阅读说明：本技术 书写工具用油性墨组合物 (Oil-based ink composition for writing instrument ) 是由 春原有美子 于 2018-03-12 设计创作，主要内容包括：本发明提供书写工具用油性墨组合物。本发明的书写工具用油性墨组合物含有着色剂、树脂、有机溶剂、氟系树脂颗粒,所述书写工具用油性墨组合物通过动态光散射法进行测定时的、前述氟系树脂颗粒的平均粒径为0.1μm以上且小于1.0μm。(The present invention provides an oil-based ink composition for writing instruments. The oil-based ink composition for a writing instrument of the present invention contains a colorant, a resin, an organic solvent, and fluorine-based resin particles, and the average particle diameter of the fluorine-based resin particles is 0.1 μm or more and less than 1.0 μm when the oil-based ink composition for a writing instrument is measured by a dynamic light scattering method.)

1. An oil-based ink composition for writing instruments, which comprises a colorant, a resin, an organic solvent, and fluorine-based resin particles,

the average particle diameter of the fluorine-based resin particles is 0.1 μm or more and less than 1.0 μm as measured by a dynamic light scattering method.

2. The oil-based ink composition for a writing instrument according to claim 1, wherein the content of the fluorine-based resin particles is 3 to 25% by mass based on the entire mass of the oil-based ink composition for a writing instrument.

3. The oil-based ink composition for a writing instrument according to claim 1 or 2, wherein the fluorine-based resin particles are perfluorinated resin particles.

4. The oil-based ink composition for a writing instrument according to claim 3, wherein the perfluorinated resin particles are polytetrafluoroethylene particles.

5. A writing instrument at least comprises an ink storage part, a writing part and a holding part,

an oil-based ink composition for a writing instrument according to any one of claims 1 to 4 is stored in the ink storage portion.

Technical Field

The present invention relates to an oil-based ink composition for writing instruments.

Background

Conventionally, oil-based ink compositions used in sign pens are required to have properties such as adhesion to writing formed on writing surfaces made of various materials, and light fastness without fading when exposed to sunlight for a long period of time. In particular, when writing on materials with poor wettability, such as synthetic resin films, paper with a resin-coated surface, metals, and the like, it is required that the oil-based ink can produce writing with sufficient adhesion.

In order to satisfy the above requirements, the invention disclosed in patent document 1 relates to an oil-based ink that can be applied to a surface that is wet with water, and a marker that can write on a surface that is wet with water. In patent document 1, the oil-based ink contains 2 or more kinds of acrylic resin particles having an average particle diameter of 1 to 15 μm, fluororesin particles, and fluororesin-modified vinyl resin particles as a fine polymer powder, either individually or in combination.

Disclosure of Invention

Problems to be solved by the invention

According to the oil-based ink composition for a writing instrument of patent document 1, an oil-based ink which can firmly adhere an ink to an object and has high workability and excellent water resistance, weather resistance and light resistance can be obtained.

However, when the oil-based ink composition for writing instruments is used, the scratch resistance of the handwriting is reduced after the ink composition is subjected to permanent ultraviolet ray resistance, and as a result, the handwriting may be peeled off even if the frictional force is weak.

Thus, there is a need to provide an oil-based ink composition for writing instruments capable of producing scratch-resistant handwriting as described below: handwriting formed by writing on various materials can withstand repeated wiping and wiping with greater strength, and can maintain wiping resistance even after being subjected to permanent ultraviolet resistance.

Means for solving the problems

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. Namely, the present invention is as follows:

<1> an oil-based ink composition for writing instruments comprising a colorant, a resin, an organic solvent, and fluorine-based resin particles,

the average particle diameter of the fluorine-based resin particles is 0.1 μm or more and less than 1.0 μm as measured by a dynamic light scattering method.

<2> the oil-based ink composition for a writing instrument according to the item <1>, wherein the content of the fluorine-based resin particles is 3 to 25% by mass based on the mass of the entire oil-based ink composition for a writing instrument.

<3> the oil-based ink composition for a writing instrument according to the item <1> or <2>, wherein the fluorine-based resin particles are perfluorinated resin particles.

<4> the oil-based ink composition for a writing instrument according to <3>, wherein the perfluorinated resin particles are polytetrafluoroethylene particles.

<5> a writing instrument comprising at least an ink reservoir, a writing section and a holding section,

the oil-based ink composition for a writing instrument according to the items <1> to <4> is stored in the ink storage unit.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided an oil-based ink composition for writing instruments capable of giving scratch-resistant writing as described below: handwriting formed by writing on various materials can withstand repeated wiping and wiping with greater strength, and can maintain wiping resistance even after being subjected to permanent ultraviolet resistance.

