JPS5913551B2 - Ink composition for plastics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention enables clear coating or writing on easily charged plastics such as polyethylene, polypropylene, polyvinyl chloride, and polyester with sufficient hiding power, and also allows the coated or written portion to be light-resistant. This invention relates to an ink composition for plastics that has excellent water resistance and low odor.

In general, plastic molded products are often colored, so the ink applied to them is required to have excellent hiding power so that traces of application can be clearly identified, as well as excellent light resistance and water resistance. Therefore, it is preferable that the ink uses a pigment as a coloring agent. However, since inks using pigments use benzene, toluene, etc. as solvents, they have a strong odor and have physiological effects on the body. Furthermore, when applying or writing on the above-mentioned easily charged plastic, the plastic becomes charged due to friction with the brush or pen tip, and the application marks or writing marks are repelled, making clear application or writing impossible. There was a problem. In addition, in order to prevent this repellency problem, it is known that surfactants such as polyoxyethylene alkylphenol ether and alkyl sulfate ester sodium salt are added to the ink composition, but these have a solubility point of 10. There have been problems in that there are restrictions on the solvents that can be used, or that even if they are sufficiently dissolved in the solvent, these surfactants are water-soluble, resulting in poor water resistance of dry application marks or dry writing marks. Therefore, in order to solve the above-mentioned problems, the present invention was developed as a result of research on 15 types of ink, which uses pigment as the main component colorant, aliphatic hydrocarbon solvent as solvent, and resin as fixing agent. 20, in which at least one amide or amine salt of dimer acid or trimer acid, which is a polymer of unsaturated fatty acids, is blended,
It was discovered that a remarkable effect of preventing repelling can be obtained, and the present invention was completed.

In other words, a plastic whose main components are pigments, aliphatic hydrocarbon solvents, and resins, and at least 25 types of amide or amine salts of dimer acid, which is a polymer of unsaturated fatty acids, or trimer acid. The gist of this paper is an ink composition for use in printing. Next, each component of the ink composition of the present invention will be explained in detail.

The pigments used in the present invention include inorganic pigments such as titanium dioxide, Bengara, Chrome Yellow 30-, and carbon black, and organic pigments such as Benzine Yellow and Lake Red. Although this pigment can be changed in various ways depending on the use, for example, as an ink for writing instruments, it is used in a range of 5 to 50% by weight of the ink composition.
It is preferable to use 5%. Examples of aliphatic hydrocarbon solvents that can sufficiently disperse the pigment include chain aliphatic hydrocarbon solvents such as n-, iso, and hexane, heptane, octane, decane, and ligroin; One or more selected from the group of cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane are used, and those having a boiling point of 80 to 180° C. are preferable because of their low odor.

The aliphatic hydrocarbon solvent may be varied depending on the use, but for example, for writing ink, it is suitable to use it in an amount of 40 to 80% by weight of the ink composition. The resin is selected from those that form a tough film at 20 cps/25°C or less when adjusted to a 10% by weight solution using the aliphatic hydrocarbon solvent, such as petroleum resin,
Examples include alicyclic hydrocarbon resin, alkylphenol resin, alkyd resin, rosin, and coumaron resin.

Dimer acid or trimer acid, which is a polymer of unsaturated fatty acids that can be suitably used in the present invention, specifically includes tall oil;
Semi-drying oils such as cottonseed oil, corn oil, sesame oil, soybean oil, sunflower oil, and rice bran oil; Adding sodium hydroxide to non-drying oils such as olive oil, camellia oil, pento oil, palm oil, and fallen seed oil, free fatty acids Completely saponified the saponified free fatty acids, removed the saponified free fatty acids with hot water, dehydrated in vacuum, and decolorized with white clay to obtain purified vegetable unsaturated fatty acids. body or trimer.

The dimerization method will be described below using linoleic acid as an example.

By thermally polymerizing linoleic acid at 300°C, DieIsAld is created between the conjugated isomer of linoleic acid and linoleic acid.
er reaction occurs and cyclohexane structure heat ::●? :vessel:
x2-W,T(': Hydrocarbon residue At this time K.K:??y?6??2?Eye-?W Pass.
is the desired amine salt of dimer acid.

Amide or amine salts of trimer acids can also be obtained in a similar manner. By adding the amide or amine salt of dimer acid or trimer acid to the ink for writing instruments, it is possible to prevent the repelling phenomenon without inhibiting the dispersion of the pigment or reducing the water resistance of the coating film.

At this time, a dimer with Daifuzo is generated. Note that anthraquinone, SO2, etc. are used as the catalyst. In addition to the method described in +, there are methods using activated clay or a Lewis acid catalyst such as phosphoric acid or BF3, and a method using a peroxide catalyst. The manufacturing method and structural formula of the amide or amine salt of the dimer acid or trimer acid are as follows. For simplicity, the structural formulas of dimer acid and trimer acid are shown below.

[Dimer acid]

HOOC-R-COOH (R: Hydrocarbon with unsaturated bonds forming the backbone of dimer monoacid) [Trimer acid] (R: Hydrocarbon having unsaturated bonds forming the backbone of trimer monoacid) [Amide of dimer acid Production method and structural formula] (1)
Dimer acid is converted to acid chloride with thionyl chloride.

