Pretreatment agent

Abstract

The present invention provides a pretreatment agent that, when ink is brought into contact with a pre-treated substrate such as a fabric by writing or other means, causes the ink to swell and thicken on the substrate, preventing the ink from seeping into the fibers or moving on the fibers, and also suppresses ink bleeding on the substrate even if there are uneven coatings. [Solution] A pretreatment agent comprising an alkali-thickening resin emulsion and water, characterized in that the pH of the pretreatment agent is 2 to 7. The pretreatment agent may also be one in which the alkali-thickening resin emulsion is an alkali-thickening acrylic resin emulsion.

Description

[Technical Field]

[0001] This disclosure relates to a pretreatment agent. [Background technology]

[0002] Traditionally, when writing on fabric using writing instruments, the ink can bleed, resulting in unclear writing and making it difficult to see letters or pictures. Therefore, in order to suppress ink bleeding, a primer for the writing surface or stamping surface of a cloth is described, which contains at least water, a resin that dissolves or disperses in the water, and an alkylolamide-type nonionic surfactant (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-074316 [Overview of the project] [Problems that the invention aims to solve]

[0004] The primer described in prior art 1 suppresses ink bleeding by coating the surface of the fabric fibers. However, if there were areas where the primer was not applied or where the coating was uneven, when writing with a writing instrument, ink bleeding could occur due to the ink soaking into the fabric fibers or moving along the fibers.

[0005] The inventors diligently studied pretreatment agents capable of suppressing ink bleeding and found that by using an alkaline thickening resin emulsion and water, and setting the pH within a specific range, when ink is brought into contact with a substrate such as a cloth that has been pretreated with the pretreatment agent by writing or other means, the ink swells and thickens on the substrate. This prevents the ink from seeping into the fibers or moving on the fibers, allowing the ink to remain on the substrate. Furthermore, even in cases of uneven coating, ink bleeding on the substrate is suppressed, leading to the completion of this disclosure. [Means for solving the problem]

[0006] [1] A pretreatment agent comprising an alkaline thickening resin emulsion and water, characterized in that the pH of the pretreatment agent is 2 to 7.

[0007] [2] The pretreatment agent according to [1], wherein the alkali-thickened resin emulsion is an alkali-thickened acrylic resin emulsion.

[0008] [3] The pretreatment agent according to [1] or [2], wherein the viscosity of the pretreatment agent is 1.0 to 100 mPa·S under conditions of 20°C and a rotation speed of 30 rpm.

[0009] [4] An ink set comprising an ink composition containing one or more selected from the group consisting of alcohols, glycols, and glycol ethers, and a pretreatment agent as described in any of [1] to [3].

[0010] [5] An applicator containing one of the pretreatment agents described in [1] to [3].

[0011] [6] A writing set comprising a writing instrument containing an ink composition selected from the group consisting of alcohols, glycols, and glycol ethers, and the applicator described in [5].

[0012] [7] Fabric that has been pretreated using any of the pretreatment agents described in [1] to [3].

[0013] 〔8〕 The fabric according to〔7〕, wherein the fabric contains synthetic fibers.

Effects of the Invention

[0014] According to the specification of the present disclosure, the pretreatment agent of the present disclosure acts on the ink to cause the ink to swell and increase in viscosity, so that the ink remains on the base material, whereby bleeding of the ink on the base material can be suppressed.

Brief Description of the Drawings

[0015] [Figure 1] It is an external view showing an example of a writing instrument in one embodiment of the present disclosure.

Modes for Carrying Out the Invention

[0016] Hereinafter, specific embodiments of the present disclosure will be described in detail. The present invention is not limited to the embodiments described below.

[0017] The terms "part", "%", "ratio" and the like indicating the addition amount in the present specification are based on mass unless otherwise specified.

[0018] The term "pretreatment" in the present specification refers to treating a base material by applying (or coating) a pretreatment agent thereto, immersing the base material in the pretreatment agent, or the like. The term "immersion" in the present specification may be a state where the pretreatment agent has penetrated into the inside of the base material, or may be a state where the pretreatment agent has not penetrated thereinto.

[0019] The term "fabric" in the present specification is not limited to woven fabrics and cloth, and refers to "fabric" in a broad sense including woven fabrics, knitted fabrics, nonwoven fabrics and the like.

[0020] The pretreatment agent disclosed in the present specification is characterized by comprising an alkali-thickening type resin emulsion and water, and having a pH in the range of 2 to 7.

[0021] <Alkali-thickening type resin emulsion> The alkali-thickened resin emulsion of this disclosure is a resin emulsion that swells and exhibits viscosity when an alkali is added to raise the pH above 7.

[0022] Examples of alkali-thickening resin emulsions include emulsions of polymers of unsaturated carboxylic acids, emulsions of polymers of unsaturated carboxylic acid esters, emulsions of copolymers of unsaturated carboxylic acids and unsaturated carboxylic acid esters, and emulsions of copolymers containing ethylenically unsaturated compound monomers in these polymers. From the standpoint of greater swelling and thickening and suppression of ink bleeding, it is preferable that the polymer or copolymer resin emulsion contains an unsaturated carboxylic acid and / or an unsaturated carboxylic acid ester having a carboxyl group in the monomer units of the polymer of the resin emulsion. The copolymer may be any copolymer, a bipolymer, or a terpolymer. Furthermore, the copolymer may be any of the following: a random copolymer, a block copolymer, an alternating copolymer, or a graft copolymer.

[0023] Unsaturated carboxylic acids are represented by general formula (1).

[0024] [ka]

[0025] R in general formula (1) 1 This is a hydrocarbon group having two or more carbon atoms that contains at least one unsaturated bond (carbon-carbon double bond).

[0026] R 1 The hydrocarbon group is not particularly limited as long as it can form a polymer or copolymer, and may be linear, branched, or cyclic. Also, R 1 The unsaturated bonds in the hydrocarbon group may be located at the terminal or non-terminal end.

