JP7176979B2 - Marker ink composition - Google Patents

Description

The present invention relates to a marker ink composition.

2. Description of the Related Art Conventionally, resins have been blended into water-based inks for writing instruments for the purpose of imparting stickiness of drawn lines to a material to be written. When a writing instrument filled with such ink is left uncapped, the resin in the ink dries and solidifies on the surface of the ink ejection mechanism, and the ink ejection performance tends to deteriorate. Markers, in particular, have a larger ink ejection mechanism area than ballpoint pens, and this tendency is remarkable. Such deterioration of the ink ejection property of the writing instrument is particularly susceptible to the type or blending amount of the resin.

The decrease in ink ejection property is caused by aggregation and precipitation of the resin due to volatilization of water, which hinders the outflow of ink from the writing section. As a method to suppress this, there is a method of creating a "lid"-like state by not causing aggregation or by causing loose aggregation, but even loose aggregation forms a bulky aggregation structure. As a result, the ink becomes as if it contains high-viscosity lumps, and although the ink dischargeability can be maintained, there is a problem such as the quality of drawn lines being degraded.

As an ink composition for writing instruments with improved ink ejection properties, a water-based ink composition for ballpoint pens containing a colorant, water, and a hyperbranched polymer has been reported (Patent Document 1). The hyperbranched polymer is a multi-branched polymer, amorphous, low-viscosity and solvent-soluble. In Patent Document 1, by adding the hyperbranched polymer to the water-based ink, unlike conventional linear polymers, the viscosity of the ink is not increased, the cap-off performance is not hindered, and the It is disclosed that the ink followability of the ink is also good and the handwriting can be formed without blurring.

Patent Document 2 also discloses at least a coloring agent, a solvent, inorganic particles having a new Mohs hardness of 4 or more, and a dendritic polymer having an ester group in a repeating molecular structure and terminal hydroxyl groups and/or carboxyl groups. A ballpoint pen ink composition containing the above is disclosed. The dendritic polymer has a terminal hydroxyl group and a carboxyl group, and an ester group in the repeating molecular structure. Adsorbs through hydrogen bonding. In Patent Document 2, since the dendritic polymer forms an adsorption structure in which the dendritic polymer sticks in a planar shape, the inorganic particles are not entangled with each other when they come into contact with each other, and the inorganic particles are sandwiched between the ball and the inner wall of the ball holder. As a result, the rollers and warpage functions of the inorganic particles are fully exhibited without damaging the metal surface, and the smooth rotation of the ball is maintained, resulting in a beautiful and continuous ball. It is disclosed that good writing can be maintained.

JP 2015-124345 A JP 2014-198757 A

However, the ink compositions disclosed in Patent Documents 1 and 2 are inks for ballpoint pens, and the ink ejection properties when used as inks for markers are unclear. As described above, a marker has a larger ink ejection mechanism area than a ballpoint pen, and if the cap-off state continues, the ink on the surface of the ink ejection mechanism dries and solidifies, easily causing poor writing. If the cap is put on, the solidified material relaxes and normal writing becomes possible again, but depending on the degree of solidification, the writing performance may not fully recover.

The present invention is intended to solve the problems in the prior art described above, and by adding a specific hyperbranched polymer, a marker exhibiting recovery of writing performance, i. An object of the present invention is to provide an ink composition for

The marker ink composition of the present invention is characterized by containing 0.5 to 20% by mass of a hyperbranched polymer represented by the following general formula (1).

Ｙは下記一般式（３）で表される置換基または水酸基を表し、

Ｍ¹は水素原子または下記一般式（４）で表される置換基を表し、

Ｍ²は水素原子または下記一般式（５）で表される置換基を表す。

In general formula (1), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ⁵ and R ⁶ are linked together to form an aliphatic 5 R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ³ and R ⁴ are linked together to form an aromatic 6-membered ring. may be formed, and X represents a substituent represented by the following general formula (2),

Y represents a substituent or a hydroxyl group represented by the following general formula (3),

M ¹ represents a hydrogen atom or a substituent represented by the following general formula (4),

^M2 represents a hydrogen atom or a substituent represented by the following general formula (5).

However, in the general formulas (2) to (5), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, R ⁸ represents an alkyl group having 12 to 18 carbon atoms, and m and n are each 12. Represents an integer from ~18.
The ink composition for a marker of the present invention is selected from the group consisting of trimethylglycine, carnitines, pentaerythritol, sugar alcohol, dextrin and reduced starch syrup, in addition to the hyperbranched polymer represented by the general formula (1). At least one kind is preferably included.

According to the present invention, by blending a specific hyperbranched polymer in the marker ink, it is possible to obtain a drawn line with high adhesion, and the ink on the surface of the ink ejection mechanism dries and solidifies due to the continued cap-off state. It is possible to provide an ink composition that can be rewritten by loosening the solidified product by capping.

