JP4435295B2 - Ink backflow preventive composition for writing instruments - Google Patents
Ink backflow preventive composition for writing instruments Download PDFInfo
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- JP4435295B2 JP4435295B2 JP2000174141A JP2000174141A JP4435295B2 JP 4435295 B2 JP4435295 B2 JP 4435295B2 JP 2000174141 A JP2000174141 A JP 2000174141A JP 2000174141 A JP2000174141 A JP 2000174141A JP 4435295 B2 JP4435295 B2 JP 4435295B2
- Authority
- JP
- Japan
- Prior art keywords
- ink
- fatty acid
- acid amide
- ink backflow
- backflow preventive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003449 preventive effect Effects 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 239000000194 fatty acid Substances 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- 238000003860 storage Methods 0.000 claims description 6
- -1 hydroxy fatty acid Chemical class 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229920002545 silicone oil Polymers 0.000 description 12
- 230000002265 prevention Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000002199 base oil Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OCJPLTQFTVIUHU-UHFFFAOYSA-N N-(cyclohexylmethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCC1CCCCC1 OCJPLTQFTVIUHU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- KJXSXHGTHSJJMJ-UHFFFAOYSA-N n-(2-methylpropyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCC(C)C KJXSXHGTHSJJMJ-UHFFFAOYSA-N 0.000 description 2
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000010356 sorbitol Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GCAONVVVMAVFDE-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC GCAONVVVMAVFDE-CLFAGFIQSA-N 0.000 description 1
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 description 1
- QRIKMBDKRJXWBV-CLFAGFIQSA-N (z)-n-[6-[[(z)-octadec-9-enoyl]amino]hexyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC QRIKMBDKRJXWBV-CLFAGFIQSA-N 0.000 description 1
- VZGOTNLOZGRSJA-ZZEZOPTASA-N (z)-n-octadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC VZGOTNLOZGRSJA-ZZEZOPTASA-N 0.000 description 1
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003862 amino acid derivatives Chemical class 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- AUZQGYVEDMZLGJ-UHFFFAOYSA-N n-(2-methylpropyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC(C)C AUZQGYVEDMZLGJ-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- VMRGZRVLZQSNHC-ZCXUNETKSA-N n-[(z)-octadec-9-enyl]hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC VMRGZRVLZQSNHC-ZCXUNETKSA-N 0.000 description 1
