JPH11130906A - Liquid composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To meet the general requirements by suppressing the occurrence of inconveniences during use such as leakage of various liquid compositions and poor leveling properties, and to improve the stability over time by long-term storage. A liquid composition capable of minimizing the occurrence of aging defects in the composition by maintaining the composition. In a liquid composition, a cross-linked poly-N-vinyl carboxylic acid amide and a water-soluble polysaccharide have a water-soluble polysaccharide content of 1/4 or less of a cross-linked poly-N-vinyl carboxylic acid amide content. It is used in combination as follows.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to cosmetics such as eyeliners, mascaras, packs for removing stains on skin, paints, poster colors, drawing materials such as ink, ballpoint pens, writing tools such as correction fluids, and the like. Ink built-in method For inks for liquids such as stamp inks, stamp pad inks, printing inks, paints, etc., by using thixotropic properties, taking into account the handling properties such as fluidity and leveling properties of the liquid composition, At the same time, the present invention relates to a liquid composition in which the stability over time of the liquid composition is considered by maintaining low reactivity.

[0002]

2. Description of the Related Art A composition which is liquid at room temperature, such as liquid cosmetics, inks for writing instruments and paints, contains water and / or a water-soluble organic solvent as a main component. Various use forms of these liquid compositions are known depending on the purpose. However, conventionally, the stability over time (when the liquid composition is stored for a long period of time, a change in viscosity occurs and the dischargeability of the composition is reduced, resulting in poor handwriting. And the traces of application are lost, and the dispersion of each component is broken and sedimentation causes a difference in the concentration of the upper and lower components (hereinafter referred to as the upper and lower concentration difference). In order to improve the composition of the composition, a surfactant or a thickener such as a solubilizing agent or a dispersing agent is selected and added, or the amount thereof is adjusted. Improve the solubility and dispersibility of each component in the product, suppress the change in viscosity by selecting and using a material with low reactivity, and increase the dispersibility of each component by increasing the viscosity of the composition. Have been maintained.

[0003]

However, if a large amount of a surfactant is added to improve the stability over time of the liquid composition, the viscosity of the liquid composition and the surface tension tend to decrease, and the Leakage (phenomenon in which the liquid composition leaks from the discharge port of the composition, etc.) and bleeding of handwriting or application marks (when the writing surface or the application surface is an absorbing surface such as paper or cloth, the composition Phenomena penetrate too widely and the width of handwriting and coating marks are not constant) and poor leveling (when the surface to be coated is upright, the coating marks do not remain,
It was highly likely that a problem would occur during use such as dropping phenomenon). When the addition amount of the surfactant is made small to suppress such a problem as much as possible, each component in the liquid composition is dissolved and insufficiently dispersed, so that the effect of improving the stability over time can be sufficiently obtained. It was difficult to suppress both liquid leakage, bleeding of handwriting and coating marks, and to achieve both good usability such as good leveling property and stability over time.

Further, in order to prevent each component from sedimenting with time, a large amount of a thickener is added to maintain the dispersibility. Chemical reaction with other components and the like easily occur, the thickened structure is destroyed, the composition becomes more viscous than requested, and the ejection property is reduced, or the viscosity is reduced to cause liquid leakage and poor leveling property. In addition, there is a problem that various problems such as dissolution and dispersion of each component being broken and sedimentation to cause a difference in upper and lower concentrations easily occur. Conversely, if the addition amount of the thickener is reduced to avoid these problems, the effect of improving the stability over time cannot be sufficiently obtained, and the addition amount of other components may be changed for adjustment, When you select a type,
Since the effects of these components are not sufficient, or the dissolution / dispersion balance in the liquid composition is lost, it has been difficult to achieve both good feeling in use and stability over time.

[0005]

SUMMARY OF THE INVENTION The present invention is directed to a method for producing a poly (N-vinylcarboxylic acid) containing at least water, a crosslinked poly (N-vinylcarboxylic acid amide) and a water-soluble polysaccharide, wherein the content of the water-soluble polysaccharide is crosslinked. The gist of the present invention is a liquid composition characterized in that the content is not more than 1/4 of the amide content. The ratio of the content of the water-soluble polysaccharide to the content of the crosslinked polyN-vinylcarboxylic acid amide is calculated from the weight percentage of each liquid composition as a whole.

