JP4762509B2 - Ink composition for writing instruments - Google Patents
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- JP4762509B2 JP4762509B2 JP2004210194A JP2004210194A JP4762509B2 JP 4762509 B2 JP4762509 B2 JP 4762509B2 JP 2004210194 A JP2004210194 A JP 2004210194A JP 2004210194 A JP2004210194 A JP 2004210194A JP 4762509 B2 JP4762509 B2 JP 4762509B2
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- 239000000203 mixture Substances 0.000 title claims description 60
- 239000002245 particle Substances 0.000 claims description 115
- 239000011246 composite particle Substances 0.000 claims description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- 239000000049 pigment Substances 0.000 claims description 23
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 238000004040 coloring Methods 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000000976 ink Substances 0.000 description 74
- 239000000126 substance Substances 0.000 description 18
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- 238000004062 sedimentation Methods 0.000 description 13
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- 239000004034 viscosity adjusting agent Substances 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001023 inorganic pigment 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
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000003973 paint Substances 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
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 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
- 239000001038 titanium pigment Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Images
Description
本発明は、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物に関する。 The present invention relates to an ink composition for a writing instrument that has a high concealability and can maintain a clear handwriting over a long period of time.
一般に、酸化チタンは、その優れた光散乱効果により、白色度、隠蔽度を付与することができる顔料であり、白色顔料及び隠蔽型修正液として使用されている。その使用方法としては、酸化チタンそのものを水や有機溶媒からなる液体媒体中に分散させた水性又は油性などのインキ組成物を調製し、修正液や筆記具用インキなどとして使用されている。
しかしながら、酸化チタン自身の比重は、3.8〜4.1と非常に大きく、分散体中の粒子径を小さくしても沈降及び分離現象が発生する大きな欠点を有している。
In general, titanium oxide is a pigment that can impart whiteness and concealment due to its excellent light scattering effect, and is used as a white pigment and concealment type correction liquid. As its use method, an aqueous or oil-based ink composition in which titanium oxide itself is dispersed in a liquid medium composed of water or an organic solvent is prepared and used as a correction liquid, a writing instrument ink, or the like.
However, the specific gravity of titanium oxide itself is very large, such as 3.8 to 4.1, and has a serious drawback that sedimentation and separation occur even if the particle size in the dispersion is reduced.
このような欠点を解消するものとして、筆記具用インキでは、例えば、酸化チタンとサクシノグルカンからなる高分子多糖類と水とより少なくともなる水性インキ組成物(例えば、特許文献1参照)や、酸化チタンとオレイン酸を必須成分として含むボールペン用水性インキ(例えば、特許文献2参照)、また、必須成分として酸化チタンを内包したマイクロカプセル顔料と、水と、水溶性有機溶剤とから少なくともなるボールペン用水性インキ組成物(例えば、特許文献3参照)が知られている。 In order to eliminate such drawbacks, in the ink for writing instruments, for example, an aqueous ink composition (for example, see Patent Document 1) comprising at least a high molecular weight polysaccharide composed of titanium oxide and succinoglucan and water, or oxidation. Water-based ink for ballpoint pens containing titanium and oleic acid as essential components (for example, see Patent Document 2), and for ballpoint pens comprising at least a microcapsule pigment containing titanium oxide as essential components, water, and a water-soluble organic solvent A water-based ink composition (for example, see Patent Document 3) is known.
しかしながら、上記特許文献1及び2に記載される水性インキ組成物では、当初は酸化チタンの沈降分離が若干抑制されるが、時間がたつにつれ沈降及び分離現象が生じるなどの点に未だ課題があるものである。また、上記特許文献3に記載される水性インキ組成物は、沈降及び分離現象は幾分解消されるものであるが、マイクロカプセル顔料製造時の隠蔽性粒子の脱落があったり、隠蔽性粒子の粒子径の均一化が難しく、更に、マイクロカプセルの粒子径の均一化及びマイクロカプセル内の粒子数の均一化が難しく、安定な品質を有するマイクロカプセル顔料を得ることが難しい点に未だ課題があるものである。
本発明は、上記従来技術の課題に鑑み、これを解消しようとするものであり、従来の白色顔料である酸化チタン粒子より比重が低く、白色性及び隠蔽性に優れる品質の安定な複合粒子を使用して、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is intended to solve this problem.Composite particles of stable quality having a lower specific gravity than conventional titanium pigment particles, which are white pigments, and excellent in whiteness and hiding properties. An object of the present invention is to provide an ink composition for a writing instrument that can be used and can maintain a clear handwriting with high concealability over a long period of time.
本発明者らは、上記従来の課題等を解決するために、鋭意研究を重ねた結果、真密度が特定値以下の高分子樹脂中に隠蔽性粒子が分散されている複合粒子を含有せしめることにより、上記目的の筆記具用インキ組成物が得られることを見い出し、本発明を完成するに至ったのである。 In order to solve the above-mentioned conventional problems, etc., the present inventors have made intensive studies, and as a result, include composite particles in which concealable particles are dispersed in a polymer resin having a true density of a specific value or less. Thus, it was found that an ink composition for a writing instrument having the above-mentioned purpose was obtained, and the present invention was completed.
すなわち、本発明は、次の(1)〜(7)に存する。
(1) 真密度が1.0g/cm3以下の高分子樹脂中に隠蔽性粒子が分散されている複合粒子を含有することを特徴とする筆記具用インキ組成物。
(2) 隠蔽性粒子が酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも1種である上記(1)記載の筆記具用インキ組成物。
(3) 複合粒子中に染料、顔料の着色性を有する色材の少なくとも1種を含有する上記(1)又は(2)に記載の筆記具用インキ組成物。
(4) 複合粒子の表面に酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも1種の隠蔽性粒子が固定化されている上記(1)〜(3)の何れか一つに記載の筆記具用インキ組成物。
(5) 複合粒子の粒径が1〜200μmである上記(1)〜(4)の何れか一つに記載の筆記具用インキ組成物。
(6) ELD粘度計における25℃、50rpmの筆記具用インキ組成物の粘度が、3〜50mPa・sである上記(1)〜(5)の何れか一つに記載の筆記具用インキ組成物。
(7) 筆記具用インキ組成物がサインペン用インキ組成物である上記(1)〜(6)の何れか一つに記載の筆記具用インキ組成物。
That is, the present invention resides in the following (1) to (7).