- PECBPCUKEFYARY-ZPHPHTNESA-N n-[(z)-octadec-9-enyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCCC\C=C/CCCCCCCC PECBPCUKEFYARY-ZPHPHTNESA-N 0.000 description 1
- WNCFYFLYHFIWIL-UHFFFAOYSA-N n-[2-(docosanoylamino)ethyl]docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCCCCCC WNCFYFLYHFIWIL-UHFFFAOYSA-N 0.000 description 1
- HETBCUMLBCUVKC-UHFFFAOYSA-N n-[2-(dodecanoylamino)ethyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC HETBCUMLBCUVKC-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- LCZJLVYYBRTSAQ-UHFFFAOYSA-N n-[4-(octadecanoylamino)butyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCNC(=O)CCCCCCCCCCCCCCCCC LCZJLVYYBRTSAQ-UHFFFAOYSA-N 0.000 description 1
- SLZWSYPJQQIDJB-UHFFFAOYSA-N n-[6-(octadecanoylamino)hexyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCCCCCNC(=O)CCCCCCCCCCCCCCCCC SLZWSYPJQQIDJB-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
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- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
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Landscapes
- Pens And Brushes (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、筆記具用インキ逆流防止体組成物に関する。さらに詳細には、インキ収容筒内に収容したインキの後端面にインキの消費に従い前進する高粘度流体である筆記具用インキ逆流防止体組成物に関する。
【0002】
【従来の技術】
従来より筆記具用のインキ逆流防止体組成物として液状ポリブテン、或いは鉱物油等の難揮発性有機溶剤からなるベースオイルを、微粒子シリカ等の増粘剤でゲル化したものが知られている。しかしながら、これらのインキ逆流防止体はベースオイルとインキ中に添加されている界面活性剤、染料或いはその他の添加剤との親和性が高いため、インキ逆流防止体の一部がインキ中へ、或いはインキ中の一部の成分がインキ逆流防止体中へ移行し、インキ逆流防止体或いはインキの物性が変動し、インキ逆流防止性能の低下やインキの変色等の問題点があった。
【0003】
この不具合を解消する目的で、インキ中の成分との親和性が低いシリコーンオイルをベースオイルとしたインキ逆流防止体が提案されている。例えば特開平11−165486号公報及び特開平11−170757号公報にはメチルシリコーンオイル、ジメチルシリコーンオイル及びその誘導体から選ばれるベースオイルに増粘剤として微粒子シリカ、金属石鹸、トリベンジリデンソルビトール等を添加したインキ逆流防止体が開示されている。
【0004】
【発明が解決しようとする課題】
上記したシリコーンオイルを微粒子シリカ等でゲル化したインキ逆流防止体は剪断力が付加された際に粘度の低下が著しく、剪断力を取り去った後に元の粘度に回復するまでに長時間を要する。また、該インキ逆流防止体を長期間保管すると徐々にゲル強度が低下し、十分なインキ逆流防止効果が得られなくなり、チップ上向き(正立)状態での放置或いは衝撃によるインキ漏出等の不具合を発生しがちであった。
またインキの逆流を防止するために増粘剤を増量すると、ゲル強度は増すが硬くなりすぎるために流動性、即ちインキ追従性が低下し、インキ出渋りや筆跡カスレが生じる。
【0005】
本発明は、前記従来の問題点を解決するものであって、インキ中の成分による劣化やインキの変質が少なく、追従性及び逆流防止性能に優れたインキ逆流防止体を提供しようとするものである。
尚、本発明において「前」とはペン先側を、「後」とはインキ逆流防止体側を指し、また「正立」とはペン先を上向き、「倒立」とはペン先を下向き状態にすることを示す。
【0006】
【課題を解決するための手段】
本発明者はインキ成分との親和性が低く、インキとの相互作用の少ないシリコーンオイルをベースオイルとしたインキ逆流防止体において、化学的、物理的に安定なゲルを形成し、長期保管後においてもゲル強度の変化が少ない増粘剤を種々検討した結果、本発明を完成するに至った。
【0007】
即ち、本発明は筆記具のインキ収容筒内に直接収容したインキの後端面に配設され、インキの消費に従い前進するインキ逆流防止体であって、前記インキ逆流防止体がシリコーンオイルに下記一般式(1)或いは一般式(2)で示される脂肪酸アマイドを添加したものであることを要件とする。
【化3】
