+

WO1997031985A1 - Encre contenant un pigment a base d'huile pour materiel d'ecriture - Google Patents

Encre contenant un pigment a base d'huile pour materiel d'ecriture Download PDF

Info

Publication number
WO1997031985A1
WO1997031985A1 PCT/JP1997/000566 JP9700566W WO9731985A1 WO 1997031985 A1 WO1997031985 A1 WO 1997031985A1 JP 9700566 W JP9700566 W JP 9700566W WO 9731985 A1 WO9731985 A1 WO 9731985A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
monomer
based pigment
acrylic
ink
Prior art date
Application number
PCT/JP1997/000566
Other languages
English (en)
Japanese (ja)
Inventor
Hiroyuki Idogawa
Original Assignee
Mitsubishi Pencil Kabushiki Kaisha
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Pencil Kabushiki Kaisha filed Critical Mitsubishi Pencil Kabushiki Kaisha
Priority to DE19781616T priority Critical patent/DE19781616T1/de
Publication of WO1997031985A1 publication Critical patent/WO1997031985A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks

Definitions

  • the present invention relates to an oil-based pigment ink for writing implements. More specifically, it has fluidity suitable for writing instruments with a discharge mechanism utilizing capillary action, and has excellent dispersion stability, and does not cause clogging with felt nibs, fiber nibs, plastic nibs, etc.
  • the present invention relates to an oil-based pigment for writing instruments having characteristics. Background art
  • Oil-based inks can be written on both ink-absorbing materials such as paper and cloth and non-ink-absorbing materials such as plastic, glass, and metal.
  • ink using pigment as a coloring material is generally known as a paint marker because of its excellent handwriting robustness, and is used not only in homes, schools and offices but also in various industrial applications.
  • Carbon black is used as the black ink pigment.
  • the oil-based pigment ink using carbon black has a high viscosity, a sufficient amount of ink cannot be obtained from a writing instrument having an ejection mechanism utilizing a capillary phenomenon, and writing blur occurs, so that paint ink is not suitable for use. A mechanism is used to obtain the discharge rate.
  • phenomena such as aggregation and settling of carbon black will occur, the fluidity will deteriorate, and the pen tip will be clogged.
  • the conventional paint maker has a method in which a stirrer such as a metal ball is put together with the ink into the ink storage section and redistributed, and has a complicated structure intertwined with the valve structure. Therefore, the number of parts was large, the assembly process was complicated, and the cost was high.
  • An object of the present invention is to provide an oil-based pigment ink for writing implements that does not need to adopt a complicated structure like a conventional paint marker.
  • Oil-based pigments for writing implements that have fluidity suitable for writing implements with a stable ejection mechanism, have excellent dispersion stability, and do not cause clogging with filter nibs, fiber nibs, plastic nibs, etc. It is for the purpose of obtaining an ink. Disclosure of the invention
  • the present inventor has conducted various studies to solve the above-mentioned problems.
  • the use of at least one solvent selected from the group consisting of alcohol-based solvents and glycol ether-based solvents and acryl-based resins For writing instruments that have fluidity suitable for writing instruments even when black is used, have excellent dispersion stability, and do not cause clogging with felt nibs, fiber nibs, plastic nibs, etc.
  • the oil-based pigment ink was successfully obtained, and the present invention was completed.
  • the oil-based pigment ink for writing implements of the present invention comprises at least one solvent selected from the group consisting of alcohol solvents and glycol ether solvents, pigments, and acryl-based monomers having at least styrene and a carboxyl group.
  • an acryl-based resin obtained by copolymerizing a mixed monomer containing at least styrene and an acryl-based monomer having an amino group is selected from the group consisting of alcohol solvents and glycol ether solvents, pigments, and acryl-based monomers having at least styrene and a carboxyl group.
  • an acryl-based resin obtained by copolymerizing a mixed monomer containing at least styrene and an acryl-based monomer having an amino group.
  • the pigment is carbon black
  • the ataryl polymer is a copolymer having a weight average molecular weight of 50,000 or less.
  • the pigment used in the ink of the present invention is preferably carbon black, and the carbon black is not limited, and commercially available carbon black can be used. Preferred in terms of fluidity.
  • Examples of carbon black include Cabot's “Regal 415 R”, “Rega 1250 R”, “Regal 350 R”, “Monarch 460”, and “Mogul—L”. # 45L manufactured by Mitsubishi Chemical Corporation, such as "P rintex 25", “P rintex 35", “P rintex 45", "S pecial B lack 250", “S pecial B lack 350” manufactured by egussa ",”# 50 ",”# 900 ",”# 980 ",”# 23 “ 0 ",” MA7 “,” MA11 “,” MCF88 “, etc. These can be used alone or in combination of two or more.
  • Its use amount is preferably 3 to 20% by weight.
  • the acryl resin used in the ink of the present invention comprises a copolymer of at least an acryl monomer having a styrene and a carboxyl group, or a mixed monomer containing at least an acrylic monomer having a styrene and an amino group. It is a copolymer having a weight average molecular weight of 5,000 or less.
  • a copolymer obtained from a mixed monomer containing an acrylyl-based monomer having a carboxyl group it is preferable to use a carbon black having a primary particle diameter of 80 nm or less.
  • the acrylic resin is effective as a carbon black dispersant, an anti-settling agent, and a binder.
  • the role of the acryl-based monomer having a carboxyl group and the acryl-based monomer having an amino group is not clear, it is considered to mainly assist the solubility in alcohol-based solvents or glycol ether-based solvents.
