WO2017122457A1 - Water-based ink composition for felt-tip pen - Google Patents

Water-based ink composition for felt-tip pen Download PDF

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Publication number
WO2017122457A1
WO2017122457A1 PCT/JP2016/086080 JP2016086080W WO2017122457A1 WO 2017122457 A1 WO2017122457 A1 WO 2017122457A1 JP 2016086080 W JP2016086080 W JP 2016086080W WO 2017122457 A1 WO2017122457 A1 WO 2017122457A1
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water
ink composition
based ink
mass
sign
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PCT/JP2016/086080
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French (fr)
Japanese (ja)
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賢亮 井上
新井　啓之
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三菱鉛筆株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K5/00—Pens with ink reservoirs in holders, e.g. fountain-pens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks

Definitions

  • the present invention relates to a water-based ink composition for sign pens.
  • Patent Document 1 in an ink composition containing at least a colorant and water, a nonionic polymer surfactant having an alkylene oxide chain in a hydrophilic group and an average molecular weight of 3000 to 200,000 is added to the ink composition.
  • a water-based ink composition for a writing instrument characterized by containing in the range of 1 to 30% by weight is disclosed.
  • Patent Document 2 discloses a water-based ink composition for a direct liquid writing instrument in which the surface tension of the water-based ink is 30 mN / m or less and the contact angle of the water-based ink with respect to the flat portion of the disc body is 30 ° or more.
  • Patent Document 2 discloses an embodiment in which an emulsion is contained in a water-based ink composition, more specifically an embodiment in which a silicone emulsion is contained.
  • Patent Document 3 discloses a ball-point pen ink containing spherical silicone resin fine particles in a ball-point pen ink composed of a colorant, a resin, a solvent, and an additive.
  • the average particle size is less than 1 ⁇ m, the clogging effect becomes too weak, and when it exceeds 10 ⁇ m, the writing property deteriorates due to strong clogging, which is not preferable.
  • water-based ink As a sign pen, it may be required to use water-based ink as a sign pen. In this case, it is conceivable to use the water-based ink as a sign pen.
  • Patent Document 2 when a water-based ink containing a silicone emulsion is used for a sign pen, a film is formed on the surface, and as a result, good writing quality cannot be obtained.
  • Patent Document 3 when a water-based ink containing spherical silicone resin fine particles having an average particle diameter of 1 ⁇ m or more is used for a sign pen, good writing quality cannot be obtained.
  • the present invention is as follows: ⁇ 1> Contains water, solid silicone particles, and a colorant, and has an average particle diameter of 20 to 500 nm when measured by a dynamic light scattering method.
  • ⁇ 2> The water-based ink composition for sign pens according to ⁇ 1>, wherein the solid silicone particles are crosslinked silicone particles.
  • ⁇ 3> The ink storage section, the writing section, and the holding section are provided at least, and the water-based ink composition for sign pens according to ⁇ 1> or ⁇ 2> is stored in the ink storage section.
  • Sign pen. ⁇ 4> The sign pen according to ⁇ 3>, wherein the writing unit is a plastic core.
  • the water-based ink composition for sign pens of the present invention contains water, solid silicone particles, a colorant, and an optional water-soluble organic solvent.
  • the solid silicone particles have an average particle diameter of 20 nm to 500 nm as measured by a dynamic light scattering method.
  • the water-based ink composition for sign pens of the present invention may further contain other components.
  • the “sign pen” means a pen having a mechanism for supplying ink stored in the ink storage part to the resin writing part by capillary action.
  • the present inventors have found that the writing quality of a sign pen using this ink composition is improved by incorporating solid silicone particles having an average particle diameter of 20 nm to 500 nm in the water-based ink composition for sign pens.
  • “improves the writing quality” means that the dynamic friction coefficient when writing with a sign pen is reduced.
  • the reason is that the elasticity of the solid silicone particles, particularly the crosslinked silicone particles, can move the pen tip well during writing, and the stability of the silicone It is thought that elasticity is not inhibited by other components in the composition. Furthermore, it is considered that the solid silicone particles are satisfactorily supplied between the writing part of the sign pen and the paper by using the solid silicone particles having a small particle diameter.
  • the content of the solid silicone particles can be 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, or 7% by mass or more with respect to the total amount of the ink composition. It can be no more than mass%, no more than 25 mass%, no more than 20 mass%, or no more than 15 mass%. In particular, from the viewpoint of reducing the viscosity of the ink composition and thereby expressing good writing quality, the content of the solid silicone particles is preferably within the above range.
  • the content of the colorant can be 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more, and 60% by mass or less, 55% by mass with respect to the total amount of the ink composition. % Or less, 50 mass% or less, or 45 mass% or less.
  • the water can be ion exchange water, distilled water, and the like.
  • the solid silicone particles have an average particle size of 20 nm to 500 nm.
  • the average particle diameter is a value of D50 obtained by a cumulant analysis method for calculating an average particle diameter by applying a scattering intensity distribution detected by a dynamic light scattering method to a normal distribution.
  • the particle size measurement by the dynamic light scattering method can be performed using, for example, a dense particle size analyzer “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
  • the solid silicone particles are crosslinked silicone particles, particularly solid silicone particles having a structure in which organopolysiloxane is crosslinked with a crosslinking substance, more particularly a solid having a structure in which organopolysiloxane is crosslinked with organohydrogenpolysiloxane. Silicone particles are preferable from the viewpoint of improving the writing quality of the sign pen of the present invention. Such a cross-linked structure is elastic, and such solid silicone particles are also referred to as “silicone rubber”.
  • crosslinked silicone particles it is preferable to use silicone rubber particles obtained by curing a liquid silicone composition sold as “RTV silicone rubber” by Shin-Etsu Chemical Co., Ltd.
  • the average particle size of the solid silicone particles can be 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 70 nm or more, or 100 nm, and 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less. Or 200 nm or less.
  • the average particle diameter of the solid silicone particles is preferably within the above range.
  • colorant various colorants that can be used in conventional inks such as dyes, pigments, or mixtures of dyes and pigments can be used.
  • Examples of the dye that can be used in the present invention include direct dyes, acid dyes, basic dyes, mordant / acid mordant dyes, spirit-soluble dyes, azoic dyes, sulfur / sulfuration vat dyes used in ordinary dye ink compositions. Further, vat dyes, disperse dyes, oil-soluble dyes, edible dyes, metal complex dyes, salt-forming dyes, dyes obtained by dyeing a resin and the like, and aqueous solutions thereof can be used.
  • pigments examples include inorganic facials such as carbon black, graphite, and titanium dioxide pigments, constitutional facials such as talc, silica, alumina, mica, and alumina silicate, azo pigments, and condensed azo pigments.
  • Organic pigments such as phthalocyanine pigments, anthraquinone pigments, quinacdolin pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, various lake pigments, metallic pigments such as fluorescent pigments, pearl pigments, gold and silver .
  • the above-mentioned dyes and pigments can be used alone, or the above-mentioned dyes and pigments can be mixed and used.
  • water-soluble organic solvents include hindered alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin or derivatives thereof (for example, polyglycerin), sorbitan, sucrose, ethylene glycol, Polyglycols such as propylene glycol and butylene glycol can be preferably used.
  • hindered alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin or derivatives thereof (for example, polyglycerin), sorbitan, sucrose, ethylene glycol, Polyglycols such as propylene glycol and butylene glycol can be preferably used.
  • the water-based ink composition for sign pens of the present invention may contain other components, for example, additives such as pH adjusters, preservatives, and non-drying agents, as long as the effects of the present invention are not impaired.
  • the sign pen refill includes an ink reservoir.
  • the water-based ink composition for sign pens is stored.
  • the sign pen refill means a replaceable part of the sign pen.
  • the sign pen refill may further include a writing portion.