[0006] The coloring agent is added to the composition for the purpose of forming a handwriting or a coating trace, forming a coating trace of the composition on the surface to be coated, or imparting concealing properties. Conventionally, dyes and pigments used in liquid compositions such as inks, paints and cosmetics can be used without limitation, but specific examples thereof include Japanol Fast Black D
Conch (CI Direct Black 17), Water Black 100L (19), Water Black L
-200 (19), Water Black # 7 (1)
9), Kayaset Black W9 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black E
X (38), Direct Deep Black (similar to 38), Direct Fast Black Conch (5
1), Kayaras Spragley VGN (Id. 71), Kayak Direct Brilliant Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (Id. 2)
6), Aizen Brimura Yellow GCLH (44), Direct Fast Yellow R (50), Aizen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (4),
Direct Fast Scarlet 4BS (23), Eisen Direct Durin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Eisen Buri Malabin Conch 2B
LH (75), Sumilight Red F3B (80),
Aizen Burimura Red 4BH (81) Kayasupurarubin BL (83), Kayasu Light Red F5G
(225), Kayasu Light Red F5B (22)
6), Kayaras Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Benzo Brilliant Sky Blue 8GS (41), Sumilight Supra Blue BRR Conch (Id. 71), Dibogen Turquoise Blue S (Id. 86), Water Blue # 3
(86), Kayara Star Koizu Blue GL (8)
6) Direct dyes such as Daiwa Blue 215H (87), Kayasusupura Blue FF2GL (106), Kayasusupura Blue FFRL (108), Kayasusupuratakoizu FBL (199) and acid blue black 10B (CI Acid Black 1), Nigrosine (2), Water Black R455 (2), Water Black R510 (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (2) 26), Kayanol Milling Black BR Conc (31), Mitsui Nylon Black GL (52), Aizen Opal Black WH Extra Conc (52), Sumilan Black WA (5)
2), Ranyl Black BG Extra Conc (10
7), Kayanol Milling Black TLB (10
9), Suminol Milling Black B (109), Kayanol Milling Black TLR (110), Eisen Opal Black New Conc (119), Water Black 187-L (154), Acid Yellow # 10 (C.I. I. Acid Yellow 1), Kayak Acid Brilliant Flavin FF (7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G140
% (17), Suminol Leveling Yellow NR (1
9), Water Yellow # 1 (23), Daiwa Torazine (25), Kayaktor Trazine (23),
Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminol Milling Yellow O (38), Suminol Milling Yellow MR (42), Water Yellow # 6 (42) , Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (6)
1), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (141), Kayanol Yellow NG
(135), Kayanol Milling Yellow 5GW (1
27), Kayano Lumiling Yellow 6GW (14
2), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9),
Solar Rubin Extra (14), Daiwa New Koksin (18), Water Scarlet (1)
8), Daiwa Red No. 102 (18), Eisenbon Saw RH (26), Daiwa Red 2 (27), Suminol Leveling Brilliant Red S3B (35),
Kayasil rubinol 3GS (37), Aizen erythrosine (51), kayak acid rhodamine FB (52), Daiwa red No. 106 (52), Suminol leveling rubinol 3GP (57), Diacid alizarin rubi Nord F3G 200% (82), Alizarin Rubinol 5G (83), Eizen Eosin GH
(87), Water Red # 2 (87), Daiwa Red 103WB (87), Water Pink # 2 (92), Eisen Acid Phloxine PB (92),
Daiwa Red No. 104 (92), Rose Bengal (9)
4), Kayanol milling scarlet FGW (11
1), Kayanol Milling Rubin 3BW (129)
Suminol Milling Brilliant Red 3BN Conc (131), Suminol Milling Brilliant Red BS (138), Aizen Opal Pink BH (1)
86), Suminol Brilliant Red B Conch (2
49), Kayak Acid Brilliant Red 3BL (254), Kayak Acid Brilliant Red BL (265), Kayanol Milling Red GW (27)
6), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Water Violet # 1 (4)
9), Water Violet # 5 (49), Daiwa Purple No. 1 (49), Ink Violet L10 (4)
9), Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue 1 (1) 9), Ink Blue L20 (9), Spranol Blue B (15), Water Blue # 116 (15), Orient Soluble Blue OBC (22), Orient Soluble-
OBX (22), Sumino-le leveling blue 4GL
(23), Mitsui Nylon Fast Blue G (2)
5), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Safirol SE
(43), Suminol Leveling Sky Blue R Extra Conc (62), Mitsui Nylon Fast Sky Blue R (78), Sumitomobrilliant Indocyanine 6Bh / e (83), Sandrancyanin N-
6B350% (90), Water Blue # 115
(90), Water Blue # 105 (90), Orient Soluble Blue OBB (93), Spranol Cyanine 7BF (100), Sumitomobrilliant Blue 5G (103), Acid Blue (10)
3), Asilane brilliant blue FFR (10
4), Kayanol Milling Ultra Sky SE (11
2), Kayanol milling cyanine 5R (113);
Aizen Opal Cyanine 2GLH (158), Daiwa Guinea Green B (CI Acid Green 3),
Acid Brilliant Milling Green (9), Daiwa Green # 70 (16), Kayanol Cyanine Green G (25), Suminol Milling Green G (27), Water Orange # 17 (CI Acid Orange 56) ) Etc., water yellow # 2
(CI Food Ero-3), Food Yellow No. 5 (C.I.
I. Food Yellow 3), Red No. 3 for Food (CI Food Red 14), Blue No. 2 for Food (CI Acid Blue 74), Green No. 2 for Food (CI Acid Green 5), etc. Food dye, Malachite Green (CI.4)
2000), Victoria Blue FB (CI. 4404)
5), methyl violet FN (C.I.
5), basic dyes such as rhodamine F4G (CI. 45160) and rhodamine 6GCP (CI. 45160).