[0027] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, crotonic acid, isocrotonic acid, tigric acid, and angelic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; and carboxyl group-containing unsaturated carboxylic acid ester compounds such as monomethyl itaconic acid, monobutyl itaconic acid, and monoethyl maleate.

[0028] Unsaturated carboxylic acid esters are represented by general formula (2).

[0029] [ka]

[0030] R in general formula (2) 2 R is a hydrocarbon group having 2 or more carbon atoms and containing at least one unsaturated bond (carbon-carbon double bond), 3 This is an organic group having one or more carbon atoms.

[0031] R 2 The hydrocarbon group is not particularly limited as long as it can form a polymer or copolymer, and may be linear, branched, or cyclic. Also, R 2 The unsaturated bonds in the hydrocarbon group may be located at the terminal or non-terminal end.

[0032] R 3 The organic group may be linear, branched, or cyclic, and may contain either saturated or unsaturated bonds. It is preferable that the organic group be a hydrocarbon group, as this has less impact on the pH of the pretreatment agent.

[0033] Examples of unsaturated carboxylic acid esters include the aforementioned carboxylic acid esters of unsaturated carboxylic acids such as acrylic acid esters and methacrylic acid esters. More specific examples include alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, and behenyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and behenyl methacrylate; and alicyclic, aromatic ring, and heterocyclic ring-containing methacrylic acid esters such as cyclohexyl methacrylate, benzyl methacrylate, and isobornyl methacrylate. Additionally, R such as 2-hydroxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate 3 may be an unsaturated carboxylic acid ester in which the organic group having 1 or more carbon atoms contains an element other than hydrocarbons.

[0034] Examples of ethylenically unsaturated compounds include ethylene, cyanovinyls such as acrylonitrile and methacrylonitrile, saturated vinyl carboxylates such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl octylate, and vinyl neodecanoate, vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether, vinyl chloride, vinylidene chloride, and the like. Of these

[0035] Among alkali-thickening resin emulsions, from the viewpoint of being easy to thicken and swell and further suppressing ink bleeding, the alkali-thickening acrylic resin emulsion selected from any of acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters as the unsaturated carboxylic acid and unsaturated carboxylic acid ester is preferred, and an alkali-thickening acrylic resin emulsion containing at least one unsaturated carboxylic acid of acrylic acid or methacrylic acid is more preferred. Alternatively, a modified acrylic resin emulsion with modified groups such as hydrophobic groups introduced may also be used.

[0036] Alkaline thickened resin emulsions and alkaline thickened acrylic resin emulsions may be synthesized as appropriate, or commercially available products may be used. Commercially available alkaline thickening resin emulsions include "Aron A-7075," "Aron A-7055," "Aron B-300K," and "Aron B-500" from Toagosei Co., Ltd., and "Chikuzol K-1000" from Kyoeisha Chemical Co., Ltd. Commercially available alkaline thickening acrylic resin emulsions include "SN Thickener 630," "SN Thickener 920," "SN Thickener 640," "SN Thickener 636," and "Bistool 3015" from Sunopco Co., Ltd., "Banstar S100," "Banstar X1581B2," "Banstar ST600," and "Banstar ST900" from Chubu Saiden Co., Ltd., "Boncoat HV-E," "Boncoat VE," and "Boncoat 3750-E" from DIC Corporation, "Movinyl 730L" and "Licabond FK-600S" from Japan Coating Resin Co., Ltd., "Acryset WR-503A" and "Acryset WR-517" from Nippon Shokubai Co., Ltd., and "Primal ASE-60," "Primal DR-72," "Primal TT-935," and "Primal TT-615" from DOW Chemical Co., Ltd.

[0037] Alkaline thickened resin emulsions and alkaline thickened acrylic resin emulsions may be used individually or in combination of two or more types.

[0038] The content of the alkali-thickened resin emulsion and alkali-thickened acrylic resin emulsion may be 0.5% to 50% by mass in terms of solid content relative to the total amount of pretreatment agent, and may be 1.0% to 20% by mass when contained in an applicator and considering stable discharge.

[0039] <Water> There are no particular restrictions on the type of water that can be used; for example, tap water, deionized water, purified water, distilled water, ultrafiltered water, pure water, deep-sea water, groundwater, etc.

[0040] The pretreatment agent contains water, so when applied to the substrate, the alkaline thickening resin emulsion penetrates together with the water, allowing the pretreatment agent to form uniformly within and on the substrate surface. Furthermore, when the substrate being treated with the pretreatment agent is fabric, ink bleeding can be suppressed without damaging the texture.

[0041] <Pretreatment agent> When an ink composition containing an alkaline component such as a basic pH adjuster, an ink composition with an alkaline pH, or an ink composition containing one or more selected from the group consisting of alcohols, glycols, and glycol ethers is brought into contact with a substrate pre-treated with the pre-treatment agent disclosed herein by writing or printing, the ink swells and thickens due to the pre-treatment agent. As a result, the ink remains in the substrate fibers without soaking into them or moving along the fibers, thus suppressing ink bleeding. In particular, when an ink composition containing one or more selected from the group consisting of alcohols, glycols, and glycol ethers reacts with the pre-treatment agent disclosed herein, the ink composition swells and thickens more easily, further suppressing ink bleeding on the substrate.

[0042] The lower limit of the pH of the pretreatment agent disclosed herein may be 2 or higher, greater than 2, or 3 or higher. The upper limit may be 7 or lower, less than 7, or 6 or lower. By setting the pH below the upper limit, ink bleeding is easily suppressed, and by setting the pH above the lower limit, pretreatment can be performed without impairing the texture or properties of the substrate. The pH of the pretreatment agent was measured using an ion meter [Toa DKK Co., Ltd., product name: IM-40S] at a temperature of 20°C.