  • the refill for the sign pen may be an ink cartridge in which only the ink storage unit can be replaced, or may be a unit in which the ink storage unit and the writing unit can be replaced together.
  • the ink storage unit stores the above water-based ink composition for sign pens.
  • any material can be used as long as it can store ink and supply ink to the writing unit.
  • the writing part should just be comprised with the material which can be used as a writing part of a sign pen.
  • a writing part a fiber core and a plastic core, especially a plastic core are mentioned, for example.
  • Fiber core is natural fiber, animal hair fiber, polyacetal resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, polyolefin resin, polyvinyl resin, polycarbonate resin, polyether resin, polyphenylene It is a core obtained by processing a fiber bundle such as a parallel fiber bundle made of one kind or a combination of two or more kinds of resin, felt, or the like, or processing these fiber bundles with a resin.
  • the plastic core (10) has an ink groove (4) for supplying ink from the ink storage section in the longitudinal direction of the rod-like resin (2).
  • the core that is.
  • FIG. 1 (a) is a side view of the plastic core (10)
  • FIG. 1 (b) is a side sectional view of the plastic core
  • FIG. 1 (c) is FIG. 1 (b).
  • FIG. 6 is a cross-sectional view taken along the line CC of FIG.
  • This rod-shaped resin may be composed of the resins mentioned for the fiber core.
  • the shape of the ink groove for example, the shape shown in FIG. 2 of JP-A-2003-268285 can be used.
  • the writing part is a plastic core
  • the writing part is a plastic core made of polyacetal
  • the advantages of the present invention are more prominent.
  • the sign pen of the present invention includes at least an ink storage unit, a writing unit, and a holding unit.
  • the holding portion is a portion held by a user using the sign pen, and is formed of resin, wood, metal, or the like, and may be formed of non-slip silicone rubber or the like.
  • the method for producing a water-based ink composition for sign pens according to the present invention includes a step for producing solid silicone particles including an emulsification step and a curing step, and a step for producing a water-based ink composition for sign pens which is blended with other ink composition materials. Consists of.
  • the emulsification step is a step of dropping the aqueous phase while stirring the oil phase, thereby performing phase inversion emulsification.
  • phase inversion emulsification means that an emulsifier is dissolved in an oil phase, an aqueous phase is added thereto, and a continuous phase is converted from an oil phase to an aqueous phase to form an O / W type (oil-in-water type) emulsion. Means the method of preparation.
  • the stirring of the oil phase can be performed at 600 rpm or more, 620 rpm or more, or 650 rpm or more, and 800 rpm or less, 780 rpm or less, or 750 rpm or less.
  • the emulsification step may include high-pressure emulsification.
  • the pressure applied during high-pressure emulsification can be 150 MPa or more, 155 MPa or more, or 160 MPa or more, and can be 200 MPa or less, 195 MPa or less, or 190 MPa or less.
  • the oil phase contains a liquid silicone composition and an emulsifier having an HLB value of 10 or less.
  • the liquid silicone composition is a composition that, when cured, forms solid silicone particles, particularly crosslinked silicone particles, having an average particle diameter of 20 nm to 500 nm as measured by a dynamic light scattering method.
  • liquid silicone composition a commercially available one can be used, for example, a liquid silicone composition sold as “RTV silicone rubber” by Shin-Etsu Chemical Co., Ltd. can be used. Among them, it is preferable to use a thermosetting liquid silicone composition that forms solid silicone particles by heating and curing, and it is preferable to use a one-component curable liquid silicone composition.
  • the emulsifier contained in the oil phase is an emulsifier having an HLB value of 10 or less.
  • the HLB value can be 10 or less, 9 or less, or 8 or less, and can be greater than 0, 1 or more, or 2 or more.
  • Examples of such an emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Oxyethylene phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, and the like can be used.
  • HLB value means a hydrophilic-lipophilic balance. More specifically, a substance having no hydrophilic group has an HLB value of 0, and a substance having no lipophilic group and having only a hydrophilic group is equally divided by an HLB value of 20 (Griffin method).
  • the aqueous phase contains water and an emulsifier with an HLB value greater than 10.
  • water the water mentioned regarding the water-based ink composition for sign pens can be used.
  • the emulsifier contained in the aqueous phase is an emulsifier having an HLB value of more than 10.
  • the HLB value can be less than 20, 19 or less, or 18 or less, and can be greater than 10, 11 or more, or 12 or more.
  • Examples of such an emulsifier include polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene Styrenated phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, and the like can be used.
  • the curing step is a step of curing the liquid silicone composition, thereby producing solid silicone particles.
  • the curing method can be appropriately selected according to the curing conditions of the liquid silicone composition.
  • the liquid silicone composition when it is a thermosetting liquid silicone composition, it can be carried out by heating the liquid silicone composition that has undergone the emulsification step.
  • the curing temperature may be 40 ° C or higher, 50 ° C or higher, 60 ° C or higher, or 70 ° C or higher, and may be 120 ° C or lower, 110 ° C or lower, 100 ° C or lower, or 90 ° C or lower. it can.
  • the production process of the solid silicone particles may include another process, for example, a process of classifying the aqueous dispersion of the solid silicone particles after curing.
  • the aqueous dispersion of solid silicone particles and the material constituting the water-based ink composition for sign pens are produced by a conventionally known method while mixing using a stirring device such as a disper.
  • Liquid silicone composition as a particle raw material KE-1844, Shin-Etsu Chemical Co., Ltd., 20.0 parts by mass
  • component name as an emulsifier product number: Emulgen 102KG, HLB: 6.3, manufacturer name: Kao Corporation
  • the oil phase containing 1.0 parts by mass is stirred at 600 rpm, and the component names as an emulsifier (product number: Emulgen 150, HLB: 18.4, manufacturer name: Kao Corporation, 9.0 parts by mass) ) was added dropwise. Thereafter, the mixed solution was processed and emulsified with a high-pressure emulsifier under conditions of 150 MPa and 10 passes.
  • the liquid mixture is heated at 80 ° C. for 12 hours to cure the liquid silicone composition, and classified at 12500 rpm for 30 minutes to be used in the aqueous ink composition of Example 1 to form crosslinked silicone particles (silicone rubber).
  • An aqueous dispersion of solid silicone particles containing was prepared.
  • Dye as a colorant Water Black 191-L conc. 15%, Orient Chemical Co., Ltd., 20.0 parts by mass
  • preservative Bioden 421, Yamato Chemical Co., Ltd., 0.3 parts by mass
  • pH adjustment Triethanolamine (0.2 parts by mass) as an agent
  • urea 7.5 parts by mass
  • glycerin 10 parts by mass
  • ethylene glycol 2.5 parts by mass
  • particle raw material 100 parts by mass of the aqueous ink composition of Example 1 were prepared using the above aqueous dispersion of solid silicone particles (3.0 parts by mass in terms of solid content) and ion-exchanged water (remainder).
  • Example 2 A water-based ink composition of Example 2 was produced in the same manner as Example 1 except that the mass part of the aqueous dispersion of solid silicone particles was changed to 10.0 parts by mass (solid content conversion).
  • Example 3 A water-based ink composition of Example 2 was produced in the same manner as in Example 1 except that the mass part of the aqueous dispersion of solid silicone particles was changed to 20.0 parts by mass (in terms of solid content).
  • Example 4 A water-based ink composition of Example 4 was produced in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1842 (Shin-Etsu Chemical Co., Ltd.).
  • Example 5 A water-based ink composition of Example 5 was produced in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1886 (Shin-Etsu Chemical Co., Ltd.).
  • Comparative Example 1 A water-based ink composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that the liquid silicone composition as a particle raw material was not contained in the oil phase.