[0007] As the pigment, Special Blac
k 6, S170, S610, 5, 5, 4,
A, 550, 35, 250, 100, Prin
tex150T, U, V, 140U, 140
V, 95, 90, 85, 80, 75, 5
5, 45, P, XE2, L6, L, 30
0, 30, 30, 35, 25, 200, A,
G (above, manufactured by Degussa Japan Co., Ltd.), # 2400
B, # 2350, # 2300, # 2200B, # 100
0, # 950, # 900, # 850, # MCF88, M
A600, MA100, MA7, MA11, # 50, #
52, # 45, # 44, # 40, # 33, # 32, # 3
0, CF9, # 20B, # 4000B (Mitsubishi Chemical Industries, Ltd.), MONARCH 1300, 110
0, 1000, 900, 880, 800, 7
00, MOGUL L, REGAL 400R, 66
0R, 500R, 330R, 300R, 99
R, ELFTEX 8, 12 and BLACK PEAR
LS 2000 (above, Cabot Co. LTD, USA)
Manufactured), Raven7000, 5750, 5250,
5000, 3500, 2000, 1500, 1255, 1250, 1200, 1170, 1
060, 1040, 1035, 1020, 10
00, 890H, 890, 850, 790, 780, 760, 500, 450, 430, 420, 410, 22, 22, 16, 14, and 825
Oil Beads, H20, C, Conduc
carbon black such as tex 975, 900, and SC (all manufactured by Colombian Carbon Japan Co., Ltd.);
A-10, same 10P, same 15, same 20, same 30, same 3
5, 60, 80, 90, KR-310, 38
0, 460, 480 (Titanium Industry Co., Ltd.
Titanium oxide such as P25 (manufactured by Nippon Aerosil Co., Ltd.), BS-605 and BS-605 (all available from Toyo Aluminum Co., Ltd.
Bronze Powder P-555, P-777 (above, manufactured by Nakajima Metal Foil Industry Co., Ltd.), Bronze Powder 3L
5. Metal powder pigments such as 3L7 (above, manufactured by Fukuda Metal Foil Industry Co., Ltd.) and black iron oxide, yellow iron oxide, red iron oxide, ultramarine, navy blue, cobalt blue, chrome green, chromium oxide, etc. Inorganic pigment, Hansa A-10G, same 5G,
3G, 4, GR, A, Benzidine Yellow, Par
Permanent Yellow NCG, Tartrazine Lake, Quinoline Yellow, Sudan 1, Permanent Orange, Indus Ren Brilliant Orange GN, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red, Brilliant Carmine BS, Pyrazolone Red, Lake Red C, Organic pigments such as quinacridone red, brilliant carmine 6B, bordeaux 5B, thioindigo red, fast violet B, dioxane violet, alkali blue lake, phthalocyanine blue, indigo, acid green lake, and phthalocyanine green. In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, calcium tungstate, and other known organic fluorescent pigments may be used. These colorants may be used alone or in combination of two or more, and the amount used may vary depending on the color tone or the like.
If the amount is too large, the colorant is insufficiently dissolved and dispersed to cause various problems. Therefore, the amount is preferably 0.1 to 50% by weight based on the total amount of the liquid composition.

