the water erasable water-based ink composition described in
一方、水性インキ組成物に界面活性剤を添加することにより、水性インキ組成物の表面張力を低下させ、非浸透面上の筆記線のはじきを低減させることができる。特に、皮脂が付着した非浸透面上の筆記線のはじきを低減するためには、水性インキ組成物の表面張力をより低下させることが可能な界面活性剤が用いられる。組成物の表面張力を大きく低下させることが可能な界面活性剤としては、フッ素系界面活性剤が挙げられるが、フッ素系界面活性剤のほとんどは、水への溶解性が極めて小さく、０．１ｇ／１００ｇ・Ｈ２Ｏ程度である。このため、水性インキ組成物に不溶のフッ素系界面活性剤が時間の経過とともに沈降し、非浸透面上の筆記線のはじきが悪化することがあった。 On the other hand, by adding a surfactant to the water-based ink composition, the surface tension of the water-based ink composition can be reduced, and the repelling of writing lines on the non-penetrating surface can be reduced. In particular, in order to reduce the repelling of the writing line on the non-penetrating surface to which sebum is adhered, a surfactant capable of further reducing the surface tension of the water-based ink composition is used. Examples of the surfactant capable of greatly reducing the surface tension of the composition include fluorine-based surfactants, but most of the fluorine-based surfactants have extremely low solubility in water, 0.1 g / 100 g · H 2 O level. For this reason, the fluorosurfactant insoluble in the water-based ink composition may precipitate over time, and the repelling of the writing line on the non-penetrating surface may be deteriorated.
本発明は、上記課題に鑑みてなされたものであり、非浸透面上に筆記した際の筆記線のはじきを低減し、水で濡れた布等による筆記線の消去性に優れた、インキ組成物、及びそれを用いたマーキングペンを提供することを目的とする。 The present invention has been made in view of the above problems, and reduces ink line repellency when writing on a non-penetrating surface, and has excellent erasability of writing lines with a cloth wetted with water, etc. It is an object to provide an object and a marking pen using the object.
本発明は、フッ素系界面活性剤、ショ糖脂肪酸エステル又は（メタ）アクリル酸由来の構成単位を有する樹脂、顔料、及び水を含有するインキ組成物を提供する。 The present invention provides an ink composition containing a fluorosurfactant, a sucrose fatty acid ester or a resin having a structural unit derived from (meth) acrylic acid, a pigment, and water.
本発明のインキ組成物によれば、非浸透面上に筆記した際の筆記線のはじきを低減し、水で濡れた布等による筆記線の消去性に優れたマーキングペンを得ることができる。 According to the ink composition of the present invention, it is possible to reduce the repelling of the writing line when writing on the non-penetrating surface and to obtain a marking pen excellent in the erasing property of the writing line with a cloth wetted with water.
上記フッ素系界面活性剤の含有量は、インキ組成物全量を基準として、１質量％以上であることが好ましい。 The content of the fluorosurfactant is preferably 1% by mass or more based on the total amount of the ink composition.
また、上記フッ素系界面活性剤は、当該フッ素系界面活性剤の０．１質量％水溶液の表面張力が２０ｍＮ／ｍ以下を示すものであることが好ましい。 Moreover, it is preferable that the said fluorosurfactant shows that the surface tension of the 0.1 mass% aqueous solution of the said fluorosurfactant is 20 mN / m or less.
フッ素系界面活性剤の含有量、及び上記水溶液の表面張力が上記範囲にあることにより、筆記線のはじきをより低減することができる傾向がある。 When the content of the fluorosurfactant and the surface tension of the aqueous solution are in the above ranges, there is a tendency that the repelling of the writing line can be further reduced.
本発明はまた、繊維芯又はプラスチック芯からなるペン先と、インキ収容部とを備え、上記インキ組成物が上記インキ収容部に収容されている、マーキングペンを提供する。 The present invention also provides a marking pen comprising a pen tip made of a fiber core or a plastic core and an ink storage portion, wherein the ink composition is stored in the ink storage portion.
本発明によれば、非浸透面上に筆記した際の筆記線のはじきを低減し、水で濡れた布等による筆記線の消去性に優れた、インキ組成物、及びそれを用いたマーキングペンを提供することができる。 According to the present invention, an ink composition that reduces repelling of writing lines when writing on a non-penetrating surface and has excellent erasability of writing lines with a cloth wet with water, etc., and a marking pen using the ink composition Can be provided.
以下、必要に応じて図面を参照しながら、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.
