JP2001214116A - Oil based ink composition for writing utensils - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil based ink composition for writing utensils or the like which smoothly comes out upon starting writing to reduce the so-called blurring at initial writing even when a pigment is used as the colorant. SOLUTION: In the oil based ink composition for writing utensils containing at least a colorant, an organic solvent, and a resin, the composition contains a perfluoropolyether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-based ink composition for a writing instrument, and more particularly to an oil-based ink composition for a writing instrument such as a ball-point pen, which is capable of smoothly discharging ink at the start of writing and has little so-called initial brushing. And particularly effective for oil-based ink compositions for ballpoint pens containing a pigment as a coloring agent.

[0002]

2. Description of the Related Art Conventionally, oil-based inks for writing implements, that is, ink compositions for ballpoint pens, etc. are prepared by preparing a colorant, a solvent such as glycols or high-boiling alcohol, a ketone resin, a xylene resin, a rosin-derived resin, or a polymer resin. As a viscosity modifier such as polyvinyl pyrrolidone and polyvinyl butyral. Conventionally, fatty acids such as oleic acid have been blended into oil-based ballpoint pen ink compositions and the like in order to make writing ink smooth and to obtain a smooth writing feel. However, these fatty acids such as oleic acid corrode the metal used for the pen tip of the ball-point pen and produce corrosion products, or deteriorate over time due to moisture entering from the pen tip or the like. As a result, there is a defect that the smoothness of the writing is lost, that is, the so-called first brush blur deteriorates with time.
Furthermore, when a pigment is contained as a coloring agent, there is a disadvantage that the ink does not smoothly come out at the start of writing with only oleic acid.

[0003]

DISCLOSURE OF THE INVENTION The present invention suppresses the deterioration of the first brush fading with time, such as that observed in fatty acids such as oleic acid, and enables writing even when a pigment is used as a coloring agent. An object of the present invention is to provide an oil-based ink composition for writing implements in which the ink is smoothly discharged at the beginning, and which has little so-called first brush fading.

[0004]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems, and as a result, have found a component effective for preventing the first brush from being blurred, and have completed the present invention. That is, the gist of the present invention is an oil-based ink composition for writing implements, characterized in that a composition comprising at least a colorant, an organic solvent and a resin contains perfluoropolyether.

[0005]

Embodiments of the present invention will be described below in detail. As the coloring agent, oil-soluble dyes conventionally used in oil-based ink compositions can be mainly used. First, as the oil-soluble dye, Taoka Dye Manufacturing Co., Ltd.
RhodamineB Base (CISolventRed49), Chugai Kasei Co., Ltd.
Soldan Red3R (CISolventRed18), National Anili
ne Div MethylViolet2BBase (CISolventViolet8),
VictoriaBlueF4R (CISolventBlue2) manufactured by BASF, NIGRO
SINE BASE LK (CISolvent Black 5), VALIFASTYELLOW3104 (CISolventYellow19) of Orient Chemical Co., Ltd.,
VALIFAST YELLOW 3105 (CISolvent Yellow 21), SPIRI
T BLACK AB (CISolvent Black 5), VALIOFAST BLACK 38
04 (CISolvent Black 34), VALIFAST YELLOW1109, VAL
IFAST ORANGE 2210, VALIFAST RED 1320, VALIFAST BLU
E 1605, VALIFAST VIOLET 1701, Hodogaya Chemical Industry Co., Ltd.
Spilon Black GMH special (CISolvent Black 4
3), Spilon Yellow C-2GH, Spilon Yellow C-GNH, Spil
on Red C-GH, Spilon Red C-BH, Spilon Blue BPNH, S.
BNBlue 701, Spilon BlueC-RH, Spilon Violet C-RH,
SPTOrange-6 and SPTBlue-111 can be exemplified.

Among the pigments, various black pigments can be used as a pigment as a black colorant. As carbon black, for example, Regal 415R, Regal 250 manufactured by Cabot Co.
R, Regal 400R, Mogul L, Monarch 460, Monarch 880,
Monarch 1000, Printex 25, Printex 3 from Degussa
0, Printex 35 Printex 40, Printex 45, Printex 55, P
rintex 75, Printex 80, Printex 85, Printex 90, Spe
cial Black 100, Special Black 250, Special Black 3
50, Special Black 550, Color Black FW 1, Color Bla
ck FW 200, manufactured by Mitsubishi Chemical Corporation, # 30, # 32, # 33, # 40,
# 44, # 45, # 52, # 45L, # 50, # 900, # 970, # 1000, # 2300,
2350, MA7, MA8, MA11, MA100, MCF88, Columbian Carbon RAVEN 11, RAVEN 15, RAVEN 35, RAVE
N 40, RAVEN 50, RAVEN 150, PEERLESS, PEERLESS155, P
EERLESS MARK II, NEO SPECTRA MARK II, NEPSPECTRA A
There are pigments such as G.