[0043] The viscosity of the pretreatment agent disclosed herein is preferably in the range of 1.0 mPa·S to 100 mPa·S, and more preferably in the range of 1.5 mPa·S to 15.0 mPa·S, when measured at a rotation speed of 30 rpm in an environment of 20°C. Having a viscosity within the above range allows for faster penetration into permeable substrates such as fabrics, shortening the time required for the work process and making it easier to suppress ink bleeding. Furthermore, because the viscosity of the pretreatment agent is within the above range, when the pretreatment agent is contained in an applicator, it can be used without being limited by the form or shape of the applicator's application part, such as a spray type or a marking pen type.

[0044] <Other additives> The pretreatment agent disclosed herein may contain additives in addition to the two components of an alkaline thickening resin emulsion and water. Examples include colorants, surfactants, sugars, UV absorbers, antioxidants, defoamers, preservatives and fungicides, and rust inhibitors. These additives are not particularly limited as long as the pH of the pretreatment agent is in the range of 2 to 7, and any known additives may be used.

[0045] As long as the pH of the pretreatment agent is within the range of 2 to 7, conventionally known colorants such as pigments and dyes may be used for the purpose of adjusting the color of the treated surface and the untreated surface of the substrate pretreated with the pretreatment agent.

[0046] If the pH of the pretreatment agent is within the range of 2 to 7, conventionally known surfactants may be used for the purpose of improving the wettability of the pretreatment agent to the substrate. Examples of these surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, surfactants containing acetylene bonds in their structure, silicone surfactants, phosphate ester surfactants, and fluorine surfactants.

[0047] By further including sugars, the sedimentation of the alkali-thickening resin emulsion in the pretreatment agent can be suppressed, and drying of the applied area can be suppressed when the pretreatment agent is contained in the applicator. In particular, when using marker-type or brush-pen-type applicators, the tip does not dry out, and stable application can be achieved even after a long period of time. Examples of sugars include monosaccharides such as glucose and fructose, disaccharides such as sucrose and maltose, and polysaccharides such as various oligosaccharides, corn syrup, and liquid sugars. Reducing sugars obtained by reducing various sugars may also be used.

[0048] Examples of UV absorbers include 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, and p-hydroxybenzophenone.

[0049] Examples of antioxidants include dibutylhydroxytoluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, and catechins.

[0050] <Base material> The substrate to be pre-treated with the pre-treatment agent is not particularly limited as long as it is a substrate that exhibits ink bleeding, and examples include paper and fabric.

[0051] Fabrics made from natural or synthetic fibers are preferred because they have a superior texture after being pre-treated with a fabric pre-treatment agent.

[0052] The type of fabric can be woven, knitted, nonwoven, or felt. The fabric may be made from one or more of the fibers described later, or it may be a fabric made from blended yarns, blended fibers, or covering yarns.

[0053] The weave structure of the fabric is not particularly limited and may be any of the following: plain weave, twill weave, herringbone weave, ribbed weave, satin weave, leno weave, jacquard weave, heavy weave, double weave, gauze weave, etc., or it may be a woven fabric that combines these weave structures.

[0054] The knitting structure of the knitted fabric is not particularly limited and may be any of the following: plain knit, rib knit, smooth knit, tricot knit, raschel knit, Milanese knit, pique knit, double knit, etc., or a knitted fabric that combines these knitting structures.

[0055] The type of nonwoven fabric is not particularly limited, and may be a nonwoven fabric manufactured by a conventionally known manufacturing method. The manufacturing method may include, for example, a nonwoven fabric produced by forming a web using the airlaid method, carding method, wet method, or spunbond method, and then bonding it using the needle punch method, spunlace method, steam jet method, stitch bond method, chemical bond method, thermal bond method, or meltblown method. Furthermore, it may be a composite nonwoven fabric such as SM nonwoven fabric (spunbond-meltblown composite nonwoven fabric), SMS (spunbond-meltblown-spunbond composite nonwoven fabric), or SMMS nonwoven fabric (spunbond-meltblown-meltblown-spunbond composite nonwoven fabric). In addition, it may be a nonwoven fabric that has undergone processing such as slitting or embossing.

[0056] The types of fibers that make up the fabric are not particularly limited and may be natural fibers such as plant fibers or animal fibers, or chemical fibers such as regenerated fibers, synthetic fibers, or semi-synthetic fibers. Furthermore, composite fibers made by mixing these natural and chemical fibers may also be used. Examples of plant fibers include cotton species such as Barbadense and Hirsutum (Upland cotton, etc.), Arboreum and Herbaceum, as well as seed fibers such as kapok, bast fibers such as flax, ramie, jute, hemp, cannabis, paper mulberry, kudzu, ganpi, and mitsumata, leaf vein fibers such as Manila hemp, sisal, and pineapple, and other plant fibers such as rush, coconut, banana, sugarcane, and bamboo. Examples of animal fibers include animal hair fibers such as sheep's wool, goat's wool, horsehair, camel's wool, alpaca wool, rabbit's wool, cow's wool, and yak's wool, cocoon fibers such as domestic silk and wild silk, and other animal fibers such as feathers and spider silk. Examples of regenerated fibers include copper ammonia rayon, viscose rayon, lyocell, and polynosic. Examples of synthetic fibers include polyamide, polyester, polylactic acid, polyacrylonitrile, aramid, vinylon, polyvinylidene chloride, polyvinyl chloride, polyethylene, polypropylene, and polyurethane. Examples of semi-synthetic fibers include cellulose acetate (acetate, diacetate, triacetate) and Promix. Alternatively, glass fibers, carbon fibers, metal fibers, etc., may also be used.

[0057] Any fabric that can be pre-treated with the pre-treatment agent disclosed herein may be a fabric that has been processed by a conventionally known processing method, without any particular limitations. Examples of processing applied to fabrics include texture adjustments such as resin-based wrinkle and shrink-proofing, water-repellent treatment, alkali-based weight reduction, calendering, pleating, opal processing, embossing, and color deepening; and processing to improve the functionality of the fabric, such as napping, water absorption, antistatic treatment, heat retention, antibacterial treatment, deodorizing treatment, stain-resistant treatment, softening treatment, heat-resistant treatment, moisture absorption treatment, anti-melting treatment, and soil release treatment.