The ink composition for markers of the present invention (hereinafter also simply referred to as "ink composition") is characterized by containing 0.5 to 20% by mass of a hyperbranched polymer represented by general formula (1).

In general formula (1), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ⁵ and R ⁶ are linked together to form an aliphatic 5 R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ³ and R ⁴ are linked together to form an aromatic 6-membered ring. may be formed.

Examples of alkyl groups having 6 to 15 carbon atoms include n-hexyl, cyclohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 1 , 4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, and n-dodecyl and the like. Among these, alkyl groups having 10 to 15 carbon atoms are preferred, and more specifically, alkyl groups having 12 carbon atoms are more preferred.

Aliphatic 5- to 8-membered rings are specifically cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
A six-membered aromatic ring is specifically benzene.
X represents a substituent represented by general formula (2).

Y represents a substituent represented by general formula (3) or a hydroxyl group.

Ｍ²は水素原子または下記一般式（５）で表される置換基を表す。

In general formulas (2) and (3), m represents an integer of 12-18, preferably 17.
In general formula (1), M ¹ represents a hydrogen atom or a substituent represented by general formula (4).

^M2 represents a hydrogen atom or a substituent represented by the following general formula (5).

In general formulas (4) and (5), n represents an integer of 12-18, preferably 17.
In general formulas (2) to (5), R ⁷ represents an alkyl group having 6 to 15 carbon atoms. Preferred forms of alkyl groups having 6 to 15 carbon atoms are as described above. R ⁸ represents an alkyl group having 12 to 18 carbon atoms. Among these, an alkyl group having 17 carbon atoms and the like are more preferable.
In general formula (1), a wavy line represents a single bond or a double bond, and in general formulas (2) to (5), * represents the position of a bond.

Specifically, the hyperbranched polymer represented by the general formula (1) is preferably compounds (1) to (5) represented by the following structural formulas.

The hyperbranched polymer represented by the general formula (1) can be obtained by a general synthesis method, that is, a method of polycondensing ABx type molecules having a total of 3 or more of two types of substituents in one molecule, or a method of polycondensing one molecule It may be produced by a method of polycondensing a molecule having a group capable of initiating polymerization and a polymerizable group, that is, a so-called inimer. Commercially available products such as S80 1700 and ZW 6403 (both registered trademarks, manufactured by DSM) may be used.

The ink composition for markers of the present invention contains 0.5 to 20% by mass, preferably 1 to 10% by mass, of the hyperbranched polymer represented by general formula (1) with respect to the total amount of the ink composition. When the content of the hyperbranched polymer represented by formula (1) is within the above range, the resulting ink composition can provide drawn lines with excellent adhesion. In addition, even if the ink on the surface of the ink ejection mechanism dries and solidifies after the cap-off state continues, the solidified substance relaxes and restores the writing performance when the cap is put on. On the other hand, when the content of the hyperbranched polymer represented by the general formula (1) exceeds 20% by mass, the viscosity of the ink composition increases, and blurring may occur.

Due to its specific molecular structure, the hyperbranched polymer represented by the general formula (1) does not form a strong crystal structure even when water volatilizes, and forms a loosely solidified product even when dried and solidified. . By putting it in an environment where moisture is supplied again, that is, by capping it, the solidified material relaxes and it becomes possible to write again.

In addition to the hyperbranched polymer represented by the general formula (1), the marker ink composition is selected from the group consisting of trimethylglycine (glycine betaine), carnitines, pentaerythritol, sugar alcohol, dextrin and reduced starch syrup. may contain at least one These ingredients act as anti-drying agents in the ink composition.
The content of these components, ie, the anti-drying agent, is generally 0.1 to 20% by mass, preferably 1 to 10% by mass, based on the total amount of the ink composition for markers.
The content ratio (mass ratio) of the hyperbranched polymer represented by the general formula (1) to the anti-drying agent is approximately 1:10 to 10:1.

In addition to the hyperbranched polymer represented by the general formula (1) and the anti-drying agent, the marker ink composition further contains water, a pigment, a pigment dispersant, and a dye within a range that does not impair the effects of the present invention. , pH adjusters, surfactants, solvents and preservatives.
As water, tap water, distilled water, ion-exchanged water, pure water, and the like are used.
Any of pigments conventionally used for water-based markers can be used as the pigment. Specifically, inorganic pigments such as carbon black, graphite and titanium dioxide; structural pigments such as talc, silica, alumina, mica and alumina silicate; azo pigments, condensed azo pigments, phthalocyanine pigments and anthraquinone pigments. , quinacdrine pigments, isoindolinone pigments, diketopyrrolopyrrole pigments and various lake pigments; fluorescent pigments, pearlescent pigments, and metallic pigments such as gold and silver. These pigments may be used alone or in combination of two or more.

