JP4799356B2 - Oil-based writing instrument - Google Patents

Description

  The present invention relates to an oil-based writing instrument. More specifically, the present invention relates to an oil-based writing instrument using an ink container mainly composed of an aluminum material.

Conventionally, a writing instrument in which highly volatile oil-based ink is housed in an aluminum shaft cylinder has been used (see, for example, Patent Document 1).
Japanese Utility Model Publication No. 6-64960

The writing instrument is a high-quality metallic member that has a good texture when held in hand, is lightweight and has high workability, and therefore aluminum is applied to the shaft tube, but aluminum has a tendency to ionize. Since it is large, it has physical properties that are likely to cause chemical changes under the influence of heat, oxygen, moisture, and the like. In particular, electrolysis may occur due to long-term contact with an element having a low ionization tendency such as copper, and aluminum may be ionized.
Therefore, when ink containing a copper phthalocyanine colorant is stored in contact with an aluminum shaft tube, the shaft tube corrodes over time, copper precipitates in the ink, The elution may cause problems such as pinholes formed in the shaft cylinder and ink leakage.
In addition, the above problem may occur due to long-term aging even when an inner surface treatment such as resin coating is performed.

  The present invention solves the above-mentioned problem, and in a writing instrument in which an ink containing a copper phthalocyanine colorant is contained in a contact state in an ink containing body mainly composed of aluminum, internal corrosion over time And an oil-based writing instrument in which elution of aluminum and aluminum hardly occurs.

The present invention requires an oil-based writing instrument in which an oil-based ink composition comprising at least a copper phthalocyanine-based colorant, an organic solvent, and a saturated fatty acid having 10 to 16 carbon atoms is contained in an ink containing body mainly composed of aluminum. To do.
Furthermore, the organic solvent is an alcohol having 2 to 4 carbon atoms, and the viscosity of the oil-based ink composition is in the range of 1.5 to 15 mPa · s.

  According to the present invention, the aluminum that forms the ink container is not corroded even if the state of contact with the ink containing the copper phthalocyanine colorant is continued for a long period of time, and there is no possibility of causing pinholes or the like. Can provide an excellent oil-based writing instrument.

  The present invention accommodates an ink, such as a structure in which an oil-based ink containing a copper phthalocyanine-based colorant is contained directly or using an ink occlusion body composed of a fiber bundle or the like in an ink containing body mainly composed of aluminum. It is an oil-based writing instrument accommodated in contact with the body wall.

As the copper phthalocyanine colorant constituting the oil-based ink composition housed in the writing instrument, general-purpose dyes that can be dissolved and dispersed in an organic solvent are used.
Specifically, copper such as Bali First Blue 1605 and 1621 manufactured by Orient Chemical Industries, Savinyl Blue GLS manufactured by Clariant Japan, Neopen Blue 807 manufactured by BASF AG, and Orazol Blue GN manufactured by Ciba Geigy Phthalocyanine dyes, Fastgen Blue 5421 manufactured by Dainippon Ink, EP-7, EP-7S, EP-CF, Chromfine Blue 5187, 5188 manufactured by Dainichi Seika Kogyo Co., Ltd., manufactured by Ciba Specialty Chemicals Examples include copper phthalocyanine pigments such as Irgaline Blue GLVO, Lionol Blue E manufactured by Toyo Ink, Renol Blue B2G-HW30 manufactured by Clariant Japan, and Heliogen Blue D6700T manufactured by BASF.

  The copper element contained in the colorant has a very large difference (1.997 V) between the standard single electrode potential of copper (+0.337 V) and the standard single electrode potential of aluminum (−1.66 V) (for example, standard single electrode potential). Since the difference between the standard monopolar potential of iron and aluminum whose polar potential is −0.44 V is 1.22 V), the aluminum corrodes (the aluminum in the ink container is eluted and copper in the ink is deposited). ).

Moreover, the said writing implement can use the general purpose dye / pigment conventionally applied to oil-based ink together with a copper phthalocyanine colorant.
Examples of the dye include organic solvent-soluble dyes classified as solvent dyes in the color index, and specifically, Balifast Black 3806 (CI Solvent Black 29) and 3807 (CI Solvent Black 29). Trimethylbenzylammonium salt), Spirit Black SB (CI Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Varifast Red 1308 (CI Basic Red 1 dye) And CI Acid Yellow 23 dye salt), Balifast Yellow AUM (CI Basic Yellow 2 dye salt and CI Acid Yellow 42 dye salt salt), Spiron Yellow C2GH (C.I. Organic acid salt of basic yellow 2 dye) Spiro Violet CRH (CI Solvent Violet 8-1), Bali Fast Violet 1701 (Salt Form of Dye of CI Basic Violet 1 and CI Acid Yellow 42), Spiron Red CGH (C.I Basic red 1 dye organic acid salt), Spiron Pink BH (CI Solvent Red 82), Nigrosine Base EX (CI Solvent Black 7), Oil Blue 613 (CI Solvent Blue 5), etc. Is mentioned.