(1) An ink composition for writing instruments, comprising composite particles in which concealable particles are dispersed in a polymer resin having a true density of 1.0 g / cm 3 or less.
(2) The ink composition for a writing instrument according to the above (1), wherein the concealable particles are at least one selected from titanium oxide, zinc oxide and hollow resin particles.
(3) The ink composition for a writing instrument as described in (1) or (2) above, wherein the composite particles contain at least one kind of coloring material having a coloring property of a dye and a pigment.
(4) The composite particle according to any one of (1) to (3), wherein at least one concealing particle selected from titanium oxide, zinc oxide, and hollow resin particles is immobilized on the surface of the composite particle. Ink composition for writing instruments.
(5) The ink composition for a writing instrument according to any one of (1) to (4), wherein the composite particles have a particle size of 1 to 200 μm.
(6) The ink composition for a writing instrument according to any one of the above (1) to (5), wherein the viscosity of the ink composition for a writing instrument at 25 ° C. and 50 rpm in an ELD viscometer is 3 to 50 mPa · s.
(7) The ink composition for writing instruments according to any one of (1) to (6), wherein the ink composition for writing instruments is an ink composition for sign pens.
本発明によれば、経時安定性に優れると共に、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in stability over time, the ink composition for writing instruments which can maintain a clear handwriting with high concealability over a long period of time is provided.
以下に、本発明の実施形態を詳しく説明する。
本発明の筆記具用インキ組成物は、真密度が1.0g/cm3以下の高分子樹脂中に隠蔽性粒子が分散されている複合粒子を含有することを特徴とするものである。
Hereinafter, embodiments of the present invention will be described in detail.
The ink composition for a writing instrument of the present invention is characterized by containing composite particles in which concealing particles are dispersed in a polymer resin having a true density of 1.0 g / cm 3 or less.
図1(a)は、本発明の第1実施形態に用いる複合粒子を示す概略断面図であり、(b)は本発明の第2実施形態に用いる複合粒子を示す概略断面図である。
この第1実施形態の複合粒子Aは、図1(a)に示すように、真密度が1.0g/cm3以下の高分子樹脂10中に隠蔽性粒子11,11…が分散されているものである。また、第2実施形態の複合粒子Bは、図1(b)に示すように、真密度が1.0g/cm3以下の高分子樹脂10中に隠蔽性粒子11,11…が分散されているものであり、この隠蔽性粒子11,11…が分散された高分子樹脂の外表面に上記隠蔽性粒子11,11と同じ隠蔽性粒子12が固定化されているもの、すなわち、この第2実施形態は、上記第1実施形態の複合粒子Aの外表面に隠蔽性粒子12が固定化されているものである。
FIG. 1A is a schematic cross-sectional view showing composite particles used in the first embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view showing composite particles used in the second embodiment of the present invention.
As shown in FIG. 1 (a), the composite particles A of the first embodiment are obtained by dispersing
これらの実施形態において、真密度が1.0g/cm3以下の高分子樹脂10としては、真密度が1.0g/cm3以下となる高分子樹脂であれば特に限定されるものでないが、好ましくは、本発明の効果を更に発揮せしめる点から、真密度が0.97g/cm3以下、更に好ましくは、0.70〜0.97g/cm3となるものが望ましい。
具体的には、低密度ポリエチレン(モアテック0218、真密度0.916g/cm3、出光石油化学社製)、高密度ポリエチレン(HD110J、真密度0.962g/cm3、出光石油化学社製)、低密度ポリプロピレン、(J707G、真密度0.910g/cm3、三井化学社製)、高密度ポリプロピレン(J105G、真密度0.910g/cm3、三井化学社製)などの少なくとも1種(各単独又は2種以上、以下同様)が挙げられる。
この真密度が1.0g/cm3を超える高分子樹脂では、複合粒子としたときの比重が大きくなり、沈降しやすくなり、好ましくない。
これらの真密度が1.0g/cm3以下の高分子樹脂の含有量は、複合粒子全量に対して、好ましくは、10〜90重量%(以下、単に「%」という)、更に好ましくは、20〜80%とすることが望ましい。
In these embodiments, the true density of 1.0 g / cm 3 or less of a
Specifically, low-density polyethylene (Moertech 0218, true density 0.916 g / cm 3 , manufactured by Idemitsu Petrochemical Co., Ltd.), high-density polyethylene (HD110J, true density 0.962 g / cm 3 , manufactured by Idemitsu Petrochemical Co., Ltd.), At least one type of each (single individual, such as low density polypropylene (J707G, true density 0.910 g / cm 3 , Mitsui Chemicals), high density polypropylene (J105G, true density 0.910 g / cm 3 , Mitsui Chemicals) Or two or more types, the same applies hereinafter).
A polymer resin having a true density exceeding 1.0 g / cm 3 is not preferable because the specific gravity when the composite particles are formed becomes large and the particles tend to settle.
The content of the polymer resin having a true density of 1.0 g / cm 3 or less is preferably 10 to 90% by weight (hereinafter simply referred to as “%”), more preferably, based on the total amount of the composite particles. It is desirable to set it as 20 to 80%.
用いることができる隠蔽性粒子11としては、隠蔽性及び白色性を発揮せしめる粒子であれば特に限定されるものでないが、例えば、酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも1種が挙げられる。これらの粒子は、粒子表面が親油性表面処理されている隠蔽性粒子であってよいものである。
好ましくは、隠蔽性が高く鮮明な筆跡を発揮せしめうる点から、用いる隠蔽性粒子としては、酸化チタン単独の使用、酸化チタンと中空樹脂粒子等との併用が挙げられる。なお、隠蔽性粒子中の酸化チタンの含有量は、50%以上とすることが望ましい。
また、高分子中に内包できるという点から、用いる隠蔽性粒子は、平均粒子径が0.05〜20μmの使用が好ましく、特に好ましくは、平均粒子径が0.1〜10μmの隠蔽性粒子が望ましい。
The
Preferably, the concealable particles used include titanium oxide alone and the combined use of titanium oxide and hollow resin particles because the concealability is high and a clear handwriting can be exhibited. The content of titanium oxide in the concealing particles is preferably 50% or more.