Pigment dispersants include, for example, resin compounds such as styrene-acrylic acid copolymers and styrene-maleic acid copolymers; surfactants such as polyoxyethylene alkyl ethers and sodium alkylbenzene sulfonate.

Any of direct dyes, acid dyes, food dyes and basic dyes conventionally used for water-based markers can be used as the dye. These dyes may be used alone or in combination of two or more. good.

Known pH adjusters such as triethanolamine and aminomethylpropanol are used depending on the need for pH adjustment.
Any of nonionic, cationic and anionic surfactants can be used as the surfactant.
As the solvent, highly water-soluble polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, propylene glycol, 3-methoxy-3-methyl-1-butanol, or glycol ethers are used.
Carboxylic acid-based, halogen-based, imidazole-based, thiazole-based, pyridine-based, triazine-based, and imide-based compounds are used as preservatives.

The content of water is usually 20 to 90% by mass with respect to the total amount of the ink composition. In addition, the content of pigments, pigment dispersants, dyes, pH adjusters, surfactants, solvents and preservatives is usually adjusted appropriately between 0.001 and 40% by mass with respect to the total amount of the ink composition. .

The marker ink composition of the present invention can be prepared by a conventionally known method. For example, it can be prepared by blending the hyperbranched polymer and each of the above-described arbitrary components in predetermined amounts with water and stirring and mixing with a stirrer such as a homomixer or a disper. Furthermore, if necessary, coarse particles and the like in the marker ink composition may be removed by filtration or centrifugation.

As described above, the marker ink composition of the present invention contains a specific hyperbranched polymer, so that it has excellent line-drawing performance with excellent adhesion, and is also excellent in rewriting properties.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to the following examples.
[Example 1]
[Preparation of Marker Ink Composition]
Carbon black (MCF88; manufactured by Mitsubishi Chemical Corporation) 10% by weight and pigment dispersant (Joncryl 60; manufactured by BASF Japan) 10% by weight were added to 71% by weight of ion-exchanged water to form an aqueous dispersion, and compound (1) was added by 5% by weight. %, pH adjuster (triethanolamine) 0.5% by mass, surfactant (LEOCOL TD-50; manufactured by Lion Corporation) 0.2% by mass, preservative (sodium benzoate) 0.3% by mass, and drying prevention A marker ink composition was prepared by adding 3% by mass of an agent (glycine betaine) and stirring at room temperature. The total amount of carbon black, pigment dispersant, ion-exchanged water, hyperbranched polymer, pH adjuster, surfactant, preservative, and anti-drying agent is 100% by mass.

[Evaluation of Marker Ink Composition]
(1) Adhesiveness A marker ink composition is filled in a pen body of PM-120T manufactured by Mitsubishi Pencil Co., Ltd. (trade name “Plocky”, pen core: ultrafine (POM resin core) + fine round core (PET fiber core)). , Draw a spiral with a diameter of about 15 mm on the PET film 8 times in an environment with a temperature of 25 ° C and a humidity of 65%. was visually evaluated (n=10). It should be noted that writing was performed with both ultra-fine and fine pen cores, and bad evaluations were described.
Evaluation criteria:
A: Same as before rubbing (no disappearance at all)
B: Less than 25% of drawn lines are erased C: 25% or more of drawn lines are erased

(2) Rewritability A PM-120T pen body manufactured by Mitsubishi Pencil Co., Ltd. was filled with each water-based pigment ink composition, and a spiral with a diameter of about 15 mm was drawn on a PET film eight times. Remove the cap and leave it sideways in an environment with a temperature of 25 ° C. and a humidity of 65%, then cap it and leave it under the same conditions for 24 hours. In comparison, visual evaluation was made according to the following evaluation criteria (n=10). It should be noted that writing was performed with both extra-fine and fine pen cores, and bad evaluations were listed.
Evaluation criteria:
A: Same as the line drawn before the test B: Slightly thinner than before the test C: Remarkably thinner than before the test .