（インキ組成物）
本実施形態のインキ組成物は、フッ素系界面活性剤、ショ糖脂肪酸エステル又は（メタ）アクリル酸由来の構成単位を有する樹脂、顔料、及び水を含有する。
(Ink composition)
The ink composition of the present embodiment contains a fluorosurfactant, a sucrose fatty acid ester or a resin having a structural unit derived from (meth) acrylic acid, a pigment, and water.
フッ素系界面活性剤はフッ素原子を含有する界面活性剤である。フッ素系界面活性剤は、水素原子の少なくとも一部がフッ素原子で置換されたフッ化アルキル基と、親水基とを有していることが好ましい。上記フッ化アルキル基の炭素数は、１〜２５であることが好ましく、４〜２０であることがより好ましい。上記フッ化アルキル基は、水素原子の一部がフッ素原子で置換されたものであってもよく、水素原子の全部がフッ素原子で置換されたものであってもよい。上記親水基としては、スルホン酸塩、硫酸エステル、リン酸エステル、カルボン酸塩、及び（ポリ）エチレンオキシド等の基が挙げられる。親水基は（ポリ）エチレンオキシド又はカルボン酸塩であることが好ましい。親水基として（ポリ）エチレンオキシド又はカルボン酸塩を有するフッ素系界面活性剤を含有するインキ組成物から得られる筆記線は、特に、皮脂等が付着した非浸透面上であってもはじきが少ない傾向がある。 The fluorine-based surfactant is a surfactant containing a fluorine atom. The fluorine-based surfactant preferably has a fluorinated alkyl group in which at least a part of hydrogen atoms are substituted with a fluorine atom and a hydrophilic group. The fluorinated alkyl group preferably has 1 to 25 carbon atoms, more preferably 4 to 20 carbon atoms. The fluorinated alkyl group may be one in which a part of hydrogen atoms are substituted with fluorine atoms, or one in which all of the hydrogen atoms are substituted with fluorine atoms. Examples of the hydrophilic group include groups such as sulfonate, sulfate, phosphate, carboxylate, and (poly) ethylene oxide. The hydrophilic group is preferably (poly) ethylene oxide or a carboxylate. Written lines obtained from an ink composition containing a fluorosurfactant having (poly) ethylene oxide or carboxylate as a hydrophilic group, especially, tend to have less repellency even on non-penetrating surfaces to which sebum is attached. There is.
フッ素系界面活性剤は、フッ素原子を含有しない界面活性剤と比べて、水等の表面張力をより低下させることができる傾向がある。たとえば、本実施形態で用いられるフッ素系界面活性剤は、０．１質量％水溶液の表面張力が３０ｍＮ／ｍ以下を示すものであることが好ましく、２５ｍＮ／ｍ以下を示すものであることがより好ましく、２０ｍＮ／ｍ以下を示すものであることがさらに好ましい。なお、上記水溶液の表面張力の下限値は特に制限されず、１３ｍＮ／ｍであることが好ましく、１５ｍＮ／ｍであることがより好ましい。フッ素系界面活性剤の０．１質量％水溶液の表面張力が上記範囲内にあることにより、得られる筆記線のはじきをさらに低減することができる傾向がある。なお、上記表面張力は、気温２５±５℃、湿度６０±２０％ＲＨにおいて、表面張力計（商品名：ＣＢＶＰ−Ｚ、協和界面科学株式会社製）を用いて測定したものである。 The fluorine-based surfactant tends to be able to further reduce the surface tension of water or the like as compared with the surfactant not containing a fluorine atom. For example, the fluorosurfactant used in the present embodiment preferably has a surface tension of a 0.1% by weight aqueous solution of 30 mN / m or less, more preferably 25 mN / m or less. Preferably, it is 20 mN / m or less. The lower limit value of the surface tension of the aqueous solution is not particularly limited, and is preferably 13 mN / m, more preferably 15 mN / m. When the surface tension of the 0.1% by mass aqueous solution of the fluorosurfactant is within the above range, the repelling of the resulting writing line tends to be further reduced. The surface tension is measured using a surface tension meter (trade name: CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) at an air temperature of 25 ± 5 ° C. and a humidity of 60 ± 20% RH.
フッ素系界面活性剤の含有量は、インキ組成物全量を基準として、０．５質量％以上であることが好ましく、１質量％以上であることがより好ましい。また、フッ素系界面活性剤の含有量は、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。フッ素系界面活性剤の含有量が０．５質量％以上であるとき、筆記線のはじきを抑制できる傾向がある。フッ素系界面活性剤の含有量が１０質量％以下であるとき、インキ組成物中に不溶物が生じにくい傾向がある。 The content of the fluorosurfactant is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total amount of the ink composition. Further, the content of the fluorosurfactant is preferably 10% by mass or less, and more preferably 5% by mass or less. When the content of the fluorosurfactant is 0.5% by mass or more, there is a tendency that the repelling of the writing line can be suppressed. When the content of the fluorosurfactant is 10% by mass or less, there is a tendency that insoluble matters are hardly generated in the ink composition.