(式中、R1 はC8 〜C22の飽和脂肪酸、不飽和脂肪酸、或いはヒドロキシ脂肪酸であり、R2 は水素又はC8 〜C22のアルキル基、或いはアルケニル基である。)
【化4】
(式中、R3 はC8 〜C22の飽和脂肪酸、不飽和脂肪酸、或いはヒドロキシ脂肪酸であり、R2 は水素又はC8 〜C22のアルキル基、アルケニル基或いはシクロアルキル置換アルキル基である。)
更には、前記脂肪酸アマイドの一種又は二種以上をインキ逆流防止体組成物全量に対して0.2〜3.0重量%添加したことを要件とする。
【0008】
【発明の実施の形態】
本発明においてベースオイルとして用いられるシリコーンオイルには、例えばメチルシリコーンオイル、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、アルキル変性シリコーンオイル、アミノ変性シリコーンオイル、カルボキシル変性シリコーンオイル等を挙げることができ、これらのシリコーンオイルから選ばれる一種或いは二種以上を混合して用いることができる。
【0009】
また増粘剤として添加される脂肪酸アマイドは前記一般式(1)或いは一般式(2)で表わされる化合物であり、一般式(1)で示される化合物で式中のR2 が水素である化合物の具体例としてはラウリン酸アマイド、ステアリン酸アマイド、オレイン酸アマイド、エルカ酸アマイド、リシノール酸アマイド、12−ヒドロキシステアリン酸アマイド等を挙げることができる。また、式中のR2 がアルキル基或いはアルケニル基である化合物の具体例としてはN−イソブチルラウリン酸アマイド、N−イソブチルステアリン酸アマイド、N−オレイルステアリン酸アマイド、N−オレイルオレイン酸アマイド、N−ステアリルステアリン酸アマイド、N−ステアリルオレイン酸アマイド、N−オレイルパルミチン酸アマイド、N−ステアリルエルカ酸アマイド等を挙げることができる。
【0010】
更に、一般式(1)で示される化合物で式中のR2 がシクロアルキル置換アルキル基である化合物の具体例としてはN−シクロヘキシルメチルラウリン酸アマイド、N−シクロヘキシルメチルカプロン酸アマイド等が例示できる。
【0011】
また、前記一般式(2)で表わされる化合物の具体例としてはN,N´−エチレンビスラウリン酸アマイド、N,N´−メチレンビスステアリン酸アマイド、N,N´−エチレンビスステアリン酸アマイド、N,N´−エチレンビスオレイン酸アマイド、N,N´−エチレンビスベヘン酸アマイド、N,N´−エチレンビス−12−ヒドロキシステアリン酸アマイド、N,N´−ブチレンビスステアリン酸アマイド、N,N´−ヘキサメチレンビスステアリン酸アマイド、N,N´−ヘキサメチレンビスオレイン酸アマイド等を挙げることができる。
【0012】
これらの脂肪酸アマイドの一種又は二種以上をインキ逆流防止体全量に対してて0.2〜3.0重量%添加することにより好適なインキ逆流防止体組成物を得ることができる。添加量が0.2重量%未満では得られるインキ逆流防止体の粘度が十分ではなく、正立放置によりインキ逆流防止体がインキ収容管の後端方向に移動する、或いは正立状態で筆記具を落下させた時にインキ逆流防止体やインキが流出或いは飛散してしまう等の不具合を生じることもある。
【0013】
また、前記脂肪酸アマイドの添加量が3重量%を超えると、得られるインキ逆流防止体が硬くなりすぎるために、筆記時にインキの消費と共にペン体方向への追従が阻害され、インキの供給が不足し、筆跡濃度低下や筆記線途切れ等が発生することもある。
前記脂肪酸アマイドは0.2〜3.0重量%の添加量が好ましいが、0.5〜2.0重量%の添加がより好ましい。
【0014】
本発明のインキ逆流防止体組成物の主成分は前述したようにシリコーンオイルと脂肪酸アマイドであるが、更にゲル強度を増すために従来からインキ逆流防止体組成物の増粘剤として汎用されている微粒子シリカ(親水性或いは疎水性)、ベンジリデンソルビトール類、アミノ酸誘導体等を補助増粘剤として少量添加することも有効である。
【0015】
本発明のインキ逆流防止体組成物に用いられる脂肪酸アマイドは、ベースオイルとして用いられるシリコーンオイルとの相溶性が低いために、単純な攪拌のみでは良好な分散体を得ることは困難である。よって、予め脂肪酸アマイドをキシレン、ミネラルターペン、エチルアルコール等の低沸点溶剤に10〜20重量%の濃度で加温溶解させたペーストを作成し、シリコーンオイル中に所定量の前記脂肪酸アマイドペーストを投入し、ディスパー等で予備攪拌したものを三本ロールで分散処理する。尚、ペースト作成に使用した低沸点溶剤は、三本ロール処理が開放状態で行なわれるため、分散処理終了までに揮散する。
【0016】
上記工程の製造方法により、脂肪酸アマイドはベースオイル中に均一な微粒子状態に分散され、微細な三次元網目構造を形成する。そのため、得られたインキ逆流防止体は高揺変性を有し、また剪断力が付加されたときも急激な粘度低下を示さず、更には、長期間保管された場合も油分の分離等が発生せず経時的に安定なゲル状態が保持される。
【0017】
【実施例】
以下、本発明のインキ逆流防止体組成物を実施例と比較例によって詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【0018】
〔脂肪酸アマイドペーストの作成〕
脂肪酸アマイドペーストA
エチルアルコール15重量部、キシロール65重量部、N−シクロヘキシルメチルラウリン酸アマイド20重量部を環流冷却器を備えたフラスコ中に投入し、105℃で均一になるまで攪拌した後、室温で放冷し脂肪酸アマイドペーストAを得た。
脂肪酸アマイドペーストB
ミネラルスピリット90重量部、N−イソブチルラウリン酸アマイド10重量部を環流冷却器を備えたフラスコ中に投入し、120℃で均一になるまで攪拌した後、室温で放冷し、脂肪酸アマイドペーストBを得た。
脂肪酸アマイドペーストC
