JPS63301263A - Printing ink composed of pigment and resin - Google Patents

Abstract

PURPOSE:To obtain the title ink excellent in flow and dispersibility, useful for, e.g., writing utensils undergoing no plugging and excellent in washing resistance and dry cleaning resistance, by mixing a pigment surface-treated with an Al coupling agent with polyvinyl butyral, nitrocellose and alcohol and/or glycol solvents. CONSTITUTION:3-20wt.% organic pigment of an azo type, phthalocyanine type, nitroso type or basic dye type, or an inorganic pigment such as TiO2, Al(OH)3, CaCO3 or carbon black (A) surface-treated with 0.01-50wt.% Al coupling agent is kneaded with 0.1-2.0pts.wt., per pt.wt. pigment, polyvinyl butyral (B) of an average degree of polymerization of, preferably, 1,000 or below, 0.5-10wt.% nitrocellulose (C) as a dispersing aid/binder and an alcohol and/or a glycol (D) as a solvent so that the viscosity of the formed dispersion may be 20cP (at 25 deg.C).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to pigment resin printing suitable for woven fabrics made of synthetic fibers such as polyester and acetate, or natural fibers such as cotton and linen, or blended woven fabrics thereof. The invention relates to ink for commercial use.

(Prior art) Conventionally, as a pigment resin printing ink suitable for woven fabrics made of synthetic fibers such as polyester and acetate, natural fibers such as cotton and hemp, or blended woven fabrics of these, O
/W type or W10 type emulsion ink is mainly used.

(Problems to be Solved by the Invention) However, when the above-mentioned O/Wm or W10 type emulsion ink is applied to a woven fabric made of synthetic fibers or natural fibers, or a blended woven fabric thereof, it is difficult to wash or dry clean it. On the other hand, in order to obtain quality with sufficient fastness.

It also requires long drying times or heat treatment. Once dried, it is inconvenient to handle because of poor resolubility. Particularly when applied to a writing instrument or the like that has a discharge mechanism that utilizes capillary action, if the pen nibs dries up, it will not recover even if the cap is put on again.

Caution was required.

Therefore, the present invention provides a pigment resin printing ink that has sufficient fastness against washing and dry cleaning like O/Wm or W10 type emulsion ink, and is easy to use and handle. With this in mind, it is suitable for writing instruments, etc., which have a discharge mechanism that utilizes capillary phenomenon at 1%.

The purpose is to obtain an ink for pigment resin textile printing.

(Means for Solving the Problems) In view of the above objectives, the present inventors have finally completed the present invention as a result of extensive research.

The gist of the invention is an ink for pigment resin printing comprising at least a solvent, a nitrocellulose, an alcohol solvent, and/or a glycol solvent.

Each component of the pigment resin textile printing ink of the present invention will be explained below.

Aluminum-based coupling agents are used to modify the surface of pigments, and specifically, they are used to modify the surface of pigments.
There is Al-M (manufactured by Ajinomoto@), which can be used as a processing agent before dispersing pigments, or can be added when dispersing a single pigment.The amount used is: It varies depending on the type of pigment, but for pigments.

001 to 50% by weight is preferred.

Pigments are used as coloring agents and are not particularly limited, and include azo pigments 1, phthalonani/based pigments,
Organic pigments such as nitroso-based pigments, nitro-based pigments, basic dye-based pigments, acid dye-based pigments, vat dye-based pigments, mordant dye-based pigments, and natural dye-based pigments, ocher, barium yellow, navy blue,
Cadmium red, barium sulfate, titanium oxide.

red iron black, aluminum hydroxide, calcium carbonate,
Examples include inorganic pigments such as carbon blank, which can be used alone or in combination, and are preferably used in an amount of 5 to 20% by weight based on the total amount of the ink.

Polyvinyl butyral resin (hereinafter abbreviated as PVB) is used as a pigment dispersant, anti-settling agent, and binder, and the amount added in the ink is important for the fastness of handwriting and the storage stability of the ink. It is preferable that there are many
When used in a writing instrument containing a pigment, if there is insufficient dispersion stability, a problem arises in that the pen tip becomes clogged and writing smudges occur.

However, if the amount added is large or if the degree of monopolymerization is high, the ink viscosity will increase. On the other hand, the viscosity of ink suitable for use in writing instruments with plastic nibs is 20 cps (at25v) or less, more preferably 15 cps (at25t7) or less, so those with an average degree of polymerization of 1000 or less are preferred. Preferably used, specifically Denka Butyral #2000-L, #5000-1,
#l OOO-2, #3000-4. #4000-
1. #4000-2 (1! Manufactured by Ki Kagaku Kogyo ■), S-LEC B L-1, B L-2, B L-5,
BL-8, BX-L, BM-1, BM-2゜BM-
5, BM-8 (there are above, Tanezu Chemical Industry (11 etc.),
Although the amount used varies depending on the average degree of polymerization, etc., it is preferably in the range of 0.1 to 2.0 in weight ratio (PVB/pigment) to the pigment.

Nitrocellulose is used as a dispersion aid and binder, and has an L1/8. Same 1/4゜ Same 1/2. H1
/16. Same 1/8. Same 1/4゜ Same 1/21 Same 21 Same 20
．． 60. 120 (grade according to JIS, 67m5-1975), etc. can be used alone or in combination, and the amount used varies depending on the molecular weight of the nitrogen content, but the amount used is from 05% to 10% by weight based on the total amount of ink. % is preferred.