  • SBR styrene butadiene rubber
  • ⁇ Comparative Example 3 Comparative Example as in Example 1, except that silicone oil (KF-96-500cs, Shin-Etsu Chemical Co., Ltd., 20.0 parts by mass) was used instead of the liquid silicone composition as the particle raw material. 1 aqueous ink composition was produced. It should be noted that the water-based ink composition of Comparative Example 1 contains a silicone emulsion, and the diameter of the droplet is described in the “Particle Size” column of Table 1.
  • Example 6 First, an aqueous dispersion of solid silicone particles was prepared in the same manner as in Example 1. Next, carbon black (8.0 parts by mass) as a colorant, styrene acrylic acid resin (1.8 parts by mass) as a pigment dispersant, preservative (Bioden 421, Daiwa Chemical Industry Co., Ltd., 0.3 parts by mass) ), Triethanolamine (0.2 parts by mass) as a pH adjuster, glycerin (10.0 parts by mass) as a solvent, and an aqueous dispersion of the above solid silicone particles as a particle raw material (10. in terms of solid content). 0 parts by mass) and ion-exchanged water (remainder) were used to produce 100 parts by mass of the aqueous ink composition of Example 6.
  • carbon black 8.0 parts by mass
  • styrene acrylic acid resin 1.8 parts by mass
  • preservative Bioden 421, Daiwa Chemical Industry Co., Ltd., 0.3 parts by mass
  • Triethanolamine 0.2 parts by
  • Example 7 A water-based ink composition of Example 7 was produced in the same manner as in Example 6 except that the liquid silicone composition as the particle raw material was changed to KE-1842 (Shin-Etsu Chemical Co., Ltd.).
  • Example 8 A water-based ink composition of Example 8 was prepared in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1886 (Shin-Etsu Chemical Co., Ltd.).
  • the prepared water-based ink composition was filled in the ink storage part of the sign pen.
  • a polyacetal core was used as the writing part of the sign pen.

Abstract

A water-based ink composition for felt-tip pens which comprises water, particles of a solid silicone having a crosslinked structure, and a colorant, wherein the solid silicone particles, when examined by a dynamic light scattering method, have an average particle diameter of 20-500 nm.

Description

サインペン用水性インク組成物Water-based ink composition for sign pens
　本発明は、サインペン用水性インク組成物に関する。 The present invention relates to a water-based ink composition for sign pens.
　近年、ボールペン、サインペン等の、インクを用いた筆記具が広く用いられている。このインクの一態様として、水を主体とする溶媒、染料、顔料等の着色剤を含有する水性インクが存在する。水性インクの性能向上のため、種々の研究が行われている。 In recent years, writing instruments using ink, such as ballpoint pens and sign pens, have been widely used. As one aspect of this ink, there is a water-based ink containing a colorant such as a solvent mainly composed of water, a dye, and a pigment. Various studies have been conducted to improve the performance of water-based inks.
　特許文献１では、少なくとも着色剤と水を含有するインキ組成物において、親水基にアルキレンオキサイド鎖を持ち、平均分子量が３０００～２０万であるノニオン性高分子界面活性剤をインキ組成物中に０．１～３０重量％の範囲で含有することを特徴とする筆記具用水性インキ組成物が開示されている。 In Patent Document 1, in an ink composition containing at least a colorant and water, a nonionic polymer surfactant having an alkylene oxide chain in a hydrophilic group and an average molecular weight of 3000 to 200,000 is added to the ink composition. A water-based ink composition for a writing instrument characterized by containing in the range of 1 to 30% by weight is disclosed.
　特許文献２では、水性インキの表面張力が３０ｍＮ／ｍ以下であり、かつ円盤体の平面部に対する水性インキの接触角が３０°以上である直液式筆記具用水性インキ組成物が開示されている。特許文献２では、水性インキ組成物に乳化物を含有している態様、より具体的にはシリコーンエマルションを含有している態様が開示されている。 Patent Document 2 discloses a water-based ink composition for a direct liquid writing instrument in which the surface tension of the water-based ink is 30 mN / m or less and the contact angle of the water-based ink with respect to the flat portion of the disc body is 30 ° or more. . Patent Document 2 discloses an embodiment in which an emulsion is contained in a water-based ink composition, more specifically an embodiment in which a silicone emulsion is contained.
　特許文献３では、着色剤、樹脂、溶剤及び添加剤とからなるボールペン用インキにおいて、球状シリコーン樹脂微粒子を含有してなるボールペン用インキが開示されている。特許文献３においては、平均粒子径が１μｍ未満の場合は目詰まり効果が弱くなり過ぎ、１０μｍをこえる場合強い目詰まりにより、筆記性が悪化するので、好ましくないとしている。 Patent Document 3 discloses a ball-point pen ink containing spherical silicone resin fine particles in a ball-point pen ink composed of a colorant, a resin, a solvent, and an additive. In Patent Document 3, when the average particle size is less than 1 μm, the clogging effect becomes too weak, and when it exceeds 10 μm, the writing property deteriorates due to strong clogging, which is not preferable.
特開２００４－２５６７５８号公報JP 2004-256758 A 特開２０１２－９７１５３号公報JP 2012-97153 A 特開平８－１３４３９１号公報JP-A-8-134391
　筆記の用途によっては、水性インクをサインペンに用いることが求められることがある。この場合、上記の水性インクをサインペンに用いることが考えられる。 Depending on the purpose of writing, it may be required to use water-based ink as a sign pen. In this case, it is conceivable to use the water-based ink as a sign pen.
　しかしながら、特許文献２のように、シリコーンエマルションを含有している水性インクをサインペンに用いた場合、表面に皮膜が形成され、その結果良好な書き味が得られない。 However, as in Patent Document 2, when a water-based ink containing a silicone emulsion is used for a sign pen, a film is formed on the surface, and as a result, good writing quality cannot be obtained.
　また、特許文献３のように、平均粒径１μｍ以上の球状シリコーン樹脂微粒子を含有している水性インクをサインペンに用いた場合にも、良好な書き味が得られない。 Also, as in Patent Document 3, when a water-based ink containing spherical silicone resin fine particles having an average particle diameter of 1 μm or more is used for a sign pen, good writing quality cannot be obtained.
　したがって、良好な書き味を有する、サインペン用水性インク組成物を提供する必要性が存在する。 Therefore, there is a need to provide a water-based ink composition for sign pens having good writing taste.
　本発明者らは、鋭意検討したところ、以下の手段により上記課題を解決できることを見出して、本発明を完成させた。すなわち、本発明は、下記のとおりである：
　〈１〉　水、固形シリコーン粒子及び着色剤を含有しており、かつ
　動的光散乱法で測定したときの、上記固形シリコーン粒子の平均粒子径が２０ｎｍ～５００ｎｍである、
サインペン用水性インク組成物。
　〈２〉　上記固形シリコーン粒子が、架橋シリコーン粒子である、上記〈１〉項に記載のサインペン用水性インク組成物。
　〈３〉　インク貯蔵部、筆記部及び保持部を少なくとも具備しており、かつ
　上記インク貯蔵部に上記〈１〉又は〈２〉項に記載のサインペン用水性インク組成物が貯蔵されている、
サインペン。
　〈４〉　上記筆記部が、プラスチック芯である、上記〈３〉項に記載のサインペン。 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. That is, the present invention is as follows:
<1> Contains water, solid silicone particles, and a colorant, and has an average particle diameter of 20 to 500 nm when measured by a dynamic light scattering method.
Water-based ink composition for sign pens.
<2> The water-based ink composition for sign pens according to <1>, wherein the solid silicone particles are crosslinked silicone particles.
<3> The ink storage section, the writing section, and the holding section are provided at least, and the water-based ink composition for sign pens according to <1> or <2> is stored in the ink storage section.
Sign pen.
<4> The sign pen according to <3>, wherein the writing unit is a plastic core.
