JPH089835B2 - Ink for pigment resin printing - Google Patents

Description

The present invention relates to a pigment resin printing suitable for a woven fabric made of synthetic fibers such as polyester and acetate or natural fibers such as cotton and hemp, or a blended woven fabric thereof. It is related to ink for use.

(Prior Art) Conventionally, a woven fabric made of synthetic fibers such as polyester and acetate, or natural fibers such as cotton and hemp, or a blended woven fabric thereof, which is suitable for a pigment resin printing ink, is O / W type or W / O type emulsion ink is mainly used.

(Problems to be Solved by the Invention) However, when the O / W type or W / O type emulsion ink is applied to a woven fabric made of synthetic fibers or natural fibers, or a mixed spun woven fabric thereof, It is necessary to dry for a long time or heat treatment as a necessary condition to obtain a quality having sufficient fastness to dry cleaning, and once dried, the re-dissolving property is poor and therefore the handling is difficult. It was inconvenient. In particular, when it is applied to a writing instrument or the like having a discharging mechanism utilizing the capillary phenomenon, it is difficult to restore even if the cap is re-dried when the pen tip is dried up.

Therefore, the present invention, for O / W type or W / O type emulsion inks, has sufficient fastness to washing and dry cleaning, and is easy to use and handle for pigment resin printing. The purpose is to obtain ink.

(Means for Solving the Problem) The present inventors have finally completed the present study as a result of earnest studies in view of the above object.

That is, the present invention provides a pigment resin printing ink comprising at least a pigment surface-treated with an aluminum coupling agent, a polyvinyl butyral resin, a butylated melamine resin, an alcohol solvent and / or a glycol ether solvent. It is a summary.

Hereinafter, each component of the pigment resin printing ink of the present invention will be described.

Aluminum-based coupling agents are used for surface modification of pigments.
Al-M (manufactured by Ajinomoto Co., Inc.) ALCH, ALCH-TR, aluminum chelate M, D, A (above, Kawaken Fine Chemicals Co., Ltd.)
Manufactured), which can be used as a treating agent before dispersing the pigment, or can be added and used when dispersing the pigment. Although the amount used varies depending on the type of pigment, it is preferably 0.01 to 50% by weight based on the pigment.

The pigment is used as a colorant, and is not particularly limited, and includes azo pigments, phthalocyanine pigments, nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, vat dyes. Pigments, organic pigments such as mordant dye pigments and natural dye pigments, ocher, barium yellow,
Navy blue, cadmium red, barium sulfate, titanium oxide,
Inorganic pigments such as red iron oxide, iron black, aluminum hydroxide, calcium carbonate, and carbon black can be used, and these can be used alone or in a mixture, and the amount is preferably 3 to 20% by weight based on the total amount of the ink.

Polyvinyl butyral resin (hereinafter abbreviated as PVB) is used as a dispersant for pigments, an anti-settling agent, and a fixing agent. For the fastness of handwriting and the dispersion stability of ink, The larger the added amount, the more preferable, and the higher the degree of polymerization of the dispersant for pigments and the anti-settling agent is. In particular, when used for a writing instrument having a discharge mechanism utilizing the capillary phenomenon, if there is not sufficient dispersion stability, there is a problem that clogging occurs at the pen tip and writing blur occurs. However, when the addition amount is large or the degree of polymerization is high, the ink viscosity becomes high. On the other hand, a writing instrument having a discharge mechanism utilizing a capillary phenomenon, for example, a felt nib, a fiber nib, or a viscosity of an ink suitable for use in a writing instrument having a plastic nib is 20 cps (at 25 ° C.) or less, More preferably 15 cps
Since it is (at 25 ° C) or less, an average degree of polymerization of 1000 or less is preferably used, and specifically, denkabutyral #
2000-L, # 3000-1, # 3000-2, # 3000-4, # 4000-
1, Same # 4000-2 (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), S-REC BL-1, Same BL-2, Same BL-3, Same BL-S, Same BX-L, Same BM-1, Same BM-
2, the same BM-5, the same BM-S (these are manufactured by Sekisui Chemical Co., Ltd.), etc., and the amount used varies depending on the average degree of polymerization, etc., but the weight ratio to the pigment (PVP / pigment) And a range of 0.1 to 2.0 is desirable.

Butylated melamine resin is used as a fixing agent,
Specifically, Super Beckamine J-820-60, L-109-65,
Same L-117-60, Same 127-60, Same G-821-60, Same L-101-60, Same L-110-
60, same 45-508-60, same L-116-70, same L-118-60, same L-121-60, same
L-120-60, TD-139, 17-590 (above, manufactured by Dainippon Ink and Chemicals, Inc.) Vansemin 115-55, 125-60, SM-940
SM-970, SM-975, SM-983 (Made by Harima Kasei Co., Ltd.) Nikkarac MS-001, MS-11, MS-21 (Made by Sanwa Chemical Co., Ltd.) ) Yuban 60, same 60R, same 61, same
62, same 20SA, same 20SB, same 20SE, same 20HV, same 20R, same 20RH, same 21R,
The 22S, 20S-Bu65, 22R, 22MV, and 23 (these are manufactured by Toyo High-Pressure Co., Ltd.) can be used alone or in combination, and the amount used is based on the total amount of ink. , 0.5 ~ 10
Weight percent is preferred.