[0058] Furthermore, these fabrics may be pre-dyed or post-dyed. Furthermore, the fabric pre-treated with the treatment agent of the present disclosure may be post-dyed.

[0059] <Substrate pre-treated with a pre-treatment agent> A pre-treated substrate can be prepared by performing a substrate pre-treatment step using the pre-treatment agent of the present disclosure, and, if necessary, a drying step of the pre-treated substrate.

[0060] The pretreatment process using a pretreatment agent is not particularly limited and can include conventionally known methods such as coating, spraying, and immersion. Specifically, examples include spin coating, cast coating, blade coating, dip coating, roll coating, bar coating, die coating, spray coating, airless spray coating, drop casting, inkjet, printing, screen printing, brush application, and pretreatment using an applicator.

[0061] By performing a drying process on the pre-treated substrate after the pre-treatment process using a pre-treatment agent, it becomes easier to process the pre-treated substrate by cutting or sewing, and when used with a writing instrument, it reduces the likelihood of writing defects. Drying methods include conventionally known methods such as natural drying, hot air drying, and vacuum drying.

[0062] When the base material is a fabric, fields in which the fabric pretreated with the pretreatment agent of the present disclosure (hereinafter, depending on the case, referred to as "pretreated fabric") is used include the industrial materials field, the civil engineering materials field, the building materials field, the consumer goods field, and the agricultural materials field. For example, if the pre-treated fabric is a name tag, names or pictures can be printed on it without bleeding. If the pre-treated fabric is a textile product such as clothing like T-shirts or interior items like curtains, patterns and letters can be printed without bleeding when using inkjet printing, screen printing, heat transfer, or sublimation transfer. When the pre-treated fabric is immersed in dye, bleeding is suppressed, and a clear pattern can be formed.

[0063] <Coating tool> Pretreatment may be performed using an applicator containing the pretreatment agent, as it allows for easy adjustment of the amount of pretreatment agent applied according to the type of base material such as fabric, its fiber ratio, basis weight, thickness, weight, and air permeability. The applicator is not particularly limited as long as it comprises a pretreatment agent storage section capable of containing a pretreatment agent and an applicator section capable of applying the pretreatment agent contained in the storage section to the substrate. The pretreatment agent may be directly stored in the pretreatment agent storage section, or it may be impregnated with cotton or absorbent material built into the pretreatment agent storage section. The applicator section may be detachable from the pretreatment agent storage section. Examples of materials for the pretreatment agent containment section include paper and plastic, while examples of materials and shapes for the application section include brushes, sponges, felt, fiber bundles, rollers, and combs. Examples of application tools include brush-type containers, brush-type containers, scraper-type containers, roller-type containers, sponge-head bottles, tubes, stamps, sprays, marking pens, ballpoint pens, brush pens, and other pen-type (or writing instrument-type) application tools.

[0064] The applicator of this disclosure may also be in the form of a cartridge (hereinafter referred to as "cartridge" depending on the case) as a detachable structure. In this case, after the pretreatment agent contained in the cartridge is used up, the cartridge can be replaced with a new one, allowing it to be used again as an applicator.

[0065] The pretreatment agent containment section may be made of a transparent material such as resin. By being formed from a transparent material such as resin, the inside of the applicator can be seen from the outside, allowing for confirmation of the amount of pretreatment agent contained and the remaining amount.

[0066] <Pen-type (or writing instrument-type) applicator> Among the aforementioned applicators, a pen-type (or writing instrument-type) applicator can also be used, as it is easy to apply to the substrate and allows the user to arbitrarily adjust the amount and width of application. As a pen-type applicator, the structure, tip shape, filling mechanism, etc., of a writing instrument conventionally used can be appropriately selected and used. Examples include ballpoint pens, marking pens, fountain pens, brush pens, and calligraphy pens. When the substrate is fabric, marking pen type or brush pen type applicators are preferred because they are less likely to snag and are easier to apply.

[0067] When the pen-type applicator is of the marking pen type, the structure and shape of the applicator itself are not particularly limited, and it is used as a refill for a marking pen-type applicator equipped with a marking pen tip and a pretreatment agent filling mechanism, or by filling a marking pen-type applicator.

[0068] Examples of marking pen tips include conventional porous materials with interconnected pores selected from a range of approximately 30-70% porosity, such as resin processed fiber bodies, heat-meltable fiber fused bodies, and felt bodies, or extruded synthetic resin bodies having multiple axially extending outlet holes. One end is then processed into a shape such as a bullet shape, rectangle, or chisel shape according to the purpose for practical use.

[0069] The aforementioned padding and absorbent material is a fiber bundle formed by gathering crimped fibers in the longitudinal direction, and is constructed by embedding it in a covering such as a plastic tube or film, and adjusting the porosity to be in the range of approximately 40-90%.

[0070] A marking pen type applicator can be formed by housing an absorbent material impregnated with a pretreatment agent inside the barrel, and connecting a marking pen tip to the barrel, either directly or via a connecting member, so as to connect to the absorbent material.

[0071] Furthermore, by housing an absorbent body impregnated with a pretreatment agent in the pretreatment agent storage section, and connecting a marking pen tip to the pretreatment agent storage section either directly or via a connecting member so as to connect to the absorbent body, a refill for a marking pen type applicator containing a pretreatment agent (hereinafter, depending on the case, referred to as a "refill containing a pretreatment agent") can be formed. By housing the refill containing this pretreatment agent in the barrel, a marking pen-type applicator can be formed.

[0072] For the pretreatment agent containment section, for example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal tubular body can be used.

[0073] A marking pen-type applicator, comprising a marking pen tip and a filling mechanism, may further include a supply mechanism for supplying the pretreatment agent, which is to be filled into the pretreatment agent filling mechanism, to the pen tip.

[0074] The pretreatment agent supply mechanism is not particularly limited, and examples include a mechanism that includes a pretreatment agent flow rate regulator using a valve mechanism, which supplies the pretreatment agent to the pen tip when the valve is opened. The valve mechanism can use a conventional pumping type that opens when pressed by the tip, and it is preferable that the spring pressure is set to allow it to be opened by the pressure of a pen.