エチルアルコール25重量部、キシロール65重量部、N−ステアリルステアリン酸アマイド10重量部を環流冷却器を備えたフラスコ中に投入し、105℃で均一になるまで攪拌した後、室温で放冷し、脂肪酸アマイドペーストCを得た。
【0019】
実施例及び比較例のインキ逆流防止体組成物の配合を以下の表に示す。表中の数字は重量部を表わす。
尚、実施例及び比較例1、2はベースオイル中に脂肪酸アマイドペースト及び微粒子シリカ(実施例6)を所定量投入し、予備攪拌をした後三本ロール処理を行なった。
また、比較例3から5についてはベースオイル中に微粒子シリカを所定量投入し、予備攪拌をした後三本ロール処理を行うことにより得ることができる。
尚、得られた実施例及び比較例のインキ逆流防止体の硬さを平行板粘度計(スプレッドメーター)で測定した値をSM値の欄に記載した。
【0020】
【表1】
【0021】
【表2】
【0022】
表中の原料を注番号に従って説明する。
(1)KF96−3000〔信越化学工業(株)製、ジメチルポリシロキサン〕
(2)KF96−6000〔信越化学工業(株)製、ジメチルポリシロキサン〕
(3)AEROSIL200〔日本アエロジル工業(株)製、親水性シリカ〕
【0023】
試料ボールペンの作製
0.7mm径の超硬合金製ボールを備えたステンレスパイプチップを先端に嵌着した、内径3.8mmのポリエチレン管に、20℃における粘度が100mPa・sの水性黒インキを充填し、インキ後端部に実施例及び比較例のインキ逆流防止体組成物をそれぞれ接触配置して試料ボールペンとし、以下の性能試験を行なった。
【0024】
逆流試験
前記試料ボールペンを、正立状態のまま4フィートの高さから落下し、インキ逆流防止体の状態を目視で観察した。
追従性試験
前記試料ボールペンを筆記荷重100g、筆記速度10m/分の条件で筆記試験を行なった。
耐剪断力試験
実施例及び比較例のインキ逆流防止体をディスパーを用いて1500rpmで5分間攪拌した直後に前記の部品及びインキを用いてボールペンを組み立て、前記と同様の逆流試験を行なった。
【0025】
上記の試験を行なった結果を以下の表に示す。尚、それぞれの試験における評価基準は以下の通りである。
逆流試験
○:インキ逆流防止体の状態に変化が認められない。
△:インキ逆流防止体の形状が崩れている。
×:インキ逆流防止体の形状が崩れ、インキが後方に漏出している。
追従性試験
○:良好に筆記できる。
×:筆記線にかすれが発生している。或いは筆記できない。
耐剪断力試験
○:インキ逆流防止体の状態に変化が認められない。
△:インキ逆流防止体の形状が崩れている。
×:インキ逆流防止体の形状が崩れ、インキが後方に漏出している。
【0026】
【表3】
【0027】
【発明の効果】
本発明のインキ逆流防止体組成物はインキ逆流防止体に要求されるインキ追従性とインキ逆流防止性の相反する二つの重要な特性を同時に満足し、更に長期の保管においても硬さの変化や油分の分離等が発生しないという特徴を有する。また、インキ収容管に充填する工程等で剪断力を付加された場合も顕著な粘度低下がなく、剪断力が取り去られた後は速やかに元の粘度に復元するため、筆記具の製造工程においても、インキ漏れ等の不具合が発生することがない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ink backflow preventive composition for a writing instrument. More specifically, the present invention relates to an ink backflow preventive composition for a writing instrument, which is a high-viscosity fluid that moves forward in accordance with ink consumption to the rear end surface of ink stored in an ink storage cylinder.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, an ink backflow preventive composition for a writing instrument is known in which a base oil composed of liquid polybutene or a hardly volatile organic solvent such as mineral oil is gelled with a thickener such as fine particle silica. However, since these ink backflow preventers have a high affinity between the base oil and the surfactant, dye or other additive added in the ink, a part of the ink backflow preventer enters the ink or the ink. Some of the components migrated into the ink backflow prevention body, and the physical properties of the ink backflow prevention body or ink fluctuated, causing problems such as a decrease in ink backflow prevention performance and discoloration of the ink.