In addition, the concealable particles used preferably have an average particle size of 0.05 to 20 μm, particularly preferably concealable particles having an average particle size of 0.1 to 10 μm, because they can be encapsulated in a polymer. desirable.
具体的に用いることができる隠蔽性粒子11として、酸化チタンとしてはルチル型、アナターゼ型等の酸化チタンが使用でき、例えば、KR−380(チタン工業社製、平均粒径0.5μm、親油性処理TiO2)、ITT−2 CR−50(日光ケミカルズ社製、平均粒径0.3μm、有機チタネート処理TiO2)、ITT−7 TTO−S−3(日光ケミカルズ社製、平均粒径0.05μm、有機チタネート処理微粒子TiO2)などが挙げられる。
酸化亜鉛としては、例えば、NANOFINE P−2(堺化学工業社製、平均粒径0.05μm)などが挙げられる。
中空樹脂粒子は、樹脂粒子中に中空部があるものであり、例えば、SX866(A)(JSR社製、平均粒径0.3μm、架橋スチレンアクリル中空粒子)などが挙げられる。
これらの隠蔽性粒子の形状は、特に限定されず、例えば、球状、楕円状、針状などが挙げられる。
これらの隠蔽性粒子の含有量は、複合粒子全量に対して、好ましくは、10〜90%、更に好ましくは、20〜80%とすることが望ましい。
この隠蔽性粒子の含有量が10%未満であると、複合粒子を含むインキの隠蔽性が不十分となり、一方、90%を超えると、高分子樹脂に内包しきれなくなり、複合粒子の比重が大きくなって沈降したりして、好ましくない。
As the
Examples of zinc oxide include NANOFINE P-2 (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.05 μm).
The hollow resin particle has a hollow portion in the resin particle, and examples thereof include SX866 (A) (manufactured by JSR, average particle size 0.3 μm, crosslinked styrene acrylic hollow particle).
The shape of these concealing particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, and a needle shape.
The content of these concealing particles is preferably 10 to 90%, more preferably 20 to 80%, based on the total amount of the composite particles.
When the content of the concealing particles is less than 10%, the concealing property of the ink containing the composite particles becomes insufficient. On the other hand, when the content exceeds 90%, the composite particles cannot be included in the polymer resin, and the specific gravity of the composite particles is low. It becomes undesirably large and settles.
また、複合粒子A又はB中には、染料、顔料の着色性を有する色材を含有せしめてもよいものである。用いることができる顔料としては、例えば、アゾ系顔料、縮合ポリアゾ系顔料、フタロシアニン系顔料、金属錯塩顔料、チオインジゴ顔料、染料レーキ顔料、蛍光顔料等の有機顔料及びカーボンブラック、酸化チタン等の無機顔料が挙げられ、更に、表面を樹脂コーティングで加工した加工顔料、例えば、マイクロリスAタイプ各種、ASブラック、ASブルー、IKレッド等の少なくとも1種が挙げられ、また、染料としては、例えば、油溶性染料、スピリットソルブル染料等のソルベント染料、ロイコ染料などの少なくとも1種を挙げることができる。
これらの色材の含有量は、複合粒子粒子全量に対して、好ましくは、0〜30%、更に好ましくは、0〜20%とすることが望ましい。
これらの色材を含有せしめることにより、更に、被筆記体の色相を隠蔽し良好に発色するマーキング性能を有した筆記具用インキ組成物を提供することができるものとなる。
The composite particles A or B may contain a coloring material having a coloring property of a dye or a pigment. Examples of pigments that can be used include organic pigments such as azo pigments, condensed polyazo pigments, phthalocyanine pigments, metal complex pigments, thioindigo pigments, dye lake pigments, fluorescent pigments, and inorganic pigments such as carbon black and titanium oxide. Further, processed pigments whose surfaces are processed with a resin coating, for example, at least one of various types such as microlith A type, AS black, AS blue, IK red, etc., and examples of dyes include oils There may be mentioned at least one of soluble dyes, solvent dyes such as spirit solver dyes, and leuco dyes.
The content of these coloring materials is preferably 0 to 30%, more preferably 0 to 20%, based on the total amount of the composite particle particles.
By including these coloring materials, it is possible to provide an ink composition for a writing instrument that has a marking performance that conceals the hue of the writing material and colors well.
この第1実施形態の複合粒子Aは、上記真密度が1.0g/cm3以下の高分子樹脂と隠蔽性粒子、必要に応じて好ましくは含有することができる上記色材をケミカル粉砕法などにより、微粒子状に調製することにより得られるものである。
ケミカル粉砕法は、湿式プロセスによる粉砕法であり、真密度が1.0g/cm3以下の高分子樹脂と隠蔽性粒子等をキシレンやトルエン又はジクロロメタン等の溶媒に溶解または分散させた後、該高分子樹脂の溶解度変化(温度、圧力変化や溶媒の添加等の操作を伴なう)を利用した後、脱溶媒し複合粒子を形成させ、更に必要に応じて解砕、分級処理して目的の複合粒子を作製する方法である。
The composite particle A according to the first embodiment includes a polymer resin having a true density of 1.0 g / cm 3 or less and a concealing particle, and preferably contains the above-described coloring material, which may be contained if necessary. Thus, it can be obtained by preparing in the form of fine particles.
The chemical pulverization method is a pulverization method by a wet process, in which a polymer resin having a true density of 1.0 g / cm 3 or less and concealing particles are dissolved or dispersed in a solvent such as xylene, toluene, or dichloromethane, After utilizing the solubility change of polymer resin (with operation such as temperature, pressure change and addition of solvent), the solvent is removed to form composite particles, and further, pulverized and classified as necessary This is a method for producing the composite particles.
