An ink composition, a fabric to which the ink composition has been applied, and clothing and fashion accessories containing the cured product of the ink composition.

Abstract

To provide an ink composition which has a high biomass degree and furthermore has performance the same as or better than performance of ink including no biomass material.SOLUTION: An ink composition is provided, having a biomass degree of 20% or more, wherein elongation at break when a cured product obtained from the ink is measured by a tensile test according to JIS K 6251 of the Japan Industrial Standards is 305% or more. The ink composition can include a polyvinyl chloride-based resin. The ink composition can include a plant-derived plasticizer. The ink composition can include a biomass-derived filler. The ink composition can be used in printing of clothing and clothing miscellaneous goods.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an ink composition, a fabric to which the ink composition is applied, and clothing and fashion accessories including a cured product of the ink composition.

Background Art

[0002] In recent years, as an industrial resource, biomass, which is a renewable resource derived from organisms excluding non-renewable fossil resources, has attracted attention. Many of the raw materials used in printing inks are derived from petroleum. By replacing some of these with biomass materials, the development and utilization of ink compositions containing biomass materials that suppress the use of petroleum resources are desired.

[0003] Regarding ink compositions containing biomass materials, for example, in Patent Document 1 below, there is disclosed a plastisol ink containing an acrylic polymer having a core-shell structure with a multilayer structure having an average particle diameter of 300 to 1000 nm and containing (meth)acrylate as a constituent unit, and a bio-plasticizer obtained from plant starch. Further, Patent Document 2 discloses an active energy ray-curable ink composition containing a (meth)acrylate compound, a rosin-modified polyester compound derived from rosin, a colorant, and a polymerization initiator.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Regarding ink compositions containing biomass materials, there is a need for a coating film that has a sufficiently high "biomass content," which indicates the amount of bio-derived resources contained in the material, while also having performance comparable to or better than inks that do not contain biomass materials. Examples of the aforementioned performance include printability, color development, and workability. In particular, with respect to ink compositions used in screen printing, it is desirable that the cured coating film has high tensile strength to prevent cracking and peeling due to external forces, and that it has excellent conformability to the object to which it is coated. The aforementioned performance can be improved, for example, by the viscosity, adhesion, and pigment dispersibility of the ink composition containing biomass material. However, until now, there were no ink compositions containing such biomass materials. This is likely because it is difficult to achieve both an increase in the biomass content of an ink composition and an improvement in its performance as an ink composition.

[0006] Therefore, the present invention aims to provide an ink composition that has a high biomass content while having performance comparable to or better than inks that do not contain biomass materials. [Means for solving the problem]

[0007] In other words, the present invention provides an ink composition having a biomass content of 20% or more, wherein the elongation at break, as measured by the following curing treatment and the following tensile test in accordance with the Japanese Industrial Standard JIS K 6251, is 305% or more. <Hardening treatment> The ink composition is applied to a glass plate to a thickness of 0.45 ± 0.1 mm, and heated at 180°C for 10 minutes to obtain a sheet of uniform thickness. The sheet is peeled from the glass plate and punched out into a dumbbell shape (type 2, compliant with JIS K6251). The resulting piece is left to stand for 24 to 48 hours in an environment of 23 ± 2°C and 50 ± 5% humidity to form a test specimen. <Tensile Test> Using a desktop precision tensile testing machine (Shimadzu Autograph AGS-X series, manufactured by Shimadzu Corporation), the test specimen is subjected to a tensile test under the conditions of a temperature of 23±2℃, a humidity of 50±5%, and a test speed of 200 mm / min. The ink composition may further contain a polyvinyl chloride resin. The ink composition may further contain a plant-derived plasticizer. The ink composition may further contain a biomass-derived filler. Furthermore, the ink composition may be used for screen printing. Furthermore, the present invention provides a fabric to which the ink composition has been applied. Furthermore, the present invention provides clothing and fashion accessories containing a cured product of the ink composition. [Effects of the Invention]

[0008] The ink composition of the present invention has a biomass content of 20% or more, yet possesses performance comparable to or better than inks that do not contain biomass materials. The present invention provides an ink composition that balances environmental considerations with the superior performance of the ink itself. The effects of the present invention are not limited to those described herein, but may be any of the effects described herein. In this specification, an ink composition containing biomass material is also referred to as a "biomass ink composition." [Modes for carrying out the invention]

[0009] Preferred embodiments of the present invention are described below. However, the present invention is not limited to the following preferred embodiments and can be freely modified within the scope of the present invention.

[0010] The biomass ink composition of the present invention has a biomass content of 20% or more, and the elongation at break measured by performing the curing treatment and the tensile test is 305% or more. Due to this property, while having a high biomass content, the cured product of the ink coating has a high strength sufficient to withstand the tensile test, so that the performance of the biomass ink composition is improved to the same level as or better than that of an ink containing no biomass material. Hereinafter, the biomass ink composition of the present invention will be described in more detail.