ショ糖脂肪酸エステルは、下記一般式（１）で表すことができる。
式（１）中、Ｒ１及びＲ２はそれぞれ独立に、水酸基又はカルボン酸エステル基であり、水酸基であることが好ましい。また、Ｒ３はカルボン酸エステル基である。Ｒ１、Ｒ２及びＲ３のカルボン酸エステル基はそれぞれ独立に−ＯＣＯＣｎＨ２ｎ＋１で表される構造を有し、ｎは１２〜２２の整数であり、１２〜１８の整数であることが好ましく、１２〜１６の整数であることがより好ましい。なお、ショ糖脂肪酸エステルは人体に対する影響が極めて少なく、安全である。
Sucrose fatty acid ester can be represented by the following general formula (1).
In formula (1), R 1 and R 2 are each independently a hydroxyl group or a carboxylic acid ester group, preferably a hydroxyl group. R 3 is a carboxylic acid ester group. The carboxylic acid ester groups of R 1 , R 2 and R 3 each independently have a structure represented by —OCOC n H 2n + 1 , where n is an integer of 12 to 22 and an integer of 12 to 18. Preferably, it is an integer of 12-16. In addition, sucrose fatty acid ester has very little influence on the human body and is safe.
本明細書において、Ｒ１及びＲ２がともに水酸基である場合のショ糖脂肪酸エステルをショ糖脂肪酸モノエステルという。また、Ｒ１及びＲ２のいずれか一方が水酸基であり、他方がカルボン酸エステル基である場合のショ糖脂肪酸エステルをショ糖脂肪酸ジエステルという。また、Ｒ１及びＲ２がともにカルボン酸エステル基である場合のショ糖脂肪酸エステルをショ糖脂肪酸トリエステルという。ショ糖脂肪酸モノエステルの含有量は、ショ糖脂肪酸エステル全量に対して、５５〜１００質量％であることが好ましく、７０〜１００質量％であることがより好ましい。ショ糖脂肪酸モノエステルの含有量が上記範囲にあることにより、少量のショ糖脂肪酸エステルでも十分な水消去性を発揮する傾向がある。 In this specification, a sucrose fatty acid ester in which R 1 and R 2 are both hydroxyl groups is referred to as a sucrose fatty acid monoester. A sucrose fatty acid ester in which either one of R 1 and R 2 is a hydroxyl group and the other is a carboxylic acid ester group is referred to as a sucrose fatty acid diester. In addition, the sucrose fatty acid ester in which both R 1 and R 2 are carboxylic acid ester groups is referred to as sucrose fatty acid triester. The content of the sucrose fatty acid monoester is preferably 55 to 100% by mass and more preferably 70 to 100% by mass with respect to the total amount of sucrose fatty acid ester. When the content of the sucrose fatty acid monoester is in the above range, even a small amount of sucrose fatty acid ester tends to exhibit sufficient water erasability.
ショ糖脂肪酸エステルのＨＬＢ（Hydrophile-Lipophile Balance）値は１０〜２０であることが好ましく、１２〜１９であることがより好ましく、１６〜１９であることがさらに好ましい。ＨＬＢ値が上記範囲にあることにより、少量のショ糖脂肪酸エステルでも十分な水消去性を発揮する傾向がある。 The HLB (Hydrophile-Lipophile Balance) value of the sucrose fatty acid ester is preferably 10 to 20, more preferably 12 to 19, and still more preferably 16 to 19. When the HLB value is in the above range, even a small amount of sucrose fatty acid ester tends to exhibit sufficient water erasability.
ショ糖脂肪酸エステルの含有量は、インキ組成物全量を基準として、３〜１５質量％であることが好ましく、５〜１０質量％であることがより好ましい。ショ糖脂肪酸エステルの含有量が、３質量％以上であるとき、インキ組成物がたとえば０．５質量％又は１質量％以上の比較的高濃度のフッ素系界面活性剤を含有していたとしても不溶物が生じにくい傾向がある。また、ショ糖脂肪酸エステルの含有量が、１５質量％以下であるとき、インキ組成物の粘度が低く、マーキングペンからのインキ組成物の排出性が維持される傾向がある。 The content of the sucrose fatty acid ester is preferably 3 to 15% by mass, more preferably 5 to 10% by mass based on the total amount of the ink composition. When the content of the sucrose fatty acid ester is 3% by mass or more, even if the ink composition contains a relatively high concentration of a fluorosurfactant such as 0.5% by mass or 1% by mass There is a tendency that insoluble materials are hardly formed. Moreover, when content of sucrose fatty acid ester is 15 mass% or less, the viscosity of an ink composition is low and there exists a tendency for the discharge property of the ink composition from a marking pen to be maintained.