上記真密度が1.0g/cm3以下の高分子樹脂と隠蔽性粒子の使用量は、上記各範囲に設定されることが好ましいものであると共に、その配合比としては、好ましくは、重量比で、10:90〜90:10、更に好ましくは、20:80〜80:20とすることが望ましい。
この配合比が10:90未満であると、隠蔽性粒子リッチとなり、複合粒子の比重が大きくなって沈降しやすくなり、一方、90:10を超えると、高分子樹脂がリッチとなり、複合粒子の比重が小さくなって、浮遊しやすくなり、また、隠蔽性が低下して、好ましくない。
The use amount of the polymer resin having the true density of 1.0 g / cm 3 or less and the concealing particles is preferably set in the above ranges, and the blending ratio is preferably a weight ratio. And 10:90 to 90:10, more preferably 20:80 to 80:20.
When the blending ratio is less than 10:90, the concealable particles are rich, and the specific gravity of the composite particles increases and the sedimentation tends to settle. On the other hand, when it exceeds 90:10, the polymer resin becomes rich and The specific gravity becomes small, and it tends to float, and the concealability is lowered, which is not preferable.
また、上記第2実施形態〔図1(b)〕の複合粒子Bは、上記複合粒子Aの外表面に酸化チタン、酸化亜鉛及び中空樹脂粒子の中から選ばれる少なくとも1種の隠蔽性粒子12,12……が固定化されているものであり、複合粒子Aと上記隠蔽性粒子を混合し、ハイブリダイザー(奈良機械製作所社製)などを利用してメカノケミカル的な衝撃を与えることにより、複合粒子(A)の表面に隠蔽性材料となる隠蔽性粒子を固定化することができるものである。なお、図1(b)中の11は酸化チタン粒子、11aは中空樹脂粒子とを併用したものである。
この第2実施形態では、第1実施形態の複合粒子Aよりも更に外表面に隠蔽性粒子が固定化されているので、更に白色度、隠蔽度を付与することができ、更に本発明の効果を発揮せしめることができることとなる。なお、複合粒子の表面に固定化される隠蔽性粒子の厚さとして、更なる本発明の効果の向上の点から、0.1〜1μmとすることが望ましい。
The composite particle B of the second embodiment [FIG. 1 (b)] has at least one
In the second embodiment, since the concealing particles are further immobilized on the outer surface as compared with the composite particles A of the first embodiment, it is possible to further impart whiteness and concealment, and the effect of the present invention. Can be demonstrated. The thickness of the concealing particles immobilized on the surface of the composite particles is preferably 0.1 to 1 μm from the viewpoint of further improving the effect of the present invention.
得られる複合粒子A又はBの平均粒径は、隠蔽性や筆記具用インキとしての流出性の点から、好ましくは、1〜200μm、更に好ましくは、10〜100μmとすることが望ましい。
この複合粒子の平均粒径が1μm未満であると、内包できる隠蔽性粒子が少なくなり、結果として複合粒子としての隠蔽性が低下し、また、この平均粒径が200μmを超えると、粒子間の隙間が大きくなり、結果として隠蔽性が低下し、好ましくない。
なお、上記好適な範囲となる複合粒子の平均粒径は、分砕、分級等を調整することにより容易に得ることができる。
The average particle diameter of the obtained composite particles A or B is preferably 1 to 200 μm, more preferably 10 to 100 μm, from the viewpoint of concealing property and flowability as ink for writing instruments.
When the average particle size of the composite particles is less than 1 μm, the number of concealable particles that can be included decreases, and as a result, the concealability as the composite particles decreases, and when the average particle size exceeds 200 μm, The gap becomes large, and as a result, the concealability is lowered, which is not preferable.
In addition, the average particle diameter of the composite particles in the preferred range can be easily obtained by adjusting the division, classification and the like.
この複合粒子A及び/又はBの含有量は、インキ種(水性、油性、ゲルインキ)、用途(ボールペン用、サインペン用等)により変動するものであるが、筆記具用インキ組成物全量に対して、1〜50%含有せしめることが好ましく、更に好ましくは、5〜30%とすることが望ましい。
この複合粒子の含有量が1%未満であると、所定の白色度や隠蔽性が得られず、一方、50%を超えて含有されると、インキ組成物の経時的な安定性が低下し、凝集及び沈降が起こることがあり、好ましくない。
The content of the composite particles A and / or B varies depending on the ink type (water-based, oil-based, gel ink) and application (for ballpoint pen, sign pen, etc.), but with respect to the total amount of the ink composition for writing instruments, The content is preferably 1 to 50%, and more preferably 5 to 30%.
When the content of the composite particles is less than 1%, predetermined whiteness and hiding properties cannot be obtained. On the other hand, when the content exceeds 50%, the stability of the ink composition with time decreases. Aggregation and sedimentation may occur, which is not preferable.
本発明の筆記具用インキ組成物は、上記複合粒子A及び/又はBを含有するものであり、当該必須成分の他、インキ種(水性、油性、ゲルインキ)により、各種の筆記具用インキの各成分を配合することができるものであり、好ましくは、上記複合粒子Aの分散性を向上させて本発明の効果を発揮せしめる点から、分散剤、粘性調整剤を更に含有せしめることが望ましい。 The ink composition for a writing instrument of the present invention contains the composite particles A and / or B, and in addition to the essential component, each component of various writing instrument inks depending on the ink type (aqueous, oily, gel ink). Preferably, from the viewpoint of improving the dispersibility of the composite particles A and exhibiting the effects of the present invention, it is desirable to further contain a dispersant and a viscosity modifier.
用いることができる分散剤としては、高級脂肪酸、水溶性高分子、界面活性剤や高分子界面活性剤、例えば、ノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性系界面活性剤、高分子型界面活性剤などが挙げられるが、これらに限定されるものではない。
これらの分散剤の含有量としては、用いる複合粒子や溶媒種によって適宜決定されるが、分散安定性やインキ粘度の点から、インキ組成物全量に対して、好ましくは、0.1〜30%、更に好ましくは、0.5〜20%とすることが望ましい。
Dispersants that can be used include higher fatty acids, water-soluble polymers, surfactants and polymer surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric interfaces. Examples thereof include, but are not limited to, an activator and a polymeric surfactant.