  • acrylic monomer having a carboxyl group examples include acrylic acid, methacrylic acid, acrylic acid 2-succinoyloxethyl, acrylic acid-12-phthaloxyl-ethyl, acrylic acid-2-phthaloyloxypropyl, and acrylic acid-2-phthaloyloxypropyl.
  • 2-Cyclic acid 2-hexafluoro-drophthaloyloxethyl, methacrylic acid 2-succinoylquinethyl, methacrylic acid-2-phthaloyloxystyl, methacrylic acid-2-phthaloyloxypropyl, methacrylic acid 2-hexahydric acid Drophthaloyloxiecil and the like can be mentioned.
  • Examples of the acryl-based monomer having an amino group include, for example, dimethylaminoethyl acrylate, getylaminoethyl acrylate, dimethylaminoethyl methacrylate, and getylaminoethyl methacrylate.
  • acryl-based monomers are used in a copolymer component (mixed monomer) in an amount of 5 to 80 mol%, preferably 10 to 70 mol%.
  • styrene Although the role of styrene is not clear, it is considered to be mainly for extracting the dispersibility of carbon black, and 5 to 70 mol%, preferably 10 to 60 mol%, is contained in the copolymer component. % To be contained.
  • non-functional acrylate esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and methacrylate
  • Non-functional methacrylic acid esters such as ethyl, ⁇ -butyl methacrylate, and 2-ethylhexyl methacrylate can be included as needed.
  • the viscosity of an ink suitable for a writing instrument having a discharge mechanism utilizing the capillary phenomenon is 2 OmPa ⁇ s or less (25 ° C.). Therefore, the weight average molecular weight of the acryl-based resin is 5 The amount is preferably not more than 000, and the amount used is preferably from 1 to 20% by weight, although it varies depending on the weight average molecular weight and the like.
  • the solvent used in the ink of the present invention is at least one selected from the group consisting of alcohol solvents and glycol ether solvents.
  • alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol , N-hexanol and the like.
  • glycol ether solvents include methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and the like.
  • a surfactant a dispersing aid, an antioxidant, a lubricant, and the like can be appropriately selected and used as needed.
  • the ink of the present invention As a method for producing the ink of the present invention, a conventionally known method can be employed.
  • the above components can be easily obtained by kneading and dispersing them in a dispersing machine such as a homomixer, ball mill, bead mill, homogenizer, sand mill, roll mill, etc.o
  • the carbon black surface can be reduced by using a specific copolymer.
  • the resin has a particularly strong adsorption effect on the resin, and as a result, exhibits excellent dispersibility and sedimentation-prevention, resulting in excellent fluidity and dispersion stability. It is considered that the carbon black does not settle even during the initial storage and clogging at the pen tip does not occur.
  • the average particle size of the carbon black dispersed in the ink was measured using a laser scattering type particle size distribution analyzer, and evaluated from the obtained values.
  • the ink was filled into a sign pen having a fiber nib made of acryl resin, left for 3 months, and then written, and the state was evaluated by visual judgment.
  • Dimethylaminoethyl methacrylate 50 mol%, styrene 40 mol%, butyl acrylate 10 mol% of a mixed monomer of 10 parts by weight was charged into a solvent ethyl alcohol 80 parts by weight, and azobis was added.
  • Solution polymerization was performed using dimethylvaleronitrile as a catalyst to obtain an acryl-based copolymer resin solution having a polymerization average molecular weight of 13,000.
  • Table 1 shows the test results of the ink.
  • Table 1 shows the monomer mixture, its mixing ratio, solvent, carbon black, and ink mixing ratio. And as shown in Table 2, an oil-based pigment for writing implements was prepared according to Example 1.
  • Tables 1 and 2 show the test results of the obtained ink.
  • Azobis dimethyl valero was charged with 10 parts by weight of a mixed monomer of 30% by mole of acrylic acid, 40% by mole of styrene, and 30% by weight of n-butyl acrylate in 80% by weight of a solvent ethyl alcohol. Solution polymerization was carried out using nitrile as a catalyst to obtain an acrylic copolymer resin solution having a polymerization average molecular weight of 1500.
  • Table 3 shows the test results of the ink.
  • An oil-based pigment for writing implements was prepared according to Example 5 with the mixed monomers and their mixing ratios, solvents, carbon black, and ink mixing ratios as shown in Tables 3 and 4.
  • Tables 3 and 4 show the test results of the obtained ink.
  • Weight average molecular weight 13000 6200 12000 6000 Composition (weight:
  • the oil-based pigment for writing implements of the present invention has excellent fluidity and dispersibility, and does not cause clogging at the pen tip even during long-term storage. It is. Industrial applicability
  • the oil-based pigment ink of the present invention is suitable for a writing instrument having a discharge mechanism utilizing capillary action. In addition, it can be used for a conventional writing instrument having a single structure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Cette invention concerne une encre contenant un pigment à base d'huile pour matériel d'écriture et qui comporte au moins un solvant sélectionné dans le groupe constitué par des alcools et des éthers glycoliques, un pigment et une résine acrylique. La résine acrylique est un copolymère ayant un poids moléculaire moyen en poids inférieur ou égal à 50000 que l'on obtient par copolymérisation d'un mélange de monomères comportant soit du styrène et un monomère acrylique carboxylé, soit du styrène et un monomère acrylique aminé.
PCT/JP1997/000566 1996-03-01 1997-02-27 Encre contenant un pigment a base d'huile pour materiel d'ecriture WO1997031985A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19781616T DE19781616T1 (de) 1996-03-01 1997-02-27 Auf Öl basierende Pigmenttinte für Schreibgeräte