（メタ）アクリル酸由来の構成単位を有する樹脂は、（メタ）アクリル酸等（すなわち、アクリル酸若しくはメタクリル酸又はこれらの誘導体）を含む単量体を、たとえば、ラジカル重合することにより得られる樹脂である。（メタ）アクリル酸由来の構成単位を有する樹脂は、上記（メタ）アクリル酸等の単独重合体であってもよく、２種類以上の（メタ）アクリル酸等の共重合体であってもよく、上記（メタ）アクリル酸等と、上記（メタ）アクリル酸等とは異なる単量体との共重合体であってもよい。上記（メタ）アクリル酸等とは異なる単量体としては、たとえば、スチレン、ブタジエン及びアクリロニトリル並びにこれらの誘導体等が挙げられる。上記（メタ）アクリル酸等とは異なる単量体はスチレン又はαメチルスチレンであることが好ましい。（メタ）アクリル酸由来の構成単位を有する樹脂は、（メタ）アクリル酸等と、（メタ）アクリル酸等とは異なる単量体、たとえばスチレンとの共重合体である場合、（メタ）アクリル酸由来の構成単位及びスチレン由来の構成単位を有する樹脂と称することもできる。 The resin having a structural unit derived from (meth) acrylic acid is a resin obtained by, for example, radical polymerization of a monomer containing (meth) acrylic acid or the like (that is, acrylic acid or methacrylic acid or a derivative thereof). It is. The resin having a structural unit derived from (meth) acrylic acid may be a homopolymer such as the above (meth) acrylic acid, or may be a copolymer of two or more types of (meth) acrylic acid. A copolymer of the (meth) acrylic acid or the like and a monomer different from the (meth) acrylic acid or the like may be used. Examples of the monomer different from the (meth) acrylic acid and the like include styrene, butadiene, acrylonitrile, and derivatives thereof. The monomer different from the (meth) acrylic acid or the like is preferably styrene or α-methylstyrene. When the resin having a structural unit derived from (meth) acrylic acid is a copolymer of (meth) acrylic acid or the like and a monomer different from (meth) acrylic acid or the like, for example, styrene, (meth) acrylic It can also be referred to as a resin having a structural unit derived from an acid and a structural unit derived from styrene.
（メタ）アクリル酸由来の構成単位を有する樹脂の全構成単位中の、（メタ）アクリル酸由来の構成単位の比率は、５モル％以上であることが好ましい。（メタ）アクリル酸由来の構成単位を有する樹脂の全構成単位中の、（メタ）アクリル酸由来の構成単位の比率が５モル％以上であることにより、インキ組成物がたとえば０．５質量％又は１質量％以上の比較的高濃度のフッ素系界面活性剤を含有していたとしても不溶物が生じにくい傾向がある。 The proportion of structural units derived from (meth) acrylic acid in all structural units of the resin having structural units derived from (meth) acrylic acid is preferably 5 mol% or more. When the ratio of structural units derived from (meth) acrylic acid in all structural units of the resin having structural units derived from (meth) acrylic acid is 5 mol% or more, the ink composition is, for example, 0.5% by mass. Or even if it contains a relatively high concentration of a fluorosurfactant of 1% by mass or more, there is a tendency that insoluble matter is hardly generated.
（メタ）アクリル酸由来の構成単位を有する樹脂の重量平均分子量は、１０００〜２００００であることが好ましく、１７００〜１６０００であることがより好ましい。（メタ）アクリル酸由来の構成単位を有する樹脂の重量平均分子量が１０００以上であることにより、筆記線が非浸透面に十分に固着する傾向がある。（メタ）アクリル酸由来の構成単位を有する樹脂の重量平均分子量が２００００以下であるとき、インキ組成物の粘度が低く、マーキングペンからのインキ組成物の排出性が維持される傾向がある。 The weight average molecular weight of the resin having a structural unit derived from (meth) acrylic acid is preferably 1000 to 20000, and more preferably 1700 to 16000. When the weight average molecular weight of the resin having a structural unit derived from (meth) acrylic acid is 1000 or more, the writing line tends to be sufficiently fixed to the non-penetrating surface. When the weight average molecular weight of the resin having a structural unit derived from (meth) acrylic acid is 20000 or less, the viscosity of the ink composition is low, and the dischargeability of the ink composition from the marking pen tends to be maintained.
