JP2006111267A - Ink storing container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink storing container with excellent convenience which exhibits good liquid dripping properties of an ink stored inside, exhibits ink repellent effect for a long time, and can clearly confirm the residual amount of the ink stored. <P>SOLUTION: The ink storing container such as an ink bottle is prepared either by providing a fluororesin layer comprising a fluororesin on the inner face of a transparent container storing the ink inside, or sticking a compound having a crosslinkable functional group and a fluorinated hydrocarbon group on the inner face of the container and crosslinking the compound with the inner face of the container. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ink container. More specifically, the present invention relates to a transparent ink container that contains writing ink, printing ink, and the like.

2. Description of the Related Art Conventionally, a container for storing ink used for various applications has an advantage that the remaining amount of ink can be visually recognized by being formed of a transparent or translucent material. However, depending on the combination of the type of ink and the material forming the ink storage container, the ink may adhere to the inner wall of the container, and even if the ink is used and the ink is substantially exhausted, the ink remains on the inner surface and remains. The amount could not be confirmed.
In addition, fine scratches may be formed on the inner surface of the ink container formed by injection molding or extrusion molding, and ink may enter and remain in the scratches.
In order to solve the above-mentioned problem, an attempt has been made to increase the visibility of the remaining liquid level by providing protrusions having a semi-cylindrical cross section in the vertical direction of the inner surface of the container (for example, see Patent Document 1).
JP-A-9-272298

  However, the container having the above-described configuration does not always allow the remaining amount of ink to be clearly confirmed, and the visibility is greatly impaired when ink adheres to the inner surface.

The present invention provides an ink storage container used for an ink bottle or the like having an ink repellency effect and excellent visibility of the remaining amount of ink, that is, on the inner surface of a transparent container that stores ink. A compound having a crosslinkable functional group and a fluorinated hydrocarbon group attached to an inner surface of an ink container having a fluororesin layer made of a fluororesin or a transparent container inner surface containing ink; And an ink container in which the inner surface of the container is cross-linked.
Furthermore, it is required that the crosslinking functional group of the compound is a silyl group.
Furthermore, the ink container contains the ink composition for writing, the container opening is covered with a removable or openable lid, the ink composition for writing is a colorant, It is a requirement that the oil-based ink composition comprises at least an alcohol-based organic solvent and a resin.

  The present invention provides an ink storage container with excellent convenience that allows the ink contained in the ink to be drained well, can exhibit a long-term ink repellent effect, and allows the remaining amount of the stored ink to be clearly confirmed. it can.

Examples of the material for the ink storage container include glass and various resins. However, since the ink needs to have transparency in order to check the remaining amount of ink to be stored, polyethylene, polypropylene, polyethylene Examples of the resin include turret, polystyrene, polycarbonate, polyamide, acrylic, and ABS.
Ink containers made of polypropylene or polyethylene are suitable in terms of low evaporation of ink, transparency, productivity, cost, etc., but a compound having a crosslinkable functional group and a fluorinated hydrocarbon group is added to the resin. In the case of attaching, since it does not have a functional group such as a hydroxyl group or a carboxylic acid group that crosslinks with the cross-linking functional group, the inner surface of the ink containing container is subjected to plasma treatment by corona discharge or high frequency, and then attached, Alternatively, a resin having a functional group may be blended and molded in a resin constituting the ink storage container, and then the compound may be attached to improve adhesion with the inner surface of the ink storage container.
Among these, the manufacturing method in which the compound is attached through the above-mentioned plasma treatment step does not impair the physical characteristics of the ink container, and the functional groups are introduced uniformly and at a high density. It can be improved further.
The transparency of the ink container includes colored transparent, translucent and colored translucent.
The shape and size of the ink container may be appropriately selected depending on the purpose of use as long as it can be molded and processed, and is not particularly limited.