Various blue pigments can be used as a pigment as a blue colorant. For example, CI Pigment Blue 1
5, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 28, 29, 3
6, CI Pigment Blue 60, etc., which may be surface-treated with a surfactant or the like at the stage of pigment production. Particularly specific examples of blue pigments include GraphhtolBlue 2GLS, Sandorin Blue RL and Sandorin manufactured by Clariant.
Blue 91052, Lutetiacyanine CSN from ICI, Palomar Blue B4806, Palomar Blue B4707, Worlee from Mobay
Endurophthal Blue BT-788D, Cappelle P
htalocyanine Blue RS1517C, Heliogen Blue from BASF
L6920, Heliogen Blue L6875F, Heliogen Blue 6901F,
Heliogen Blue L6905F, Heliogen Blue L6975F, Helio
gen Blue6989F, Heliogen Blue L7072D, Heliogen Blue
L7080, Heliogen Blue L7101F, Heliogen Blue L6700F,
Monastral Blue FBN, Monastral Blue C manufactured by Zeneca
SN, Monastral Blue FNX, Mondite Blue RL, Francolor
CatuliaCyanineL.PS, CyanineBl from WooSung
ueA-1700, CyanineBlueB-7000, CyanineBlueB-7800, Cy
anineBlueB-7800, CyanineBlueB-8000, Sunf from Sun
astBlue249-1282,

[0008] Catulia Cyanine L. JS, H manufactured by Francolor
oechst Hostaperm Blue BLF, Renol Blue A2RE,
Irgalite Blue GLNF, Irgalite Blu manufactured by CibaGeigy
e GLVD, Irgazin Blue ATC, Sovereig from Shepherd
n Blue 385, Holland Blue 212, Kingfisher Blue 211,
Kingfisher Blue 211, Olympic Blue 190, Luh
UltramarineBlue, BlueEP37, Ch made by DaiColor Italy
romofineBlue 4920, Endurophtal Blue B from Worlee
T-729D, Heucosin Blue G1737, Heucos manufactured by Heubach
in Blue HS-5000, Lackecht Blue G1737, Kenalake LFBRX, CibaSpecialty Chemicals
CROMOPHTAL Blue A3R, MICROLITH Blue4G-WA, CibaGei
gy's MICROLITH Blue 4G-A, Dainichi Seika Kogyo's Chromofine Blue4930, Chromofine Blue 5188, Chrom
ofine Blue SR5020, manufactured by Dainippon Ink and Chemicals, Inc.
Fastogen Blue 5030L, Fastogen Blue 5420SD, Fastoge
nBlue 5502, Fastogen Blue TGR-F, Fastogen Blue EP-
7, Cyanine Blue G-134, Cyanine B manufactured by Sanyo Pigment Co., Ltd.
There are pigments such as lue SAS, Cyanine Blue KRS and Cyanine Blue 4033.