（メタ）アクリル酸由来の構成単位を有する樹脂（固形分）の含有量は、インキ組成物全量を基準として、２．５〜１５質量％であることが好ましい。（メタ）アクリル酸由来の構成単位を有する樹脂の含有量が、２．５質量％以上であるとき、インキ組成物がたとえば０．５質量％又は１質量％以上の比較的高濃度のフッ素系界面活性剤を含有していたとしても不溶物が生じない傾向がある。また、（メタ）アクリル酸由来の構成単位を有する樹脂の含有量が、１５質量％以下であるとき、インキ組成物の粘度が低く、マーキングペンからのインキ組成物の排出性が維持される傾向があり、さらに、非浸透面上における筆記線の水消去性と固着性とが両立できる傾向がある。（メタ）アクリル酸由来の構成単位を有する樹脂の含有量は、インキ組成物の固着性の観点から、インキ組成物全量を基準として、５〜１０質量％であることがより好ましい。 The content of the resin (solid content) having a structural unit derived from (meth) acrylic acid is preferably 2.5 to 15% by mass based on the total amount of the ink composition. When the content of the resin having a structural unit derived from (meth) acrylic acid is 2.5% by mass or more, the ink composition is, for example, 0.5% by mass or 1% by mass or more of a relatively high concentration fluorine-based resin Even if a surfactant is contained, there is a tendency that insoluble matter does not occur. Further, when the content of the resin having a structural unit derived from (meth) acrylic acid is 15% by mass or less, the viscosity of the ink composition is low, and the dischargeability of the ink composition from the marking pen tends to be maintained. Furthermore, there is a tendency that both the water erasability and the sticking property of the writing line on the non-penetrating surface can be compatible. The content of the resin having a structural unit derived from (meth) acrylic acid is more preferably 5 to 10% by mass based on the total amount of the ink composition from the viewpoint of the sticking property of the ink composition.
顔料としては、たとえば、カーボンブラック及び金属粉等の無機顔料、アゾ系、フタロシアニン系及びキナクドリン系等の有機顔料、並びに蛍光顔料等が挙げられる。顔料の含有量は、インキ組成物全量を基準として、３〜２０質量％であることが好ましく、８〜１５質量％であることがより好ましい。 Examples of the pigment include inorganic pigments such as carbon black and metal powder, organic pigments such as azo, phthalocyanine, and quinacrine, and fluorescent pigments. The pigment content is preferably 3 to 20% by mass, more preferably 8 to 15% by mass, based on the total amount of the ink composition.
本実施形態のインキ組成物は、上述の成分の水溶液又は水分散液として、或いは上述の成分とは別に、水を含有する。水の含有量は、インキ組成物全量を基準として、好ましくは５０〜９０質量％であり、より好ましくは６０〜８０質量％である。 The ink composition of the present embodiment contains water as an aqueous solution or water dispersion of the above components or separately from the above components. The water content is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, based on the total amount of the ink composition.
本実施形態のインキ組成物は、上述の成分に加えて、防錆剤、ｐＨ調整剤、増粘剤、防腐剤（防黴剤）、潤滑剤、顔料分散剤、及び固着樹脂等の添加剤を含有していてもよい。 In addition to the above-described components, the ink composition of the present embodiment includes additives such as a rust inhibitor, a pH adjuster, a thickener, an antiseptic (an antifungal agent), a lubricant, a pigment dispersant, and a fixing resin. May be contained.
本実施形態のインキ組成物は、フッ素系界面活性剤、ショ糖脂肪酸エステル又は（メタ）アクリル酸由来の構成単位を有する樹脂、顔料及び水、必要に応じて添加剤を、たとえば、ディゾルバー、ヘンシェルミキサー及びホモミキサーなどの攪拌機を用いて混合することにより得られる。攪拌機の攪拌条件は特に制限されないが、たとえば、ディゾルバー攪拌機を用いて、回転数１００〜１０００ｒｐｍで３０〜１８０分間攪拌することにより、各成分が均一に分散したインキ組成物を得ることができる。 The ink composition of the present embodiment comprises a fluorosurfactant, a sucrose fatty acid ester or a resin having a structural unit derived from (meth) acrylic acid, a pigment and water, and additives as necessary, for example, a dissolver, Henschel, etc. It can be obtained by mixing using a stirrer such as a mixer or a homomixer. The stirring conditions of the stirrer are not particularly limited. For example, by using a dissolver stirrer and stirring at a rotational speed of 100 to 1000 rpm for 30 to 180 minutes, an ink composition in which each component is uniformly dispersed can be obtained.
（マーキングペン）
本実施形態のマーキングペンは、繊維芯又はプラスチック芯からなるペン先と、インキ収容部とを備え、上記インキ組成物が上記インキ収容部に収容されている。
(Marking pen)
The marking pen of the present embodiment includes a pen tip made of a fiber core or a plastic core and an ink storage unit, and the ink composition is stored in the ink storage unit.