[0003]
In order to solve this problem, there has been proposed an ink backflow preventer using a silicone oil having a low affinity with components in the ink as a base oil. For example, in JP-A-11-165486 and JP-A-11-170757, fine silica, metal soap, tribenzylidene sorbitol and the like are added as a thickener to a base oil selected from methyl silicone oil, dimethyl silicone oil and derivatives thereof. An ink backflow preventer is disclosed.
[0004]
[Problems to be solved by the invention]
The ink backflow preventive body obtained by gelling the above silicone oil with fine particle silica or the like has a significant decrease in viscosity when a shearing force is applied, and it takes a long time to recover the original viscosity after removing the shearing force. In addition, if the ink backflow preventive body is stored for a long period of time, the gel strength gradually decreases, and a sufficient ink backflow prevention effect cannot be obtained, and problems such as ink leakage due to leaving the chip in an upward (upright) state or impact. Tended to occur.
Further, when the amount of the thickening agent is increased in order to prevent the backflow of the ink, the gel strength is increased but the gel becomes too hard, so that the fluidity, that is, the ink follow-up property is lowered, resulting in ink bleeding and handwriting blurring.
[0005]
The present invention solves the above-mentioned conventional problems, and is intended to provide an ink backflow prevention body that is less deteriorated due to components in the ink and less deteriorated in ink, and has excellent followability and backflow prevention performance. is there.
In the present invention, “front” refers to the pen tip side, “rear” refers to the ink backflow preventer side, “upright” refers to the pen tip upward, and “inverted” refers to the pen tip downward. Indicates to do.
[0006]
[Means for Solving the Problems]
The present inventor forms a chemically and physically stable gel in an ink backflow prevention body based on silicone oil that has low affinity with ink components and has little interaction with ink, and even after long-term storage. As a result of various investigations on thickeners with little change in gel strength, the present invention has been completed.
[0007]
That is, the present invention is an ink backflow preventive body that is disposed on the rear end surface of the ink stored directly in the ink storage cylinder of the writing instrument and moves forward according to the consumption of the ink. It is a requirement that the fatty acid amide represented by (1) or general formula (2) is added.
[Chemical 3]
(In the formula, R 1 is a C 8 -C 22 saturated fatty acid, unsaturated fatty acid, or hydroxy fatty acid, and R 2 is hydrogen, a C 8 -C 22 alkyl group, or an alkenyl group.)
[Formula 4]
Wherein R 3 is a C 8 to C 22 saturated fatty acid, unsaturated fatty acid or hydroxy fatty acid, and R 2 is hydrogen or a C 8 to C 22 alkyl group, alkenyl group or cycloalkyl-substituted alkyl group. .)
Furthermore, it is a requirement that one or more of the fatty acid amides are added in an amount of 0.2 to 3.0% by weight based on the total amount of the ink backflow preventer composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the silicone oil used as the base oil in the present invention include methyl silicone oil, dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, and the like. One or a mixture of two or more selected from oils can be used.
