JP2003226089A - Applicator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an applicator preventing the scattering of a back-flow preventing agent or ink even if receiving an impact by falling or the like. <P>SOLUTION: The applicator is characterized in that the complex modulus of the back-flow preventing agent is adjusted. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a tip, a fiber bundle, a spatula tip, a ball-point pen tip, or the like, which is connected to an application destination.
The present invention relates to an applicator in which at least an ink and a backflow preventing agent containing at least an ink insoluble or hardly soluble in the ink and / or water and a viscosity modifier are contained and arranged in an ink tank.

[0002]

2. Description of the Related Art Conventionally, there is known a ballpoint pen in which a backflow preventive agent made of polybutene or a gelled product of polybutene is disposed in contact with the trailing end interface of ink in a cylindrical ink tank.

[0003]

In order for the anti-reflux agent to exert its anti-reflux function, it must be immiscible or extremely incompatible with the ink. And gelled products of polybutene can be preferably used.

However, in the case of an ink in which a pigment having a high specific gravity such as titanium oxide is used in a high concentration, when the pen tip is left facing upwards, the backflow preventive agent may be changed due to the difference in specific gravity between the ink and the backflow preventive agent. If there is a reversal phenomenon in which it moves in the direction of the pen tip as if it was submerged in it, or if the applicator drops (especially upward pen tip), the impact causes the backflow preventive agent and ink to move backward and leak. There was a problem that problems such as putting out occurred.

By the way, the applicator using the anti-reflux agent is
After filling the ink tank with the ink and backflow preventive agent, usually centrifuge by rotating with the pen tip facing outwards,
A process is provided to remove air bubbles that were mixed in during the production of ink or backflow preventive agent, and bubbles that were mixed in when the ink tank was filled. However, when a strong centrifugal force is applied, dispersed solids such as pigments may settle or leakage from the pen tip may occur, so it is desirable that the removal of air bubbles be achieved by a relatively small centrifugal force. Was there.

[0006]

That is, the present invention provides an applicator in which an ink backflow inhibitor composition is placed in contact with an interface on the side opposite to the ink discharge destination, which is accommodated in a container in a free state. And the complex elastic modulus of the anti-reflux agent composition is 50P.
a ・ s or more 800 Pa ・ s (Temperature 25 ℃, Shear stress 5P
(a, frequency 1 Hz) is the gist.

The details will be described below. The tip of the applicator is a tip valve type in which a rod-shaped or spherical applicator is pressed forward by an elastic body such as a spring and pressed against the inner edge of the application liquid outlet, or a fiber bundle or brush tip. The used one can be appropriately adopted. In particular, if the ink used uses a volatile solvent, it is preferable to use a valve or the like so as to suppress the evaporation of the solvent from the coating destination. In the case of the tip valve type, as the material of the coating member that also serves as the valve body, resins such as polyacetal and polybutylene terephthalate, metals such as stainless steel and brass, and the like can be appropriately used.

As the material of the ink tank, generally used materials can be appropriately used, but as an example, nylon, polyethylene terephthalate, polypropylene,
Examples thereof include polyethylene, fluororesins, polybutylene terephthalate, and the like, and nylons, polyethylene terephthalates, fluororesins, and polybutylene terephthalates are preferable in consideration of solvent resistance. In addition, in order to prevent ink from adhering to the inner wall of the ink tank, the inner wall surface of the storage tube has an arithmetic average roughness (Ra) of 500 nm or less and a maximum height difference (P
-V) surface roughness of less than 5000 nm (JIS B06
01) is preferred. Further, the shape of the ink tank is preferably a cylindrical body having a circular cross section such as a general synthetic resin extruded pipe, but the inner diameter may be different depending on the part, or the cross section may be a polygon such as a square. For example, an injection-molded product having a free shape may be used.

The ink is used to form a handwriting or a pattern and to conceal the formed handwriting or a figure (correction liquid). Basically, a colorant (hiding agent), a solvent and / or a solvent are used. It consists of water and at least.