　本発明によれば、良好な書き味を有する、サインペン用水性インク組成物を提供することができる。 According to the present invention, it is possible to provide a water-based ink composition for sign pens having a good writing quality.
本発明のサインペンの筆記部の一態様の概略図である。It is the schematic of the one aspect | mode of the writing part of the sign pen of this invention.
　《サインペン用水性インク組成物》
　本発明のサインペン用水性インク組成物は、水、固形シリコーン粒子、及び着色剤、並びに随意の水溶性有機溶剤を含有している。この固形シリコーン粒子は、動的光散乱法で測定したときの平均粒子径が２０ｎｍ～５００ｎｍである。 << Water-based ink composition for sign pens >>
The water-based ink composition for sign pens of the present invention contains water, solid silicone particles, a colorant, and an optional water-soluble organic solvent. The solid silicone particles have an average particle diameter of 20 nm to 500 nm as measured by a dynamic light scattering method.
　本発明のサインペン用水性インク組成物は、他の成分を更に含有していてもよい。 The water-based ink composition for sign pens of the present invention may further contain other components.
　ここで、本発明において「サインペン」とは、インク貯蔵部に貯蔵されているインクを、毛細管現象により樹脂製の筆記部に供給する機構を有するペンを意味する。 Here, in the present invention, the “sign pen” means a pen having a mechanism for supplying ink stored in the ink storage part to the resin writing part by capillary action.
　本発明者らは、平均粒子径が２０ｎｍ～５００ｎｍの固形シリコーン粒子をサインペン用水性インク組成物に含有させることにより、このインク組成物を用いたサインペンの書き味が向上することを見出した。ここで、「書き味が向上する」とは、サインペンで筆記した際の動摩擦係数が低減することを意味するものである。 The present inventors have found that the writing quality of a sign pen using this ink composition is improved by incorporating solid silicone particles having an average particle diameter of 20 nm to 500 nm in the water-based ink composition for sign pens. Here, “improves the writing quality” means that the dynamic friction coefficient when writing with a sign pen is reduced.
　理論に拘束されることを望まないが、この理由としては、固形シリコーン粒子、特に架橋シリコーン粒子が有する弾性により、筆記時にペン先を良好に移動させることができ、かつシリコーンの安定性によって、この弾性が組成物中の他の成分によって阻害されないことに起因すると考えられる。更に、粒子径が小さい固形シリコーン粒子を用いることにより、サインペンの筆記部と紙との間に固形シリコーン粒子が良好に供給されると考えられる。 Although not wishing to be bound by theory, the reason is that the elasticity of the solid silicone particles, particularly the crosslinked silicone particles, can move the pen tip well during writing, and the stability of the silicone It is thought that elasticity is not inhibited by other components in the composition. Furthermore, it is considered that the solid silicone particles are satisfactorily supplied between the writing part of the sign pen and the paper by using the solid silicone particles having a small particle diameter.
　固形シリコーン粒子の含有率は、インク組成物の全量に対して、１質量％以上、２質量％以上、３質量％以上、５質量％以上、又は７質量％以上であることができ、また３０質量％以下、２５質量％以下、２０質量％以下、又は１５質量％以下であることができる。特に、インク組成物の粘度を小さくし、それにより良好な書き味を発現させる観点から、固形シリコーン粒子の含有率は上記の範囲であることが好ましい。 The content of the solid silicone particles can be 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, or 7% by mass or more with respect to the total amount of the ink composition. It can be no more than mass%, no more than 25 mass%, no more than 20 mass%, or no more than 15 mass%. In particular, from the viewpoint of reducing the viscosity of the ink composition and thereby expressing good writing quality, the content of the solid silicone particles is preferably within the above range.
　着色剤の含有率は、インク組成物の全量に対して、１質量％以上、２質量％以上、３質量％以上、又は５質量％以上とすることができ、また６０質量％以下、５５質量％以下、５０質量％以下、又は４５質量％以下とすることができる。 The content of the colorant can be 1% by mass or more, 2% by mass or more, 3% by mass or more, or 5% by mass or more, and 60% by mass or less, 55% by mass with respect to the total amount of the ink composition. % Or less, 50 mass% or less, or 45 mass% or less.
　以下では、本発明のサインペン用水性インク組成物の各構成要素について説明する。 Hereinafter, each component of the water-based ink composition for sign pens of the present invention will be described.
　〈水〉
　水は、イオン交換水、蒸留水等であることができる。 <water>
The water can be ion exchange water, distilled water, and the like.
　〈固形シリコーン粒子〉
　固形シリコーン粒子は、平均粒子径が２０ｎｍ～５００ｎｍである。なお、ここでいう平均粒子径とは、動的光散乱法により検出された散乱強度分布を正規分布に当てはめて平均粒子径を算出するキュムラント解析法により求めたＤ５０の値である。 <Solid silicone particles>
The solid silicone particles have an average particle size of 20 nm to 500 nm. Here, the average particle diameter is a value of D50 obtained by a cumulant analysis method for calculating an average particle diameter by applying a scattering intensity distribution detected by a dynamic light scattering method to a normal distribution.
　ここで、動的光散乱法による粒径の測定は、例えば大塚電子株式会社の濃厚系粒径アナライザー「ＦＰＡＲ－１０００」を用いて行うことができる。 Here, the particle size measurement by the dynamic light scattering method can be performed using, for example, a dense particle size analyzer “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
　また、固形シリコーン粒子は、架橋シリコーン粒子、特にオルガノポリシロキサンが架橋物質で架橋されている構造を有する固形シリコーン粒子、より特にオルガノポリシロキサンがオルガノハイドロジェンポリシロキサンで架橋されている構造を有する固形シリコーン粒子であることが、本発明のサインペンの書き味を向上させる観点から好ましい。この架橋されている構造により、弾性を有することとなるため、このような固形シリコーン粒子は、「シリコーンゴム」としても言及される。 Further, the solid silicone particles are crosslinked silicone particles, particularly solid silicone particles having a structure in which organopolysiloxane is crosslinked with a crosslinking substance, more particularly a solid having a structure in which organopolysiloxane is crosslinked with organohydrogenpolysiloxane. Silicone particles are preferable from the viewpoint of improving the writing quality of the sign pen of the present invention. Such a cross-linked structure is elastic, and such solid silicone particles are also referred to as “silicone rubber”.
　架橋シリコーン粒子としては、信越化学工業株式会社が「ＲＴＶシリコーンゴム」として販売している液状シリコーン組成物を硬化させたシリコーンゴム粒子を用いることが好ましい。 As the crosslinked silicone particles, it is preferable to use silicone rubber particles obtained by curing a liquid silicone composition sold as “RTV silicone rubber” by Shin-Etsu Chemical Co., Ltd.
　固形シリコーン粒子の平均粒子径は、２０ｎｍ以上、３０ｎｍ以上、４０ｎｍ以上、５０ｎｍ以上、７０ｎｍ以上、又は１００ｎｍであることができ、また５００ｎｍ以下、４５０ｎｍ以下、４００ｎｍ以下、３５０ｎｍ以下、３００ｎｍ以下、２５０ｎｍ以下、又は２００ｎｍ以下であることができる。特に、サインペンの筆記部と紙との間に固形シリコーン粒子を良好に供給する観点から、固形シリコーン粒子の平均粒子径は上記の範囲であることが好ましい。 The average particle size of the solid silicone particles can be 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 70 nm or more, or 100 nm, and 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less. Or 200 nm or less. In particular, from the viewpoint of satisfactorily supplying the solid silicone particles between the writing part of the sign pen and the paper, the average particle diameter of the solid silicone particles is preferably within the above range.