[0075] When a marking pen-type applicator is equipped with a pretreatment agent supply mechanism, the pretreatment agent filling mechanism can be a pretreatment agent container that can be directly filled with the pretreatment agent, in addition to an adsorbent. Alternatively, the shaft itself may be used as a pretreatment agent filling mechanism, and the pretreatment agent may be filled directly into it.

[0076] 1) A marking pen type applicator for containing the pretreatment agent of the present disclosure may be configured such as: (1) a marking pen type applicator in which a storage body made of a fiber bundle impregnated with the pretreatment agent is contained in the barrel, and a marking pen tip made of a fiber processed body or resin molded body having capillary gaps is connected to the barrel directly or via a connecting member so that the storage body and the tip are connected; (2) a marking pen type applicator in which the pretreatment agent is directly filled in the barrel, and a mechanism is provided to supply the pretreatment agent to the pen tip by interposing a pretreatment agent guide core made of a comb-groove-shaped pretreatment agent flow rate regulator or a fiber bundle as a pretreatment agent flow rate regulator; (3) a marking pen type applicator in which the pretreatment agent is directly filled in the barrel, and a mechanism is provided to supply the pretreatment agent to the pen tip via the pen core; and (4) a marking pen type applicator in which the tip and a pretreatment agent storage body are provided via a valve mechanism that opens when the tip is pressed, and the pretreatment agent is directly filled into the pretreatment agent storage body.

[0077] A pen-type applicator may also be a capped applicator, provided it has a cap that covers the applicator part. By using a capped applicator, contamination and damage to the applicator part can be prevented. Furthermore, the cap may be made of a transparent material such as resin, and by using a transparent cap, the pen tip can be seen without removing the cap.

[0078] If the applicator of this disclosure is of the marking pen type, the applicator tip may have a window that allows the user to see the direction of application. By having an applicator tip with a window, the user of the applicator can apply while confirming the area to be applied.

[0079] The form of the applicator of this disclosure is not limited to the form described above, and may also be a double-ended applicator equipped with applicator parts of different shapes at both ends of the applicator's barrel. Examples of double-ended applicators include an applicator in which a partition wall is provided inside the barrel and applicator parts are fixed to both ends of the barrel directly or via an intermediate member, or an applicator in which two or more refills are housed inside the barrel so that the applicator parts are located at both ends of the barrel, and a pretreatment agent is housed inside the refills. Furthermore, the applicator may have multiple coating parts fixed to one end of the shaft, either directly or via intermediate members. Alternatively, these applicators may be double-ended writing instruments containing a pretreatment agent and an ink composition, with the applicator portion having a writing tip that dispenses the ink composition described later.

[0080] The inks used for writing or printing on a substrate pre-treated with the pre-treatment agent of the present disclosure, and the outer packaging that contains them, are described below.

[0081] <Ink composition> It may be a writing instrument ink composition (hereinafter, depending on the circumstances, referred to as "writing instrument ink" or "writing instrument ink"), or it may be a printing ink composition such as letterpress printing ink, intaglio printing ink, lithographic printing ink, stencil printing ink, on-demand printing ink, offset printing ink, or digital offset printing ink.

[0082] The ink composition preferably contains at least an alkaline component such as a basic pH adjuster, or at least one of alcohols, glycols, or glycol ethers, and more preferably at least one of alcohols, glycols, or glycol ethers. When an ink composition contains alcohols, glycols, or glycol ethers, it reacts with pretreatment agents applied to the substrate during pretreatment when printing or writing on a substrate such as fabric. This causes swelling and thickening, making it difficult for the ink to penetrate into the fibers of the substrate or move along the fibers of the substrate, thus suppressing ink bleeding.

[0083] The pH of the ink composition is not particularly limited and may be acidic, neutral, or alkaline, but if it is alkaline, bleeding is more easily suppressed.

[0084] The ink composition is not particularly limited as long as it is an ink that swells and thickens when a substrate pre-treated with a pre-treatment agent, and may be an oil-based ink or an aqueous ink. It may also be a gel ink, an oil-in-water droplet type or water-in-oil droplet type ink composition, or an ink composition containing a deep eutectic solvent.

[0085] <Oil-based ink for writing instruments> When the aforementioned ink composition is used as an oil-based ink composition for writing instruments (hereinafter, depending on the circumstances, referred to as "oil-based ink," "oil-based ink composition," or "oil-based ink for writing instruments"), it is more preferable that the oil-based ink uses an organic solvent such as alcohols, glycols, or glycol ethers, considering the swelling and thickening properties of the ink due to the pretreatment agent.

[0086] Examples of organic solvents such as alcohols, glycols, and glycol ethers include those commonly used in oil-based inks for writing instruments. The alcohols may be lower alcohols or higher alcohols, and examples include benzyl alcohol, methanol, ethanol, 1-propanol, 2-propanol, isopropanol, isobutanol, t-butanol, propagyl alcohol, allyl alcohol, 3-methyl-1-butyne-3-ol, ethylene glycol monomethyl ether acetate, and other higher alcohols. Examples of glycols include diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and ethylene glycol. Examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, 3-methoxybutanol, and 3-methoxy-3-methylbutanol. These alcohols, glycols, and glycol ethers may be used individually or in combination of two or more, and are preferably present in amounts of 0.1% to 99% by mass, and more preferably 0.5% to 90% by mass, relative to the total amount of the oil-based ink composition.

[0087] Organic solvents other than alcohols, glycols, and glycol ethers may be used in combination with conventionally used organic solvents in oil-based inks for writing instruments. Examples include hydrocarbon organic solvents such as n-heptane, n-octane, isooctane, methylcyclohexane, ethylcyclohexane, toluene, xylene, ethylbenzene, and naphthalene; ketone organic solvents such as methyl isobutyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, and di-n-propyl ketone; and ester organic solvents such as n-butyl formate, isobutyl formate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl propionate, n-butyl propionate, methyl butyrate, and ethyl butyrate.