図１は本発明の一実施形態に係るマーキングペンの断面図である。図１のマーキングペン１０は中綿式であるが、本実施形態のマーキングペンは直液式であってもよい。また、図１のマーキングペン１０は本実施形態のマーキングペンは、その両端にペン先を備えるが、一端のみにペン先を備えていてもよい。図１のマーキングペン１０は、インキ収容部１、ペン先２ａ，２ｂ、軸体３、中綿４及びキャップ５ａ，５ｂを備える。マーキングペン１０においては、軸体３内部の空隙がインキ収容部１となっており、このインキ収容部１に本実施形態のインキ組成物を含む中綿４が収容される。なお、軸体３とは別に、軸体３内部に円筒状の中軸を設け、その中軸内部の空隙をインキ収容部１としてもよい。
FIG. 1 is a cross-sectional view of a marking pen according to an embodiment of the present invention. Although the marking pen 10 of FIG. 1 is a batting type, the marking pen of this embodiment may be a direct liquid type. Moreover, although the marking pen 10 of FIG. 1 includes the pen tip at both ends, the marking pen 10 of FIG. 1 may include the pen tip only at one end. The marking pen 10 of FIG. 1 includes an ink storage unit 1,
ペン先２ａ，２ｂは、一般的なマーキングペンのペン先であり、インキ組成物を供給できるような繊維芯又はプラスチック芯で形成されている。マーキングペン１０において、ペン先２ａ，２ｂの先端形状は、砲弾形状となっている。なお、マーキングペン１０において、ペン先２ａ，２ｂの先端形状は砲弾形状に限定されず、チゼル形状、筆ペン形状等であってもよい。
The
また、キャップ５ａ，５ｂはそれぞれ、ペン先３ａ，３ｂを覆うように配置される。
The
本実施形態のマーキングペンはガラス板、樹脂板及び金属板等の非浸透面上への筆記のために好適に使用される。本実施形態のマーキングペンによる筆記線は、皮脂の付着した非浸透面上でのはじきが少なく、微細な傷を有する非浸透面上での水消去性に優れる。 The marking pen of this embodiment is suitably used for writing on non-penetrating surfaces such as glass plates, resin plates, and metal plates. The writing line by the marking pen of this embodiment has little repelling on the non-penetrating surface to which sebum is adhered, and is excellent in water erasability on the non-penetrating surface having fine scratches.
本発明に係るインキ組成物は、筆記用具、マーキング用具、及びインキジェット等の印字用具に適用され、特にマーキングペンに好適に適用される。 The ink composition according to the present invention is applied to a writing tool, a marking tool, and a printing tool such as an ink jet, and is particularly preferably applied to a marking pen.
以下に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.
［インキ組成物の調製］
（実施例１、参考例２〜４及び比較例１〜５）
下記表１に記載される各材料を混合し、実施例１、参考例２〜４及び比較例１〜５のインキ組成物を得た。表中の数値の単位は、特に断りのない場合は、質量部である。
[Preparation of ink composition]
(Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5)
The materials described in Table 1 below were mixed to obtain ink compositions of Example 1 , Reference Examples 2 to 4, and Comparative Examples 1 to 5. The unit of numerical values in the table is parts by mass unless otherwise specified.
表１に記載される材料の名称の詳細は以下のとおりである。
メガファックＦ−４４４（フッ素系界面活性剤、ＤＩＣ株式会社製、０．１質量％水溶液の表面張力１６．８ｍＮ／ｍ）
ラピゾールＡ−８０（アニオン系界面活性剤、日油株式会社製）
シュガーエステルＬ１６９５（ショ糖脂肪酸エステル、三菱化学フーズ株式会社製、ＨＬＢ値１６）
ジョンクリルＪＤＸ−６５００（（メタ）アクリル酸由来の構成単位を有する樹脂の水溶液（固形分２９．５質量％）、ＢＡＳＦジャパン株式会社製）
ジョンクリル５７Ｊ（（メタ）アクリル酸由来の構成単位を有する樹脂の水溶液（固形分３７．０質量％）、ＢＡＳＦジャパン株式会社製）
カーボンブラック界面活性剤分散体（カーボンブラック２５質量％、界面活性剤８質量％、ジエチレングリコール８質量％、水５９質量％）
The details of the names of the materials described in Table 1 are as follows.