[0011] (1) Properties of the biomass ink composition

[0012] (1)-1 Biomass content In the present specification, the biomass content refers to the weight ratio of the biomass material contained in the ink composition in the biomass ink composition, and is calculated by the following formula 1.

[0013]

Equation

[0014] (1)-2 Biomass material A biomass material is a material obtained from a renewable resource derived from a living organism, for example, a material derived from a plant. Since plants grow by absorbing CO2 in the atmosphere through photosynthesis using sunlight as energy, biomass materials derived from plants do not affect the increase or decrease of CO2 even when burned. That is, since the amount of CO2 absorbed during the growth of plants matches the amount of CO2 emitted during combustion, it can be said that it is carbon neutral because it does not increase greenhouse gases that cause global warming. Examples of plants used as raw materials for biomass materials include soybeans, corn, cottonseed, rapeseed, rice, and bamboo.

[0015] (1)-3 Method for quantifying biomass material Quantification of the biomass material is by measuring the radiocarbon concentration ( 14It is carried out by measuring the C biomass degree. The radiocarbon 14 targeted by the measurement method exists in a certain proportion in the carbon dioxide in the atmosphere and plants, and is a radioactive isotope element with a half-life of 5,730 years. Here, petroleum-derived carbon does not have radiocarbon 14. Since the petroleum-derived carbon has been stored underground for over one million years, the carbon 14 in the petroleum-derived carbon has decayed and no longer exists. Therefore, it is possible to measure only the carbon concentration derived from plants excluding petroleum-derived carbon by measuring the radiocarbon concentration.

[0016] In the present invention, the measurement of the radiocarbon concentration is carried out by accelerator mass spectrometry (AMS).

[0017] (1)-4 Curing treatment Examples of the curing treatment method of the biomass ink composition include, but are not limited to, curing by heating, penetration drying, polymerization by UV irradiation, and polymerization by oxidation.

[0018] In the present invention, the curing treatment method by heating is preferred. The temperature applied to the curing treatment is, for example, 100 °C or higher, preferably 120 °C or higher, more preferably 140 °C or higher. The temperature is, for example, 250 °C or lower, preferably 230 °C or lower, more preferably 210 °C or lower. By being cured within such a temperature range, the biomass ink composition can be sufficiently cured even at a relatively low temperature.

[0019] The time maintained at the temperature is, for example, 5 seconds or longer, preferably 10 seconds or longer, more preferably 30 seconds or longer. The time is, for example, 10 minutes or shorter, preferably 5 minutes or shorter, more preferably 1 minute or shorter. By being cured within such a time, the biomass ink can be sufficiently cured even in a short time.

[0020] (1)-5 Tensile properties The coating film obtained using the biomass ink composition of the present invention exhibits performance comparable to or better than that of an ink composition that does not contain biomass materials. The performance of the biomass ink composition can be evaluated by the following physical properties.

[0021] (1)-5-1 Tensile strength The tensile strength of the cured coating film in the biomass ink composition of the present invention is evaluated by a tensile test in accordance with the Japanese Industrial Standard JIS K 6251. The aforementioned tensile strength refers to the maximum tensile force recorded when the test specimen is pulled until it breaks, divided by the initial cross-sectional area of ​​the test specimen.

[0022] The aforementioned tensile strength TS (MPa) is equal to the maximum tensile force F. m (N) and the initial cross-sectional area S of the test specimen (mm²) 2 The value of ) is calculated using the following formula 2.

[0023]

number

[0024] The tensile strength is, for example, 1 MPa or more, preferably 2.5 MPa or more, and more preferably 5 MPa or more. Within this numerical range, cracking and peeling do not occur in the cured product of the biomass ink composition coating.

[0025] (1)-5-2 Elongation at break The elongation at break of the cured coating film in the biomass ink composition of the present invention is evaluated by a tensile test in accordance with the Japanese Industrial Standard JIS K 6251. The elongation at break refers to the elongation when the test piece is tensile until it breaks, expressed as a ratio to the initial elongation.

[0026] The elongation Eb (%) at the time of cutting is calculated from the distance between gauge marks Lo (mm) and the distance between gauge marks L1 (mm) at the time of cutting using the following formula 3.

[0027]

number

[0028] The elongation at break is, for example, 100% or more, preferably 150% or more, and more preferably 200% or more. Within this numerical range, the cured product of the biomass ink coating exhibits excellent conformability to the object to which it is applied.

[0029] (1)-5-3 Tensile Test The aforementioned tensile properties are evaluated by a tensile test in accordance with JIS K 6251, as described above. The tensile test is performed according to the following procedure.