Examples of alcohol solvents and glycol ether solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, n
-Amyl alcohol, isoamyl alcohol, sec-amyl alcohol, n-hexanol and methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether and the like.

In addition, as components other than the above, resins, surfactants, rust preventives, dispersion aids, lubricants and the like can be appropriately used if necessary.

As a method for producing the ink for pigment resin printing according to the present invention, a conventionally known method can be adopted, and each component described above is kneaded and dispersed by a dispersing machine such as a homomixer, a ball mill, a homogenizer, a sand mill and a roll mill. You can get it easily.

(Function) The pigment resin printing ink according to the present invention is suitable for a woven fabric made of synthetic fibers or natural fibers or a mixed-spun woven fabric thereof, and particularly suitable for a writing instrument having a discharge mechanism utilizing a capillary phenomenon. Although it is not clear whether the pigment surface-treated with an aluminum-based coupling agent has a good affinity with PVB, the fluidity and dispersion stability suitable for a writing instrument having a discharge mechanism utilizing the capillary phenomenon can be obtained. At the same time, a strong fixing property to a woven fabric made of synthetic fibers or natural fibers, or a mixed-spun woven fabric thereof by the interaction of the combination of the pigment surface-treated with the aluminum-based coupling agent, PVB and the butylated melamine resin. Is supposed to appear.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The numerical values in Table 1 indicate parts by weight.

1. Ink composition Comparative Example 4 MA-100 12.0 parts Styrene-acrylic acid amine salt 4.5 parts (dispersant) ethylene glycol 10.0 parts water 35.5 parts Matsumisol MR-1000 40.0 parts (acrylic ester copolymer emulsion, Matsui Dye Chemical Industry Co., Ltd. )) In the above composition, other components except the resin emulsion are mixed, dispersed in a ball mill for 30 hours, added with the resin emulsion, and stirred with a homomixer for 1 hour to print a black pigment resin. I got the ink.

2. Pigment surface treatment method In Examples 1 to 4 and Comparative Examples 2 and 3, the coupling agent was dissolved in ethanol in an amount twice that of the pigment, and the pigment was added thereto.
After stirring and mixing with a closed homomixer to treat the pigment surface, ethanol was removed.

3. Method for producing ink An ink base is prepared by mixing a surface-treated pigment, PVP or butylated melamine resin, and an appropriate amount of solvent, mixing and dispersing with a roll mill to obtain an ink base, and adding the remaining components to this ink base with stirring and mixing. Got

(Effect of the Invention) The inks obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were tested. Table 2 shows the results.

Washability: Performed according to JIS L0844-1973, Dyeing fastness test method for washing, A-2 method.

Dry-cleaning resistance method: Performed according to JIS L0860-1974, Dye fastness test method for dry cleaning.

Viscosity: B-type viscometer, BL adapter, measured at 25 ° C.

Dispersion stability test: Each ink was put in a test tube with a lid, and a heat cycle (10 cycles at 50 ° C to -5 ° C, 1 cycle for 24 hours) was performed to observe the state of the pigment settling at the bottom.

◯: No sediment is observed at all.

Δ: There is a sediment, but the amount is small.

X: The pigment settles and separates into two layers.

Pen tip clogging test: Each ink was filled in a felt-tip pen having a fiber nib in which acrylic resin fibers were hardened with a thermosetting resin, left for 3 months, and then written, and the handwriting was visually judged.

○: Good handwriting without clogging.

X: Clogging occurs and the handwriting is blurred Pen tip resilience test: Each ink was filled in a felt-tip pen having a fiber nib made by hardening acrylic resin fibers with a thermosetting resin, and the cap was removed to completely write After leaving it until it became, the cap was put on and the writing performance was observed after leaving it at room temperature for 24 hours.

○: Can be completely restored and written.

×: Writing is not possible without restoration.

Note) The test piece used for the wash resistance and dry cleaning resistance test is a 10 × 5 cm size cotton broad cloth (65% polyester, 35% cotton) printed with a pattern paper and dried at room temperature for 2 hours. Was used. Also, discoloration is JIS L0804
(Discoloration and fading gray scale).

As described above in detail, the pigment resin printing ink according to the present invention naturally exhibits good washing resistance and dry cleaning resistance without long-term drying or heat treatment,
Even when used in a writing instrument, it has excellent fluidity and dispersibility, and even when it is dried up with a pen tip, it is an excellent one that is restored by capping.

The pigment resin printing ink of the present invention can be used not only for writing instruments but also as a so-called writing brush type.

Claims (1)

[Claims] 1. A pigment resin printing ink comprising at least a pigment surface-treated with an aluminum coupling agent, a polyvinyl butyral resin, a butylated melamine resin, an alcohol solvent and / or a glycol ether solvent.