The content of these dispersants is appropriately determined depending on the composite particles and solvent type to be used. From the viewpoint of dispersion stability and ink viscosity, it is preferably 0.1 to 30% with respect to the total amount of the ink composition. More preferably, the content is 0.5 to 20%.
また、本発明の筆記具用インキ組成物には、粘性調整剤を含有することができる。
用いることができる粘性調整剤は、水に分散又は溶解して使用するものであり、例えば、スメクタイト、変性スメクタイト、ヒドロキシエチルセルロースや、ヒドロキシプロピルセルロース、結晶性セルロース、ポリビニルピロリドン、ポリビニルアルコールなどの少なくとも1種が挙げられる。
具体的に用いることができる粘性調整剤としては、ルーセンタイトSWN(合成スメクタイト、コープケミカル社製)、ゴーセノール GL−05(日本合成化学工業社製、ポリビニルアルコール)、ゼオラスクリーム(旭化成社製、結晶セルロース分散品)などが挙げられる。
これらの粘性調整剤の含有量は、沈降防止、インキ粘度の点から、複合粒子全量に対して、好ましくは、0.1〜10%、更に好ましくは、0.1〜5%とすることが望ましい。
Moreover, the ink composition for writing instruments of this invention can contain a viscosity modifier.
The viscosity modifier that can be used is one that is dispersed or dissolved in water and used, for example, at least one of smectite, modified smectite, hydroxyethylcellulose, hydroxypropylcellulose, crystalline cellulose, polyvinylpyrrolidone, polyvinyl alcohol, and the like. Species are mentioned.
Specific examples of viscosity modifiers that can be used include Lucentite SWN (synthetic smectite, manufactured by Corp Chemical), Gohsenol GL-05 (manufactured by Nippon Synthetic Chemical Industry, polyvinyl alcohol), Zeolus cream (produced by Asahi Kasei Co., Ltd., crystal) Cellulose dispersion).
The content of these viscosity modifiers is preferably 0.1 to 10%, more preferably 0.1 to 5%, based on the total amount of the composite particles, from the viewpoint of sedimentation prevention and ink viscosity. desirable.
本発明の筆記具用インキ組成物は、上記複合粒子A及び/又はB、分散剤、粘性調整剤のほか、インキ種(水性、油性、ゲルインキ)により、好適な溶媒、例えば、水性では、水を含む水溶性溶剤、油性では有機溶剤を含有せしめることができ、更にインキ種により顔料、水溶性染料、油溶性染料等を含有せしめることができ、更にまた、本発明の効果を損なわない範囲で、任意成分(添加剤)、例えば、アニオン系、ノニオン系、カチオン系などの界面活性剤、乾燥防止剤、防錆剤、防黴剤、沈降抑制剤、染料や顔料等の色材などを適宜必要に応じて含有することができる。 In addition to the composite particles A and / or B, the dispersant, and the viscosity modifier, the ink composition for a writing instrument of the present invention contains water in a suitable solvent, for example, aqueous, depending on the ink type (aqueous, oily, gel ink). Including water-soluble solvents, oily organic solvents, pigments, water-soluble dyes, oil-soluble dyes, and the like depending on the type of ink, and in the range not impairing the effects of the present invention, Necessary components (additives) such as anionic, nonionic and cationic surfactants, drying inhibitors, rust inhibitors, antifungal agents, sedimentation inhibitors, and coloring materials such as dyes and pigments are necessary Depending on the content.
本発明の筆記具用インキ組成物は、上記特性の複合粒子A及び/又はB、分散剤、粘性調整剤、各インキ成分(溶剤、樹脂、色材、添加剤)等を用いて従来公知の筆記具用インキ組成物の製造方法を適用して製造することができる。すなわち、複合粒子A及び/又はB、分散剤、粘性調整剤、色材、樹脂、溶剤、添加剤を分散混合機、撹拌機を用いて、混合することによって目的の筆記具用の水性インキ、油性インキ、ゲルインキ組成物等を得ることができる。
なお、製造時、有機顔料などの粗大粒子を除去するためにフィルター、遠心分離機等を用いることなど必要に応じて使用できる。
The ink composition for a writing instrument of the present invention is a conventionally known writing instrument using the composite particles A and / or B having the above characteristics, a dispersant, a viscosity modifier, each ink component (solvent, resin, coloring material, additive) and the like. It can manufacture by applying the manufacturing method of an ink composition. That is, by mixing the composite particles A and / or B, a dispersant, a viscosity modifier, a coloring material, a resin, a solvent, and an additive using a dispersion mixer and a stirrer, a water-based ink for an intended writing instrument, oily Ink, gel ink composition and the like can be obtained.
In addition, a filter, a centrifuge, etc. can be used as needed, such as using a filter to remove coarse particles such as organic pigments during production.
本発明の筆記具用インキ組成物の粘度は、好ましくは、流出量やインキ安定性の点から、ELD粘度計における25℃、50rpmの粘度が、3〜50mPa・s、更に好ましくは、3〜30mPa・sとすることが望ましい。
この粘度が50mPa・sを越えて粘度が高くなると、筆感が重くなり、滑らかに書きづらくなり、逆に、3mPa・s未満であると、著しいペン先での顔料沈降、滲み等があり、好ましくない。
The viscosity of the ink composition for a writing instrument according to the present invention is preferably 3 to 50 mPa · s, more preferably 3 to 30 mPa, at 25 ° C. and 50 rpm in an ELD viscometer, from the viewpoint of the outflow amount and ink stability.・ S is desirable.
If this viscosity exceeds 50 mPa · s, the writing feel becomes heavier and it becomes difficult to write smoothly, and conversely, if it is less than 3 mPa · s, there is significant pigment sedimentation and bleeding at the nib, It is not preferable.