　〈着色剤〉
　着色剤としては、染料、顔料、又は染料と顔料との混合物等、従来のインクに用いることができる種々の着色剤を使用することができる。 <Colorant>
As the colorant, various colorants that can be used in conventional inks such as dyes, pigments, or mixtures of dyes and pigments can be used.
　本発明で使用することができる染料としては、通常の染料インク組成物に用いられる直接染料、酸性染料、塩基性染料、媒染・酸性媒染染料、酒精溶性染料、アゾイック染料、硫化・硫化建染染料、建染染料、分散染料、油溶染料、食用染料、金属錯塩染料、造塩染料、樹脂に染料を染着した染料等の中から任意のもの、及びこれらの水溶液を使用することができる。 Examples of the dye that can be used in the present invention include direct dyes, acid dyes, basic dyes, mordant / acid mordant dyes, spirit-soluble dyes, azoic dyes, sulfur / sulfuration vat dyes used in ordinary dye ink compositions. Further, vat dyes, disperse dyes, oil-soluble dyes, edible dyes, metal complex dyes, salt-forming dyes, dyes obtained by dyeing a resin and the like, and aqueous solutions thereof can be used.
　本発明で使用することができる顔料としては、カーボンブラック、グラファイト、二酸化チタン顔料等の無機顔科、タルク、シリカ、アルミナ、マイカ、アルミナシリケート等の体質顔科、アゾ系顔料、縮合アゾ系顔料、フタロシアニン系顔料、アンスラキノン顔料、キナクドリン顔料、イソインドリノン系顔料、ジケトピロロピロール系顔料、各種レーキ顔料等の有機顔料、蛍光顔料、パール顔料、金色、銀色等のメタリック顔料等が挙げられる。 Examples of pigments that can be used in the present invention include inorganic facials such as carbon black, graphite, and titanium dioxide pigments, constitutional facials such as talc, silica, alumina, mica, and alumina silicate, azo pigments, and condensed azo pigments. Organic pigments such as phthalocyanine pigments, anthraquinone pigments, quinacdolin pigments, isoindolinone pigments, diketopyrrolopyrrole pigments, various lake pigments, metallic pigments such as fluorescent pigments, pearl pigments, gold and silver .
　本発明で使用する着色剤は、上記した染料、顔料を単独で使用することができ、あるいは上記した染料、顔料を混合して使用することもできる。 As the colorant used in the present invention, the above-mentioned dyes and pigments can be used alone, or the above-mentioned dyes and pigments can be mixed and used.
　〈水溶性有機溶剤〉
　水溶性有機溶剤としては、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール等のヒンダードアルコール、グリセリン又はその誘導体（例えば、ポリグリセリンなど）、ソルビタン、蔗糖、エチレングリコール、プロピレングリコール、ブチレングリコール等のポリグリコール類等が好ましく使用できる。 <Water-soluble organic solvent>
Examples of water-soluble organic solvents include hindered alcohols such as neopentyl glycol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin or derivatives thereof (for example, polyglycerin), sorbitan, sucrose, ethylene glycol, Polyglycols such as propylene glycol and butylene glycol can be preferably used.
　〈他の成分〉
　本発明のサインペン用水性インク組成物は、本発明の作用を損なわない範囲で、他の成分、例えばｐＨ調整剤、防腐剤、ノンドライ剤等の添加剤等を含有していてもよい。 <Other ingredients>
The water-based ink composition for sign pens of the present invention may contain other components, for example, additives such as pH adjusters, preservatives, and non-drying agents, as long as the effects of the present invention are not impaired.
　《サインペン用リフィル》
　サインペン用リフィルは、インク貯蔵部を具備している。このインク貯蔵部には、上記のサインペン用水性インク組成物が貯蔵されている。 《Refill for sign pen》
The sign pen refill includes an ink reservoir. In the ink storage unit, the water-based ink composition for sign pens is stored.
　サインペン用リフィルは、サインペンにおける交換可能な部位を意味する。 The sign pen refill means a replaceable part of the sign pen.
　また、サインペン用リフィルは、筆記部を更に具備していてもよい。 The sign pen refill may further include a writing portion.
　すなわち、サインペン用リフィルは、インク貯蔵部のみが交換可能な部位となるインクカートリッジであってもよく、インク貯蔵部と筆記部とが一体となって交換可能な部位となるものであってもよい。 That is, the refill for the sign pen may be an ink cartridge in which only the ink storage unit can be replaced, or may be a unit in which the ink storage unit and the writing unit can be replaced together. .
　〈インク貯蔵部〉
　インク貯蔵部には、上記のサインペン用水性インク組成物が貯蔵されている。 <Ink storage section>
The ink storage unit stores the above water-based ink composition for sign pens.
　インク貯蔵部は、インクを貯蔵し、かつ筆記部にインクを供給することができる物であれば、任意の物を用いることができる。 As the ink storage unit, any material can be used as long as it can store ink and supply ink to the writing unit.
　〈筆記部〉
　筆記部は、サインペンの筆記部として用いることができる材料で構成されていればよい。筆記部としては、例えば繊維芯及びプラスチック芯、特にプラスチック芯が挙げられる。 <Writing part>
The writing part should just be comprised with the material which can be used as a writing part of a sign pen. As a writing part, a fiber core and a plastic core, especially a plastic core are mentioned, for example.
　繊維芯は、天然繊維、獣毛繊維、ポリアセタール系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリウレタン系樹脂、ポリオレフィン系樹脂、ポリビニル系樹脂、ポリカーボネート系樹脂、ポリエーテル系樹脂、ポリフェニレン系樹脂などの１種又は２種以上の組合せからなる平行繊維束、フェルト等の繊維束を加工又はこれらの繊維束を樹脂加工した芯である。 Fiber core is natural fiber, animal hair fiber, polyacetal resin, acrylic resin, polyester resin, polyamide resin, polyurethane resin, polyolefin resin, polyvinyl resin, polycarbonate resin, polyether resin, polyphenylene It is a core obtained by processing a fiber bundle such as a parallel fiber bundle made of one kind or a combination of two or more kinds of resin, felt, or the like, or processing these fiber bundles with a resin.
　プラスチック芯（１０）は、図１（ａ）～（ｃ）に示すように、棒状樹脂（２）の長軸方向に、インクをインク貯蔵部から供給するためのインク溝（４）が形成されている芯である。ここで、図１（ａ）は、プラスチック芯（１０）の側面図であり、図１（ｂ）は、プラスチック芯の側面断面図であり、かつ図１（ｃ）は、図１（ｂ）のＣ－Ｃ断面の断面図である。 As shown in FIGS. 1 (a) to 1 (c), the plastic core (10) has an ink groove (4) for supplying ink from the ink storage section in the longitudinal direction of the rod-like resin (2). The core that is. Here, FIG. 1 (a) is a side view of the plastic core (10), FIG. 1 (b) is a side sectional view of the plastic core, and FIG. 1 (c) is FIG. 1 (b). FIG. 6 is a cross-sectional view taken along the line CC of FIG.
　この棒状樹脂は、繊維芯に関して挙げた樹脂で構成されていてよい。インク溝の形状としては、例えば特開２００３－２６８２８５号公報の図２に挙げられている形状であることができる。 This rod-shaped resin may be composed of the resins mentioned for the fiber core. As the shape of the ink groove, for example, the shape shown in FIG. 2 of JP-A-2003-268285 can be used.
　特に、筆記部がプラスチック芯である場合、より特にはポリアセタールで構成されているプラスチック芯である場合に、本発明の利点がより顕著に表れる。 In particular, when the writing part is a plastic core, more particularly when the writing part is a plastic core made of polyacetal, the advantages of the present invention are more prominent.
　《サインペン》
　本発明のサインペンは、インク貯蔵部、筆記部及び保持部を少なくとも具備している。 《Sign pen》
The sign pen of the present invention includes at least an ink storage unit, a writing unit, and a holding unit.