As a pigment as a red colorant, various red pigments can be used. For example, CI Pigment Red
17, 144, 166, 170, 177, 202, 214, 220, 254, etc., and may be surface-treated with a surfactant or the like at the pigment production stage. A specific commercial name is Cro from CibaSpecialty Chemicals.
mophtal DPP Red BO, Cromophtal DPP Red Bp, Cromoph
talRed DPP, Irgazin DPP Red BO, Irgazin DPP Red BT
R, Cromophtal Red A2B, Cromophtal Red A3B, Cromoph
tal ScarletR, Cromophtal Scarlet RN, Cromophtal Re
d BR, Cromophtal Red BRN, Cinquasia Magenta B-RT 3
43D, Cinquasia Magenta RT235D, Cinquasia Magenta R
T 343D, Cinquasia Magenta TR235-6, Dainichi Fast Poppy Red G, Dainichi Fast manufactured by Dainichi Seika Kogyo Co., Ltd.
Poppy Red R, Bayer Bayferrox Red 110M, Bayf
errox Red 120MN, Bayferrox Red 130M, Toluidine Red GO335C, Toluidine Red RNO333C, Bon from Cappelle
itol Red BM, Bonitol Red4844C, LysopacRed 4841C, C
appoxyt Red 4435B, Cappoxyt Red 4437B, Mineral Ora
nge Thiosol GL, Mineral Orange Thiosol G, Mineral
Orange SolipurGH, Mineral Red Solipur 3BH, Lysopac
Red 7030C, Coppers Red R9998 from Harcos, Sicored L3750, Lithol Scharlach L4301, Litholec from BASF
htmaroon L4763, Sicoflush-P-Maroon4763, Paliogen R
ed Violet L5080, Sicotrans RedL2817, SicominRedL30
25, Sicomin Red L3230S, SicoFast Scarlet L4252, He
ubach Heucotron Red230, Paliogen Red3880HD, Pa
liogen MarronL3920, Paliogen RedL4210, Ciba-Geigy
"HornaMolybdator.MLN-74-SQ", "HornaMolybdator"
MLH740Q "," IrgliteRed3RS ", WooSung ToluidineRe
dL, ToluidineRedK, BonRedSR, BonRed3M, BonRedMP, F
astBordeauxC, LakeRedC500, LakeRedC900, FastRedFG
R, ChromophtalRedA2B, ChromophtalRedA3B, NovopermRedVioletMRSnew, PermanentBordeaux FGR, manufactured by Hoechst
PermanentRedFGR70, HostapermRosaE, Novoperm Reel F
3RK70, QuindoMagentaRV6832 from Miles, BayerMobay
PerrindoMaroonR6422, Sandoz GraphhtolRed
There are pigments such as 5BLS.

Various yellow pigments can be used as a pigment as a yellow colorant. For example, CI Pigment Yell
ow 1, 3, 12, 13, 14, 16, 17, 55, 81, 83, 74, 93, 9
4, 95, 97, 109, 110, 120, 128, 138, 147, 154, 155,
167, 185, 191 and the like, and may be surface-treated with a surfactant or the like in the pigment production stage. A specific example is Palliotol Yellow 21 manufactured by BASF.
40HD, Sicopal YellowL1110, Sicopal YellowL1100, Si
cotan Yellow L1912, Sicomin Yellow L1622, Sicomin Y
ellow L1630S, Sicomin Yellow L1635S, Sicotrans Ywl
low L1916, Sico Yellow 1252HD, Paliogen Yellow L14
82, Paliogen Yellow L1560, PaliotolYellow D1155, P
aliotol Yellow L0960HD, Horma chr from Ciba-Geigy
ome Yellow GMXAH-15, Horma chrome Yellow GMXAH-35,
Horma chrome Yellow GU-15-SQ, Irgazin Yellow GO,
Irgazin Yellow 2RLT, Irgazin Yellow 3RLTN, Irgazin
Yellow5GLT, Irgazin Yellow 2GLTE, Bayer Bayferr
ox 915, Bayferrox 920, Bayferrox 3420, Bayferrox 39
10, Bayferrox 3920, Novoperm Yellow H from Hoechst
2G, Hostaperm Yellow H4G, Hostaperm Yellow H3G, Ho
staperm YellowH6G, Nopvoperm Yellow F2G, Nopvoperm
Yellow HR70, Pigment Yellow 171 manufactured by Sanyo Pigment Co., Ltd.
7, Pigment Yellow 1450, Pigment Yellow 1710, Pigme
nt Yellow1711, Pigment Yellow 1707, Pigment Yellow
8104, Pigment Yellow 1425, Light Fast Pigment Yel
low R, SEIKA FAST YELLOW 10G manufactured by Dainichi Seika Kogyo Co., Ltd.
H, SEIKA FAST YELLOW A-3, SEIKA FAST YELLOW 2035, S
EIKA FAST YELLOW 2054, SEIKA FAST YELLOW 2300, SEIK
A FAST YELLOW 2200, SEIKA FAST YELLOW 2270, SEIKA F
AST YELLOW 2400 (B), SEIKA FAST YELLOW 2500, SEIKA
FAST YELLOW2600, SEIKA FAST YELLOW ZAY-260, SEIKA
FAST YELLOW 2700 (B), SEIKA FAST YELLOW 2770, Clari
Sandrin Yellow 4G, PV Fast Yellow HGR, Nov
operm Yellow FGL, Novoperm Yellow H10G01, HANSA Ye
llow 10G, PV Fast Yellow H2G-01, Permanent Yellow
There are pigments such as NCG.