[0088] As colorants, general-purpose dyes and pigments that have been conventionally used in oil-based inks are used as appropriate.

[0089] There are no particular restrictions on the dyes used; conventional, general-purpose dyes can be applied. Examples include organic solvent-soluble dyes, basic dyes, acid dyes, direct dyes, and food dyes, which are classified as solvent dyes in the color index.

[0090] Examples of pigments include inorganic pigments such as carbon black, ultramarine, and titanium dioxide pigment; organic pigments such as azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, surene pigments, quinacridone pigments, anthraquinone pigments, surene pigments, diketopyrrolopyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, and isoindolinone pigments; metallic pigments obtained by treating aluminum powder or the surface of aluminum powder with a colored resin; metallic luster pigments obtained by forming a metal vapor-deposited film such as aluminum on a transparent or colored transparent film; metallic pigments with a thickness of 0.01 to 0.1 μm obtained by peeling off a metal vapor-deposited film such as aluminum formed on a substrate such as a film; colloidal particles with an average particle size of 5 to 30 nm selected from gold, silver, platinum, and copper; fluorescent pigments; phosphorescent pigments; thermochromic pigments; and pearl pigments obtained by coating the surface of a transparent film piece with a metal oxide such as titanium dioxide as a core material, such as natural mica, synthetic mica, glass fragments, alumina, or titanium dioxide.

[0091] These colorants may be used individually or in combination of two or more, and it is preferable to use them in an amount of 1 to 25% by mass relative to the total amount of the oil-based ink composition.

[0092] Furthermore, in addition to organic solvents and colorants, oil-based inks for writing instruments may also contain various additives as needed, such as resins, modified silicones, antioxidants, ultraviolet absorbers, rust inhibitors, lubricants, viscosity modifiers, release agents, pigment dispersants, defoamers, shear viscosity reducers, and surfactants.

[0093] <Water-based ink for writing instruments> When the aforementioned ink composition is an aqueous ink composition for writing instruments (hereinafter, depending on the circumstances, referred to as "aqueous ink," "aqueous ink composition," or "aqueous ink for writing instruments"), it is more preferable that the aqueous ink contains an organic solvent such as alcohols, glycols, or glycol ethers, considering the swelling and thickening properties of the ink due to the pretreatment agent.

[0094] Furthermore, while the pH of the water-based ink is not particularly limited, it is preferable that it be alkaline, greater than 7, as this promotes greater swelling and further suppresses bleeding.

[0095] The organic solvent, whether alcohol, glycol, or glycol ether, is preferably a water-soluble organic solvent. Water-soluble organic solvents such as alcohols, glycols, and glycol ethers can be selected from those conventionally used in water-based inks and used as appropriate. Specifically, examples include, but are not limited to, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, hexylene glycol, 1,3-butanediol, neoprene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 2-pyrrolidone, and N-methyl-2-pyrrolidone. The water-soluble organic solvent may be used alone or in combination of two or more types, and its content is not particularly limited, but for example, it may be 2 to 60% by mass relative to the total amount of water-based ink.

[0096] As colorants, general-purpose dyes and pigments that have been conventionally used in water-based inks are used as appropriate.

[0097] Examples of dyes include acid dyes, basic dyes, direct dyes, oil-soluble dyes, and disperse dyes.

[0098] Examples of pigments include inorganic pigments, organic pigments, luminescent pigments, fluorescent pigments, phosphorescent pigments, and other microcapsule pigments containing dyes or pigments; white resin particles that do not contain colorants; resin particles such as colored resin particles containing dyes or pigments; and capsule pigments in which thermochromic compositions, photochromic compositions, fragrances, etc., are directly or microencapsulated.

[0099] The coloring agent may be used alone or in combination of two or more types.

[0100] Water-based inks for writing instruments may contain, in addition to solvents such as water or organic solvents and colorants, additives commonly used in water-based inks for writing instruments. Examples of additives include shear viscosity reducers, water-soluble resins, specific gravity adjusters, surfactants, pH adjusters, resin particles, rust inhibitors, wetting agents, viscosity modifiers, bubble absorbers, or oxygen absorbers.

[0101] Furthermore, a pH adjusting agent may be included to adjust the pH to a desired level in accordance with the characteristics of the ink composition. Conventional known acidic and basic substances can be used as pH adjusters. Examples of acidic substances include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, lactic acid, citric acid, tartaric acid, and malic acid. Examples of basic substances include strong alkalis such as sodium hydroxide and potassium hydroxide, and weak alkalis such as sodium carbonate, ammonia, sodium hydrogen phosphate, and potassium hydrogen phosphate.

[0102] <Writing implements> The structure and shape of the writing instrument itself, which is filled with the aforementioned writing instrument ink, are not particularly limited, and conventional general-purpose ones can be used. These may include marking pens (sign pens) with fiber tips, felt tips, or plastic tips, ballpoint pens with ballpoint pen tips, fountain pens with metal tips, fiber bundles such as brushes in which fibers are tightly bundled together in the longitudinal direction, plastic porous bodies with continuous pores, heat-fused or resin-processed bodies of synthetic resin fibers, or brush pens and calligraphy pens with brush-shaped tips made of extruded soft resin or elastomer.

[0103] Furthermore, the ink filling mechanism may be configured to directly fill the ink composition, or it may be equipped with an ink container or ink absorber capable of being filled with writing instrument ink. Furthermore, the writing instrument may be an ink cartridge type or converter type in which the ink reservoir or ink absorber is detachably replaceable from the writing instrument body.

[0104] Furthermore, examples of writing instruments that can use the ink composition for writing instruments include capped writing instruments equipped with a cap that covers the pen tip, and retractable writing instruments such as push-button, twist-button, and slide-button writing instruments in which the pen tip can be stored inside the barrel.