1-0) (+00IF-SOCl2→ClαH to K.K
℃l+gift? (2) Reacting the acid chloride with a primary amine or a secondary amine.

α00丑℃(1)l+2蛘,→Fake℃H ℃v 『CIO(
+(1)7+2WBi←MrN°CHW,W: Hydrocarbon residue Blood NOC-R-CONHW R/BiNOC-R-CONWBi is the target dimer acid amide.

[Production method and structural formula of amine salt of dimer acid] Dimer acid and primary amine or secondary amine and CO? ? ? ? ? ?
3R-COO3NWWH2 Monoacid or trimer acid alone, primary amine or secondary
The repellency phenomenon cannot be prevented by using a class amine alone. Therefore, the amount of the amide or amine salt of dimer acid or trimer acid used can be varied depending on the application, but for example, as an ink for writing instruments, the amount of the ink composition is 0. .5-5% by weight
It is suitable when it can be used.

The ink composition of the present invention includes a pigment, an aliphatic hydrocarbon solvent,
Obtained by adding and blending at least one amide or amine salt of dimer acid or trimer acid, which is a polymer of unsaturated fatty acids, into a resin, and dispersing the blend with a dispersing machine such as a ball mill, atlyzer, or sand mill. However, if necessary, homogenol Ll8 (manufactured by Kao Atlas Co., Ltd.), Disparon◆301 (manufactured by Kusumoto Kasei Co., Ltd.)
Oil-based dispersants such as the following can be added.

Next, an example of the present invention will be described regarding an ink for a writing instrument. In the examples, "parts" simply indicate parts by weight. [Example 1] Titanium dioxide 35 parts Argon P-12510 parts (alicyclic hydrocarbon resin, manufactured by Arakawa Forestry Co., Ltd.) Ethylcyclohexane 50 parts Versadime 282 (obtained from a mixture of linoleic acid and oleic acid purified from tall oil) Dimer acid, Pengel Japan (
stearylamide (manufactured by Co., Ltd.)
The two-part dimer acid stearylamide is obtained by reacting dimer acid chloride with stearylamine, as described above.

The above components are blended and the blend is dispersed in a ball mill for 24 hours.

Fill a writing instrument with the obtained ink and store at a temperature of 45°C and a humidity of 3.
Even if you write on a charged surface of a polyethylene molded product that has been left under 0% conditions for one day by rubbing it with a dry cloth, the phenomenon of the writing marks being repelled in all directions is not observed, and clear writing marks are obtained. It was done. [Example 2] Lake Red C2O part Hytanol 113315 parts (Ano lephenol resin, manufactured by Hitachi Chemical Co., Ltd.) Isopa1 E2O parts (Isoparaffinic solvent, manufactured by Etsu Standard Oil Co., Ltd.) Ethylcyclohexane 30
Cyclohexylamide of 3-part Versadime 282 (dimer acid obtained from a mixture of linoleic acid and oleic acid purified from tall oil) 3-part dimer acid cyclohexylamide is produced in the form of a wax by reacting dimer acid chloride with cyclohexylamine as described above. Obtained as a substance.

The above ingredients were blended and the blend was dispersed in a ball mill for 24 hours.

When a writing instrument was filled with the obtained ink and the same test as in Example 1 was conducted, no phenomenon of the writing marks being repelled in all directions was observed, and clear writing marks were obtained. [Example 3] Titanium dioxide 35 parts Argon P-12510 parts (alicyclic hydrocarbon resin, manufactured by Arakawa Forestry Co., Ltd.) Ethylcyclohexane 50 parts Versadime 228 (obtained from a mixture of linoleic acid and oleic acid purified from tall oil) Monoethanolamine salt of dimer acid (manufactured by Pengel Japan Co., Ltd.)
7.0 parts of monoethanolamine is added to 28.5 parts of a 2-part dimer acid (acid value: 200, trade name: Versadime 228) and reacted with stirring for 30 minutes to obtain a dimer acid monoethanolamine salt.

The above components are blended and the blend is dispersed in a ball mill for 24 hours.

Fill a writing instrument with the obtained ink and store at a temperature of 45°C and a humidity of 3.
Even if you write on a charged surface of a polyethylene molded product that has been left under 0% conditions for one day by rubbing it with a dry cloth, the phenomenon of the writing marks being repelled in all directions is not observed, and clear writing marks are obtained. It was done. [Example 4] Lake Red C2O part Hytanol 113,315 parts (Anoyu phenol resin, manufactured by Hitachi Chemical Co., Ltd.) Isopa1 E2O parts (Isoparaffinic solvent, manufactured by Etsustandakodo Oil Co., Ltd.) Ethylcyclohexane 3
0 parts Laurylamine salt of Versadime 228 (dimer acid obtained from a mixture of linoleic acid and oleic acid purified from tall oil) 3 parts Dimer acid laurylamine salt is obtained in the same manner as in Example 3.

The above components are blended and the blend is dispersed in a ball mill for 24 hours.

Claims (1)

[Claims] 1 The main components are pigments, resins, aliphatic hydrocarbons and/or alicyclic hydrocarbons, and at least one amide or amine salt of dimer acid or trimer acid, which is a polymer of unsaturated fatty acids, is blended therewith. An ink composition for plastics.