A pigment or dye can be used as the colorant, but the amount used is preferably adjusted to 3 to 65% by weight based on the total amount of the ink. As a specific example, TITON SR
-1, 650, R62N, R3L, R7E (above, manufactured by Sakai Chemical Industry Co., Ltd.), Kronos KR-310, KR-380, 480 (above, Titanium Industry Co., Ltd.).
Manufactured), TYPURE R-900, same R-602, same R-9
60, the same R-931 (above, manufactured by DuPont Japan Limited), TITANIX JR301, the same JR80
5, the same JR602, the same JR800 (above, Teika Co., Ltd.
Made of) Titanium oxide, Special Black
6, S170, S610, S5, S4, S4A, S550, S35, S250, S100, Printex
150T, U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 4
5, same P, same XE2, same L6, same L, same 300, same 3
0, the same 3, the same 35, the same 25, the same 200, the same A, the same G (above, manufactured by Degussa Japan KK), # 2400B, # 2.
350, # 2300, # 2200B, # 1000, # 9
50, # 900, # 850, # MCF88, MA60
0, MA100, MA7, MA11, # 50, # 52,
# 45, # 44, # 40, # 33, # 32, # 30, C
F9, # 20B, # 4000B (above, manufactured by Mitsubishi Kasei Co., Ltd.), MONARCH 1300, 1100,
1000, 900, 880, 800, 70
0, MOGUL L, REGAL 400R, 660
R, 500R, 330R, 300R, 99R,
ELFTEX 8, 12 and BLACK PEARLS
2000 (above, Cabot Co. Ltd., USA
Manufactured by Raven 7000, 5750, 5250,
Same 5000, Same 3500, Same 2000, Same 1500, Same 1255, Same 1250, Same 1200, Same 1170, Same 1
060, 1040, 1035, 1020, 10
00, 890H, 890, 850, 790, 780, 760, 500, 450, 430, 420, 410, 22, 22, 16, 14, 825.
Oil Beads, H20, C, Conduc
carbon black such as tex 975, 900, SC (Colombyan Carbon Japan Co., Ltd.), B
S-605, 607 (above, manufactured by Toyo Aluminum Co., Ltd.),
Bronze powder P-555, P-777 (Nakajima Metal Foil Industry Co., Ltd.), bronze powder 3L5, 3L7 (Fukuda Metal Foil Industry Co., Ltd.) and other metal powder pigments, or black Inorganic pigments such as iron oxide, low order titanium oxide, yellow iron oxide, red iron oxide, ultramarine blue, navy blue, cobalt blue, chrome green, and chrome oxide, Hansa A-1
0G, 5G, 3G, 4, GR, A, benzidine yellow, permanent yellow NCG, tartrazine lake, quinoline yellow, sudan 1, permanent orange, indanthrene brilliant orange GN, permanent brown FG. , Para Brown, Permanent Red 4R, Fire Red, Brilliant Carmine B
Organic pigments such as S, pyrazolone red, lake red C, quinacridone red, brilliant carmine 6B, bordeaux 5B, thioindigo red, fast violet B, dioxane violet, alkaline blue lake, phthalocyanine blue, indigo, acid green lake, phthalocyanine green Is mentioned. In addition to these, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, and calcium tungstate can be cited.

In the case of a water-based ink, water is used as a main solvent, and in addition, a water-soluble organic solvent such as ethylene glycol, glycerin or propylene glycol may be used to prevent the nib from drying. For oil-based inks, ethylene glycol, diethylene glycol, glycerin, ethylene glycol monophenyl ether,
Benzyl alcohol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, hexylene glycol, tetralin, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene Glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and the like can be mentioned, and these may be mixed or used by mixing two or more kinds.

In the case of a hydrocarbon solvent, an aliphatic hydrocarbon solvent such as normal hexane (boiling point 68.7 ° C.), isopentane, normal heptane (boiling point 98.4 ° C.), normal octane, cyclopentane (boiling point 49.2). ° C), methylcyclopentane (boiling point 71.8 ° C), cyclohexane (boiling point 80.0 ° C), methylcyclohexane (boiling point 1
00.9 ° C), ethylcyclohexane (boiling point 132 ° C)
Other than alicyclic hydrocarbon solvents such as Exol DSP 1
00/140 (initial boiling point 102 ℃, dry point 138 ℃), D
30 (initial boiling point 141 ° C, 172 ° C), the same D40 (initial boiling point 153 ° C, dry point 196 ° C), the same D80 (initial boiling point 204
℃, dry point 230 ℃), the same D110 (initial boiling point 243 ℃, end point 272 ℃), the same D130 (initial boiling point 277 ℃, end point 31)
0 ° C), Isopar C (initial boiling point 97 ° C, dry point 104)
℃), the same E (initial boiling point 115 ℃, dry point 138 ℃), the same G
(Initial boiling point 156 ° C, dry point 175 ° C, same H (initial boiling point 176 ° C
℃, dry point 192 ℃), same L (initial boiling point 188 ℃, dry point 21
0 ° C.), the same M (initial boiling point 208 ° C., dry point 254 ° C.) (all manufactured by Exxon Chemical Co., Ltd.) and the like, and mixtures of aliphatic hydrocarbon solvents. These can be used alone or as a mixture, and the amount used is 3 with respect to the total amount of ink.
0 to 95% by weight is preferred.