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP8/44847 1996-03-01
JP8/44848 1996-03-01
JP4484796 1996-03-01
JP4484896 1996-03-01

Publications (1)

Publication Number Publication Date
WO1997031985A1 true WO1997031985A1 (fr) 1997-09-04

Family

ID=26384819

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/000566 WO1997031985A1 (fr) 1996-03-01 1997-02-27 Encre contenant un pigment a base d'huile pour materiel d'ecriture

Country Status (2)

Country Link
DE (1) DE19781616T1 (fr)
WO (1) WO1997031985A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110770A (ja) * 1983-10-20 1985-06-17 ビデオジェット　システムズ　インターナショナル　インコーポレイテッド インクジエツト印刷用インク組成物
JPS61235478A (ja) * 1985-04-11 1986-10-20 Dainichi Seika Kogyo Kk 筆記および記録用水性顔料インキ組成物
JPS62283144A (ja) * 1986-05-30 1987-12-09 Dainichi Color & Chem Mfg Co Ltd 顔料組成物
JPH04227670A (ja) * 1990-03-28 1992-08-17 Pentel Kk インキ組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110770A (ja) * 1983-10-20 1985-06-17 ビデオジェット　システムズ　インターナショナル　インコーポレイテッド インクジエツト印刷用インク組成物
JPS61235478A (ja) * 1985-04-11 1986-10-20 Dainichi Seika Kogyo Kk 筆記および記録用水性顔料インキ組成物
JPS62283144A (ja) * 1986-05-30 1987-12-09 Dainichi Color & Chem Mfg Co Ltd 顔料組成物
JPH04227670A (ja) * 1990-03-28 1992-08-17 Pentel Kk インキ組成物

Also Published As

Publication number Publication date
DE19781616T1 (de) 1999-04-08

Similar Documents

Publication Publication Date Title
JPS5880368A (ja) 筆記具用顔料水性インキ組成物
WO1998040441A1 (fr) Encre a bille a base aqueuse du type a remplissage direct presentant un reflet metallique
JPH10259337A (ja) 水性インキ用着色樹脂微粒子水性分散液
JP2003292838A (ja) 保存安定性に優れたインクジェット用水性組成物の製造方法、その方法によって製造されたインクジェット用組成物及び該組成物を含むインクジェット用記録液
EP3733789A1 (fr) Dispersion de fines particules de résine colorée pour encre aqueuse, et composition d'encre aqueuse employant celle-ci, à utiliser dans des instruments d'écriture
WO1997031985A1 (fr) Encre contenant un pigment a base d'huile pour materiel d'ecriture
JP6585433B2 (ja) 筆記具用油性インク組成物
WO2001072914A1 (fr) Encre pour stylo a bille a base d'huile
JPS63145380A (ja) パステル調筆記具用水性インキ組成物
WO1997039070A1 (fr) Composition d'encre contenant des pigments, a base d'huile, destinee a ecrire sur des ustensiles
JPS63145382A (ja) 筆記具用白色水性インキ組成物
JPH1030074A (ja) 記録液組成物
JP2009280659A (ja) 水性インク組成物
JP2014208746A (ja) 油性ボールペン用インキ
JPH09291248A (ja) 記録液
JPH03157466A (ja) 筆記具用白色水性インキ組成物
JP2662599B2 (ja) 修正液
JP2017171712A (ja) 油性メタリックカラーインキ
JP4537695B2 (ja) 非水分散型インクバインダ−用樹脂組成物
JPH1135868A (ja) 記録液組成物
JP3338222B2 (ja) 直液ノック式水性ボールペン用インキ
JPS6397670A (ja) パステル調筆記具用インキ組成物
WO2016163291A1 (fr) Dispersion liquide de microparticules de résine de couleur pour encre aqueuse, et composition d'encre aqueuse pour instrument d'écriture mettant en œuvre celle-ci
JP7316795B2 (ja) 着色樹脂粒子のエタノール分散体
JPS63145381A (ja) 筆記具用黒色水性インキ組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): DE US

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
RET De translation (de og part 6b)

Ref document number: 19781616

Country of ref document: DE

Date of ref document: 19990408

WWE Wipo information: entry into national phase

Ref document number: 19781616

Country of ref document: DE

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载