As the green colorant, various color pigments can be used. For example, CI Pigment Green 7, 17, 36, 5
0, 70 and the like, which may be surface-treated with a surfactant or the like during the pigment production stage. A specific example is Chromofine Cyani manufactured by Dainippon Ink and Chemicals, Inc.
ne Green 2GN, Chromofine Green 2GN, Chromofine Gre
en 5301, Dainichi Cyanine Green 537, Dainichi Cyan
ine Green FG, Dainichi Cyanine Green FGH, Chromofi
ne Green 5370, Fastogen Gree manufactured by Dainichi Seika Kogyo Co., Ltd.
n 5005, Fastogen Green 5710, Fastogen Green B, Fas
togen Green S, Fastogen Green SF, Fastogen Green S
O, Fastogen Green 2YK, Heliogen Green 86 manufactured by BASF
80, Heliogen Green 8681K, Heliogen Green 8682T, He
liogen Green 8730, Heliogen Green 8730K, Heliogen
Green A, Heliogen Green D 8730, Heliogen Green G,
Heliogen Green GA, Heliogen Green GN, Heliogen Gre
enGNA, Heliogen Green GTA, Heliogen Green GV, Heli
ogen Green GWS, Heliogen Green K 8730, Heliogen Gr
een L8730, Fastogen Green MY, Fastogen GreenYCN, H
elio Fast Green GT, Heliogen Green 6G, Heliogen Gr
een 6GA, Heliogen Green 8GA, Heliogen Green 9360,
Heliogen Green K 9360, Heliogen Green L9140, Heliog
en Green L9361, Irga from Ciba Specialty Chemicals
lite FastBrilliant Green 3GL, Irgalite Fast Brilli
ant Green GL, Irgalite Green GLN, Irgalite Green 6
G, Liofast Green B 237, Lionol Gre manufactured by Toyo Ink
enB 201, Lionol Green Y 102, Lionol GreenYS07, Lio
nol Green 2Y301, LionolGreen2YS, Lionol Green 6YK,
Lionol Green 6YKPCN, Polymo Green FBH, Polymo Green FGH, Polymo Gre manufactured by Polymon Developments Ltd.
en 6G, Polymo Green G, Polymo Green GN, Polymo Gre
en GN500, SanyoCyanine Green, Sa manufactured by Sanyo Pigment Co., Ltd.
nyoPhthalocyanine Green F6G, SanyoPhthalocyanineGr
een FB, SanyoPhthalocyanineGreenFBpure, SAX, SAX (p
igment) and Sanyo Phthalocyanine Green 6YS. These colorants can be used alone or as a mixture. The use amount thereof is desirably 10 to 45% by weight based on the total amount of the oil-based ink composition for a ballpoint pen.

Examples of the solvent include glycol solvents such as ethylene glycol, diethylene glycol, propylene glycol and hexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and ethylene glycol monophenyl. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mononormal butyl ether, propylene Glycol monophenyl ether,
Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mononormal butyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mononormal butyl ether, tripropylene glycol Ether solvents such as monomonophenyl ether; alcohol solvents such as benzyl alcohol and α-methylbenzyl alcohol; propylene glycol methyl ether acetate; propylene glycol diacetate; N-methyl-2-
Pyrrolidone, water and the like can be used. These solvents can be used alone or as a mixture. The amount used is 35 to 80 with respect to the total amount of the oil-based ink composition for a ballpoint pen.
% By weight is preferred.

Resins are added to improve fixability and prevent hand-through of handwriting, as well as to function as a pigment dispersion, adjust viscosity, and promote dissolution of dyes. Resin, cyclohexanone condensation resin and hydrogenated resin, maleic acid resin, copolymer of styrene and maleic ester, copolymer of styrene and acrylic acid or its ester, polyvinylpyrrolidone, polyvinylbutyral , Polyvinyl acetal, polyamide which is a condensation of a polymerized fatty acid and polyamines, epoxy resin, polyvinyl alkyl ether, coumarone-indene resin, polyterpene, xylene resin, rosin-based resin and hydrogenated product thereof, rosin-modified maleic acid resin, Vinylpyrrolidone-vinyl acetate Copolymer, polymethacrylic acid esters, polyacrylic acid polymethacrylic acid copolymer,
Examples thereof include polyoxyethylene and phenol resin. These resins can be used alone or as a mixture. The amount used is preferably 5 to 50% by weight based on the total amount of the oil-based ink composition for a ballpoint pen.