[0009]
The fatty acid amide added as a thickener is a compound represented by the general formula (1) or the general formula (2), and is a compound represented by the general formula (1), in which R 2 is hydrogen. Specific examples thereof include lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide and the like. Specific examples of the compound in which R 2 in the formula is an alkyl group or an alkenyl group include N-isobutyl lauric acid amide, N-isobutyl stearic acid amide, N-oleyl stearic acid amide, N-oleyl oleic acid amide, N -Stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide etc. can be mentioned.
[0010]
Furthermore, specific examples of the compound represented by the general formula (1) in which R 2 is a cycloalkyl-substituted alkyl group include N-cyclohexylmethyl lauric acid amide, N-cyclohexylmethyl caproic acid amide and the like. .
[0011]
Specific examples of the compound represented by the general formula (2) include N, N′-ethylenebislauric acid amide, N, N′-methylenebisstearic acid amide, N, N′-ethylenebisstearic acid amide, N, N′-ethylenebisoleic acid amide, N, N′-ethylenebisbehenic acid amide, N, N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N'-hexamethylene bis stearic acid amide, N, N'-hexamethylene bis oleic acid amide, etc. can be mentioned.
[0012]
A suitable ink backflow preventive composition can be obtained by adding 0.2 to 3.0% by weight of one or more of these fatty acid amides with respect to the total amount of the ink backflow preventive. If the amount added is less than 0.2% by weight, the viscosity of the ink backflow preventive body obtained is not sufficient, and the ink backflow preventive body moves toward the rear end of the ink storage tube when left standing upright, or the writing instrument is placed in the upright state. In some cases, the ink backflow prevention body or ink may flow out or scatter when dropped.
[0013]
Also, if the amount of fatty acid amide added exceeds 3% by weight, the resulting ink backflow preventive body becomes too hard, which obstructs follow-up in the direction of the pen body as ink is consumed during writing, and ink supply is insufficient. In some cases, however, handwriting density drop or writing line interruption may occur.
The fatty acid amide is preferably added in an amount of 0.2 to 3.0% by weight, more preferably 0.5 to 2.0% by weight.
[0014]
As described above, the main components of the ink backflow preventive composition of the present invention are silicone oil and fatty acid amide. However, in order to further increase the gel strength, it has been widely used as a thickener for the ink backflow preventive composition. It is also effective to add a small amount of fine particle silica (hydrophilic or hydrophobic), benzylidene sorbitols, amino acid derivatives and the like as auxiliary thickeners.
[0015]
Since the fatty acid amide used in the ink backflow preventive composition of the present invention has low compatibility with the silicone oil used as the base oil, it is difficult to obtain a good dispersion only by simple stirring. Therefore, a paste prepared by heating and dissolving fatty acid amide in a low-boiling solvent such as xylene, mineral terpene, and ethyl alcohol at a concentration of 10 to 20% by weight is prepared in advance, and a predetermined amount of the fatty acid amide paste is put into silicone oil. Then, the material preliminarily stirred with a disper or the like is dispersed with a three roll. Note that the low boiling point solvent used for preparing the paste is volatilized by the end of the dispersion process because the three-roll process is performed in an open state.
[0016]
The fatty acid amide is dispersed in the base oil in a uniform fine particle state by the production method of the above process, and forms a fine three-dimensional network structure. Therefore, the obtained ink backflow preventive body has high thixotropic properties, does not show a drastic decrease in viscosity when shearing force is applied, and further, oil separation occurs even when stored for a long time. Without maintaining a stable gel state over time.
[0017]
【Example】
Hereinafter, although the ink backflow prevention body composition of this invention is demonstrated in detail by an Example and a comparative example, this invention is not limited to these Examples.