Here, when a pigment is used as a colorant,
A dispersant can be used in combination, but as the dispersant, a water-soluble or water-soluble resin generally used conventionally,
Those used as pigment dispersants such as anionic or nonionic surfactants can be used. For example, as a water-soluble resin, lignin sulfonate, natural polymers such as shellac, polyacrylate, styrene-
Salts of acrylic acid copolymers, salts of vinyl naphthalene-maleic acid copolymers, sodium salts of β-naphthalene sulfonic acid formalin condensate, anionic polymers such as phosphates, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol And the like. As surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylates, α- Anionic surfactants such as olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and nonionics such as polyoxyethylene alkyl ethers, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters Surfactants. These may be used alone or in combination of two or more. Its usage is
When the amount is small, the dispersing effect to be added is weak, and when the amount is large, the dissolution / dispersion balance of each component in the composition is disrupted, and various problems occur. Therefore, 1 to 20% by weight based on the total amount of the liquid composition Is preferred.

Further, when a pigment is used, it is advantageous to use an aqueous base in which the pigment is dispersed in an aqueous medium in the production of a pigment-containing composition. Specifically, Fuji
SPBlack 8031, 8119, 8167,
8276, 8381, 8406, Fuji SP
Red 5096, 5111, 5193, 52
20, Fuji SP Bordeaux 5500,
Fuji SP Blue 6062, 6133, 6134, Fuji SP Green 7051, F
uji SP Yellow 4060, Fuji S
P Violet 9011, Fuji SP Pin
k 9524, k 9527, FujiSP Orange
e 534, FUji SP Brown 3074
(The above are manufactured by Fuji Dye Co., Ltd.), Emacol Blac
k CN, Emacol Blue FBB, FB,
Same KR, Emacol Green LXB, Emac
ol Violet BL, Emacol Brown
3101, Emacol Carmmine FB,
Emacol Red BS, Emacol Oran
geR, Emacol Yellow FD, IR
N, 3601, FGN, GN, GG, F5
G, F7G, 10GN, 10G, Sandye
Super Black K, Super C, Sandy S
upper Gray B, Sandy Super
Brown SB, FRL, RR, Sandye
Super Green L5G, GXB, Sand
yeSuper Navy Blue HRL, GL
L, HB, FBL-H, FBL-160, FB
B, Sandye Super Violet BLH
/ C, BL, Sandy Super Borde
aux FR, Sandy Super Pink
FBL, F5B, Sandy Super Rub
ine FR, Sandye super Carmm
ine FB, Sandy Super Red F
FG, RR, BS, SandySuper Or
angel FL, same R, same BO, Sandy Gol
dYellow 5GR, R, 3R, Sandye
Yellow GG, F3R, IRC, FG
N, GN, GRS, GSR-130, GSN-
130, same GSN, same 10GN (above, Sanyo Dyeing Co., Ltd.
Manufactured), Rio Fast Black Fx 801
2, 8313, 8169, Rio FastRed
FX 8209, 8172, Rio Fast R
ed S Fx8315, 8316, Rio Fas
t Blue Fx 8170, Rio Fast B
lue FX 8170, Rio Fast Blue
SFx 8312, Rio Fast Green
S Fx 8314 (all manufactured by Toyo Ink Co., Ltd.), N
KW-2101, 2102, 2103, 210
4, 2105, 2106, 2107, 210
8, 2117, 2127, 2137, 216
7, 2101P, 2102P, 2103P, 2
104P, 2105P, 2106P, 2107
P, 2108P, 2117P, 2127P, 2
137P, 2167P, NKW-3002, 300
3, 3004, 3005, 3007, 307
7, 3008, 3402, 3404, 340
5, 3407, 3408, 3477, 360
2, 3603, 3604, 3605, 360
7, 3677, 3608, 3702, 370
3, 3704, 3705, 3777, 370
8, 6013, 6038, 6559 (all manufactured by Nippon Fluorescence Co., Ltd.), Cosmo Color S 1000F series (manufactured by Toyo Soda Co., Ltd.), Victoria Yellow G-1
1, G-20, Victoria Orange G-16, G
-21, Victoria Red G-19, Victoria G-22, Victoria Pink G-17, Victoria G-23, Victoria Green G-18, Victoria G-24, Victoria Blue G
-15 and G-25 (all manufactured by Mikuni Dyestuffs Co., Ltd.), and these can be used alone or in combination of two or more.