[0030] (1)-5-3-1 Preparation of samples for tensile testing First, the biomass ink composition is applied to a glass plate to a thickness of 0.45 ± 0.10 mm and heated at 180°C for 10 minutes to obtain a sheet of uniform thickness. The sheet is peeled from the glass plate and punched out into a dumbbell shape (type 2, compliant with JIS K6251). This is then left to stand for 24 to 48 hours in an environment with a temperature of 23 ± 2°C and a humidity of 50 ± 5% to obtain the sample for the tensile test.

[0031] (1)-5-3-2 Evaluation by tensile test The aforementioned tensile test samples will be subjected to tensile testing using a benchtop precision tensile testing machine (Shimadzu Autograph AGS-X series, manufactured by Shimadzu Corporation) under conditions of 23±2°C and 50±5% humidity, and the tensile strength (MPa) and elongation at break (%) will be measured. The test speed will be 200 mm / min.

[0032] (2) Components of the biomass ink composition In addition to exhibiting the physical properties described above, the biomass ink composition of the present invention may further contain a polyvinyl chloride resin, a plant-derived plasticizer, and a biomass-derived filler. The aforementioned composition improves the viscosity, adhesion, and pigment dispersibility of the biomass ink composition, and in particular, the plant-derived plasticizer and biomass-derived filler improve the biomass content. The composition of the biomass ink of the present invention will be described in more detail below.

[0033] (2)-1 Polyvinyl chloride resin The polyvinyl chloride resin is a synthetic resin having a structure represented by CH2-CHCl-. The polyvinyl chloride resin may be a monopolymer of vinyl chloride, or, for example, a copolymer of a vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer.

[0034] Other monomers having unsaturated bonds copolymerizable with the vinyl chloride monomer include, specifically, vinyl acetate, vinylidene chloride, ethylene, propylene, butadiene, styrene, isobutylene, acrylic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylonitrile, and various vinyl ethers. Furthermore, one or more monomers selected from this group may be used as other monomers having unsaturated bonds copolymerizable with the vinyl chloride monomer.

[0035] Furthermore, the polyvinyl chloride resin may be a polymer blend, provided that it does not impair the physical properties of the biomass ink composition in the present invention. Examples of such polymer blends include linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, ethylene-propylene copolymer, polypropylene, polypropylene-α-olefin copolymer, polybutene, polypentene, chloropolyethylene, and chloropolypropylene, and one or more selected from the group consisting of these may be used.

[0036] The preferred average degree of polymerization of the polyvinyl chloride resin is, for example, 500 or more, preferably 700 or more, and more preferably 800 or more. The average degree of polymerization may be, for example, 5000 or less, preferably 3000 or less, and more preferably 2000 or less. Having the average degree of polymerization within this numerical range is preferable in order to impart appropriate physical properties to the biomass ink composition and to provide the cured coating film with excellent conformability to the target object. It is also preferable in order to improve the miscibility of the plant-derived plasticizer and biomass-derived filler described later.

[0037] In the biomass ink composition of the present invention, the polyvinyl chloride resin is preferably polyvinyl chloride (homopolymer of vinyl chloride) and a vinyl chloride-vinyl acetate copolymer. The polyvinyl chloride has good rotary screen properties (printability). Furthermore, the vinyl chloride-vinyl acetate copolymer has low viscosity and good gelling properties, and the vinyl acetate groups create wide gaps between polymer chains, making it easy to absorb the plant-derived plasticizer described later, thus making it suitable for obtaining excellent performance in the biomass ink composition.

[0038] The polyvinyl chloride resin may be manufactured by a manufacturing method known in the art. The polyvinyl chloride resin can be manufactured by various polymerization methods, such as emulsion polymerization, suspension polymerization, or bulk polymerization. Alternatively, a commercially available polyvinyl chloride resin may be used.

[0039] The polyvinyl chloride resin can be classified into paste polyvinyl chloride resin, blended polyvinyl chloride resin, and suspension polyvinyl chloride resin depending on characteristics such as particle shape and particle size. The polyvinyl chloride resin used in the biomass ink composition of the present invention may be any of these, but is preferably a paste polyvinyl chloride resin or a blended polyvinyl chloride resin. Paste polyvinyl chloride resins and blended polyvinyl chloride resins have excellent fluidity and are preferred from the viewpoint of improving the workability of applying the ink composition.

[0040] The paste vinyl chloride resin may be a fine powder with precisely controlled particle size. The paste vinyl chloride resin becomes a highly fluid paste when mixed with, for example, a plasticizer. The vinyl chloride particles in the paste vinyl chloride resin are preferably spherical. A suitable particle size for the vinyl chloride particles is, for example, 60 μm or less, more preferably 50 μm or less, and even more preferably 40 μm or less.

