JP6991465B2 - Ink for tire marking - Google Patents

Description

The present invention relates to a tire marking ink, and more particularly to a tire marking ink that prevents cracks generated in a coating film applied to a tire.

Generally, in the inspection process of manufactured vehicle tires, unbalance measurement and uniformity measurement are performed. As a result of the inspection, for example, the position where the weight is the lightest (light point) in the circumferential direction of the tire and the part where the outer diameter of the tire is the largest are marked with an arbitrary color. When applying such a mark to the sidewall of a tire, a method of transferring and applying a mark having a predetermined shape by a stamp method has been adopted. As the ink used for the stamp, the stamp pad ink described in the examples of Patent Document 1 has been used.

Japanese Unexamined Patent Publication No. 2006-22609

It is necessary to set the film thickness of the coating film to be applied to the tire to 1 μm or more in order to prevent the black background on the tire surface from showing through, and to enhance the hiding power. However, if the film thickness is increased, the surface of the coating film shrinks when the coating film dries, cracks occur, and the drying time of the coating film becomes longer. If the tires were soiled or rubbed, the paint film would come off. For example, when the ink for the stamp pad described in the examples of Patent Document 1 is used as the ink for tire marking, when the coating film having a thickness of 12 μm applied to the tire is left for 24 hours under the condition of 20 ° C. × 65%. There were cracks in the coating film.

The present invention provides a tire marking ink that is stable over time to prevent cracks caused by shrinkage of the coating film surface after the coating film dries, while maintaining good hiding power and drying property of the coating film applied to the tire. do.

The first invention completed to solve the above-mentioned problems contains at least an organic solvent, a resin soluble in the solvent, titanium oxide, and an alkylsulfonic acid phenyl ester or polyoxyethylene laurylamine, and is blended. The amount of alkyl sulfonic acid phenyl ester is 0.6 to 5.6% by weight based on the total amount of ink, and the amount of polyoxyethylene laurylamine is 0.6 to 1.7% by weight based on the total amount of ink. Ester marking ink.

The second invention completed to solve the above problems is characterized in that the film thickness when the tire marking ink according to the first invention is applied to a tire is 1 μm to 100 μm. Ink for use.

In the first invention, an organic solvent, a resin soluble in the solvent, titanium oxide, and an alkyl sulfonic acid phenyl ester or a polyoxyethylene lauryl amine are contained at least, and the total amount of the alkyl sulfonic acid phenyl ester is the ink. The content of polyoxyethylene laurylamine is 0.6 to 1.7% by weight based on the total amount of the ink, and the amount of polyoxyethylene laurylamine is 0.6 to 1.7% by weight . Even if the applied coating film dries and shrinks, the occurrence of cracks can be prevented.

The second invention is a tire marking ink having a film thickness of 1 μm to 100 μm when the tire marking ink according to the first invention is applied to the tire. Therefore, the coating applied to the tire is applied. It is possible to prevent the occurrence of cracks over time while maintaining good hiding power and dryness of the film.

Hereinafter, the present invention will be described in detail. In the present invention, the organic solvent includes alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and benzyl alcohol, alicyclic hydrocarbons such as methylcyclohexane, dimethylcyclohexane and ethylcyclohexane, and fats such as hexane and octane. Group hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone, dimethyl ketone, diethyl ketone and 4-methoxy-4-methylpentanone, methyl acetate, ethyl acetate, propyl acetate and acetate. Esters such as butyl, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 2-methoxypropanol, 3-methoxy-3-methylbutanol and other glycol ethers. Alternatively, a mixture of two or more kinds is used. As the organic solvent, 40 to 99% by weight can be used with respect to the total amount of the ink, and 50 to 95% by weight is particularly preferable.

In the present invention, titanium oxide is blended in order to enhance the concealing property. The titanium oxide used has an average particle size of 0.001 μm or more, and both rutile type and anatase type can be used. For example, Bayertitan R-FD-1, R-KB-3, R-CK- 20 (above, manufactured by Bayer), TIPAQUE R-630, R-615, R-830 (above, manufactured by Ishihara Sangyo Co., Ltd.), Unitane OR-342 (manufactured by AC.C.), Ti- Commercially available products such as pure R-900 / R-901 (manufactured by EI Dupont), MICROLITH White RA / R-AB (manufactured by Ciba Geigy), ENCE PRINT White 0027 (manufactured by BASF), etc. Known titanium oxide such as a processing pigment can be used.
The blending amount of titanium oxide is 0.1 to 80% by weight, preferably 5 to 40% by weight, based on the total amount of ink.