As the solvent or dispersion medium, various water-soluble organic solvents can be used in addition to water, which is an essential requirement, and these have various qualities as a liquid composition, for example, the liquid composition comes into contact with air. It is used for the purpose of preventing the composition from drying out in parts, preventing the composition from freezing at low temperatures, and the like. Specifically, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 1,3-butylene glycol, thiodiethylene glycol, and glycerin; ethylene glycol monomethyl ether; diethylene glycol monomethyl ether; Pyrrolidone and the like can be used, and these can be used alone or in combination of two or more. In addition, when the amount is small, insoluble / aggregate is generated due to insufficient dissolution or dispersion of each component in the liquid composition, and when the amount is large, the concentration of each component in the composition is reduced and the effect is reduced. Since the composition becomes small and various problems occur, the content is preferably 5 to 40% by weight based on the total amount of the liquid composition.

The cross-linked poly-N-vinylcarboxylic acid amide improves the feeling of use of the above-mentioned various liquid compositions by imparting thixotropic properties to the liquid compositions, and further, the water-soluble polysaccharides and the water-soluble It is used to hinder the reaction between the polysaccharide and other components, assist in maintaining the dispersed state of the other components, and minimize the occurrence of aging defects in the liquid composition. The water-soluble polysaccharide is used to stabilize the dispersion and dissolution of each component. Since both act as water-soluble thickeners in the composition, the viscosity of the entire composition is increased to stabilize the dispersion by retaining each component, and the liquid is leaked by lowering the fluidity of the entire composition. It plays a part in the effects of the thixotropy, such as prevention and improvement of the leveling property, so that various problems can be suppressed. Specific examples of water-soluble polysaccharides include starch, cellulose, glucans such as glycogen, fructans such as inulin and levan, mannans such as elegans, xylan, pectic acid, chitin, alginic acid, glucomannan, chondroitin sulfate, hyaluronic acid Diheteroglycans such as acids, galactomannans, gatch gum, triheteroglycans such as meskit gum, tetraheteroglycans such as arabic gum, guar gum, polysaccharides such as xanthan gum and their polyhydroxypropylated, polyhydroxyethylated, carboxymethyl , Acetate, methylation, and derivatives such as salts. Crosslinked poly N-
The water-soluble polysaccharide is preferably a heteroglycan and / or a derivative thereof, since the effect of the interaction between the vinylcarboxylic acid amide and the water-soluble polysaccharide is enhanced. One or two or more of these can be selected and used in combination. If the total amount of the cross-linked poly N-vinyl carboxylic acid amide and the water-soluble polysaccharide is small, various effects due to the addition of thixotropy and the dispersion stability of the cross-linked poly N-vinyl carboxylic acid amide and each component The effect is weakened, and if the amount is large, the composition becomes too thick and the fluidity becomes low, and it becomes difficult to use in various applications such as cosmetics and inks. ~ 15.0% by weight
Is preferred.

In addition to the cross-linked poly N-vinyl carboxylic acid amide and the water-soluble polysaccharide, a water-soluble polymer may be used in combination for adjusting the viscosity of the composition and stabilizing the dispersion of each component. Specifically, polyvinyl alcohol, polyvinyl methyl ether, sodium polyacrylate, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinylpyrrolidone, alkali metal salt of acrylic resin, copolymer of acrylic acid and alkyl methacrylate And the like.

[0013] In addition, the outflow of the liquid composition in the container in the flow passage due to the generation of molds, the effect on the skin when the liquid composition is a cosmetic, the change in viscosity of the composition due to the chemical reaction between the mold and each component. An appropriate amount of an antiseptic or fungicide such as sodium dehydroacetate, 1,2-benzothiazalin-3-one or sodium benzoate can also be added to suppress a decrease in thixotropy.

Further, in the case of a writing instrument or a paint in which a metal is used in a portion that comes into contact with the composition, an anticorrosive such as benzotriazole or ethylenediaminetetraacetic acid for preventing corrosion of the metal, or oleic acid as a solubilizer is used. Such fatty acids can also be added.

In producing the liquid composition of the present invention, various conventionally known methods can be employed. For example, when a dye is used as a coloring material, the mixture is stirred and mixed with a stirrer such as a turbo mixer, and when a pigment is used as a coloring material, a ball mill, a sand grinder, a speed line mill, a disperser such as a roll mill is used. It is easily obtained by mixing and grinding.