　インク貯蔵部及び筆記部としては、サインペン用リフィルに関して挙げたものを用いることができる。また、保持部は、サインペンを使用する使用者が保持する部分であり、樹脂、木材、金属等で形成されており、滑り止めのシリコーンゴム等で形成されていてもよい。 As the ink storage part and writing part, those mentioned for the refill for sign pens can be used. The holding portion is a portion held by a user using the sign pen, and is formed of resin, wood, metal, or the like, and may be formed of non-slip silicone rubber or the like.
　《サインペン用水性インク組成物製造方法》
　本発明のサインペン用水性インク組成物の製造方法は、乳化工程、及び硬化工程を含む固形シリコーン粒子の製造工程と、これを他のインク組成物材料とともに配合するサインペン用水性インク組成物の製造工程からなる。 << Method for producing water-based ink composition for sign pen >>
The method for producing a water-based ink composition for sign pens according to the present invention includes a step for producing solid silicone particles including an emulsification step and a curing step, and a step for producing a water-based ink composition for sign pens which is blended with other ink composition materials. Consists of.
〔固形シリコーン粒子の製造工程〕
　〈乳化工程〉
　乳化工程は、油相を撹拌させながら、水相を滴下し、それによって転相乳化を行う工程である。 [Production process of solid silicone particles]
<Emulsification process>
The emulsification step is a step of dropping the aqueous phase while stirring the oil phase, thereby performing phase inversion emulsification.
　ここで、「転相乳化」とは、乳化剤を油相に溶かし、ここに水相を添加し、連続相を油相から水相に転化させてＯ／Ｗ型（水中油滴型）エマルションを調製する方法を意味する。 Here, “phase inversion emulsification” means that an emulsifier is dissolved in an oil phase, an aqueous phase is added thereto, and a continuous phase is converted from an oil phase to an aqueous phase to form an O / W type (oil-in-water type) emulsion. Means the method of preparation.
　油相の撹拌は、６００ｒｐｍ以上、６２０ｒｐｍ以上、又は６５０ｒｐｍ以上で、かつ８００ｒｐｍ以下、７８０ｒｐｍ以下、又は７５０ｒｐｍ以下で行うことができる。 The stirring of the oil phase can be performed at 600 rpm or more, 620 rpm or more, or 650 rpm or more, and 800 rpm or less, 780 rpm or less, or 750 rpm or less.
　また、乳化工程は、高圧乳化させることを含んでもよい。高圧乳化の際に印加する圧力は、１５０ＭＰａ以上、１５５ＭＰａ以上、又は１６０ＭＰａ以上であることができ、また２００ＭＰａ以下、１９５ＭＰａ以下、又は１９０ＭＰａ以下であることができる。 Further, the emulsification step may include high-pressure emulsification. The pressure applied during high-pressure emulsification can be 150 MPa or more, 155 MPa or more, or 160 MPa or more, and can be 200 MPa or less, 195 MPa or less, or 190 MPa or less.
　｛油相｝
　油相は、液状シリコーン組成物、及びＨＬＢ値が１０以下の乳化剤を含有している。 {Oil phase}
The oil phase contains a liquid silicone composition and an emulsifier having an HLB value of 10 or less.
　（液状シリコーン組成物）
　液状シリコーン組成物は、硬化させることにより、動的光散乱法で測定したときの平均粒子径が２０ｎｍ～５００ｎｍである固形シリコーン粒子、特に架橋シリコーン粒子を形成する組成物である。 (Liquid silicone composition)
The liquid silicone composition is a composition that, when cured, forms solid silicone particles, particularly crosslinked silicone particles, having an average particle diameter of 20 nm to 500 nm as measured by a dynamic light scattering method.
　液状シリコーン組成物としては、市販のものを用いることができ、例えば信越化学工業株式会社が「ＲＴＶシリコーンゴム」として販売している液状シリコーン組成物を用いることができる。中でも、加熱して硬化させることにより固形シリコーン粒子を形成する熱硬化性液状シリコーン組成物を用いることが好ましく、また一液硬化型の液状シリコーン組成物を用いることが好ましい。 As the liquid silicone composition, a commercially available one can be used, for example, a liquid silicone composition sold as “RTV silicone rubber” by Shin-Etsu Chemical Co., Ltd. can be used. Among them, it is preferable to use a thermosetting liquid silicone composition that forms solid silicone particles by heating and curing, and it is preferable to use a one-component curable liquid silicone composition.
　（油相の乳化剤）
　油相が含有している乳化剤は、ＨＬＢ値が１０以下の乳化剤である。このＨＬＢ値は、１０以下、９以下、又は８以下であることができ、また０超、１以上、又は２以上であることができる。このような乳化剤としては、例えばグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンアルキルフェニルエーテル等を用いることができる。 (Oil phase emulsifier)
The emulsifier contained in the oil phase is an emulsifier having an HLB value of 10 or less. The HLB value can be 10 or less, 9 or less, or 8 or less, and can be greater than 0, 1 or more, or 2 or more. Examples of such an emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Oxyethylene phenyl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, and the like can be used.
　ここで、「ＨＬＢ値」とは、親水性親油性バランス（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ－Ｂａｌａｎｃｅ）を意味するものである。より具体的には、親水基を持たない物質をＨＬＢ値０とし、親油基を持たず親水基のみを持つ物質をＨＬＢ値２０として等分したものである（グリフィン法）。 Here, “HLB value” means a hydrophilic-lipophilic balance. More specifically, a substance having no hydrophilic group has an HLB value of 0, and a substance having no lipophilic group and having only a hydrophilic group is equally divided by an HLB value of 20 (Griffin method).
　｛水相｝
　水相は、水、及びＨＬＢ値が１０超の乳化剤を含有している。水としては、サインペン用水性インク組成物に関して挙げた水を用いることができる。 {Water phase}
The aqueous phase contains water and an emulsifier with an HLB value greater than 10. As water, the water mentioned regarding the water-based ink composition for sign pens can be used.
　（水相の乳化剤）
　水相が含有している乳化剤は、ＨＬＢ値が１０超の乳化剤である。このＨＬＢ値は、２０未満、１９以下、又は１８以下であることができ、また１０超、１１以上、又は１２以上であることができる。このような乳化剤としては、例えばポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンアルキルフェニルエーテル等を用いることができる。 (Emulsifier in water phase)
The emulsifier contained in the aqueous phase is an emulsifier having an HLB value of more than 10. The HLB value can be less than 20, 19 or less, or 18 or less, and can be greater than 10, 11 or more, or 12 or more. Examples of such an emulsifier include polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, polyoxyethylene Styrenated phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene alkylphenyl ether, and the like can be used.
　〈硬化工程〉
　硬化工程は、液状シリコーン組成物を硬化させ、それによって固形シリコーン粒子を生成する工程である。 <Curing process>
The curing step is a step of curing the liquid silicone composition, thereby producing solid silicone particles.
　硬化方法は、液状シリコーン組成物の硬化条件に応じ、適宜選択することができる。 The curing method can be appropriately selected according to the curing conditions of the liquid silicone composition.
　例えば、液状シリコーン組成物が熱硬化性液状シリコーン組成物である場合、乳化工程を経た液状シリコーン組成物を加熱することにより行うことができる。この場合、硬化温度は、４０℃以上、５０℃以上、６０℃以上、又は７０℃以上であることができ、また１２０℃以下、１１０℃以下、１００℃以下、又は９０℃以下であることができる。 For example, when the liquid silicone composition is a thermosetting liquid silicone composition, it can be carried out by heating the liquid silicone composition that has undergone the emulsification step. In this case, the curing temperature may be 40 ° C or higher, 50 ° C or higher, 60 ° C or higher, or 70 ° C or higher, and may be 120 ° C or lower, 110 ° C or lower, 100 ° C or lower, or 90 ° C or lower. it can.