The compound attached to the inner surface of the ink container is a compound having a cross-linking functional group and a fluorinated hydrocarbon group, and the ink container is contained in a treatment liquid diluted with the compound, for example, a treatment liquid diluted with perfluoropolyether. In a series of manufacturing processes, that is, in the pre-processing stage in which ink is filled, a treatment liquid is sprayed on the inner surface of the ink container, and the compound is adhered and solidified by heating and drying. Can do.
The cross-linked functional group of the compound is cross-linked with the functional group on the inner surface of the ink container, and therefore has good adhesion and hardly peels off due to aging or the influence of the solvent.
In particular, when ink containing hydrocarbons or alcohols is contained as a solvent, conventional ink containing containers provided with a water-repellent resin layer dissolve or swell and easily peel off. The unique compound of the present invention has excellent solvent resistance and can retain the initial ink repellency effect.
Examples of the crosslinking functional group of the compound include a silyl group, a titanate group, a cyanate group, a melamine group, etc., but does not require a catalyst, and is excellent in monomer stability, safety, and solvent resistance of the cross-linked reaction product. Moreover, a silyl group that does not elute harmful substances such as formalin is preferred.
Examples of the silyl group include chlorosilane, alkoxysilane, acetoxysilane, isopropenoxysilane, aminosilane, and the like, which are hydrolyzed to become a silanol group, a functional group such as a hydroxyl group or a carboxyl group on the inner surface of the ink container, or The adjacent silanol groups are firmly bonded by dehydration condensation by heating at 80 to 150 ° C., and three-dimensionally crosslinked.
On the other hand, examples of the fluorinated hydrocarbon group of the compound include a perfluoroalkyl group, a fluoroalkyl group, a perfluoroalkyl ether group, and a fluoroalkyl ether group.
The compound can be obtained by copolymerizing or grafting a monomer having a crosslinking functional group and a monomer having a fluorinated hydrocarbon group.
The compound used in the present invention is not only insoluble in water-based or oil-based inks, but is chemically bonded to the inner surface of the ink container, has a low surface tension, is excellent in water repellency and oil repellency, and is transparent. It is excellent and does not impair internal transparency.

On the other hand, in a system in which a fluororesin layer made of a fluororesin is provided on the inner surface of the container, a treatment liquid obtained by diluting a fluoropolymer into perfluorocarbon, for example, a fluorocoating agent [manufactured by Sumitomo 3M Limited, trade name: Fluorard FC- 722, a fluorine-based homopolymer] in a fully fluorinated inert liquid (perfluorocarbon).
More specifically, after immersing the container in a treatment liquid composed of a perfluorocarbon liquid containing 0.01 to 2% by weight of a fluoropolymer, the container is taken out and a dry film is formed, or a series of manufacturing processes, that is, ink is used. In the pre-processing stage of storing, a treatment process for spraying the treatment liquid is provided on the inner surface of the container, and the fluororesin can be adhered and solidified by a drying treatment.
Examples of the treatment agent other than the above include fluorine-based coating agents (Fluorard FC-725 (product name), manufactured by Sumitomo 3M Co., Ltd., 30% by weight of n-butyl acetate solution of fluorine-based copolymer), ethyl acetate, A similar fluororesin layer can be formed and put to practical use by attaching and drying a treatment liquid diluted to an appropriate concentration with butyl acetate, methyl isobutyl ketone, 1.1.1-trichloroethane, or the like.
In addition, when providing the said fluororesin layer, the plasma processing similar to the above can also be performed.
The fluororesin layer formed as described above is not only insoluble in water-based or oil-based ink, but also has low surface tension, water and oil repellency, excellent transparency, and hinders internal transparency. I don't have to.

Examples of the ink stored in the ink storage container include ink for writing instruments in which a colorant is dissolved or dispersed in a solvent.
As the solvent, an organic solvent is used in the case of oil-based ink, and water and, if necessary, a water-soluble organic solvent are used in the case of water-based ink.
As the organic solvent used in the oil-based ink, a general-purpose solvent can be used conventionally, and it is used in the range of 40 to 80% by weight in the ink.
Examples of the organic solvent include benzyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, benzyl glycol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, propylene glycol mono Ethyl 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, methyl lactate, ethyl lactate, γ -Butyrolac Emissions, methyl ethyl ketone and methyl isobutyl ketone can be exemplified.