[0016]

The effect of improving the stability over time of the composition can be attained by using it together with the composition so that the content of the water-soluble polysaccharide is 1/4 or less of the content of the cross-linked poly-N-vinylcarboxylic acid amide. It is speculated as follows as to whether it exists. The water-soluble polysaccharide has a plurality of hydroxyl groups in its molecule, and expands in a network or layer in water and / or a water-soluble organic solvent to form a thickened structure. In addition, the crosslinked poly N-vinylcarboxylic acid amide swells in water and / or a water-soluble organic solvent to form a fine microgel and disperse, thereby imparting a strong thixotropy to the composition. When the cross-linked poly N-vinyl carboxylic acid amide fine particles are dispersed in the liquid composition in a state in which the primary particles are large by stirring conditions, appropriately selecting a dispersant, and the like, and when a water-soluble polysaccharide is present therein, During the mixing and stirring, the water-soluble polysaccharide and other components are uniformly dispersed, and when the water-soluble polysaccharide eventually builds a thickened structure, the cross-linked poly-N-vinyl carboxylic acid amide is contained in the structure. It is taken in while being uniformly dispersed with the components. At this time, the amide group of the crosslinked poly N-vinyl carboxylic acid amide and the hydroxyl group of the water-soluble polysaccharide form a hydrogen bond, and
Since the components such as vinyl carboxylic acid amide and pigments, dyes, and surfactants have an affinity, the dispersion state of the crosslinked poly (N-vinyl carboxylic acid amide) fine particles and other components is firmly maintained, and at the same time, the water-soluble polysaccharide The reaction between comrades and water-soluble polysaccharides with other components is suppressed. For this reason, thixotropic properties are imparted to the composition, and at the same time, the stability over time of the composition can be favorably maintained. Therefore, the thixotropy does not cause liquid leakage or poor leveling property, and it is possible to minimize the occurrence of discharge failure, liquid leakage, difference in upper and lower concentrations, etc. over time. The content of water-soluble polysaccharide is cross-linked poly N
-When the content of the vinyl carboxylic acid amide is 1/4 or more, the crosslinked poly N-vinyl carboxylic acid amide cannot suppress the reactivity between the water-soluble polysaccharides and the water-soluble polysaccharide and other components, and cannot be completely removed. Therefore, the stability over time of the composition is reduced, and a trouble over time is likely to occur.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. The viscosity of each ink in Examples and Comparative Examples is less than 50 cp measured with a Tokimec ELD viscometer standard cone rotor at 10 rpm, and 50 cp or more and less than 600 cp is measured with a Tokimec ELD viscometer standard core. Measured with a rotor-1 rpm, 600 to 2000 cp, ELD viscometer ST rotor-10 manufactured by Tokimec Co., Ltd.
rpm: 2000 to less than 20,000 cp for ELD viscometer ST rotor-1r manufactured by Tokimec
20,000 cp or more was measured with a Tokimec ELD viscometer ST rotor 0.5 rpm. The temperature during the measurement was 25 ° C. In each of the examples, “parts” simply indicates “weight percentage”.

Example 1 (Ink for ballpoint pen) NKW-6559 (black aqueous pigment base, manufactured by Nippon Fluorescent Chemical Co., Ltd.) 60.00 parts Xanthan gum 0.20 parts Crosslinked poly N-vinyl carboxylic acid amide 1.60 parts Sarcosinate OH (oleoyl sarcosine, Nikko Chemicals Co., Ltd.) 0.80 parts Proxel GXL (preservative, ICI Japan Co., Ltd.) 0.10 parts Glycerin 4.00 parts Water 32.30 parts 25% 2-amino -2-methyl-1,3-propanediol 1.00 part Xanthan gum in each of the above components, 25% 2-amino-2-
After mixing and stirring with a stirrer for 3 hours except for methyl 1,3-propanediol, then adding xanthan gum and stirring again for 2 hours, 25% 2-amino-2-methyl-1,3-propanediol was added. To give a viscosity of 1080
A black ink for a ballpoint pen of cp was obtained.