In addition to the above components, in the case of water-based inks, ammonium salts of styrene-acrylic acid copolymers and α-methylstyrene-acryl are used in order to improve the fixability on the writing surface of paper, glass and the like. A water-soluble resin such as an ammonium salt of an acid copolymer can be used. Further, a water-insoluble resin such as an acrylic resin, a vinyl acetate resin, or a styrene-butadiene resin copolymer can also be used.
The water-insoluble resin is used in the form of emulsion.

In the case of an oil-based ink using an alcohol-based and / or glycol-based solvent, ketone resin, xylene resin, polyethylene oxide, rosin resin, terpene resin, coumarone-indene resin, polyvinyl butyral, polyvinyl pyrrolidone and the like can be mentioned.

When a hydrocarbon-based solvent is used, for example,
Teslac 2158-100 (Hitachi Polymer Ltd.)
), Phthalkid DX615 (50 wt% xylene solution, manufactured by Hitachi Chemical Co., Ltd.) and other alkyd resins, acrylic resin such as Acryloid B66 and B67 (manufactured by Rohm and Haas, UK), Califlex TR-110.
7 (manufactured by Shell Chemical Co., Ltd.), Tufrene A, Asaprene T-431 (manufactured by Asahi Chemical Industry Co., Ltd.) and other styrene elastomers, Sumitate RB-11 (manufactured by Sumitomo Chemical Co., Ltd.), Evaflex Examples thereof include ethylene / vinyl acetate copolymers such as 150 (manufactured by Mitsui Polychemical Co., Ltd.). Considering the fixability and coatability, the amount used is preferably 1 to 20% by weight with respect to the entire ink.

Further, in order to adjust the viscosity, in the case of aqueous ink, guar gum, hydroxypropylated guar gum, carboxymethyl hydroxypropylated guar gum, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum,
Welan gum, rumzan gum, gellan gum, alginic acid, sodium alginate, ammonium alginate, potassium alginate, propylene glycol alginate, locust bean gum, tamarind gum, gum arabic, tragacanth gum, karaya gum, carrageenan, water-soluble polysaccharides such as succinoglucan, polyacrylic Acid, polyvinyl alcohol, polyethylene oxide,
Synthetic polymers such as polyvinylpyrrolidone and N-vinylacetamide co-crosslinked products, and viscosity minerals such as smectite are added. These can be used alone or in combination of two or more. In the case of ink using a hydrocarbon solvent,
Disparlon A670-2 consisting of fatty acid amide
0M (active ingredient 20%), 6900-20X (effectiveness 20%) (manufactured by Kusumoto Kasei Co., Ltd.), Aerosil R972, R974, and 200 (manufactured by Nippon Aerosil Co., Ltd.) made of fine particle silica are used. it can.

Further, for the stability of pigment dispersion, anionic surfactants such as alkyl sulfate ester salts, alkyl phosphate salts and polycarboxylic acid polymers, polyethylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene fatty acid esters. Dispersants such as nonionic surfactants, quaternary ammonium salts, alkylamine salts and the like can be added.

When the coloring agent is titanium oxide having a high hiding property and the solvent is a volatile solvent having a low polar hydrocarbon and a boiling point of 40 to 150 ° C., it can be used as a correction liquid.

The ink is obtained by dispersing and mixing the above components using a stirring and dispersing machine such as a ball mill, an attritor, a sand grinder or an impeller.