MegaFuck F-444 (Fluorine surfactant, manufactured by DIC Corporation, surface tension of 0.1% by weight aqueous solution 16.8 mN / m)
Lapisol A-80 (anionic surfactant, manufactured by NOF Corporation)
Sugar ester L1695 (sucrose fatty acid ester, manufactured by Mitsubishi Chemical Foods Corporation, HLB value 16)
Joncrill JDX-6500 (Aqueous solution of resin having a structural unit derived from (meth) acrylic acid (solid content 29.5 mass%), manufactured by BASF Japan Ltd.)
Joncryl 57J (Aqueous solution of resin having a structural unit derived from (meth) acrylic acid (solid content: 37.0% by mass), manufactured by BASF Japan Ltd.)
Carbon black surfactant dispersion (carbon black 25% by mass, surfactant 8% by mass, diethylene glycol 8% by mass, water 59% by mass)
［インキ組成物の評価］
図１に示した構造を有するマーキングペンのインキ収容部に、実施例１、参考例２〜４及び比較例１〜５で得られた各インキ組成物を中綿式マーキングペンに充填し、ペン先にインキ組成物を染み込ませた。ペン先には砲弾形状のポリエステル繊維芯を用いた。得られたインキ組成物及びマーキングペンを用いて、後述の評価を行った。評価結果を表１に示す。
[Evaluation of ink composition]
In the ink containing part of the marking pen having the structure shown in FIG. 1, each ink composition obtained in Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5 is filled into a batting type marking pen, and the pen tip Soaked the ink composition. A bullet-shaped polyester fiber core was used for the nib. The following evaluation was performed using the obtained ink composition and marking pen. The evaluation results are shown in Table 1.
（試験１：不溶物の有無）
実施例１、参考例２〜４及び比較例１〜５で得られたインキ組成物の気温２５±５℃、湿度６０±２０％ＲＨでの不溶物の有無を、目視にて確認した。
(Test 1: Presence or absence of insoluble matter)
The presence or absence of insoluble matter at an air temperature of 25 ± 5 ° C. and a humidity of 60 ± 20% RH of the ink compositions obtained in Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5 was visually confirmed.
（試験２：消去性Ａ）
実施例１、参考例２〜４及び比較例１〜５のインキ組成物を充填したマーキングペンを用いて、ガラス板へ筆記し、気温２５±５℃、湿度６０±２０％ＲＨで１週間放置した後、筆記線を乾燥した市販のティッシュで擦り、筆記線が完全に消去するまでの擦った回数を数えた。
(Test 2: Eraseability A)
Using a marking pen filled with the ink compositions of Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5, writing was made on a glass plate and left for 1 week at a temperature of 25 ± 5 ° C. and a humidity of 60 ± 20% RH. After that, the writing lines were rubbed with a dry commercial tissue, and the number of rubs until the writing lines were completely erased was counted.
（試験３：消去性Ｂ）
実施例１、参考例２〜４及び比較例１〜５のインキ組成物を充填したマーキングペンを用いて、ガラス板へ筆記し、気温２５±５℃、湿度６０±２０％ＲＨで１週間放置した後、筆記線を濡れたティッシュで擦り、筆記線が完全に消去するまでの擦った回数を数えた。
(Test 3: Eraseability B)
Using a marking pen filled with the ink compositions of Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5, writing was made on a glass plate and left for 1 week at a temperature of 25 ± 5 ° C. and a humidity of 60 ± 20% RH. After that, the writing line was rubbed with a wet tissue, and the number of times of rubbing until the writing line was completely erased was counted.
（試験４：はじきの有無）
実施例１、参考例２〜４及び比較例１〜５のインキ組成物を充填したマーキングペンを用いて、人口皮脂を付着させたガラス板へ筆記し、筆記線のはじきの有無を目視にて確認した。
(Test 4: Presence or absence of repelling)
Using the marking pen filled with the ink compositions of Example 1 , Reference Examples 2 to 4 and Comparative Examples 1 to 5, writing was performed on a glass plate to which artificial sebum was adhered, and the presence or absence of writing line repelling was visually observed. confirmed.
なお、上記人口皮脂の組成は、ヤシ油４０質量％、コレステロール１０質量％、スクアレン１５質量％、及びオレイン酸３５質量％である。 The composition of artificial sebum is 40% by mass of palm oil, 10% by mass of cholesterol, 15% by mass of squalene, and 35% by mass of oleic acid.
フッ素系界面活性剤を特定量以上含むインキ組成物において、ショ糖脂肪酸エステル及び（メタ）アクリル酸由来の構成単位を有する樹脂のいずれも含まない比較例１のインキ組成物には不溶物が確認された。 In an ink composition containing a specific amount or more of a fluorosurfactant, insoluble matter was confirmed in the ink composition of Comparative Example 1 which did not contain any of sucrose fatty acid ester and a resin having a structural unit derived from (meth) acrylic acid. It was done.