[0105] Furthermore, the supply mechanism for a writing instrument that can use an ink composition for writing instruments is not particularly limited; for example, (Mechanism 1) A mechanism that supplies an ink composition to the pen tip, comprising an ink guide section made of a fiber converging body or the like as an ink flow rate adjustment member. (Mechanism 2) A mechanism that includes a comb-shaped ink flow rate adjustment member, which is interposed to supply the ink composition to the pen tip. (Mechanism 3) A mechanism that supplies ink composition to the pen tip, equipped with an ink flow rate adjustment member by a valve mechanism. (Mechanism 4) A mechanism that directly supplies the ink composition to the pen tip without an ink flow rate adjustment member. Examples include:

[0106] The structure and mechanism of the writing instrument described above may be combined as appropriate depending on the type and physical properties of the ink. [Examples]

[0107] The present disclosure is described in detail below, but the pretreatment agents of the present disclosure are not limited to these examples.

[0108] The pretreatment agents used in the examples and comparative examples are shown in Table 1 below. Note that the composition values ​​in Table 1 represent parts by mass. Pretreatment agents 1 to 3 are examples of pretreatment agents, while pretreatment agents 4 and 5 are comparative examples of pretreatment agents.

[0109] [Table 1]

[0110] The contents of the raw materials in Table 1 are explained according to the note numbers. (1) Alkali-thickened resin emulsion [Acrylic, 28% solids content, Product name: Primal ASE-60, manufactured by Dow Chemical] (2) Alkali-thickened resin emulsion [Acrylic, solids content 30%, product name: Bistur 3015, manufactured by Sunopco Corporation] (3) Alkali-thickened resin emulsion [Acrylic, solids content 46%, product name: Movinyl 730L, manufactured by Japan Coating Resin Co., Ltd.] (4) Non-alkaline thickening resin emulsion [Acrylic, 40% solids content, Product name: Movinyl 7320, manufactured by Japan Coating Resin Co., Ltd.] (5) Non-alkaline thickening resin emulsion [urethane, solids content 35%, product name: Hydran AP-40N, manufactured by DIC Corporation]

[0111] <Preparation of pretreatment agent> The raw materials were mixed in the proportions specified in the examples and comparative examples, and the mixture was stirred at 20°C for 1 hour to obtain a pretreatment agent.

[0112] <pH of pretreatment agent> The pH of the obtained pretreatment agent was measured at 20°C using an ion meter [Toa DKK Corporation, product name: IM-40S]. The measured pH values ​​are shown in Table 1.

[0113] <Viscosity of pretreatment agent> The viscosity of each pretreatment agent obtained was measured at 20°C using a BL-type rotational viscometer [manufactured by Toki Sangyo Co., Ltd., product name: TVB-M type viscometer, L-type rotor]. The measured viscosities are shown in Table 1.

[0114] <Preparation of application tools> A pretreatment agent was impregnated into a storage body made of polyester sliver coated with a synthetic resin film, and this body was housed in a polypropylene barrel. A resin-processed polyester fiber pen body (chisel type) was connected to the storage body at the tip of the barrel, and a cap was attached to create a marking pen type applicator.

[0115] <Preparation of pre-treated substrates using coating tools> Using the prepared applicators (marking pen type), each substrate was pre-treated by applying the material evenly in a 3cm square area without overlapping, and then dried at 20°C for 30 seconds to create test fabrics. The base materials used were fabric A [cotton, product name: Color Broadcloth Plain 001 Off-White YBC40205] and fabric B [polyester, product name: Tetron Ceramica Satin #310 15, manufactured by Toray Industries, Inc.].

[0116] <Preparation of substrates pre-treated by immersion> Fabrics A and B were immersed in bathtubs filled with the prepared pretreatment agents and dried for 24 hours at 20°C to produce test fabrics.

[0117] <Preparation of oil-based ink for writing instruments and manufacture of writing instruments containing it> Table 2 below shows the oil-based ink compositions for writing instruments used to evaluate ink bleeding. Note that the composition values ​​in Table 2 represent parts by mass.

[0118] [Table 2]

[0119] The contents of the raw materials in Table 2 are explained according to the note numbers. (6) Black dye [Product name: Vali Fast Black 3830, manufactured by Orient Chemical Industries, Ltd.] (7) Red dye [Product name: Vali Fast Red 1308, manufactured by Orient Chemical Industries, Ltd.] (8) Yellow dye [Product name: Spilon Yellow C-GNH, manufactured by Hodogaya Chemical Industry Co., Ltd.] (9) Terpene phenol resin [Product name: YS Polystar K-125, manufactured by Yasuhara Chemical Co., Ltd.] (10) Rosin maleic acid resin [Product name: Marquid No. 33, manufactured by Arakawa Chemical Industries, Ltd.] (11) Ketone resin [Product name: Ketone resin K-90, manufactured by Arakawa Chemical Industries, Ltd.]

[0120] Preparation of oil-based ink for writing instruments Oil-based ink for writing instruments was obtained by mixing each raw material in the proportions listed in Table 2 and stirring at 20°C for 2 hours.

[0121] Preparation of writing instruments 1 and 2 Writing instruments 1 and 2 were prepared by filling 4g of each of the obtained oil-based inks for writing instruments into a commercially available capped marking pen [product name: SCA-100, manufactured by Pilot Corporation].

[0122] <Preparation of water-based ink for writing instruments and manufacture of writing instruments containing it> Table 3 below shows the aqueous ink compositions for writing instruments used to evaluate ink bleeding. Note that the composition values ​​in Table 3 represent parts by mass.

[0123] [Table 3]

[0124] The contents of the raw materials in Table 3 are explained according to the note numbers. (12) Blue dye [Product name: Brilliant Blue FCF, manufactured by Daiwa Chemical Co., Ltd.] (13) Red dye [acid dye, product name: Acid Red FB, manufactured by Daiwa Chemical Co., Ltd.] (14) Black pigment dispersion [Product name: Emacol Black C, manufactured by Sanyo Shikkei Co., Ltd.] (15) Black pigment dispersion [carbon black, product name: Aqua-Black 162, manufactured by Tokai Carbon Co., Ltd.] (16) Resin emulsion [acrylic type, product name: Boncoat AN-1190S, manufactured by DIC Corporation] (17) Surfactant [Product name: Olphine E1010, manufactured by Nisshin Chemical Industry Co., Ltd.] (18) Surfactant [Product name: Emal 20C, manufactured by Kao Corporation] (19) Preservative [Product name: Proxel XL-2, manufactured by Arcsarda Japan Co., Ltd.]