Drawings

In fig. 1, (a) in fig. 1 is a schematic view of an oil-based ink layer formed from the oil-based ink composition for a writing instrument according to the present invention before a frictional force is applied. Fig. 1 (b) is a schematic view of the oily ink layer formed from the oily ink composition for a writing instrument of the present invention after application of a frictional force. Fig. 1 (c) is a schematic view of the oily ink layer formed from the oily ink composition for a writing instrument of the present invention after further application of a frictional force.

Fig. 2 (a) is a schematic view of an oil-based ink layer formed from a conventional oil-based ink composition for a writing instrument, before frictional force is applied. Fig. 2 (b) is a schematic view of an oil-based ink layer formed from a conventional oil-based ink composition for a writing instrument after application of a frictional force. Fig. 2 (c) is a schematic view of an oil-based ink layer formed from a conventional oil-based ink composition for a writing instrument after further application of a frictional force.

Detailed Description

Oil-based ink composition for writing instruments

The oil-based ink composition for a writing instrument of the present invention contains a colorant, a resin, an organic solvent, and fluorine-based resin particles, and the average particle diameter of the fluorine-based resin particles is 0.1 μm or more and less than 1.0 μm when the oil-based ink composition for a writing instrument is measured by a dynamic light scattering method.

As mentioned in patent document 1, the oil-based ink composition for writing instruments containing fluorine-based resin particles having an average particle diameter of 1 to 15 μm can firmly adhere ink to an object. That is, conventionally, as a method for improving the adhesion of handwriting, the following proposals have been considered: the ink contains fluorine-based resin particles to improve the wettability of the ink composition to the writing surface, thereby improving the adhesion at the interface between the writing surface and the ink composition.

However, even when writing is performed using the above-described oil-based ink composition for a writing instrument containing fluorine-based resin particles, there is a case where the adhesion of handwriting after the long-lasting ultraviolet ray resistance becomes insufficient.

The inventors of the present invention found that: the problem can be solved by using fluorine-based resin particles having an average particle diameter of 0.1 μm or more and less than 1.0. mu.m. This is explained with reference to fig. 1 and 2.

In the conventional oil-based ink composition for writing instruments, when the ink composition is written on a writing surface, the wettability of the writing surface with the ink composition becomes good, and the adhesion is improved.

Meanwhile, if the oily ink composition for a writing instrument containing the fluorine-based resin particles is applied to a substrate and dried to form an oily ink layer (10) as handwriting, as shown in fig. 2 (a), it is considered that the fluorine-based resin particles (12) are exposed on the surface of the oily ink layer (10), and thus the friction coefficient of the surface of the oily ink layer (10) is reduced, and as a result, the scratch resistance of the handwriting is improved.

However, if the oil-based ink layer (10) is made to resist ultraviolet rays and the like for a long time, it is considered that the attached component (14) exposed on the surface of the oil-based ink layer (10) is deteriorated by the energy of ultraviolet rays. As a result, if a frictional force is applied as shown by the arrow in fig. 2 (a), the attached component (14) may be physically detached as shown in fig. 2 (b). As a result, if a further frictional force is applied, the entire oil-based ink layer (10) may be peeled off from the writing surface (20) as shown in fig. 2 (c).

On the other hand, when the oil-based ink composition for a writing instrument of the present invention is applied to a substrate and dried to form the oil-based ink layer (10), as shown in fig. 1 (a), the average particle diameter of the fluorine-based resin particles (12) is small, and thus the area of the portion of the attached component (14) exposed on the surface can be reduced.

Further, it is considered that the average particle diameter of the fluorine-based resin particles (12) is small, and therefore the fluorine-based resin particles (12) are dispersed to form a layer in the thickness direction of the oil-based ink layer (10). As a result, even when the adherend component (14) on the surface is deteriorated and temporarily peeled off, the fluorine-based resin particles of the lower layer in which the layer is formed are exposed, and the abrasion resistance of the handwriting can be maintained.

Therefore, it is considered that even if a frictional force is applied as shown by an arrow in fig. 1 (a) after the ultraviolet resistance is maintained, the attached component (14) is not easily physically detached, and even if the attached component (14) is temporarily detached, only the attached component (14) exposed on the surface of the oil-based ink layer (10) is physically detached as shown in fig. 1 (b), and as a result, even if a further frictional force is applied, the fluorine-based resin particles (12) present inside the oil-based ink layer (10) are re-exposed as shown in fig. 1 (c), and the abrasion resistance of the handwriting can be maintained.