　〈他の工程〉
　固形シリコーン粒子の製造工程は、他の工程、例えば硬化後の固形シリコーン粒子の水分散体を分級する工程を含んでもよい。 <Other processes>
The production process of the solid silicone particles may include another process, for example, a process of classifying the aqueous dispersion of the solid silicone particles after curing.
〔サインペン用水性インクの製造工程〕
　前記固形シリコーン粒子の水分散体、及びサインペン用水性インク組成物を構成する材料をディスパー等の攪拌機器を用いて混合しながら、従来公知の方法で製造する。 [Manufacturing process of water-based ink for sign pens]
The aqueous dispersion of solid silicone particles and the material constituting the water-based ink composition for sign pens are produced by a conventionally known method while mixing using a stirring device such as a disper.
　実施例及び比較例により本発明を具体的に説明するが、本発明は、これらに限定されるものではない。 The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　《組成物の作製》
　〈実施例１〉
　粒子原料としての液状シリコーン組成物（ＫＥ－１８４４、信越化学工業株式会社、２０．０質量部）及び乳化剤としての成分名（品番：エマルゲン１０２ＫＧ、ＨＬＢ：６．３、メーカー名：花王株式会社、１．０質量部）を含有している油相を６００ｒｐｍで撹拌し、そこに乳化剤としての成分名（品番：エマルゲン１５０、ＨＬＢ：１８．４、メーカー名：花王株式会社、９．０質量部）を含有している水相を滴下した。その後、混合液を高圧乳化機により、１５０ＭＰａ、１０パスの条件で処理して乳化した。次いで、混合液を８０℃で１２時間加熱して液状シリコーン組成物を硬化させ、そして１２５００ｒｐｍで３０分間分級して、実施例１の水性インク組成物に用いるための、架橋シリコーン粒子（シリコーンゴム）を含有している固形シリコーン粒子の水分散体を作製した。 << Production of composition >>
<Example 1>
Liquid silicone composition as a particle raw material (KE-1844, Shin-Etsu Chemical Co., Ltd., 20.0 parts by mass) and component name as an emulsifier (product number: Emulgen 102KG, HLB: 6.3, manufacturer name: Kao Corporation, The oil phase containing 1.0 parts by mass) is stirred at 600 rpm, and the component names as an emulsifier (product number: Emulgen 150, HLB: 18.4, manufacturer name: Kao Corporation, 9.0 parts by mass) ) Was added dropwise. Thereafter, the mixed solution was processed and emulsified with a high-pressure emulsifier under conditions of 150 MPa and 10 passes. Next, the liquid mixture is heated at 80 ° C. for 12 hours to cure the liquid silicone composition, and classified at 12500 rpm for 30 minutes to be used in the aqueous ink composition of Example 1 to form crosslinked silicone particles (silicone rubber). An aqueous dispersion of solid silicone particles containing was prepared.
　着色剤としての染料（Ｗａｔｅｒ　Ｂｌａｃｋ　１９１－Ｌ　ｃｏｎｃ．１５％、オリエント化学工業株式会社、２０．０質量部）、防腐剤（バイオデン４２１、大和化学工業株式会社、０．３質量部）、ｐＨ調整剤としてのトリエタノールアミン（０．２質量部）、ノンドライ剤としての尿素（７．５質量部）、溶剤としてのグリセリン（１０質量部）及びエチレングリコール（２．５質量部）、粒子原料としての上記の固形シリコーン粒子の水分散体（固形分換算で３．０質量部）並びにイオン交換水（残部）を用い、実施例１の水性インク組成物を１００質量部作製した。 Dye as a colorant (Water Black 191-L conc. 15%, Orient Chemical Co., Ltd., 20.0 parts by mass), preservative (Bioden 421, Yamato Chemical Co., Ltd., 0.3 parts by mass), pH adjustment Triethanolamine (0.2 parts by mass) as an agent, urea (7.5 parts by mass) as a non-drying agent, glycerin (10 parts by mass) and ethylene glycol (2.5 parts by mass) as a solvent, as a particle raw material 100 parts by mass of the aqueous ink composition of Example 1 were prepared using the above aqueous dispersion of solid silicone particles (3.0 parts by mass in terms of solid content) and ion-exchanged water (remainder).
　〈実施例２〉
　固形シリコーン粒子の水分散体の質量部を、１０．０質量部（固形分換算）に変更したことを除き、実施例１と同様にして、実施例２の水性インク組成物を作製した。 <Example 2>
A water-based ink composition of Example 2 was produced in the same manner as Example 1 except that the mass part of the aqueous dispersion of solid silicone particles was changed to 10.0 parts by mass (solid content conversion).
　〈実施例３〉
　固形シリコーン粒子の水分散体の質量部を、２０．０質量部（固形分換算）に変更したことを除き、実施例１と同様にして、実施例２の水性インク組成物を作製した。 <Example 3>
A water-based ink composition of Example 2 was produced in the same manner as in Example 1 except that the mass part of the aqueous dispersion of solid silicone particles was changed to 20.0 parts by mass (in terms of solid content).
　〈実施例４〉
　粒子原料としての液状シリコーン組成物を、ＫＥ－１８４２（信越化学工業株式会社）に変更したことを除き、実施例２と同様にして、実施例４の水性インク組成物を作製した。 <Example 4>
A water-based ink composition of Example 4 was produced in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1842 (Shin-Etsu Chemical Co., Ltd.).
　〈実施例５〉
　粒子原料としての液状シリコーン組成物を、ＫＥ－１８８６（信越化学工業株式会社）に変更したことを除き、実施例２と同様にして、実施例５の水性インク組成物を作製した。 <Example 5>
A water-based ink composition of Example 5 was produced in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1886 (Shin-Etsu Chemical Co., Ltd.).
　〈比較例１〉
　粒子原料としての液状シリコーン組成物を油相に含有させなかったことを除き、実施例１と同様にして、比較例１の水性インク組成物を作製した。 <Comparative example 1>
A water-based ink composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that the liquid silicone composition as a particle raw material was not contained in the oil phase.
　〈比較例２〉
　粒子原料としての液状シリコーン組成物の代わりに、添加粒子としてのスチレンブタジエンゴム（ＳＢＲ）粒子（Ｎｉｐｏｌ（商標）ＬＸ１１２、日本ゼオン株式会社、２０．０質量部）を用いたことを除き、実施例１と同様にして、比較例１の水性インク組成物を作製した。 <Comparative example 2>
Example except that styrene butadiene rubber (SBR) particles (Nipol (trademark) LX112, Nippon Zeon Co., Ltd., 20.0 parts by mass) as additive particles were used instead of the liquid silicone composition as the particle raw material In the same manner as in Example 1, a water-based ink composition of Comparative Example 1 was produced.
　〈比較例３〉
　粒子原料としての液状シリコーン組成物の代わりに、シリコーンオイル（ＫＦ－９６－５００ｃｓ、信越化学工業株式会社、２０．０質量部）を用いたことを除き、実施例１と同様にして、比較例１の水性インク組成物を作製した。比較例１の水性インク組成物は、シリコーンエマルションを含有しており、表１の「粒径」の欄には液滴の径を記載している点に留意されたい。 <Comparative Example 3>
Comparative Example as in Example 1, except that silicone oil (KF-96-500cs, Shin-Etsu Chemical Co., Ltd., 20.0 parts by mass) was used instead of the liquid silicone composition as the particle raw material. 1 aqueous ink composition was produced. It should be noted that the water-based ink composition of Comparative Example 1 contains a silicone emulsion, and the diameter of the droplet is described in the “Particle Size” column of Table 1.