The backflow preventing agent moves following the movement of the ink interface due to ink consumption, and may prevent backflow of the ink and prevent adhesion of the ink to the inner surface of the ink tank. . As the base material, a solvent which is not compatible with the ink or hardly compatible with the ink is used. In the case of an aqueous ink or an oil-based ink using an alcohol-based or glycol-based solvent, specifically, Mobil SHF21 (40 ° C. kinematic viscosity 5.2 cSt) and ibid 41 (4
0 ° C kinematic viscosity 17.5 cSt), the same 61 (40 ° C kinematic viscosity 2
8.8 cSt), 82 (40 ° C. kinematic viscosity 47.6 cS)
t), the same 401 (40 ° C kinematic viscosity 420 cSt), the same 10
03 (40 ° C kinematic viscosity 1374 cSt) (above, Mobil Chemical Products International Inc.), polybutene LV-7 (40 ° C kinematic viscosity 11 cS)
t), LV-10 (40 ° C kinematic viscosity 19 cSt), LV-
25 (40 ° C kinematic viscosity 52.5 cSt), LV-50 (4
0 ° C kinematic viscosity 110cSt), LV-100 (40 ° C kinematic viscosity 205cSt), HV-15 (40 ° C kinematic viscosity 655c)
St), HV-35 (40 ° C. kinematic viscosity 2300 cSt),
HV-50 (40 ° C kinematic viscosity 3450 cSt), HV-1
00 (40 ° C kinematic viscosity 9500 cSt), HV-300
(40 ° C kinematic viscosity 26000 cSt), HV-1900
(Kinematic viscosity at 40 ° C (above, manufactured by Nippon Oil Co., Ltd.), ethylene-
Lucant HC-10 (40 ° C kinematic viscosity 60 cSt) consisting of α-olefin, HC-20 (40 ° C kinematic viscosity 155)
cSt), the same HC-40 (40 ° C kinematic viscosity 380 cS
t), the same HC-100 (40 ° C kinematic viscosity 1300 cS
t), the same HC-150 (40 ° C kinematic viscosity 2200 cS
t), the same HC-600 (Kinematic viscosity at 40 ° C. 9850 cS
t), HC-2000 (40 ° C kinematic viscosity 37500 cS
t) (above, manufactured by Mitsui Petrochemical Co., Ltd.), liquid paraffin, silicone oil, or other low-polarity nonvolatile or hardly volatile solvent can be used, and these can be used alone or in combination. . In the case of an ink using a hydrocarbon solvent having a low polarity, a solvent having a high polarity is used.
Specifically, in addition to water, ethylene glycol, propylene glycol, glycerin, glycerin monoacetate, diethylene glycol, tetraethylene glycol, trimethylolethane, trimethylolpropane, 1,3-butanediol, which is a highly polar polyhydric alcohol, 1,4-butanediol, 1,4-butenediol, polypropylene glycol, polyethylene glycol and the like can be used. These can be used alone or in combination.

Aerosil R972 and R974 made of fine particle silica when a low-polarity solvent is used for a water-based ink and an oil-based ink using an alcohol-based or glycol-based solvent as a viscosity modifier of the backflow preventive agent. Same 20
0 (manufactured by Nippon Aerosil Co., Ltd.), Disparlon A670-20M and 6900-20X made of fatty acid amide
(Above, Kusumoto Kasei Co., Ltd.) and the like can be used, and when a highly polar solvent is used as the substrate, guar gum, hydroxypropylated guar gum, carboxymethylhydroxypropylated guar gum, carboxymethyl cellulose,
Hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum, welan gum, ramzan gum, gellan gum, alginic acid, sodium alginate, ammonium alginate, potassium alginate, propylene glycol alginate ester, locust bean gum, tamarind gum, gum arabic, tragacanth gum, karaya gum, carrageenan, succinoglucan. Water-soluble polysaccharides such as polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone,
Synthetic polymers such as N-vinylacetamide co-crosslinked products, viscous minerals such as smectite, etc. can be added,
These can be used alone or in combination of two or more.