According to the above constitution, an oil-based ink composition for writing instruments which can produce scratch-resistant handwriting as described below can be obtained: the ink composition has scratch resistance which enables handwriting formed by writing on various materials to withstand repeated wiping and wiping with higher strength due to the presence of the fluorine-based resin particles, and has scratch resistance which is maintained even after enduring ultraviolet resistance due to the small average particle size of the fluorine-based resin particles.

The content of the fluorine-based resin particles in the oil-based ink composition for a writing instrument of the present invention is preferably 3 mass% or more, 4 mass% or more, or 5 mass% or more from the viewpoint of sufficiently providing the fluorine-based resin particles in the writing and thereby improving the scratch resistance of the writing, and is preferably 25 mass% or less, 22 mass% or less, or 20 mass% or less from the viewpoint of ensuring the adhesion between the oil-based ink composition for a writing instrument and the writing surface.

The content of the colorant in the oil-based ink composition for a writing instrument of the present invention may be 1 mass% or more, 2 mass% or more, 3 mass% or more, or 5 mass% or more, and may be 25 mass% or less, 20 mass% or less, or 15 mass% or less.

The content of the resin in the oil-based ink composition for a writing instrument of the present invention may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 25% by mass or less, 20% by mass or less, or 15% by mass or less.

Next, each constituent element of the present invention will be explained.

< coloring agent >

As the colorant, various colorants usable in conventional inks, such as dyes, pigments, or mixtures of dyes and pigments, can be used.

As the dye that can be used in the present invention, any of direct dyes, acid dyes, basic dyes, mordant acid mordant dyes, alcohol-soluble dyes, azo dyes, sulfur and sulfur vat dyes, disperse dyes, oil-soluble dyes, food dyes, metal complex salt dyes, salt-forming dyes, dyes dyed on resins, and the like, which are used in general dye ink compositions, and solutions thereof can be used.

Examples of the pigment that can be used in the present invention include: inorganic pigments such as carbon black, graphite and titanium dioxide pigments, pigment fillers such as talc, silica, alumina, mica and aluminum silicate, azo pigments, condensed azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, organic pigments such as various lake pigments, fluorescent pigments, pearl pigments, metallic pigments such as gold and silver.

The colorant used in the present invention may be the above dye or pigment alone, or may be a mixture of the above dye or pigment.

< resin >

As the resin, a ketone resin, a sulfonamide resin, a maleic acid resin, a terpene phenol resin, an ester gum, a xylene resin, an alkyd resin, a phenol resin, a butyral resin, a rosin, polyvinylpyrrolidone, polyvinyl alcohol, an acrylic resin, a melamine resin, a cellulose resin, or the like, and derivatives thereof can be used. These resins may be used alone or in combination.

In particular, when the fluorine-based resin particles are Polytetrafluoroethylene (PTFE) particles, it is preferable that at least a butyral resin is contained as the resin from the viewpoint of well dispersing the Polytetrafluoroethylene (PTFE) particles. In this case, the mass ratio of the butyral resin to the Polytetrafluoroethylene (PTFE) particles may be 0.01 or more, 0.03 or more, or 0.05 or more, and may be 0.3 or less, 0.2 or less, or 0.1 or less.

< organic solvent >

As the organic solvent, for example: aromatic compounds, alcohols, polyols, glycol ethers, hydrocarbons, esters, and the like. These solvents may be used alone or in combination.

As aromatic species, for example: benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, phenyl alkylsulfonate, butyl phthalate, ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and the like.

As alcohols, for example: ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 1-pentanol, isopentanol, sec-pentanol, 3-pentanol, t-pentanol, n-hexanol, methylpentanol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 3,5, 5-trimethylhexanol, nonanol, n-decanol, undecanol, n-decanol, trimethylnonanol, tetradecanol, heptadecanol, cyclohexanol, 2-methylcyclohexanol, and the like.

As polyols, for example: ethylene glycol, diethylene glycol, 3-methyl-1, 3-butanediol, triethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 5-pentanediol, hexanediol, octanediol, and the like.

As glycol ethers, for example: methyl isopropyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3-methyl-3-methoxy-1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol tertiary-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, and the like.

As hydrocarbons, for example: linear hydrocarbons such as hexane, isohexane, heptane, octane, nonane and decane, and cyclic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane.