本発明において、筆記具用インキ組成物は、ボールペン用、サインペン用、筆ペン用の水性インキ、油性インキ、ゲルインキ等に好適に用いることができるものであり、本発明の筆記具用インキ組成物を充填する筆記具の構造としては、上記筆記具用インキ組成物が充填され本発明の効果が発揮できるように筆記できるものであれば、その構造は特に限定されるものではない。
好ましくは、低粘度であり、隠蔽性を有する複合粒子を長期間安定に分散せしめるインキという点から、本発明の筆記具用インキ組成物を吸蔵するインキ吸蔵体を収容した中綿式筆記具用のサインペン用インキとして好適に用いることができる。
In the present invention, the ink composition for writing instruments can be suitably used for water-based inks, oil-based inks, gel inks, etc. for ballpoint pens, sign pens, brush pens, etc., and is filled with the ink composition for writing instruments of the present invention. The structure of the writing instrument is not particularly limited as long as it can be written so that the ink composition for a writing instrument is filled and the effects of the present invention can be exhibited.
Preferably, for a sign pen for a batting type writing instrument that contains an ink occlusion body that occludes the ink composition for a writing instrument of the present invention from the viewpoint of an ink that stably disperses composite particles having low viscosity and concealment for a long period of time. It can be suitably used as an ink.
このように構成される本発明の筆記具用インキ組成物が、何故これまでの発明と比較して優れているという理由としては、以下のように推察される。
従来、酸化チタン顔料を使用した筆記具用インキ組成物は、その比重の大きさのため、インキ組成物中に長期的安定に分散させることができなかった。これに対して、本発明の筆記具用インキ組成物では、用いる複合粒子が、真密度が1.0g/cm3以下の高分子樹脂中に隠蔽性粒子が分散されている複合粒子A、及び/又は、該複合粒子Aの表面に隠蔽性材料となる隠蔽性粒子を固定化してなる複合粒子Bが含有されるものとなるので、比重が小さく、隠蔽性、白色性に優れ、長期に安定で沈降しない白色性、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物を提供することができるものとなる。
また、特開2000−265105号公報に記載される酸化チタンを内包したマイクロカプセル顔料を含有するボールペン用水性インキ組成物は、沈降及び分離現象は幾分解消されるものであるが、マイクロカプセル顔料製造時の隠蔽性粒子の脱落があったり、隠蔽性粒子の粒子径の均一化が難しく、更に、マイクロカプセルの粒子径の均一化及びマイクロカプセル内の粒子数の均一化が難しいものであるが、本発明では、真密度が1.0g/cm3以下の高分子樹脂中に隠蔽性粒子が分散されている複合粒子を用いるので、隠蔽性粒子の脱落がなく、隠蔽性粒子の粒子径の均一化、更に、複合粒子径の均一化及び粒子数の均一化が達成された安定な品質を有する複合粒子を用いることとなるため、単に酸化チタンを内包したマイクロカプセル顔料に較べ、優れた機能、すなわち、今までにない長期に安定で沈降しない白色性、隠蔽性が高く鮮明な筆跡を長期に亘り維持することができる筆記具用インキ組成物が得られるものとなる。
The reason why the ink composition for a writing instrument of the present invention configured as described above is superior to the conventional invention is presumed as follows.
Conventionally, an ink composition for a writing instrument using a titanium oxide pigment cannot be stably dispersed in the ink composition for a long period of time because of its large specific gravity. In contrast, in the ink composition for a writing instrument of the present invention, the composite particles used are composite particles A in which concealable particles are dispersed in a polymer resin having a true density of 1.0 g / cm 3 or less, and / or Alternatively, since composite particles B formed by immobilizing concealable particles as a concealable material are contained on the surface of the composite particles A, the specific gravity is small, the concealability and whiteness are excellent, and stable for a long time. It is possible to provide an ink composition for a writing instrument that can maintain a clear white handwriting and high concealing property and a clear handwriting over a long period of time.
In addition, the water-based ink composition for ballpoint pens containing a microcapsule pigment encapsulating titanium oxide described in JP-A-2000-265105 has a slightly reduced sedimentation and separation phenomenon. Although the concealable particles may fall off during production, the particle size of the concealable particles is difficult to make uniform, and further, the particle size of the microcapsules and the number of particles in the microcapsules are difficult to make uniform. In the present invention, composite particles in which concealing particles are dispersed in a polymer resin having a true density of 1.0 g / cm 3 or less are used, so that the concealing particles are not dropped and the particle diameter of the concealing particles is uniform. In addition, since composite particles having stable quality in which a uniform particle diameter and a uniform number of particles have been achieved are used, a microcapsule simply containing titanium oxide is used. Compared to pigments, an ink composition for writing instruments that has excellent functions, that is, whiteness that does not settle for a long period of time and does not settle, high concealment, and clear writing over a long period of time can be obtained. .
次に、実施例及び比較例により、本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.
〔実施例1〜6及び比較例1〜4〕
下記表1に示す各配合組成(複合粒子、隠蔽性粒子、分散剤、粘性調整剤、溶媒)をガラスビーズを用いてペイントシェーカーで60分間分散し、筆記具用インキ組成物を調製した。
用いた複合粒子1〜4、隠蔽性粒子1〜3、分散剤1〜2、粘性調整剤1〜2は、下記の材料を用いた。
[Examples 1 to 6 and Comparative Examples 1 to 4]
Each composition shown in the following Table 1 (composite particles, hiding particles, dispersant, viscosity modifier, solvent) was dispersed for 60 minutes with a paint shaker using glass beads to prepare an ink composition for writing instruments.
The following materials were used for the used composite particles 1-4, concealable particles 1-3, dispersants 1-2, and viscosity modifiers 1-2.