また、フッ素系界面活性剤を含まない比較例２〜５のインキ組成物では、不溶物は確認されなかったものの、いずれのインキ組成物においても筆記線のはじきが確認された。 Moreover, in the ink compositions of Comparative Examples 2 to 5 containing no fluorosurfactant, insoluble matter was not confirmed, but in any of the ink compositions, writing line repelling was confirmed.
一方、フッ素系界面活性剤とショ糖脂肪酸エステル又は（メタ）アクリル酸由来の構成単位を有する樹脂とを含む実施例１、参考例２〜４のインキ組成物には不溶物がなく、かつ、上記インキ組成物を充填したマーキングペンにより、皮脂が付着した非浸透面上にもはじきなく筆記することができた。また、上記筆記線は、乾燥したティッシュによる消去が困難であり、水に濡らしたティッシュにより容易に消去できることが確認された。 On the other hand, the ink compositions of Example 1 and Reference Examples 2 to 4 containing a fluorosurfactant and a resin having a structural unit derived from sucrose fatty acid ester or (meth) acrylic acid have no insoluble matter, and With the marking pen filled with the ink composition, it was possible to write on the non-penetrating surface to which sebum adhered. Further, it was confirmed that the writing line was difficult to erase with a dry tissue and could be easily erased with a tissue wetted with water.
１・・・インキ収容部、２ａ，２ｂ・・・ペン先、３・・・軸体、４・・・中綿（インキ組成物）、５ａ，５ｂ・・・キャップ、１０・・・マーキングペン。
DESCRIPTION OF SYMBOLS 1 ... Ink accommodating part, 2a, 2b ... Pen tip, 3 ... Shaft body, 4 ... Filling (ink composition), 5a, 5b ... Cap, 10 ... Marking pen.
Claims (3)
前記インキ組成物が、フッ素系界面活性剤、ショ糖脂肪酸エステル、顔料、及び水を含有する、マーキングペン。 A pen tip made of a fiber core or plastic core, and a ink containing portion, Lee Nki composition is housed in the ink reservoir portion,
A marking pen, wherein the ink composition contains a fluorosurfactant, a sucrose fatty acid ester, a pigment, and water .
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| JP2013039280A JP6154157B2 (en) | 2013-02-28 | 2013-02-28 | Marking pen |
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| JPH0816206B2 (en) * | 1987-12-28 | 1996-02-21 | 株式会社サクラクレパス | Aqueous erasable marking pen ink composition |
| JP3275021B2 (en) * | 1993-08-09 | 2002-04-15 | 株式会社サクラクレパス | Water-based erasable marking pen ink composition |
| JPH06200200A (en) * | 1993-01-06 | 1994-07-19 | Seiko Epson Corp | Ink composition for ink jet recording |
| JPH1129733A (en) * | 1997-07-11 | 1999-02-02 | Mitsubishi Pencil Co Ltd | Ink composition for writing utensil |
| JPH11124529A (en) * | 1997-10-23 | 1999-05-11 | Pilot Ink Co Ltd | Ink for aqueous marking pen for writing board |
| JP4344058B2 (en) * | 2000-01-19 | 2009-10-14 | 株式会社サクラクレパス | Ink composition for oil-based marking pen |
| JP4614496B2 (en) * | 2000-04-05 | 2011-01-19 | 株式会社サクラクレパス | Oil-based erasable marking pen ink composition |
| JP3477175B2 (en) * | 2001-01-22 | 2003-12-10 | ゼブラ株式会社 | Writing implement |
| JP2005023292A (en) * | 2003-06-09 | 2005-01-27 | Sakura Color Prod Corp | Ink composition for erasable inside core type aqueous marking pen |
| JP2006124562A (en) * | 2004-10-29 | 2006-05-18 | Pilot Ink Co Ltd | Marking pen ink composition for notation surface of recording medium and marking pen including the same |
| JP4953625B2 (en) * | 2005-12-19 | 2012-06-13 | シヤチハタ株式会社 | Water-erasable oil-based ink |
| JP2008024875A (en) * | 2006-07-24 | 2008-02-07 | Pilot Ink Co Ltd | Ink composition for oil-based marking pen for writing board |
| JP2008279629A (en) * | 2007-05-09 | 2008-11-20 | Mitsubishi Pencil Co Ltd | Writing implement |
| JP2012136657A (en) * | 2010-12-27 | 2012-07-19 | Pentel Corp | Erasable ink composition for note-taking board |
| JP2013071094A (en) * | 2011-09-29 | 2013-04-22 | Tokyo Univ Of Science | Method for producing water-in-oil emulsion and water-in-oil emulsion ink using the same |
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