As the dispersant for titanium oxide, silica, alumina, talc, aluminum silicate, calcium carbonate, magnesium carbonate and the like can be used. Among them, silica and aluminum silicate are particularly preferable. These dispersants may be used alone or in combination of two or more.
In the present invention, the above dispersants can be used alone or in combination of two or more, and the blending amount thereof is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the ink. ..

In the present invention, conventionally known organic pigments and inorganic pigments can be used as colorants, and they can be blended in combination with titanium oxide. For example, organic pigments such as azo, phthalocyanine, anthraquinone, dioxazine, indigo / thioindigo, verinone / verylene, isoindrenone, azomethyleneazo, carbon black, mica, pearl pigment, iron / aluminum powder. -Inorganic pigments such as metal pigments such as brass can be used. If these pigments are kneaded into a styrene-acrylic acid copolymer, a polyacrylic acid resin, polyvinyl alcohol, polyvinyl butyral, or the like to form a processed pigment, it is convenient because they are easily dispersed when mixed with a solvent. Further, a commercially available processed pigment in which the pigment is already kneaded into the dispersant may be used.
In addition, it is permissible to add a dye as a colorant. As the dye, conventionally known oil-soluble dyes such as monoazo-based, disazo-based, metal complex salt-type monoazo-based, anthraquinone-based, phthalocyanine-based, and triallylmethane-based dyes can be used without particular limitation.
The dyes and pigments can be used alone or in combination, and the blending amount thereof is preferably 1 to 40% by weight based on the total amount of the ink.

As the resin used in the present invention, a rosin-based resin is used, and a rosin-modified maleic acid resin, a rosin-modified ester resin, a rosin-modified phenol resin, a rosin-modified fumaric acid resin, and the like are used.
The above rosin-based resin can be used alone or in combination of two or more, and the blending amount thereof is 5 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of the ink.
In addition to the rosin-based resin, other oil-soluble resins can be blended, such as acrylic resin, ester resin, cellulose resin, phenol resin, polybutylbutyral, ketone formaldehyde resin, alkylphenol resin, and styrene-maleic acid resin. It may be blended in a small amount.

In the present invention, alkyl sulfonic acid phenyl ester or polyoxyethylene lauryl amine is used as the crack inhibitor. Since the crack inhibitor has the property of softening the resin, the resin does not completely cure even when the coating film dries, and a certain degree of flexibility can be maintained. Therefore, it is considered that the stress applied to the surface of the coating film due to drying shrinkage can be relaxed and the occurrence of cracks over time can be prevented.
Specific examples of the alkyl sulfonic acid phenyl ester used in the present invention include MESAMOLL manufactured by LANXESS Co., Ltd. In addition to this, various plasticizing agents can be used, specifically, dimethylphthalate, diethylphthalate, dibutylphthalate, diheptylphthalate, di-2-ethylhexylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, and butyl. Phthalate-based plasticizers such as benzylphthalate, adipic acid ester-based plasticizers such as dimethyl adipate, dibutyl adipate, diisobutyl adipate, dihexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, dibutyl diglycol adipate, trimethylphosphate, triethyl Phthalate-based plasticizers such as phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixilenyl phosphate, cresylphenyl phosphate, tri-2-ethylhexyltri Trimellitic acid ester-based plasticizers such as melitate, sevatinic acid ester-based plasticizers such as dimethylsevacate, dibutylsevacate, di-2-ethylhexyl sebacate, and aliphatic-based plastics such as poly-1,3-butanediol adipate. Phthalate plasticizers such as polyester plasticizers, diethylene glycol dibenzoate, dibutylene glycol dibenzoate, epoxidized ester plasticizers such as epoxidized soybean oil, alicyclic dibasic acid ester plasticizers, polypropylene glycol, polybutylene Examples thereof include polyether-based plasticizers such as glycol and citrate-based plasticizers such as acetyltributyl citrate.
Specific examples of the polyoxyethylene laurylamine used in the present invention include NOF Corporation's Nymine L-201, L-202, L-207 and the like. In addition to the above, Nymine L-703 (polyoxyethylene polyoxypropylene laurylamine), F-202, F-215 (above, polyoxyethylene alkyl (palm) amine) manufactured by Nichiyu Co., Ltd., T2-202, T2-210, T2-230 (above, polyoxyethylene beef alkylamine), S-202, S-204, S-210, S-215, S-220 (Same as above) As mentioned above, polyoxyethylene stearylamine), O-205 (polyoxyethylene oleylamine), DT-203, DT-208 (polyoxyethylene alkyl propylene diamine) and the like can be mentioned. These crack inhibitores can be used alone or in combination of two or more, and the blending amount thereof is preferably 0.5 to 8.0% by weight based on the total amount of ink from the viewpoint of crack resistance and drying property. , More preferably 0.6 to 5.6% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The ink for tire marking of the present invention is adjusted by adding an organic solvent, a resin soluble in the solvent, titanium oxide, an alkylsulfonic acid phenyl ester or polyoxyethylene laurylamine, and various additives as necessary, and stirring the mixture. do.