Examples of pigments include inorganic pigments such as carbon black, ultramarine, and titanium dioxide pigments, azo pigments, indigo pigments, thioindigo pigments, selenium pigments, quinacridone pigments, anthraquinone pigments, selenium pigments, diketopyrrolopyrrole pigments, dioxazines Metal pigments such as aluminum pigments, organic pigments such as perylene pigments, perinone pigments, isoindolinone pigments, metal pigments whose surfaces are treated with colored resins, and transparent or colored transparent films Average particle selected from metal pigment, gold, silver, platinum and copper having a thickness of 0.01 to 0.1 μm obtained by peeling a metal vapor deposition film such as aluminum formed on a base material such as a metallic luster pigment and film Colloidal particles with a diameter of 5 to 30 nm, fluorescent pigments, luminous pigments, thermochromic pigments, natural clouds as core materials , Synthetic mica, glass pieces, it is possible to use alumina, metal oxide coated pearl pigments such as surface titanium oxide of the transparent film pieces.
The dye / pigment may be used alone or in combination of two or more, and is used in the range of 3 to 40% by weight in the ink composition.

The C10-16 saturated fatty acid suppresses the reaction between the copper phthalocyanine colorant and aluminum in the organic solvent. It is estimated that this is because the carboxyl group of the fatty acid is chemically adsorbed on the aluminum surface, thereby sterically hindering the contact of the copper element with the aluminum surface. Therefore, it is considered that an alkyl chain having a certain length is necessary to exhibit the above-described effect.
When the saturated fatty acid has less than 10 carbon atoms, the effect on aluminum corrosion cannot be obtained, and when the carbon number exceeds 16, the solubility in organic solvents deteriorates, so that it is likely to precipitate in the ink and has a corrosion inhibiting effect. It becomes difficult to obtain.
The saturated fatty acid may be used alone or in combination of two or more, and is used in the range of 0.5 to 10% by weight in the ink composition.

Examples of the organic solvent include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, tert-amyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, Propylene glycol, benzyl glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, propylene Glycolmo Methyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monophenyl ether, n -Heptane, n-octane, isooctane, methylcyclohexane, ethylcyclohexane, toluene, xylene, ethylbenzene, methyl isobutyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, di-n-propyl ketone, n-butyl formate, isobutyl formate Methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propionate Le, n- butyl propionate, methyl butyrate, ethyl butyrate, dimethyl carbonate, diethyl carbonate, propyl carbonate, etc. can be exemplified. In particular, alcohol having 2 to 4 carbon atoms is suitably used as the main solvent because it has excellent hand-drying properties.
The said organic solvent may use together 1 type, or 2 or more types, and is used in 40 to 90 weight% in the ink composition.

Furthermore, the ink composition can be applied without limitation to a resin that is soluble in an organic solvent usually used in an oil-based ink composition, and imparts handwriting blur suppression, fixing property improvement, fastness, and the like. It becomes possible.
Specifically, ketone resin, amide resin, alkyd resin, rosin modified resin, rosin modified phenol resin, phenol resin, xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin, polyvinyl pyrrolidone, polyethylene oxide, polymethacryl Examples include acid esters, ketone-formaldehyde resins, α- and β-pinene / phenol polycondensation resins, polyvinyl butyral resins, acrylic resins, and polyacrylic acid-polymethacrylic acid copolymers.
These resins may be used alone or in combination of two or more, and are used in the range of 0.5 to 40% by weight, preferably 1 to 35% by weight in the ink composition. If the amount is less than 0.5% by weight, sufficient effects such as suppression of handwriting on paper, improvement of fixing property, imparting fastness and the like cannot be exerted. If the amount exceeds 40% by weight, the solubility of the resin in the solvent decreases. In addition, the fluidity of the ink decreases.

In the oil-based ink composition, if necessary, in addition to the above components, an antioxidant, a dry-up-resistance imparting agent, an ultraviolet absorber, a rust inhibitor, a lubricant, a viscosity modifier, a release agent, and a pigment Various additives such as a dispersant, an antifoaming agent, a shear thinning agent, and a surfactant can be used.
For example, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, etc. can be used as a rust inhibitor.
As the antioxidant, dibutylhydroxyl toluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, catechins and the like can be used.
As UV absorbers, 2- (2'-hydroxy-3'-t-butyl 5'-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, p-benzoic acid-2-hydroxybenzophenone, and the like can be used.
As the antifoaming agent, dimethylpolysiloxane or the like can be used.
Examples of the shear thinning agent include a crosslinked acrylic resin, a crosslinked N-vinylcarboxylic acid amide polymer or copolymer, a non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer, hydrogenated castor oil, Fatty acid amide wax and the like can be used.
The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

  Further, when the ballpoint pen is applied as the writing instrument of the present invention, higher fatty acid such as oleic acid, nonionic surfactant having a long chain alkyl group, polyether-modified silicone oil, thiophosphorous acid tri (alkoxycarbonylmethyl ester) Or a lubricant such as thiophosphite triester such as thiophosphite triester (alkoxycarbonylethyl ester) can be added as necessary, and in particular, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester. If an ester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether diester, or a metal salt, ammonium salt, amine salt, alkanolamine salt, or the like is used, the ball seat wear-preventing effect is excellent.