Moreover, when the solvent whose vapor pressure in 20 degreeC which is easy to volatilize as an organic solvent is 5.0-50 mmHg is used as a main solvent, it is excellent in the drying property of handwriting.
Examples of the organic solvent having a vapor pressure of 5.0 to 50 mmHg (20 ° C.) include ethyl alcohol (45), n-propyl alcohol (14.5), isopropyl alcohol (32.4), and n-butyl alcohol (5.5). ), Alcohol organic solvents such as isobutyl alcohol (8.9), sec-butyl alcohol (12.7), tert-butyl alcohol (30.6), tert-amyl alcohol (13.0),
Glycol ether organic solvents such as ethylene glycol monomethyl ether (8.5), ethylene glycol diethyl ether (9.7), ethylene glycol monoisopropyl ether (6.0), propylene glycol monomethyl ether (7.6),
n-heptane (35.0), n-octane (11.0), isooctane (41.0), methylcyclohexane (37.0), ethylcyclohexane (10.0), toluene (24.0), xylene ( 5.0-6.0), hydrocarbon organic solvents such as ethylbenzene (7.1),
Ketone organic solvents such as methyl isobutyl ketone (16.0), methyl n-propyl ketone (12.0), methyl n-butyl ketone (12.0), di-n-propyl ketone (5.2),
N-butyl formate (22.0), isobutyl formate (33.0), n-propyl acetate (25.0), isopropyl acetate (48.0), n-butyl acetate (8.4), isobutyl acetate (13 0.0), ethyl propionate (28.0), n-butyl propionate (45.0), methyl butyrate (25.0), ethyl butyrate (11.0), and other organic organic solvents.
The numbers in parentheses indicate the vapor pressure of each organic solvent at 20 ° C.

In the case of a water-based ink using water as a solvent, a water-soluble organic solvent compatible with water can be added.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2- Pyrrolidone, and the like.

  As resins, ketone resins, ketone-formaldehyde resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, phenol resins, xylene resins, polyvinylpyrrolidone, α- and β-pinene / phenol polycondensation resins, polyvinyl butyral resins An acrylic resin, a styrene maleic acid copolymer, a cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, and the like can also be used, and can be used for fixing to a paper surface or imparting viscosity.

  In addition, in the case of water-based inks, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite as necessary. Rust, diisopropylammonium nitrite, saponin and other rust preventives, carboxylic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3 5,6-tetrachloro-4- (methylsulfonyl) pyridine and other preservatives or fungicides, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclo Dextrin, glucose, dextst Emissions, sorbitol, mannitol, wetting agents such as pyrophosphate sodium, defoamers, may be used a dispersing agent, a fluorine based surfactant to improve ink permeability and nonionic surfactants.

As the colorant used in the ink, a pigment or a dye is used. Examples of the pigment include azo, anthraquinone, condensed polyazo, thioindigo, metal complex, phthalocyanine, perinone, perylene, dioxazine and Examples thereof include inorganic pigments such as quinacridone organic pigments, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, and iron oxide. These pigments can be used alone or in combination of two or more as required. Furthermore, fluorescent pigments, metal powder pigments, pearl pigments, phosphorescent pigments, reversible thermochromic pigments and the like can also be mentioned as special pigments.