[0125] Preparation of water-based ink for writing instruments Each aqueous ink composition was prepared by stirring each component except the colorant and resin emulsion at 20°C for 30 minutes, then adding the colorant and resin emulsion and stirring for another 30 minutes.

[0126] <pH of water-based ink> The pH of the obtained water-based ink was measured at 20°C using an ion meter [manufactured by Toa DKK Corporation, product name: IM-40S]. The measured pH values ​​are shown in Table 3.

[0127] Manufacturing of writing instruments 3 and 4 Writing instruments 3 and 4 were prepared by filling 2.4g each of the obtained water-based inks 1 and 2 into commercially available capped marking pens [product name: Super Petit (SEG-10M), manufactured by Pilot Corporation].

[0128] Fabrication of writing instrument 5 (see Figure 1) A brush pen-type writing instrument 5 was created by filling the ink filling mechanism of a brush pen, which has a brush-shaped tip as the pen tip, a barrel with an ink storage chamber inside as the ink filling mechanism, and an ink supply mechanism, with the pen tip and the ink filling mechanism joined via the ink supply mechanism, with the prepared water-based ink 3, and attaching a cap. Specifically, the brush pen (11) is equipped with an ink supply mechanism (13) mounted on the front part of a barrel (12) formed of a bottomed polyethylene cylinder, the ink supply mechanism (13) having a pen nib (14) formed of an extruded soft resin body whose surface is coated with polyurethane, and an ink storage chamber (15) is formed in the barrel at the rear of the ink supply mechanism (13). In the ink supply mechanism (13), a large number of disc bodies (16) are arranged in parallel with comb-groove-like intervals therebetween, slit-shaped ink guide grooves (17) extending longitudinally through the disc bodies (16) in the axial direction and vent holes (18) wider than the grooves are provided, an ink guide core (19) is arranged at the axis, and the ink guide core (19) is connected to the pen nib (14).

[0129] <Ink Bleeding Evaluation> Using the test fabrics (Fabric A and B) pretreated with Pretreatment Agents 1 to 5 and the prepared writing instruments 1 to 5, the character "永" was handwritten in an environment at 25°C. Ink bleeding was visually confirmed and evaluated. The evaluation results are as shown in Tables 4 and 5. It should be noted that only evaluation "A" was regarded as acceptable. A: No ink bleeding is observed, and the characters are sufficiently visible. B: Although the characters are visible, ink bleeding is observed. C: There are portions where ink bleeding is significant, making the characters difficult to see. D: Ink bleeding is significant, and the characters are not visible.

[0130] The prepared test fabrics and the ink bleeding evaluation are shown in Tables 4 and 5 below.

[0131]

Table 4

[0132]

Table 5

[0133] These results show that the pretreatment agent in the example configuration suppresses ink bleeding regardless of the type of ink. Furthermore, it was confirmed that bleeding was significantly improved in fabrics containing synthetic fibers.

[0134] <Pretreatment using a spray-type applicator> Next, pretreatment agents 1 to 5 were placed in a commercially available spray bottle to create a spray-type applicator, and ink bleeding was evaluated using the same configuration as in Examples 1 to 12 and Comparative Examples 1 to 8. Similar to Examples 1-12 and Comparative Examples 1-8, fabrics A and B were used as base materials, and pre-treated by spraying using each spray-type applicator, followed by drying to prepare test fabrics.

[0135] As a result, even when using a spray-type applicator, the same level of ink bleeding suppression as with marking pen type and immersion pretreatment was obtained, confirming that ink bleeding can be suppressed even when using applicators such as spray types. Furthermore, it was confirmed that ink bleeding is suppressed even when uneven coating occurs when spraying with a spray type or similar method.

[0136] <Evaluation of ink bleeding with a changed substrate> Furthermore, the base material was changed to fabric C [cotton and polyester blend fabric, cotton:polyester = 35:65, product name: T / C broad off-white YTC45205-OW, Yuzawaya Trading Co., Ltd.] and fabric D [nylon, product name: 210-thread basic taffeta fluorescent bleached 713Z-1, Yuzawaya Trading Co., Ltd.], and the ink bleeding with pretreatment agents was evaluated. Similar to Examples 1-12 and Comparative Examples 1-8, test fabrics were prepared by pre-treatment using a marking pen type applicator and immersion, followed by drying. Ink bleeding was then evaluated using the same method. The evaluation results are shown in Tables 6 and 7.

[0137] [Table 6]

[0138] [Table 7]

[0139] These results confirm that the pretreatment agent disclosed herein can suppress ink bleeding regardless of the type of fabric fiber.

Claims

1. A pretreatment agent comprising an alkaline thickening resin emulsion and water, characterized in that the pH of the pretreatment agent is 2 to 7.

2. The pretreatment agent according to claim 1, wherein the alkali-thickened resin emulsion is an alkali-thickened acrylic resin emulsion.

3. The pretreatment agent according to claim 1 or 2, wherein the viscosity of the pretreatment agent is 1.0 to 100 mPa·s under conditions of 20°C and a rotation speed of 30 rpm.

4. An ink set comprising an ink composition containing one or more selected from the group consisting of alcohols, glycols, and glycol ethers, and a pretreatment agent according to any one of claims 1 to 3.

5. A coating device containing a pretreatment agent according to any one of claims 1 to 3.

6. A writing set comprising a writing instrument containing an ink composition comprising one or more selected from the group consisting of alcohols, glycols, and glycol ethers, and an applicator as described in claim 5.

7. A fabric that has been pre-treated using the pre-treatment agent described in any one of claims 1 to 3.

8. The fabric according to claim 7, wherein the fabric includes chemical fibers.

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