表中のアルキルスルホン酸フェニルエステル、ポリオキシエチレンラウリルアミンはそれぞれＬＡＮＸＥＳＳ(株)製のメザモール（ＭＥＳＡＭＯＬＬ）、日油(株)製のナイミーンＬ－２０２である。 Table 1 shows the ink formulations of Examples and Comparative Examples.

The alkyl sulfonic acid phenyl ester and polyoxyethylene lauryl amine in the table are MESAMOLL manufactured by LANXESS Co., Ltd. and Naimeen L-202 manufactured by NOF Corporation, respectively.

The examples and comparative examples were tested under the following conditions.
A. Crack resistance test
(Test method)
Regarding the produced ink, the hand coater No. 0 (thickness 4 μm), No. 1 (thickness 6 μm), No. 2 (thickness 12 μm), No. 8 (thickness 100 μm), No. A uniform coating using 500 (thickness 500 μm) (all manufactured by Matsuo Sangyo Co., Ltd.) so as to have each predetermined film thickness was allowed to stand for 24 hours under the condition of 20 ° C. × 65%. After that, it was visually confirmed whether or not cracks were generated on the surface of the coating film, and the crack resistance was evaluated as “◯” when no cracks were generated and “×” when cracks were generated.
B. Coating film drying property test (test method)
Similar to the crack resistance test, the tire pieces coated with ink at each predetermined film thickness were left for 24 hours under the condition of 20 ° C. × 65%. After that, in order to check the dryness of the coating film, check whether the ink adheres when the coating film is rubbed with a finger. If the ink does not adhere, "○", if the ink adheres, "×" The dryness of the coating film was evaluated as.

From Examples 1 to 8 and Comparative Example 1 in Table 1, it can be seen that cracks generated in the coating film can be prevented by blending an alkylsulfonic acid phenyl ester or polyoxyethylene laurylamine. Further, from Examples 1 to 4, both crack resistance and coating film drying property are good in the range of the film thickness of 1 μm to 100 μm. Here, the minimum value of the film thickness is set to 1 μm as a critical value at which the black background of the tire piece does not set off. On the other hand, as compared with Comparative Example 3, when the film thickness is increased to 500 μm, the coating film does not dry even after 24 hours have passed, and the drying property of the coating film is significantly lowered. From the above, it is possible to reliably prevent the occurrence of cracks over time while maintaining good drying and hiding properties in the film thickness range of 1 μm to 100 μm. The crack resistance test of Comparative Example 3 (thickness 500 μm) has not been performed because the coating film was not dried even after 24 hours had passed.
From Examples 3, 5 and 6, the coating film drying property is good when the blending amount of the alkyl sulfonic acid phenyl ester is in the range of 0.6 to 5.6% by weight. On the other hand, when the blending amount of the alkyl sulfonic acid phenyl ester was increased to 10.6% by weight as compared with Comparative Example 3, the coating film drying property was remarkably improved even though the film thickness was the same as in Examples 3, 5 and 6. At the same time as the decrease, the alkyl sulfonic acid phenyl ester softens (dissolves) the tire piece, causing problems such as the coating film turning black. From the above, it is considered that the blending amount of the crack inhibitor is preferably 0.5 to 8.0% by weight, more preferably 0.6 to 5.6% by weight.

As described above, the present invention has been described in relation to the most practical and preferable embodiments at the present time, but the present invention is not limited to the embodiments disclosed in the present specification. It is understood that tire marking inks with such changes are also included in the technical scope, as they can be changed as appropriate within the scope of the claims and within the scope not contrary to the gist or idea of the invention that can be read from the entire specification. There must be.

Claims (2)

It contains at least an organic solvent, a resin soluble in the solvent, titanium oxide, and an alkyl sulfonic acid phenyl ester or polyoxyethylene lauryl amine, and the blending amount of the alkyl sulfonic acid phenyl ester is 0.6 with respect to the total amount of ink. An ink for tire marking, characterized in that the amount of polyoxyethylene laurylamine is ~ 5.6% by weight and the amount of polyoxyethylene laurylamine is 0.6 to 1.7% by weight based on the total amount of the ink. A tire marking ink having a film thickness of 1 μm to 100 μm when the tire marking ink according to claim 1 is applied to a tire.