Example 2 (Mascara liquid) Iron oxide (black) 14.00 parts Hydroxypropylcellulose 0.35 parts Crosslinked poly N-vinylcarboxylic acid amide 2.10 parts Sodium dehydroacetate (preservative) 0.20 parts Butylene glycol 2.50 parts Water 80.85 parts Components other than hydroxypropyl cellulose and cross-linked poly N-vinyl carboxylic acid amide in each of the above components were mixed and stirred for 1 hour with a stirrer, and then cross-linked poly N-vinyl carboxylic acid. The acid amide was added and the mixture was stirred again for 1 hour, and then hydroxypropylcellulose was added and stirred again for 3 hours to obtain a black aqueous mascara liquid having a viscosity of 5000 cp.

Example 3 (packing agent) Titanium oxide 4.00 parts Sodium carboxymethyl cellulose 0.02 parts Polyvinyl alcohol 10.00 parts Crosslinked poly N-vinylcarboxylic acid amide 4.00 parts Polyhydroxypropylated guar gum 0.03 Part Polyoxyethylene hydrogenated castor oil 1.20 parts Ethanol 9.00 parts Sodium benzoate 0.15 parts Water 71.60 parts Of the above components, sodium carboxymethylcellulose, cross-linked poly N-vinyl carboxylic acid amide, polyhydroxypropylated Heat all but guar gum to 50 ° C and 3
After mixing and stirring for hours, the cross-linked poly N-vinyl carboxylic acid amide was added and mixed and stirred for 2 hours with a stirrer. Further, sodium carboxymethyl cellulose and polyhydroxypropylated guar gum were added, and the mixture was stirred for 3 hours with a stirrer. And a white aqueous pack agent having a viscosity of 56000 cp.

Example 4 (Ink for Stamp Stand) Water Pink # 2 (Dye, manufactured by Orient Chemical Industry Co., Ltd.) 3.00 parts Polyhydroxypropylated guar gum 0.02 parts Crosslinked poly N-vinylcarboxylic acid amide 0 0.08 parts Ethylene glycol 32.00 parts Glycerin 3.00 parts Polyoxyethylene octyl phenyl ether 0.50 parts Sodium dehydroacetate (preservative) 0.15 parts Water 60.25 parts Polyhydroxypropylation in each of the above components After mixing and stirring components other than guar gum for 4 hours, polyhydroxypropylated guar gum was added, and the mixture was stirred again for 2 hours to obtain a viscosity of 87 c.
Thus, a pink water-based ink for a stamp table was obtained.

Example 5 (Aqueous paint) Ultramarine 30.00 parts Calcium carbonate 10.00 parts Gum arabic 0.10 parts Dextrin 0.10 parts Crosslinked poly N-vinylcarboxylic acid amide 4.00 parts Glycerin 8.00 parts Carbonic acid (preservative) 0.60 parts Water 47.20 parts The above components were mixed and stirred with a stirrer for 3 hours to obtain a viscosity of 18
A blue aqueous paint of 000 cp was obtained.

Example 6 (Red ink for ballpoint pen) Water Red # 2 (Dye, manufactured by Orient Chemical Industry Co., Ltd.) 0.10 part Crosslinked poly N-vinylcarboxylic acid amide 1.80 parts Locust bean gum 0.01 Part guar gum 0.02 part glycine betaine 3.00 parts glycerin 4.00 parts water 87.07 parts 25% 2-amino-2-methyl-1,3-propanediol 4.00 parts xanthan gum, guar gum, 25 % 2-
After stirring and mixing each component other than amino-2-methyl 1,3-propanediol with a stirrer for 1 hour, xanthan gum and guar gum were added, and the mixture was stirred again for 2 hours.
5% 2-amino-2-methyl-1,3-propanediol was added and stirred for 1 hour to obtain a red ink for a ballpoint pen having a viscosity of 480 cp.

Example 7 (Blue ink for ballpoint pen) Phthalocyanine blue 20.00 parts Titanium oxide 30.00 parts Crosslinked poly N-vinylcarboxylic acid amide 3.00 parts Xanthan gum 0.75 parts DDP-8 (surfactant, Nikko Chemicals Co., Ltd.) 1.50 parts Propylene glycol 7.00 parts Proxel GXL 0.25 parts Water 36.00 parts 25% sodium hydroxide 1.50 parts Among the above components, a cross-linked N-vinylcarboxylic acid amide, After stirring and mixing each component other than xanthan gum and 25% sodium hydroxide with a stirrer for 3 hours, add cross-linked N-vinylcarboxylic acid amide and xanthan gum, further stir for 3 hours, and then add 25% sodium hydroxide. And stirred for 1 hour to obtain a blue ink for ballpoint pens of 21600 cp.