Examples of the dye include acid dyes, basic dyes, direct dyes, and oil-soluble dyes.
Examples of the acid dye include New Coxin (CI. 16255), Tartrazine (CI. 19140), Acid Blue Black 10B (C.I. 20470), Guinea Green (C.I. 42085), and Brilliant Blue. FCF (C.I. 42090), Acid Violet 6BN (C.I. 43525), Soluble Blue (C.I. 42755), Naphthalene Green (C.I. 44425), Eosin (C.I. 45380), Phloxin (C.I. 45410), erythrosine (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) and the like can be exemplified.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( C.I.44045), rhodamine B (C.I.45170), acridine orange NS (C.I.46005), methylene blue B (C.I.
Examples of fluorescent basic dyes include C.I. I. BASIC YELLOW 1, C.I. I. BASIC YELLOW 9, C.I. I. BASIC YELLOW 35, C.I. I. BASIC YELLOW 40, C.I. I. BASIC RED 1, C.I. I. BASIC RED 1-1, C.I. I. BASIC RED 2, C.I. I. BASIC RED 12, C.I. I. BASIC RED 13, C.I. I. BASIC RED 14, C.I. I. BASIC RED 15, C.I. I. BASIC RED 36, C.I. I. BASIC VIOLET 7, C.I. I. BASIC VIOLET 10, C.I. I. BASIC VIOLET 11, C.I. I. BASIC VIOLET 15, C.I. I. BASIC VIOLET 16, C.I. I. BASIC VIOLET 27, C.I. I. BASIC ORANGE 15, C.I. I. BASIC ORANGE 22, C.I. I. BASIC BLUE 1, C.I. I. BASIC BLUE 3, C.I. I. BASIC BLUE 7, C.I. I. BASIC BLUE 9, C.I. I. BASIC GREEN 1 etc. can be illustrated.
Examples of the direct dye include Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Examples thereof include Caillas Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), and Phthalocyanine Blue (C.I. 74180).
Examples of the oil-soluble dye include C.I. I. SOLVENT BLACK 7, C.I. I. SOLVENT BLACK 123, C.I. I. SOLVENT BLUE 2, C.I. I. SOLVENT BLUE 25, C.I. I. SOLVENT BLUE 55, C.I. I. SOLVENT BLUE 70, C.I. I. SOLVEN RED 8, C.I. I. SOLVENT RED 49, C.I. I. SOLVEN RED 100, C.I. I. SOLVENT VIOLET 8, C.I. I. SOLVENT VIOLET 21, C.I. I. SOLVENT GREEN 3, C.I. I. SOLVENT GREEN 3, C.I. I. SOLVENT YELLOW 21, C.I. I. SOLVENT YELLOW 44, C.I. I. SOLVENT YELLOW 61, C.I. I. Examples include SOLVENT ORANGE 37 and the like.

  Furthermore, as the colorant, colored resin particles containing a pigment, colored resin particles in the form of microcapsules encapsulating the pigment, and colored resin particles containing a dye can also be used.

  The following examples and comparative examples illustrate the present invention, but the present invention is not limited to these examples.

Preparation of oil-based ink composition In 90 parts by weight of ethanol, 5 parts by weight of a red dye [made by Hodogaya Chemical Co., Ltd., trade name: Spiron Red CGH], α- and β-pinene / phenol resin [manufactured by Yasuhara Chemical Co., Ltd.] , Trade name: YS Polyster S145] 5 parts by weight were mixed and stirred to obtain an oil-based ink composition.

Preparation of water-based ink composition In 38.5 parts by weight of water, 40 parts by weight of black dye [Orient Chemical Industries, Ltd., trade name: Water Black 100L], 10 parts by weight of diethylene glycol, 10 parts by weight of glycerin, triethanolamine 1 part by weight and 0.5 part by weight of carboxylic acid were mixed and stirred to obtain a water-based ink composition.

Example 1
Preparation of ink storage container Fluorine-based coating agent (manufactured by Sumitomo 3M Co., Ltd., trade name: Fluorad FC-722, liquid obtained by diluting 2% of fluorine-based polymer solids into perfluorocarbon) in a transparent polypropylene container, 97 parts by weight After dipping in a treatment solution diluted with 5 parts by weight of perfluorocarbon (C ₆ F ₁₄ is the basic structure), it is taken out and dried at room temperature to form a fluororesin layer on the inner wall to obtain an ink container It was.
20 g of the oil-based ink was accommodated in the ink container, and a removable lid was attached to the opening to obtain an ink bottle.