[Example 2]
In Example 1, the type of anti-drying agent was changed from glycine betaine to carnitine, the amount of compound (1) was changed from 5% by mass to 1% by mass, and the amount of ion-exchanged water was changed from 71% by mass to 75% by mass. A marker ink composition was prepared in the same manner as in Example 1, except that the mass % was changed.
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

[Example 3]
In Example 1, the type of anti-drying agent was changed from glycine betaine to pentaerythritol, the amount of compound (1) was changed from 5% by mass to 10% by mass, and the amount of ion-exchanged water was changed from 71% by mass. A marker ink composition was prepared in the same manner as in Example 1, except that the concentration was changed to 66% by mass.
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

[Example 4]
A marker ink composition was prepared in the same manner as in Example 1, except that no anti-drying agent was used and the amount of ion-exchanged water was changed from 71% by mass to 74% by mass. .
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

[Example 5]
A marker ink composition was prepared in the same manner as in Example 1, except that the type of anti-drying agent was changed from glycine betaine to xylitol.
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

[Example 6]
A marker ink composition was prepared in the same manner as in Example 1, except that the type of anti-drying agent was changed from glycine betaine to dextrin (MALTRIN M100; manufactured by Sankei Co., Ltd.).
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

[Example 7]
A marker ink composition was prepared in the same manner as in Example 1, except that glycine betaine in Example 1 was changed to reduced starch (H-PDX; manufactured by Matsutani Chemical Industry Co., Ltd.).
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

実施例１と同様にマーカー用インク組成物を評価した。
結果を表１に示す。 [Example 8]
A marker ink composition was prepared in the same manner as in Example 1, except that the type of the hyperbranched polymer was changed from compound (1) to compound (2).

The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

実施例１と同様にマーカー用インク組成物を評価した。
結果を表１に示す。 [Example 9]
A marker ink composition was prepared in the same manner as in Example 8, except that the type of the hyperbranched polymer was changed from compound (2) to compound (5).

The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

実施例１と同様にマーカー用インク組成物を評価した。
結果を表１に示す。 [Example 10]
A marker ink composition was prepared in the same manner as in Example 8, except that the type of the hyperbranched polymer was changed from compound (2) to compound (3).

The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results.

Unlike Examples 1-3 and 5-10, Example 4, in which no anti-drying agent was used, was slightly inferior to Examples 1-3 and 5-10 in resuming properties. It is considered that this is because some of the water in the ink composition was volatilized.

[Comparative Example 1]
A marker ink composition was prepared in the same manner as in Example 1, except that the hyperbranched polymer was not used and the amount of ion-exchanged water was changed from 71% by mass to 76% by mass. .
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results. Comparative Example 1 showed poor adhesion. From this result, it can be seen that in Comparative Example 1, since neither the hyperbranched polymer nor the fixing resin was used, the fixing property was insufficient.

[Comparative Example 2]
In Example 1, instead of 5% by mass of hyperbranched polymer, 10% by mass of fixing resin (Joncryl 7100; manufactured by BASF Japan) was used, and the amount of ion-exchanged water was changed from 71% by mass to 66% by mass. A marker ink composition was prepared in the same manner as in Example 1, except for the above.
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results. In Comparative Example 2, the fixability was excellent, but the rewriting performance was poor. From these results, it was found that the hyperbranched polymer has excellent rewriting properties while having adhesion properties equivalent to those of conventional fixing resins.

[Comparative Example 3]
A marker ink composition was prepared in the same manner as in Example 1, except that 5% by mass of the fixing resin (HUX-564; manufactured by ADEKA) was used instead of 5% by mass of the hyperbranched polymer. .
The marker ink composition was evaluated in the same manner as in Example 1.
Table 1 shows the results. In Comparative Example 3, similarly to Comparative Example 2, the adhesion was excellent, but the rewriting property was poor. From these results, it was found that the hyperbranched polymer has excellent rewriting properties while having adhesion properties equivalent to those of conventional fixing resins.

Claims (2)

A marker ink composition containing 0.5 to 20% by mass of a hyperbranched polymer represented by the following general formula (1).

(In general formula (1), R ¹ , R ² , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ⁵ and R ⁶ are linked together to form an aliphatic R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 6 to 15 carbon atoms, and R ³ and R ⁴ are linked together to form an aromatic 6-membered ring. may form a membered ring,
X represents a substituent represented by the following general formula (2)

(in general formula (2), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, R ⁸ represents an alkyl group having 12 to 18 carbon atoms, and m represents an integer of 12 to 18),
Y represents a substituent or a hydroxyl group represented by the following general formula (3)

(in general formula (3), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and m represents an integer of 12 to 18);
M ¹ represents a hydrogen atom or a substituent represented by the following general formula (4),

(in general formula (4), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and n represents an integer of 12 to 18);
M ² represents a hydrogen atom or a substituent represented by the following general formula (5)

(In general formula (5), R ⁷ represents an alkyl group having 6 to 15 carbon atoms, and n represents an integer of 12 to 18). ) 2. The method according to claim 1, further comprising at least one selected from the group consisting of trimethylglycine, carnitines, pentaerythritol, sugar alcohol, dextrin and reduced starch syrup, in addition to the hyperbranched polymer represented by the general formula (1). marker ink composition.