Further, in the backflow preventive agent using a highly polar solvent, a surfactant can be used to further prevent the ink from adhering to the ink tank.
Anionic, cationic, and fluorine-based surfactants can be used. Specific examples of the nonionic surfactant include polyoxyethylene glycerin fatty acid esters such as polyoxyethylene (5-15) glyceryl monostearate and polyoxyethylene monooleate (5-15), hexaglyceryl monolaurate, mono Hexaglyceryl myristate, Hexaglyceryl monostearate, Monooleic acid, Decaglyceryl monolaurate, Decaglyceryl monomyristate, Decaglyceryl monostearate, Decaglyceryl monooleate, Decaglyceryl monoisostearate, Decaglyceryl monoisostearate, Polyglycerin fatty acid ester such as decaglyceryl diisostearate and decaglyceryl trioleate,
Monococonut oil fatty acid polyoxyethylene (20) sorbitan, monopalmitate polyoxyethylene (20) sorbitan, monostearate polyoxyethylene (20)
Sorbitan, polyoxyethylene monooleate (2
0) Polyoxyethylene such as sorbitan and polyoxyethylene monoisostearate (20) sorbitan, fatty acid ester of sorbitan, polyoxyethylene monolaurate (6) sorbit, polyoxyethylene such as polyoxyethylene tetrastearate (30 to 60) sorbit Sorbit fatty acid ester, polyoxyethylene (2
Castor oil, polyoxyethylene (20-10)
0) Polyoxyethylene castor oil and other polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene (5-30) phytosterols, polyoxyethylene (25) phytostanol, polyoxyethylene (30) cholestanol and other polyoxyethylene sterols -Polyethylene glycol fatty acid ester such as hydrogenated sterol polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene (4.2-25) lauryl ether, polyoxyethylene ( 2-40) cetyl ether, polyoxyethylene (2-20) stearyl ether, polyoxyethylene (10-50) oleyl ether, polyoxyethylene (10-3) ) Polyoxyethylene alkyl ethers such as behenyl ether, polyoxyethylene (7.
5-20) Nonyl phenyl ether, polyoxyethylene (10-30) octyl phenyl ether, and other polyoxyethylene alkyl phenyl ethers, polyoxyethylene (5-15) stearylamine, polyoxyethylene (5-15) oleylamine, poly Polyoxyethylene alkylamine / fatty acid amides such as oxyethylene (8) stearyl propylene diamine, polyoxyethylene (4 to 15) stearic acid amide, polyoxyethylene (5) oleic acid amide, polyoxyethylene lanolin, polyoxyethylene ( 5-40) lanolin alcohol, N-propyl-N- (2-hydroxyethyl) perfluorooctane sulfonamide, polyoxyethylene higher fatty acid alcohol ether, acetylene glycol (Surfino 465, the 485, Shin-Etsu Chemical Co., Ltd.
Manufactured), polyoxyethylene (3 to 20) -N-propylperfluorooctanesulfonamide, and other fluorine-based surfactants. Specific examples of the anionic surfactant, sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, alkyl sulfates such as hydrogenated coconut oil fatty acid glyceryl sodium sulfate, poly Oxyethylene (2-4)
Sodium lauryl ether sulfate, polyoxyethylene (2-4) triethanolamine lauryl ether sulfate, polyoxyethylene (2) ammonium lauryl ether sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, cocoyl sarcosine N-acyl amino acid salts such as sodium, sodium lauroyl sarcosine, potassium lauroyl sarcosine, sodium myristoyl sarcosine, sodium palmitoyl sarcosine, sodium lauroyl methylalanine, sodium polyoxyethylene (3-6) tridecyl ether acetate, polyoxyethylene (4. 5) Alkyl ether carboxylic acid salts such as sodium lauryl ether acetate; Berlin salts, polyoxyethylene (1) polyoxyethylene alkyl ether salts such as lauryl ether phosphoric acid salts, N- methyl cocoyl taurate, sodium, N- lauroyl methyl taurate, sodium,
N-acyl taurine salts such as N-myristoyl methyl taurine sodium, N-palmitoyl methyl taurine sodium and N-stearoyl methyl taurine sodium,
Sulfonates such as dioctyl sodium sulfosuccinate, sodium lauryl sulfoacetate, sodium tetradecene sulfonate, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl trimethyl ammonium chloride, alkyl Ammonium salts, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, perfluorooctane sulfonic acid, potassium perfluorooctane sulfonate, lithium perfluorooctane sulfonate, ammonium perfluorooctane sulfonate, N-propyl-N-perfluorooctylsulfonylglycine potassium salt , Bis [2- (N-
Propylperfluorooctylsulfonylamino) ethyl] ammonium salt, perfluorocaprylic acid, ammonium perfluorooctanoate, and other fluorosurfactants,
Examples thereof include sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulphonate, potassium alkyl phosphate and the like. Specific examples of the cationic surfactant include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride,
Examples thereof include alkylammonium salts such as distearyldimethylammonium chloride and fluorine-based surfactants such as N- [3- (perfluorooctanesulfonamido) propyl] -N, N, N, -trimethylammonium iodide. Specific examples of the amphoteric surfactant include betaine-type amphoteric surfactants such as lauryl betaine, stearyl betaine, and coconut oil fatty acid aminopropyldimethylaminoacetic acid betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine. Sodium, N-coconut oil fatty acid acyl-N-carboxymethyl-
Examples include imidazoline-type amphoteric surfactants such as N-hydroxyethylethylenediamine and sodium lauryl sulfate. In the above, the number in parentheses indicates the number of moles of ethylene oxide added.