  When the ink composition formed by blending the above components is accommodated in a marking pen, it is preferable to adjust the viscosity within the range of 1.5 to 15 mPa · s. By setting it as the said range, also in the marking pen which used the fiber bundling body and the porous resin for the pen point, it becomes difficult to produce handwriting blur.

The oil-based writing instrument that contains an ink composition in contact with the ink containing body containing aluminum as a main component is put to practical use by filling a marking pen or a ball-point pen with a tip attached to the writing tip.
When filling the marking pen, the structure and shape of the marking pen itself is not particularly limited. For example, a fiber bundle, felt tip, or plastic tip attached to the writing tip, A structure in which ink is impregnated in a porous material and ink is supplied to the tip of writing, ink is stored directly inside the shaft tube, and ink flow control consisting of comb groove-shaped ink flow control members and fiber bundles Examples include a marking pen having a structure in which a member is interposed, and a structure in which ink is directly stored in a shaft cylinder and a predetermined amount of ink is supplied to the writing tip portion by a valve mechanism.
When filling the ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited.For example, an ink occlusion body made of a fiber bundle or a porous material housed inside the shaft tube is impregnated with ink, and the tip of the writing is filled. Ink supply structure, ink is stored directly in the shaft cylinder, and ink flow control members consisting of comb-groove-shaped ink flow control members and fiber bundles are interposed, and ink storage in which the ink composition is filled in the shaft cylinder A structure in which an ink follower such as a liquid stopper or a solid stopper is in close contact with the end face of the ink to prevent backflow. The ballpoint pen can be illustrated.

  The ink container is composed mainly of aluminum, but the proportion of metal elements other than aluminum is less than 0.5% (that is, the aluminum purity is 99.5% or more) among other components. It is preferable. When the ratio is 0.5% or more, the content of a metal (particularly copper) having a large standard unipolar potential value contained in the metal element is increased, so that the possibility of corrosion is increased.

  The compositions of the inks used in the examples and comparative examples are shown in the following table. In addition, the numerical value of a composition in a table | surface shows a weight part. The ink viscosity was measured using a BL type viscometer (BL adapter, 20 ° C., 60 rpm).

The contents of the raw materials in the table are explained according to the note numbers.
(1) Product name: Savinyl Blue GLS, manufactured by Clariant Japan
(2) Product name: Neopen Blue 807, manufactured by BASF AG
(3) Product name: Renol Blue B2G-HW30, manufactured by Clariant Japan
(4) Orient Chemical Industry Co., Ltd., trade name: Ospi Yellow RY
(5) Arakawa Chemical Industries, Ltd., trade name: Marquide 33A

Preparation of ink Each raw material was mixed by the compounding quantity of the said Example and comparative example, and the oil-based ink composition for writing instruments was obtained by stirring and dissolving at 25 degreeC for 3 hours.

Production of marking pens A cylindrical aluminum can opened at one end formed of pure aluminum No. 1080 (purity of 99.8% or more) defined by JIS standards is used as an ink container, and ink composed of fiber bundles in the aluminum can After storing the occlusion body, each ink composition obtained is filled into the ink occlusion body, and the pen tip holding member is attached to the opening in a state where the rear end of the nib made of a fiber converging body is connected to the ink occlusion body. As a result, an oil-based marking pen was obtained.

Corrosion test After each oil-based marking pen prepared was allowed to stand at 50 ° C. for 3 months, the aluminum can was opened and the state of the inner surface where the ink contacted was observed with a microscope.
Filtration test Each of the prepared oil-based inks was allowed to stand at 25 ° C. for 1 hour, then filtered through a membrane filter having a pore diameter of 5 μm, and the top of the filter was visually observed.
The test results are shown in the following table.

The contents of the symbols in the table will be described below.
Corrosion test ○: No change compared to the initial stage.
X: Corrosion is confirmed.
Filtration test ○: No residue is observed on the filter.
X: A residue is confirmed on the filter.

Claims (3)

  An oil-based writing instrument in which an oil-based ink composition comprising at least a copper phthalocyanine-based colorant, an organic solvent, and a saturated fatty acid having 10 to 16 carbon atoms is contained in an ink containing body mainly composed of aluminum.   The oil-based writing instrument according to claim 1, wherein the organic solvent is an alcohol having 2 to 4 carbon atoms.   The oil-based writing instrument according to claim 1 or 2, wherein the oil-based ink composition has a viscosity of 1.5 to 15 mPa · s.