Examples of alcohol solvents and glycol ether solvents include methanol, ethanol, n-propyl alcohol, and isopropyl alcohol.

n-phthyl alcohol, 5ee-butyl alcohol, t
Examples include crt-butyl alcohol, n-amyl alcohol, isoamyl alcohol, se c-amyl alcohol, rhohexanol and hymethyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, probile/glycol monomethyl ether, and the like.

As components other than those mentioned above, resins, surfactants, rust preventive agents, dispersion aids, lubricants, etc. may be used as appropriate.

As a method for producing the pigment resin printing ink according to the present invention, conventionally known methods can be adopted, and each of the above-mentioned components is mixed using a homomixer, a ball mill, a homogenizer, a sand mill,
It can be easily obtained by cross-dispersing using a dispersing machine such as a roll mill.

(Action Why is the pigment resin textile printing ink according to the present invention useful?

Woven fabrics or fabrics made of synthetic or natural fibers.

It is not clear whether it is suitable for these blended woven fabrics, especially for writing instruments that have a discharge mechanism that utilizes capillary action, but it is because PVB has a good affinity with pigments whose surface has been treated with an aluminum coupling agent. Fluidity and dispersion stability suitable for writing instruments with a discharge mechanism that utilizes capillary action can be obtained, and at the same time, the interaction between the pigment surface-treated with an aluminum coupling agent, PVB, and nitrocellulose allows it to be used in synthetic fibers or It is presumed that strong fixing properties appear in woven fabrics made of natural fibers or blended woven fabrics thereof.

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

1. Ink composition table 1 *1 Carbon black, manufactured by Mitsubishi Chemical Corporation *2 Permanent Red 4, manufactured by Dainippon Ink *5 Copper phthalocyanine, manufactured by Dainippon Ink *4 Vat dye pigment, Toyo Ink *4 *5 Rosin ester manufactured by Rika Percules *6 Oil-soluble alkanolamide compound (dispersing aid,
Comparative Example 4 MA-10012, 0 parts Styrene-Amine salt of acrylic acid (Dispersant: 45 parts Ethylene glycol: 10.0 parts Water)
335 parts Matsumizor M-1000 (acrylic acid ester copolymer emulsion, manufactured by Matsui Shiki Kagaku Kogyo Co., Ltd.) 40.0 parts Mix the other components except for the 1 resin emulsion in the above composition,
After performing dispersion treatment in a ball mill for 50 hours, a resin emulsion was added.

The mixture was stirred for 1 hour using a homomixer to obtain a black pigment resin printing ink.

2. Pigment surface treatment method Examples 1 to 4 and Comparative Examples 2 and 5 Dissolve the coupling agent in ethanol twice the amount of the pigment, add the pigment to this,
Stir and mix using a closed type homomixer, treat the pigment surface, and then remove ethanol.

5. Method for producing ink The surface-treated pigment, PVB or nitrocellulose, and an appropriate amount of solvent are mixed and dispersed in a roll mill to obtain an ink base, and the remaining components are added to this ink paste and mixed with stirring to obtain an ink.

(Effect of the invention) Tests were conducted on the inks obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results are shown in Table 2.

(Table 2) Washing resistance: JIS L0844-1973° washing color fastness test method.

It was carried out according to Method A-2.

Dry cleaning resistance 2 JIS LO860-
1974, color fastness test method for dry cleaning.

Viscosity: Measured with a B-type viscometer, BL adapter, 25C.

Dispersibility test: Each ink was placed in an oil-based membrane filter 0
．． 50 μm (TM-5P.

Toyo filter paper is instilled into the product, and its condition The condition was visually determined.

○: Completely passes ΔD Partially does not pass ×: Barely passes Pen tip clogging test 2 Each ink was filled into a felt-tip pen with a fiber nib made of acrylic resin fiber hardened with thermosetting resin. After being left for 5 months, writing was performed, and the condition was visually judged.

○: Good handwriting without clogging ×: Clogging occurs and handwriting becomes blurred Pen nib recovery test: Each ink was filled into a felt-tip pen having a fiber nib made of acrylic resin fiber hardened with thermosetting resin. After removing the cap and leaving it until it became completely impossible to write.

Cap and leave at room temperature for 24 hours. I put it there and looked at its writing performance.

O2 Completely restored and writable ×: Unrestored and unwritable Note) The test piece used for the washing resistance test and dry cleaning resistance test was a cotton broad cloth (65% polyester, 55% cotton) with a size of 1C x 5α. %) using a paper pattern and printing at room temperature.
The one that had been dried for a while was used. In addition, discoloration and fading are caused by J I
Judgment was made using SLO804 (discoloration fading gray scale).

As described above in detail, the pigment resin printing ink according to the present invention not only exhibits good washing resistance and dry IJ+ resistance without long-term drying or heat treatment, but also can be used for writing instruments. It has excellent fluidity and dispersibility even when wet, and does not clog the pen tip, and even if the pen tip dries up, it can be restored by capping it.

It goes without saying that the single-pigment resin textile printing ink can not only be used for basket marking tools, but also suitably used as a so-called dipping brush type.

Claims (1)

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