[0014] The perfluoropolyether is used to prevent the initial brushing of the oil-based boume pen ink composition. This includes those having the following structural formula. A specific example is FOMBLIN HC manufactured by Nikko Chemicals Co., Ltd.
/ 01 Same HC / 02do Same HC / 03 Same HC / 04 Same HC / 05 Same HC / 25
HC / R and HC / M. The perfluoropolyether can be used alone or as a mixture.
The amount used is preferably from 0.1 to 7% by weight based on the total amount of the oil-based ink composition for ballpoint pens. Also, there is no problem if the viscosity is high even if it does not dissolve uniformly due to the solubility,
In particular, when a pigment is contained as a colorant, there is adsorption or the like, and no separation or the like is observed. Of course, a solubilizing agent may be separately dispersed with a solubilizing agent or the like.

For the preparation of the oil-based ink composition for writing, a conventionally known method for producing an ink composition can be applied. That is, by dissolving each component of the solvent-soluble component with a stirring mixer, an oil-based ink composition for ball-point pens and the like can be obtained. When a pigment is used, the oil-based ink composition for a writing instrument or the like can be obtained by dispersing the pigment together with a dispersant and other components using a dispersion mixer and then additionally mixing the necessary components. At the time of production, heating to dissolve solids such as dyes, and use of a filter or a centrifuge to remove coarse particles such as pigments can be used as necessary.

[0016]

EXAMPLES Next, the present invention will be described in more detail with reference to examples and test examples, but the present invention is not limited thereto.

Example 1 The components shown in Table 1 were selected as a coloring agent, an organic solvent, a resin and a perfluoropolyether, and the mixture was heated and stirred at a mixing ratio shown in Table 1 at 55 ° C. for 3 hours. The mixture was filtered under pressure at a temperature to obtain a red ink composition for a ballpoint pen.

Example 2 After dispersing some of the pigments and components among the components shown in Table 1,
The other components were mixed at the mixing ratio shown in Table 1 with a stirrer at a temperature of 55.
After heating and stirring at 3 ° C. for 3 hours, the mixture was filtered under pressure at a temperature to obtain a black ink composition for ballpoint pens.

Example 3 Of the components shown in Table 1, after dispersing some of the pigments and components,
The other components were mixed at the mixing ratio shown in Table 1 with a stirrer at a temperature of 55.
After heating and stirring at 3 ° C. for 3 hours, the mixture was filtered under pressure at a temperature to obtain a red ink composition for ballpoint pens.

Comparative Example 1 Perfluoropolyether of Example 1 (FOMBLIN HC / R)
Example 1 except that was replaced with the same amount of benzyl alcohol
In the same manner as in the above, a red ink composition for a ballpoint pen was obtained.

Comparative Example 2 The perfluoropolyether of Example 2 (FOMBLIN HC / 0
A black ink composition for a ballpoint pen was obtained in the same manner as in Example 2, except that 4) was replaced with the same amount of benzyl alcohol.

Comparative Example 3 The perfluoropolyether of Example 3 (FOMBLIN HC / 0
A red ink composition for a ballpoint pen was obtained in the same manner as in Example 3, except that 1) was replaced with the same amount of benzyl alcohol.

[0023]

[Table 1]

The ink compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to the following first brush rub tests 1 and 2 on the test samples shown below. Table 2 shows the results. (1) Preparation of Test Samples The ink compositions for ballpoint pens obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were commercially available oil-based ballpoint pens (SA-S, manufactured by Mitsubishi Pencil Co., Ltd .; It consists of a tip and a cemented carbide ball.)
2 g was filled to obtain a test sample. (2) First brush blur test 1 Each test sample is left sideways in a thermostat at a temperature of 25 ° C. and a humidity of 60%. One week later, handwriting is performed, and the blur length is measured with a ruler (unit: mm). (3) First brush blur test 2 Each test sample is left sideways in a thermostat at a temperature of 50 ° C. and a humidity of 80%, and one month later, handwriting is performed, and the blur length is measured with a ruler (unit: mm).

[0025]

[Table 2]

[0026]

As described above in detail, the ink composition for a writing instrument according to the present invention has an excellent writing feel as well as almost no initial brush blur even after long-term storage. It has the effect.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Taka ▲ Yanagi ▼ Toshiaki 1091 Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd. Inside Gunma R & D Center (72) Inventor Susumu Suzuki 1091 Tateishi, Fujioka-shi, Gunma Pref. Inside the Gunma R & D Center (72) Inventor Masaaki Morita 1091 Tateishi, Fujioka-shi, Gunma Mitsubishi Pencil Co., Ltd.F-term in the Gunma R & D Center (Reference)

Claims (1)

[Claims] 1. An oil-based ink composition for a writing instrument, characterized in that the composition comprises at least a colorant, an organic solvent and a resin and contains perfluoropolyether.