複合粒子1〔図1(a)準拠〕:
低密度ポリプロピレン(真比重0.91g/cm3)/隠蔽性粒子、平均粒径0.3μmの酸化チタン(ITT−2 CR−50、日光ケミカルズ社製、有機チタネート処理TiO2)〔重量比60:40〕の複合粒子、平均粒径12μm
複合粒子2〔図1(a)準拠〕:
低密度ポリプロピレン(真比重0.91g/cm3)/隠蔽性粒子、平均粒径0.05μmの酸化チタン(ITT−7 TTO−S−3、日光ケミカルズ社製、有機チタネート処理微粒子TiO2)/平均粒径0.3μmの中空粒子〔SX866(A)、JSR社製、架橋スチレンアクリル中空粒子〕〔重量比60:20:20〕の複合粒子、平均粒径15μm
Composite particle 1 (based on FIG. 1A):
Low density polypropylene (true specific gravity 0.91 g / cm 3 ) / hiding particles, titanium oxide having an average particle size of 0.3 μm (ITT-2 CR-50, manufactured by Nikko Chemicals, organic titanate-treated TiO 2 ) [weight ratio 60 : 40] composite particles,
Composite particle 2 (based on FIG. 1 (a)):
Low density polypropylene (true specific gravity 0.91 g / cm 3 ) / hiding particles, titanium oxide having an average particle size of 0.05 μm (ITT-7 TTO-S-3, manufactured by Nikko Chemicals, organic titanate-treated fine particles TiO 2 ) / Composite particles of hollow particles [SX866 (A), manufactured by JSR, cross-linked styrene acrylic hollow particles] [weight ratio 60:20:20], average particle size 15 μm, average particle size 0.3 μm
複合粒子3〔図1(b)準拠〕:
低密度ポリプロピレン(真比重0.91g/cm3)/隠蔽性粒子、平均粒径0.3μmの酸化チタン(ITT−2 CR−50、日光ケミカルズ社製、有機チタネート処理TiO2)〔重量比80:20〕の複合粒子 + 平均粒径0.05μmの酸化チタン(ITT−7 TTO−S−3、日光ケミカルズ社製、有機チタネート処理微粒子TiO2)のコーティング〔複合粒子/ITT−7 TTO−S−3コーティングの重量比=10:1〕、平均粒径13μm
複合粒子4〔図1(a)準拠〕:
低密度ポリプロピレン(真比重0.91g/cm3)/隠蔽性粒子,平均粒径0.3μmの酸化チタン(ITT−7 CR−50、日光ケミカルズ社製、有機チタネート処理微粒子TiO2)〔重量比70:30〕の複合粒子、平均粒径12μm
複合粒子5〔図1(a)準拠〕:
アクリル樹脂(MX−1000,綜研化学社製、真比重1.19g/cm3)/隠蔽性粒子、平均粒径0.3μmの酸化チタン(ITT−2 CR−50、日光ケミカルズ社製、有機チタネート処理TiO2)〔重量比60:40〕の複合粒子、平均粒径12μm
Composite particle 3 (based on FIG. 1B):
Low density polypropylene (true specific gravity 0.91 g / cm 3 ) / hiding particles, titanium oxide having an average particle size of 0.3 μm (ITT-2 CR-50, manufactured by Nikko Chemicals, organic titanate-treated TiO 2 ) [weight ratio 80 : 20] composite particles + coating of titanium oxide (ITT-7 TTO-S-3, manufactured by Nikko Chemicals, organic titanate-treated fine particles TiO 2 ) having an average particle diameter of 0.05 μm [composite particles / ITT-7 TTO-S -3 coating weight ratio = 10: 1], average particle size 13 μm
Composite particle 4 (based on FIG. 1A):
Low density polypropylene (true specific gravity 0.91 g / cm 3 ) / hiding particles, titanium oxide with an average particle size of 0.3 μm (ITT-7 CR-50, manufactured by Nikko Chemicals, organic titanate-treated fine particle TiO 2 ) [weight ratio 70:30],
Composite particle 5 (based on FIG. 1 (a)):
Acrylic resin (MX-1000, manufactured by Soken Chemicals Co., Ltd., true specific gravity 1.19 g / cm 3 ) / hiding particles, titanium oxide having an average particle size of 0.3 μm (ITT-2 CR-50, manufactured by Nikko Chemicals Co., Ltd., organic titanate) Treated TiO 2 ) [weight ratio 60:40] composite particles,
上記複合粒子1、2、4及び5は、上記各構成の真密度の高分子樹脂と隠蔽性粒子をキシレンに溶解または分散させた後、該高分子樹脂の溶解度変化、温度、圧力変化や溶媒の添加等の操作を伴なうを利用して、脱溶媒、解砕、分級して各複合粒子1、2、4及び5を作製した。
また、上記複合粒子3は、上記方法と同様に作製した上述の複合粒子を上述の隠蔽性粒子を上記重量比で混合し、ハイブリダイザー(奈良機械製作所社製)を利用してメカノケミカル的な衝撃を与えることにより、複合粒子の表面に隠蔽性粒子(厚さ0.5μm)を固定化することにより作製した。
The composite particles 1, 2, 4 and 5 are prepared by dissolving or dispersing the true-density polymer resin and the concealing particles having the above-described structures in xylene, and then changing the solubility, temperature, pressure, and solvent of the polymer resin. Each of the composite particles 1, 2, 4, and 5 was prepared by removing the solvent, pulverizing, and classifying using operations such as addition of the above.
The composite particle 3 is prepared by mixing the above-described composite particles prepared in the same manner as the above method with the above-described concealing particles at the above-mentioned weight ratio, and using a hybridizer (manufactured by Nara Machinery Co., Ltd.) It was prepared by immobilizing concealable particles (thickness 0.5 μm) on the surface of the composite particles by applying an impact.