[0018]
[Creation of fatty acid amide paste]
Fatty acid amide paste A
15 parts by weight of ethyl alcohol, 65 parts by weight of xylol and 20 parts by weight of N-cyclohexylmethyl lauric acid amide were put into a flask equipped with a reflux condenser, stirred at 105 ° C. until uniform, and then allowed to cool at room temperature. Fatty acid amide paste A was obtained.
Fatty acid amide paste B
90 parts by weight of mineral spirits and 10 parts by weight of N-isobutyl lauric acid amide are put into a flask equipped with a reflux condenser, stirred at 120 ° C. until uniform, and then allowed to cool at room temperature to obtain fatty acid amide paste B. Obtained.
Fatty acid amide paste C
25 parts by weight of ethyl alcohol, 65 parts by weight of xylol and 10 parts by weight of N-stearyl stearic acid amide were put into a flask equipped with a reflux condenser, stirred at 105 ° C. until uniform, and then allowed to cool at room temperature. Fatty acid amide paste C was obtained.
[0019]
The formulation of the ink backflow preventive compositions of Examples and Comparative Examples is shown in the following table. The numbers in the table represent parts by weight.
In Examples and Comparative Examples 1 and 2, a predetermined amount of fatty acid amide paste and fine-particle silica (Example 6) was added to the base oil, pre-stirred, and then subjected to a three-roll treatment.
Further, Comparative Examples 3 to 5 can be obtained by putting a predetermined amount of fine particle silica into the base oil, pre-stirring, and then performing a three-roll treatment.
In addition, the value which measured the hardness of the obtained ink backflow prevention body of the Example and the comparative example with the parallel plate viscometer (spread meter) was described in the column of SM value.
[0020]
[Table 1]
[0021]
[Table 2]
[0022]
The raw materials in the table will be described according to the note numbers.
(1) KF96-3000 [Shin-Etsu Chemical Co., Ltd., dimethylpolysiloxane]
(2) KF96-6000 [Shin-Etsu Chemical Co., Ltd., dimethylpolysiloxane]
(3) AEROSIL200 [Nippon Aerosil Industries, Ltd., hydrophilic silica]
[0023]
Preparation of sample ball-point pen Filled with 3.8 mm ID polyethylene pipe fitted with stainless steel pipe tip with 0.7 mm diameter cemented carbide ball at the tip, water-based black ink with viscosity at 20 ° C. of 100 mPa · s The ink backflow preventive compositions of Examples and Comparative Examples were placed in contact with the rear end portion of the ink to form a sample ballpoint pen, and the following performance tests were performed.
[0024]
Backflow test The sample ballpoint pen was dropped from a height of 4 feet in an upright state, and the state of the ink backflow prevention body was visually observed.
Follow-up test A writing test was performed on the sample ballpoint pen under the conditions of a writing load of 100 g and a writing speed of 10 m / min.
Shear resistance test The ink backflow preventers of Examples and Comparative Examples were stirred at 1500 rpm for 5 minutes using a disper and immediately after assembling the ballpoint pen using the above components and ink, and the same backflow test was performed.
[0025]
The following table shows the results of the above tests. In addition, the evaluation criteria in each test are as follows.
Backflow test ○: No change is observed in the state of the ink backflow preventer.
Δ: The shape of the ink backflow preventer is broken.
X: The shape of the ink backflow preventer is broken, and the ink leaks backward.
Follow-up test ○: Can be written well.
X: The writing line is faint. Or I can't write.
Shear resistance test ○: No change was observed in the state of the ink backflow preventer.
Δ: The shape of the ink backflow preventer is broken.
X: The shape of the ink backflow preventer is broken, and the ink leaks backward.
[0026]
[Table 3]
[0027]
【The invention's effect】
The ink backflow preventive composition of the present invention simultaneously satisfies the two important characteristics of the ink followability and ink backflow preventive properties required for the ink backflow preventive body, and further changes in hardness even during long-term storage. It has a feature that separation of oil does not occur. In addition, when shearing force is applied in the process of filling the ink containing tube, etc., there is no significant decrease in viscosity, and after the shearing force is removed, the original viscosity is quickly restored. However, problems such as ink leakage do not occur.
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