When water is used as a solvent, antiseptic and mildew-proofing agents such as sodium dehydroacetate, 1,2-benzothiazolin-3-one and sodium benzoate are used to prevent the generation of mold of the anti-reflux agent. You can add an appropriate amount.
In addition, in the case of a material that easily evaporates, such as water, in order to suppress evaporation, non-volatile and / or insoluble and / or insoluble materials in the base material are used.
Alternatively, a hardly volatile organic solvent, or a solvent in which viscosity is adjusted, synthetic rubber or elastomer having rubber elasticity,
It is also possible to use a molded article such as plastic as an anti-drying agent by arranging it at the interface of the anti-reflux agent and using it together. When a liquid composition is used as the anti-drying agent, polybutene, α-olefin, ethylene-α-olefin, liquid paraffin, etc. can be used as the organic solvent, and they can be used alone or in combination of two or more, and can be used for viscosity adjustment. For the Aerosil R
972, R974 (manufactured by Nippon Aerosil Co., Ltd.) and other fine particle silica, Disparlon 305 (Kusumoto Kasei Co., Ltd.)
Hydrogenated castor oil-based products, such as Soloid (Sansei Co., Ltd.)
Cellulose-based products such as those manufactured by K.K.), metal soaps, bentonite, and the like can be used alone or in admixture of two or more. Further, it is also possible to use an anti-drying agent for a solid molded article and an anti-drying agent for a liquid composition in combination.

In any case, it is necessary that the backflow preventive agent has a complex elastic modulus of 50 to 800 Pa.
The complex elastic modulus referred to herein is an amplitude generated when a shear stress of 5 Pa is applied to the anti-reflux agent at a frequency of 1 Hz, and is a value obtained by dividing the amplitude by the amplitude of the shear stress. The anti-reflux agent having a larger complex elastic modulus has a larger resistance to impact such as falling and requires a larger centrifugal force to remove bubbles.

Further, in order to ensure the backflow preventing function of the backflow preventing agent, and to enhance the drying preventing function and the backflow preventing function of the liquid composition, the drying preventing agent is positioned inside the backflow preventing agent. It is also possible to arrange such a float. This float can be arranged in each of the anti-reflux agent and the anti-drying agent prepared as a liquid composition, or only one of them,
It is also possible to have a common float on both. When a solid anti-drying agent is used, the tip portion of the anti-drying agent can be positioned inside the anti-reflux agent to provide the function of the float. As the shape of the float,
Examples thereof include a cylindrical shape, a ball shape, a disk shape, a polygonal column shape, and a cup shape.

[0026]

The anti-reflux agent according to the present invention can be provided with impact resistance by adjusting the complex elastic modulus. The complex elastic modulus here is a value that indicates whether or not the original state tends to return to its original state even if it deforms due to an external force.For example, the backflow preventer is momentarily deformed when the applicator is impacted by falling. Also, it can quickly return to its original shape and prevent ink leakage. In addition, the bubbles can be removed by a centrifugal force that does not cause the pigment to settle and become unreadable.

[0027]

EXAMPLES The present invention will be described in detail below based on examples. Ink 1 TITON R62N (titanium oxide, manufactured by Sakai Chemical Industry Co., Ltd.) 55. 0 parts by weight Acryloid B67 (acrylic resin, manufactured by Rohm and Haas Co.) 9.0 parts by weight methylcyclohexane 35.0 parts by weight Homogenol L18 (polycarboxylic acid type polymer surfactant, manufactured by Kao Corporation) 1.0 parts by weight Parts The above components were dispersed in a ball mill for 24 hours to obtain a white ink.

Ink 2 TITON R62N (described above) 25.0 parts by weight TAROX LL-XLO (yellow iron oxide, manufactured by Titanium Industry Co., Ltd.) 25. 0 parts by weight Acryloid B67 (described above) 5.0 parts by weight ethylcyclohexane 44.0 parts by weight Homogenol L18 (described above) 1.0 parts by weight The above components were dispersed in a ball mill for 24 hours to obtain a yellow ink.

Ink 3 TITANIX JR301 (titanium oxide, manufactured by Teika Co., Ltd.) 30.0 parts by weight LUMIKOL NKW2018 (blue resin particles, solid content 53%, manufactured by Nippon Fluorescence Co., Ltd.) 15.0 parts by weight John Cryl 61J ( Water-soluble styrene-acrylic copolymer, solid content 30%, manufactured by Johnson Polymer Co., Ltd. 8.0 parts by weight ethylene glycol 5.0 parts by weight glycerin 5.0 parts by weight Kelzan AR 6% aqueous solution (xanthan gum, Sansho (stock) )) 8.0 parts by weight water 29.0 parts by weight Among the above components, each component other than LUMIKOL NKW2108 Kelzan AR 6% aqueous solution is crushed and subjected to a dispersion treatment with a ball mill for 24 hours, and then LUMIKOL21.
08, Kerzan AR 6% aqueous solution was added and stirred for 1 hour to obtain a light blue ink.