隠蔽性粒子1:平均粒径0.3μmの酸化チタン(ITT−2 CR−50、日光ケミカルズ社製、有機チタネート処理TiO2)
隠蔽性粒子2:平均粒径0.05μmの酸化チタン(ITT−7 TTO−S−3、日光ケミカルズ社製、有機チタネート処理微粒子TiO2)
隠蔽性粒子3:平均粒径0.3μmの中空粒子〔SX866(A)、JSR社製、架橋スチレンアクリル中空粒子〕
分散剤1:不均化ロジン酸エステル(バンディス G−25K、ハリマ化成社製)
分散剤2:ポリオキシエチレンアルキルフェニルエーテル硫酸エステルアンモニウム(エレミノール ES−12、三洋化成工業社製)
粘性調整剤1:結晶セルロース分散品(ゼオラスクリーム、旭化成社製)
粘性調整剤2:合成スメクタイト(ルーセンタイトSWN、コープケミカル社製)
Hiding particles 1: Titanium oxide having an average particle size of 0.3 μm (ITT-2 CR-50, manufactured by Nikko Chemicals, organic titanate-treated TiO 2 )
Hiding particles 2: Titanium oxide having an average particle diameter of 0.05 μm (ITT-7 TTO-S-3, manufactured by Nikko Chemicals, organic titanate-treated fine particles TiO 2 )
Hiding particles 3: hollow particles having an average particle size of 0.3 μm [SX866 (A), manufactured by JSR, cross-linked styrene acrylic hollow particles]
Dispersant 1: Disproportionated rosin acid ester (Bandis G-25K, manufactured by Harima Chemicals)
Dispersant 2: Ammonium polyoxyethylene alkylphenyl ether sulfate ester (Eleminol ES-12, manufactured by Sanyo Chemical Industries)
Viscosity modifier 1: Crystalline cellulose dispersion (Zeolus cream, manufactured by Asahi Kasei Corporation)
Viscosity modifier 2: Synthetic smectite (Lucentite SWN, manufactured by Co-op Chemical)
得られた各筆記具用インキ組成物の粘度、沈降性、隠蔽性、経時保存後の隠蔽性、筆記性を下記評価方法で評価した。
これらの結果を下記表1に示す。
The viscosity, sedimentation property, concealing property, concealing property after storage over time, and writing property of each ink composition for writing instruments thus obtained were evaluated by the following evaluation methods.
These results are shown in Table 1 below.
(粘度の測定方法)
得られた各実施例及び比較例の水性インキ組成物の25℃条件下におけるELD型粘度計〔TV−20(トキメック社製)〕で50rpmの粘度を測定した。
(Measurement method of viscosity)
Viscosity at 50 rpm was measured with an ELD type viscometer [TV-20 (manufactured by Tokimec)] under the conditions of 25 ° C. of the obtained water-based ink compositions of Examples and Comparative Examples.
(沈降性の評価方法)
得られた各実施例及び比較例の筆記具用インキ組成物を、直径2cm、長さ20cmの沈降管に充填し、室温(25℃)下で1ヶ月放置し、沈降性を目視で下記の評価基準で評価した。
評価基準
○:分離、凝集はなく、沈降は認められない。
△:上層部に若干の濃淡の変化が認められる。
×:分離又は凝集があり、沈降が明確に認められる。
(Evaluation method for sedimentation)
The obtained ink compositions for writing instruments of each Example and Comparative Example were filled in a settling tube having a diameter of 2 cm and a length of 20 cm, and left for 1 month at room temperature (25 ° C.). Evaluated by criteria.
Evaluation criteria ○: There is no separation or aggregation, and no sedimentation is observed.
Δ: A slight change in shading is observed in the upper layer.
X: There is separation or aggregation, and sedimentation is clearly recognized.
(隠蔽性の評価方法)
得られた各インキを黒画用紙に100μmのバーコーターで塗布し、白色度を目視で下記の評価基準で評価した。
評価基準:
○:白色である。
△:やや黒味を帯びた白色である。
×:隠蔽が弱く黒味を強く感じる。
(Concealment evaluation method)
Each ink obtained was applied to black paper with a 100 μm bar coater, and the whiteness was visually evaluated according to the following evaluation criteria.
Evaluation criteria:
○: White.
Δ: Slightly blackish white.
X: The concealment is weak and the blackness is felt strongly.
(経時保存後の隠蔽性の評価方法)
得られた各インキ組成物を三菱鉛筆社製PWB−7M(中綿式タイプマーキングペン)軸に6g充填し、ペン先を上向きの状態で25℃下で1ヵ月保存した後の黒画用紙への筆記描線の隠蔽性を目視で下記の評価基準で評価した。
評価基準:
○:白色である。
△:やや黒味を帯びた白色である。
×:隠蔽が弱く黒味を強く感じる。
(Method for evaluating concealment after storage over time)
6 g of each ink composition obtained was filled into a PWB-7M (filling type marking pen) shaft manufactured by Mitsubishi Pencil Co., Ltd. and written on black drawing paper after storing for one month at 25 ° C. with the pen tip facing upward. The concealability of the drawn lines was visually evaluated according to the following evaluation criteria.
Evaluation criteria:
○: White.
Δ: Slightly blackish white.
X: The concealment is weak and the blackness is felt strongly.
(筆記性の評価方法)
得られた各インキ組成物を三菱鉛筆社製PWB−7M(中綿式タイプマーキングペン)軸に6g充填し、下記評価基準で筆記性を評価した。
評価基準:
○:良好に筆記できる。
△:ややカスレを感じる。
×:筆記できない、あるいは、著しくカスレを感じる。
(Writing evaluation method)
6 g of each obtained ink composition was filled into a PWB-7M (batting type marking pen) shaft manufactured by Mitsubishi Pencil Co., Ltd., and the writing property was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Can be written well.
Δ: Slightly blurry.
×: Cannot be written or feels noticeable.
上記表1の結果から明らかなように、本発明の範囲となる実施例1〜6は、本発明の範囲外となる比較例1〜4に比べて、沈降もなく、筆記性、隠蔽性に優れ、加えて経時安定性にも優れたものであることが判明した。 As is clear from the results of Table 1 above, Examples 1 to 6, which are within the scope of the present invention, have no sedimentation, and are less writable and concealed than Comparative Examples 1 to 4, which are outside the scope of the present invention. In addition, it was proved that it was excellent in stability over time.
A 複合粒子
10 真密度が1.0g/cm3以下の高分子樹脂
11 隠蔽性粒子
A
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