　〈実施例６〉
　まず、固形シリコーン粒子の水分散体を、実施例１と同様にして作製した。次いで、着色剤としてのカーボンブラック（８．０質量部）、顔料分散剤としてのスチレンアクリル酸樹脂（１．８質量部）、防腐剤（バイオデン４２１、大和化学工業株式会社、０．３質量部）、ｐＨ調整剤としてのトリエタノールアミン（０．２質量部）、溶剤としてのグリセリン（１０．０質量部）、粒子原料としての上記の固形シリコーン粒子の水分散体（固形分換算で１０．０質量部）及びイオン交換水（残部）を用い、実施例６の水性インク組成物を１００質量部作製した。 <Example 6>
First, an aqueous dispersion of solid silicone particles was prepared in the same manner as in Example 1. Next, carbon black (8.0 parts by mass) as a colorant, styrene acrylic acid resin (1.8 parts by mass) as a pigment dispersant, preservative (Bioden 421, Daiwa Chemical Industry Co., Ltd., 0.3 parts by mass) ), Triethanolamine (0.2 parts by mass) as a pH adjuster, glycerin (10.0 parts by mass) as a solvent, and an aqueous dispersion of the above solid silicone particles as a particle raw material (10. in terms of solid content). 0 parts by mass) and ion-exchanged water (remainder) were used to produce 100 parts by mass of the aqueous ink composition of Example 6.
　〈実施例７〉
　粒子原料としての液状シリコーン組成物を、ＫＥ－１８４２（信越化学工業株式会社）に変更したことを除き、実施例６と同様にして、実施例７の水性インク組成物を作製した。 <Example 7>
A water-based ink composition of Example 7 was produced in the same manner as in Example 6 except that the liquid silicone composition as the particle raw material was changed to KE-1842 (Shin-Etsu Chemical Co., Ltd.).
　〈実施例８〉
　粒子原料としての液状シリコーン組成物を、ＫＥ－１８８６（信越化学工業株式会社）に変更したことを除き、実施例２と同様にして、実施例８の水性インク組成物を作製した。 <Example 8>
A water-based ink composition of Example 8 was prepared in the same manner as in Example 2 except that the liquid silicone composition as the particle raw material was changed to KE-1886 (Shin-Etsu Chemical Co., Ltd.).
　〈比較例４〉
　粒子原料としての液状シリコーン組成物の代わりに、添加粒子としてのシリコーン粒子（トスパール１２０、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社、固形分換算で９．７質量部）を用いたことを除き、実施例６と同様にして、比較例４の水性インク組成物を作製した。 <Comparative example 4>
Except for using silicone particles (Tospearl 120, Momentive Performance Materials Japan GK, 9.7 parts by mass in terms of solid content) as additive particles instead of the liquid silicone composition as the particle raw material, In the same manner as in Example 6, a water-based ink composition of Comparative Example 4 was produced.
　〈比較例５〉
　粒子原料としての液状シリコーン組成物の代わりに、添加粒子としてのシリコーン粒子（トスパール１１１０、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社、固形分換算で９．７質量部）を用いたことを除き、実施例６と同様にして、比較例５の水性インク組成物を作製した。 <Comparative Example 5>
Except for using silicone particles as additive particles (Tospearl 1110, Momentive Performance Materials Japan GK, 9.7 parts by mass in terms of solid content) instead of the liquid silicone composition as the particle raw material, In the same manner as in Example 6, a water-based ink composition of Comparative Example 5 was produced.
　《評価》
　作製した水性インク組成物を、サインペンのインク貯蔵部にそれぞれ充填した。サインペンの筆記部としては、ポリアセタール芯を用いた。 <Evaluation>
The prepared water-based ink composition was filled in the ink storage part of the sign pen. A polyacetal core was used as the writing part of the sign pen.
　各サインペンについて、表面性測定器（ＨＥＩＤＯＮ－１４Ｄ、新東化学株式会社）を用い、筆記速度３．３ｍ／分、荷重１００ｇ、並びに筆記角度９０°の条件で、１０ｃｍの直線動作をした際の摩擦抵抗を３回ずつ測定し、その平均値から摩擦係数を求めた。筆記用紙としては、標準紙（しらおい）を用いた。 For each sign pen, using a surface property measuring instrument (HEIDON-14D, Shinto Chemical Co., Ltd.), when a linear motion of 10 cm was performed at a writing speed of 3.3 m / min, a load of 100 g, and a writing angle of 90 °. The frictional resistance was measured three times, and the coefficient of friction was determined from the average value. Standard paper (Shiraoi) was used as writing paper.
　結果を表１及び表２に示す。 Results are shown in Tables 1 and 2.
　なお、表１及び表２中の平均粒子径は、実施例１～８及び比較例１～３については上記の動的光散乱法により測定したものであるが、比較例４及び５については、粒径が大きいことに起因して動的光散乱法で測定できないため、粒子径分布解析装置ＨＲＡ９３２０－Ｘ１００（日機装株式会社製）を用いて、レーザー回折法により体積基準で算出されたＤ５０の値である。 The average particle sizes in Tables 1 and 2 were measured by the dynamic light scattering method for Examples 1 to 8 and Comparative Examples 1 to 3, but for Comparative Examples 4 and 5, Since it cannot be measured by the dynamic light scattering method due to the large particle size, the value of D50 calculated on the volume basis by the laser diffraction method using the particle size distribution analyzer HRA9320-X100 (manufactured by Nikkiso Co., Ltd.) It is.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１及び２から、平均粒子径が２０ｎｍ～５００ｎｍの架橋シリコーン粒子を含有している実施例１～８の水性インク組成物は、比較例１～５の水性インク組成物と比較して、サインペンに用いた場合に良好な書き味が得られることが理解されよう。なお、比較例３では、上記の評価結果は比較的良好であったものの、長く使用するとペン先に皮膜が形成されて、筆記性が極端に劣化した。 From Tables 1 and 2, the aqueous ink compositions of Examples 1 to 8 containing crosslinked silicone particles having an average particle diameter of 20 nm to 500 nm were compared with the aqueous ink compositions of Comparative Examples 1 to 5 as a sign pen. It will be understood that a good writing quality can be obtained when used in the above. In Comparative Example 3, the evaluation result was relatively good, but when used for a long time, a film was formed on the pen tip, and the writing property was extremely deteriorated.
　２　　棒状樹脂
　４　　インク溝
　１０　　プラスチック芯 2 Rod-shaped resin 4 Ink groove 10 Plastic core

Claims (4)

  1. 　水、固形シリコーン粒子及び着色剤を含有しており、かつ
    　動的光散乱法で測定したときの、前記固形シリコーン粒子の平均粒子径が２０ｎｍ～５００ｎｍである、
    サインペン用水性インク組成物。     Containing water, solid silicone particles and a colorant, and having an average particle diameter of 20 nm to 500 nm when measured by a dynamic light scattering method,
    Water-based ink composition for sign pens.
  2. 　前記固形シリコーン粒子が、架橋シリコーン粒子である、請求項１に記載のサインペン用水性インク組成物。 The water-based ink composition for sign pens according to claim 1, wherein the solid silicone particles are crosslinked silicone particles.
  3. 　インク貯蔵部、筆記部及び保持部を少なくとも具備しており、かつ
    　前記インク貯蔵部に請求項１又は２のいずれか一項に記載のサインペン用水性インク組成物が貯蔵されている、
    サインペン。     It comprises at least an ink storage part, a writing part and a holding part, and the water-based ink composition for sign pens according to any one of claims 1 or 2 is stored in the ink storage part.
    Sign pen.
  4. 　前記筆記部が、プラスチック芯である、請求項３に記載のサインペン。 The sign pen according to claim 3, wherein the writing part is a plastic core.
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EP3753746A1 (en) * 2019-06-20 2020-12-23 Société BIC Writing felt pen

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