Anti-reflux agent 1 Kelzan T (xanthan gum, manufactured by Sansei Co., Ltd.) 4.0 parts by weight water 94.8 parts by weight sodium sulfite 1.0 part by weight Proxel GXL (1,2-benzothiazoline-3one, ICI) Made in England) 0.2 parts by weight The above components were mixed and dissolved by a propeller stirrer to obtain a backflow preventive agent having a complex elastic modulus of 380 Pa.

Anti-reflux agent 2 Kelzan XLC (xanthan gum, manufactured by Sansho Co., Ltd.) 2.0 parts by weight water 97.8 parts by weight Proxel GXL (previously described) 0.2 parts by weight The above components were mixed by a propeller stirrer, It melt | dissolved and the backflow preventive agent of 90 Pa of complex elastic modulus was obtained.

Anti-reflux agent 3 Kelzan T (described above) 3.0 parts by weight water 94.8 parts by weight Emulgen 709 (polyoxyethylene higher alcohol ether, manufactured by Kao Corporation) 2.0 parts by weight Proxel GX L (described above) 0.2 parts by weight The above components were mixed and dispersed by a propeller stirrer to obtain a backflow preventive agent having a complex elastic modulus of 220 Pa.

Anti-reflux agent 4 Smecton SA (Synthetic smectite, manufactured by Kunimine Industries Co., Ltd.) 7.0 parts by weight water 82.8 parts by weight glycerin 10.0 parts by weight Proxel GXL (previously described) 0.2 parts by weight Each of the above components Were mixed and dispersed with a propeller stirrer to obtain a backflow preventive agent having a complex elastic modulus of 400 Pa.

Anti-reflux agent 5 Kelzan T (described above) 5.0 parts by weight water 93.8 parts by weight Neoperex No. 6 (sodium dodecylbenzenesulfonate, manufactured by Kao Co., Ltd.) 1.0 part by weight Proxel GXL (previously described) 0.2 part by weight The above components are mixed and dissolved by a propeller-type stirrer to prevent a backflow of a complex elastic modulus of 500 Pa. I got an agent.

Anti-reflux agent 6 Kelzan T (described above) 7.0 parts by weight Water 92.8 parts by weight Proxel GXL (described above) 0.2 parts by weight The above components were mixed and dissolved by a propeller stirrer to obtain a complex elastic modulus. A backflow inhibitor of 800 Pa was obtained.

Anti-reflux agent 7 Jaguar HP60 (hydroxypropylated guar gum, manufactured by Sansei Co., Ltd.) 2. 5 parts by weight Water 97.3 parts by weight Proxel GXL (previously described) 0.2 parts by weight The above components were mixed and dissolved by a propeller-type stirrer to obtain a backflow preventive agent having a complex elastic modulus of 30 Pa.

Anti-reflux agent 8 Kelzan XLC (above) 10.0 parts by weight water 89.8 parts by weight Proxel GXL (above) 0.2 parts by weight The above components were mixed and dissolved with a propeller stirrer to obtain a complex elastic modulus. A backflow preventive agent of 1000 Pa was obtained.

[0038] Anti-reflux agent 9 Polybutene HV15 (Polybutene, manufactured by Nippon Oil Co., Ltd.) 46.5 parts by weight Mobil SHF1003 (α-olefin oligomer, Mobil Chemical, USA Product ink) 46.5 parts by weight Aerosil R972 (dry process silica, manufactured by Nippon Aerosil Co., Ltd.)                                             4.0 parts by weight Leopard KL (dextrin fatty acid ester, Chiba Flour Milling Co., Ltd.)                                             2.0 parts by weight of each of the above components 14 A complex elastic modulus of 100 Pa backflow preventive agent was obtained by mixing and stirring at 0 to 150 ° C. for 2 hours. .

Anti-drying substance Polybutene HV15 (described above) 91.0 parts by weight Aerosil R972 (described above) 5.4 parts by weight Leopard KL (described above) 3.6 parts by weight The above components are mixed at 140 to 150 ° C. for 2 hours. The mixture was stirred to obtain an anti-drying substance.