Example 2
Preparation of ink storage container A transparent polypropylene container was subjected to plasma treatment with oxygen radicals, immersed in a 4% isopropyl alcohol solution of a compound represented by the following formula (1), then heated and dried at 130 ° C. for 20 minutes to dry the inner surface. To obtain an ink container.
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (1)
20 g of the oil-based ink was accommodated in the ink container, and a removable lid was attached to the opening to obtain an ink bottle.

（式中、ｍ、ｎは１以上の整数を示し、Ｒはアルコキシ基を示す。）
前記インキ収容容器内に前記油性インキを２０ｇ収容し、開口部に着脱自在の蓋体を取り付けてインキ瓶を得た。 Example 3
Preparation of ink storage container A transparent polypropylene container was subjected to plasma treatment with oxygen radicals, immersed in a 7% perfluoropolyether solution of a copolymer of the following formulas (2) and (3), and then at 130 ° C. for 30 minutes. The ink container was obtained by heating and drying to adhere to the inner surface.

(In the formula, m and n represent an integer of 1 or more, and R represents an alkoxy group.)
20 g of the oil-based ink was accommodated in the ink container, and a removable lid was attached to the opening to obtain an ink bottle.

Example 4
Preparation of ink container After dipping in a 7% perfluoropolyether solution of the same copolymer as in Example 2 in a transparent glass container, it was heated and dried at 130 ° C. for 30 minutes to adhere to the inner surface and accommodate ink. A container was obtained.
20 g of the water-based ink was stored in the ink storage container, and an openable / closable lid was attached to the opening to obtain an ink bottle.

Comparative Example 1
20 g of the oil-based ink was accommodated in a transparent polypropylene container, and a removable lid was attached to the opening to obtain an ink bottle.

Comparative Example 2
Preparation of ink container After dipping in a transparent polypropylene container in a 7% perfluoropolyether solution of the same copolymer as in Example 2, it was heated and dried at 130 ° C. for 30 minutes to adhere to the inner surface. A container was obtained.
20 g of the oil-based ink was accommodated in the ink container, and a removable lid was attached to the opening to obtain an ink bottle.

Comparative Example 3
20 g of the water-based ink was accommodated in a transparent glass container, and an openable / closable lid was attached to the opening to obtain an ink bottle.

The following tests were performed using the ink bottles (ink storage containers).
Visibility test A (initial test)
Each ink bottle immediately after production was inverted and allowed to stand for 1 minute, and the state of the inner surface of the container was visually observed.
Visibility test B (aging test)
After the production, each ink bottle left for 30 days at 50 ° C. was inverted and left for 1 minute, and the state of the inner surface of the container was visually observed.
The test results are shown in the following table.

The evaluation criteria for the performance test are as follows.
○: Ink is not adhered to the inner surface of the ink container, and the remaining amount of ink is clearly visible.
Δ: Ink slightly adhered to the inner surface of the ink container, but the remaining amount of ink can be confirmed.
X: Ink adheres to the inner surface of the ink container and the remaining amount of ink cannot be confirmed.

Claims (5)

  An ink storage container in which a fluororesin layer made of a fluororesin is provided on the inner surface of a transparent container that stores ink.   An ink storage container in which a compound having a cross-linking functional group and a fluorinated hydrocarbon group is attached to the inner surface of a transparent container that stores ink therein, and the compound and the inner surface of the container are cross-linked.   The ink container according to claim 2, wherein the crosslinking functional group of the compound is a silyl group.   An ink container comprising the ink composition for writing in the ink container according to any one of claims 1 to 3, wherein the container opening is covered with a detachable or openable lid.   The ink container according to claim 4, wherein the writing ink composition is an oil-based ink composition comprising at least a colorant, an alcohol-based organic solvent, and a resin.