As esters, for example: propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, butyl formate, isobutyl formate, isoamyl formate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, methyl trimethylacetate, ethyl trimethylacetate, propyl trimethylacetate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, methyl octanoate, ethyl octanoate, methyl laurate, ethyl hexanoate, propyl octanoate, methyl laurate, ethyl hexanoate, methyl octanoate, propyl octanoate, methyl laurate, ethyl hexanoate, methyl isovalerate, Methyl oleate, ethyl oleate, caprylic triglyceride, tributyl acetate citrate, octyl hydroxystearate, propylene glycol monoricinoleate, methyl 2-hydroxyisobutyrate, 3-methoxybutyl acetate, and the like.

< fluororesin pellets >

The fluorine-based resin particles are particles made of a polymer obtained by polymerizing a fluorine-containing monomer. In particular, the fluorine-based resin particles in the oil-based ink composition for a writing instrument of the present invention are fluorine-based resin particles having an average particle diameter of 0.1 μm or more and less than 1.0 μm as measured by a dynamic light scattering method. Here, the average particle diameter obtained by the dynamic light scattering method is a value of an average particle diameter analyzed by an accumulative amount method in a scattering intensity distribution calculated by a thick particle diameter analyzer FPAR-1000 (Otsuka electronics Co.).

The average particle diameter is preferably 0.1 μm or more, 0.2 μm or more, or 0.3 μm or more from the viewpoint of easily exposing the fluorine-based resin particles on the surface of the handwriting and thereby improving the scratch resistance of the handwriting, and is preferably less than 1.0 μm, 0.9 μm or less, or 0.8 μm or less from the viewpoint of preventing the handwriting from being affected by the persistent ultraviolet resistance and maintaining the scratch resistance of the handwriting even after the persistent ultraviolet resistance.

As the fluorine-based resin particles, perfluorinated resin particles, partially fluorinated resin particles and fluorinated resin-olefin copolymer particles can be used, and among them, perfluorinated resin particles are preferably used from the viewpoint of reducing the friction coefficient of the surface of the handwriting and consequently improving the scratch resistance of the handwriting.

Examples of the perfluorinated resin particles include: polytetrafluoroethylene (PTFE) particles, Perfluoroalkoxyalkane (PFA) particles, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) particles, and the like, PTFE is preferred among them from the viewpoint of chemical stability, cost, and the like.

Examples of the partially fluorinated resin particles include: polyvinylidene fluoride (PVDF) particles, Polychlorotrifluoroethylene (PCTFE) particles, and the like.

The fluorinated resin-olefin copolymer particles are perfluorinated resin and/or copolymer particles of a partially fluorinated resin and an olefin, and examples thereof include: tetrafluoroethylene-ethylene copolymer (ETFE) pellets, chlorotrifluoroethylene-Ethylene Copolymer (ECTFE) pellets, and the like.

< other ingredients >

The oil-based ink composition for a writing instrument of the present invention may further contain other components arbitrarily selected. Examples of other components include: leveling agents, rust inhibitors, preservatives, lubricants, resins, and the like.

As the leveling agent, for example: fluorine-based surfactants, silicone oils, phosphate ester-based surfactants, and the like.

Writing tools

The writing instrument of the present invention includes at least an ink storage unit, a writing unit, and a holding unit. The above-described oil-based ink composition for writing instruments is stored in the ink storage portion. The writing instrument of the present invention may be a marker pen or may be a ball point pen.

Here, the "marker pen" in the present specification refers to a pen having a mechanism for supplying ink stored in an ink storage portion to a writing portion made of resin by utilizing a capillary phenomenon, and includes a pen mentioned as a "sign pen" by a person skilled in the art. In the present specification, the term "ball point pen" refers to a pen having a mechanism for bleeding out ink stored in an ink storage portion by rotation of a ball provided in a writing portion.

< ink reservoir >

In the ink storage portion, the above-described oil-based ink composition for writing instruments is stored.

Any article may be used as the ink storage portion as long as it can store ink and supply ink to the writing portion.

< writing part >

The writing section may be formed of any selected material depending on the use of the writing instrument. When the writing instrument of the present invention is a marker, examples of the writing section include a fiber core and a plastic core. In the case where the writing instrument of the present invention is a ballpoint pen, the writing section may be a writing section having a ballpoint pen tip at its tip.

Method for producing oil-based ink composition for writing instrument

The oil-based ink composition for a writing instrument can be produced as follows: the above colorant, resin, organic solvent and fluorine resin particles are mixed with a stirrer such as a disperser, and the mixture is produced by a conventionally known method.