An example of the structure of an applicator suitable for accommodating and arranging the ink and the backflow preventive will be described with reference to the drawings. As a structure common to those illustrated in FIGS. 1 and 2, a ball-point pen tip type coating unit 3 including a ball 1 (material: super hard) having a diameter of 1.0 mm and a stainless steel ball holder 2 has a cylindrical ink having an inner diameter of 3 mm. It is attached to the tank 4. An ink C and a backflow preventive agent G are filled in such an applicator structure. Since the anti-reflux agent G'using water that easily dries is used, the one shown in FIG. 2 is further filled with the anti-drying agent K to obtain an applicator. For inks 1 and 2 using a hydrocarbon-based solvent, backflow preventives 1 to 8 using water and polyhydric alcohol having a large polarity, and ink 3 using water as a main solvent, use a low polarity solvent. It carried out by the combination of the anti-reflux agent 9 used. Table 1 shows the relationship among each ink, the backflow preventive agent, the material of the ink tank, and the structure of the applicator.

[0041]

The above-mentioned applicator structure was combined with and accommodated in the ink and the backflow preventive agent, respectively, to obtain Examples and Comparative Examples. The following tests were conducted on these examples and comparative examples. The results are shown in Table 1.

Measurement of complex elastic modulus of anti-reflux agent Measuring conditions Measuring device: CVO rheometer (BOHLIN INST
(Manufactured by RUMENTS) Temperature: 25 ° C. Shear stress: 5 Pa Frequency: 1 Hz Rotor: φ40 mm, 4 ° Cone plate The complex elastic modulus was measured under the above measurement conditions.

Reverse Flow Reversal Agent Reversal Test The applicator of each Example and Comparative Example was allowed to stand with the pen tip facing upward at 50 ° C. for one month, and it was confirmed whether or not the back flow inhibitor moved toward the pen tip.

Drop Test The applicator of each Example and Comparative Example was placed with the pen tip facing upward at 50c.
m, 100 cm, 150 cm, 200 cm, 250 cm
The drop height was measured when the backflow preventer leaked from the rear end of the ink tank.

Defoaming Test The applicators of Examples and Comparative Examples were subjected to centrifugal treatment under a plurality of conditions shown below with varying degrees of centrifugal force, and visually checked for the presence or absence of air bubbles in the anti-reflux agent. It was confirmed that the ink was ejected by handwriting the minimum number of revolutions in which bubbles were removed and the applicator from which bubbles were removed at that number of revolutions.

Centrifugal conditions 1000 rpm × 10 minutes 2000 rpm × 10 minutes 3000 rpm × 10 minutes 4000 rpm × 10 minutes 5000 rpm × 10 minutes Centrifuge used: KOKUSAN H103N (manufactured by Kokusan Co., Ltd.)

[0047]

[Table 1]

As described above in detail, in the applicator of the present invention, it is difficult for the ink to flow back, and the reverse flow phenomenon of the backflow preventive agent and the backflow preventive agent and the ink due to impact move backward to leak out. Even in the centrifugal step for removing air bubbles, the air bubbles can be removed under the condition that the pigment does not settle, which is extremely good.

[Brief description of drawings]

FIG. 1 is an enlarged vertical sectional view of an essential part showing an example.

FIG. 2 is an enlarged vertical sectional view of a main part showing another example.

[Explanation of symbols]

1 ball 2 ball holder 3 coating section 4 ink tank C ink G anti-reflux agent K anti-drying agent

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2C350 GA03 GA04 KC02 KC11 KF03                       NA10 NA11 NC20                 4J039 BA04 BA12 BA13 BA35 BC01                       BE01 BE02 BE12 CA03 CA06                       GA26 GA27

Claims (3)

[Claims] 1. A complex elasticity of the anti-reflux agent composition in an applicator in which the ink anti-reflux agent composition is placed in contact with the interface on the opposite side of the ink discharge destination, which is accommodated in a container in a free state. An applicator whose rate is 50 Pa · s or more and 800 Pa · s (temperature 25 ° C, shear stress 5 Pa, frequency 1 Hz). 2. The ink comprises at least a colorant and a hydrocarbon solvent, and the backflow preventing composition comprises an organic solvent and / or water insoluble or hardly soluble in the hydrocarbon solvent of the ink and a viscosity modifier. The applicator according to claim 1, comprising at least 3. The applicator according to claim 1, wherein the antireflux agent composition contains at least water and xanthan gum.