Comparative Example 1 The procedure of Example 1 was repeated except that 1.00 g of the cross-linked poly-N-vinylcarboxylic acid amide of Example 1 was removed and that amount of xanthan gum was added. An ink was obtained.

Comparative Example 2 A black aqueous mascara having a viscosity of 3800 cp was obtained in the same manner as in Example 2 except that water was added in the same amount as in Example 2 except for the crosslinked poly N-vinylcarboxylic acid amide.

Comparative Example 3 Except for the crosslinked poly N-vinylcarboxylic acid amide, sodium carboxymethylcellulose and polyhydroxypropylated guar gum of Example 3, 1.0 g of sodium polyacrylate and 2 g of polyoxyethylene sorbitan monooleate were used. A white aqueous pack having a viscosity of 21600 cp was obtained in the same manner as in Example 3 except that water was added in an amount of 0.0 g and the remaining amount.

Comparative Example 4 Pink for a stamp pad having a viscosity of 20 cp was prepared in the same manner as in Example 4 except that the amount of the crosslinked polyN-vinylcarboxylic acid amide was added except for the polyhydroxypropylated guar gum of Example 4. A color water-based ink was obtained.

Comparative Example 5 Except for the crosslinked poly N-vinylcarboxylic acid amide of Example 5, except that 2.00 g of gum arabic and 2.00 g of polyoxyethylene oleyl ether were added, the same procedure as in Example 5 was carried out. A blue aqueous paint having a viscosity of 22,000 cp was obtained.

Comparative Example 6 Except that 0.40 g of the cross-linked poly-N-vinylcarboxylic acid amide of Example 6 was removed and guar gum was added in that amount.
In the same manner as in Example 6, a red ink for a ballpoint pen having a viscosity of 720 cp was obtained.

[0031]

As described above, the liquid compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were filled in glass test tubes,
After aging at 0 ° C. for 24 hours, the following tests were performed. The results are shown in Tables 1 and 2.

Liquid Leak Test A ballpoint pen refill in which a metal ballpoint pen tip is attached to the tip of a polypropylene pipe immediately after the liquid compositions obtained in Examples 1, 6, and 7 and Comparative Examples 1 and 6 are blended. (K105 refill, manufactured by Pentel Co., Ltd.) and left at 50 ° C. with the pen tip downward for 24 hours, and then visually inspected for liquid leakage (ink leakage) from the tip of the ballpoint pen tip.

Leveling property test Immediately after mixing the liquid compositions obtained in Examples 2 to 5 and Comparative Examples 2 to 5, 2 ml thereof was placed on a glass plate at 5 cm × 5 cm.
And the glass plate was allowed to stand vertically at room temperature of 25 ° C. for 1 hour, and the flow distance of the applied liquid was measured.

Heating and aging treatment The liquid composition immediately after mixing and the glass test tube were filled with 5.0 g of the liquid composition, and the mixture was placed in a water bath for 90 g.
After standing for 24 hours while being heated to ℃, the viscosity was measured for the one which was allowed to cool at room temperature (25 ℃). still,
It is considered that 24 hours of aging at 90 ° C. corresponds to 1 to 3 years of aging at room temperature.

Viscosity change rate The viscosity of the liquid composition was measured before and after the heat treatment, and the rate of change in the viscosity was calculated by the following formula 1 and compared.

[0036]

Formula 1: Rate of change in viscosity (%) = (1−viscosity after heat treatment and aging treatment / viscosity before heat treatment and aging treatment) × 100

Sedimentation Depth After the liquid composition was heated and treated with time, the difference in color between the upper and lower parts of the composition was visually observed, and the depth from the upper surface of the composition to the boundary between the upper and lower parts was measured.

[0038]

[Table 1]

[0039]

[Table 2]

As described in detail above, the liquid composition according to the present invention suppresses the occurrence of inconveniences during use, such as leakage of various liquid compositions and poor leveling property, to meet general requirements. And by maintaining the stability over time due to long-term storage, it is possible to minimize the occurrence of aging problems in the liquid composition.

Claims (1)

[Claims] 1. A composition comprising at least water, a cross-linked poly-N-vinyl carboxylic acid amide and a water-soluble polysaccharide, wherein the content of the water-soluble polysaccharide is 1/4 of the content of the cross-linked poly-N-vinyl carboxylic acid amide. A liquid composition characterized by the following.