[0041] The content of the polyvinyl chloride resin is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, per 100 parts by mass of the biomass ink composition. The content of the polyvinyl chloride resin may be, for example, 70 parts by mass or less, preferably 65 parts by mass or less, and more preferably 60 parts by mass or less, per 100 parts by mass of the biomass ink composition. Content within such numerical ranges is preferable in order to improve the workability of applying the ink composition.

[0042] (2)-2 Plant-derived plasticizers The aforementioned plant-derived plasticizer imparts plasticity to the polyvinyl chloride resin. Because it is plant-derived, it has less environmental impact and adverse effects on the human body compared to phthalate-based and non-phthalate-based plasticizers, and contributes to improving the biomass content of the ink composition.

[0043] Examples of the plant-derived plasticizers include vegetable oils, epoxidized esters and glycerin fatty acid esters derived from the vegetable oils.

[0044] Examples of the aforementioned vegetable oils include epoxidized soybean oil, linseed oil, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, safflower oil, olive oil, tall oil, castor oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, rapeseed oil, jatropha oil, algal oil, corn oil, and tung oil, and a mixture of two or more of these may also be used.

[0045] Examples of epoxidized esters derived from the aforementioned vegetable oil include epoxidized esters and epoxidized fatty acid monoesters. The epoxidized ester may be, for example, an epoxidized product of the aforementioned vegetable oil. Examples of the epoxidized fatty acid monoester may be epoxidized tall oil fatty acid 2-ethylhexyl, epoxidized soybean oil fatty acid 2-ethylhexyl, epoxidized tall oil fatty acid octyl, epoxidized soybean oil fatty acid octyl, epoxidized oleate octyl, epoxidized soybean oil fatty acid methyl, and mixtures of two or more of these. From the viewpoint of biomass content, epoxidized soybean oil is preferred as the plant-derived plasticizer of the present invention.

[0046] Examples of the glycerol fatty acid ester include monoglycerides, organic acid monoglycerides which are derivatives of the monoglycerides, and acetylated monoglycerides. The glycerol fatty acid ester may be made from the vegetable oil mentioned above.

[0047] The content of the plant-derived plasticizer is, for example, 40 parts by mass or more, preferably 50 parts by mass or more, and more preferably 60 parts by mass or more, per 100 parts by mass of the polyvinyl chloride resin. The content of the plant-derived plasticizer may be, for example, 150 parts by mass or less, preferably 130 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the polyvinyl chloride resin. Content within such numerical ranges is preferable for improving biomass content.

[0048] (2)-3 Biomass-derived fillers The biomass-derived filler increases the biomass content of the biomass ink composition and adds functionality to the biomass ink. The filler is a micro- or nano-sized substance called a filler, and by mixing the filler into the biomass ink composition, it is possible to improve strength, heat resistance, workability, and cost-effectiveness. The biomass-derived filler used in the present invention may also be used to adjust the viscosity of the biomass ink composition.

[0049] The biomass-derived filler may be, for example, a plant-derived filler and an inorganic filler. The plant-derived filler may be, for example, one or more plant-derived fillers selected from the group consisting of wood, pulp, bamboo, sugarcane, Eucommia ulmoides, rice husks, and rice (starch). The inorganic filler may be, for example, a calcium compound obtained from eggshells and seashells, or a silicate mineral obtained from talc or mica. From the viewpoint of improving the biomass content and ink properties, a calcium compound filler is preferred as the biomass-derived filler of the present invention.

[0050] The biomass-derived filler may be in the form of a fine powder, and its shape may include, for example, a flat plate, a spherical shape, a needle shape, a fibrous shape, and a plate shape. From the viewpoint of pigment dispersibility and viscosity in the ink composition, a spherical shape is preferred for the biomass-derived filler of the present invention.

[0051] The particle size of the spherical biomass-derived filler is, for example, 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. The particle size of the spherical biomass-derived filler may be, for example, 15 μm or less, preferably 13 μm or less, and more preferably 10 μm or less. Having a particle size within such a numerical range is preferable for optimizing ink characteristics. If the particle size is larger than the above range, there is a risk of printing defects due to clogging of the mesh of the screen printing plate or damage to the screen printing plate.

[0052] The biomass-derived filler is preferably monodispersible, meaning it has a nearly uniform particle size and low particle size dispersion. A biomass-derived filler with a nearly uniform particle size is preferable because it allows the biomass ink composition to have excellent pigment dispersibility. Furthermore, to make the particle size as uniform as possible, the biomass-derived filler may be sieved using a filter with pores.

[0053] The biomass-derived filler may be surface-treated. Surface-treated biomass-derived fillers can avoid aggregation and may be used to add excellent pigment dispersibility to the biomass ink composition.

[0054] The content of the biomass-derived filler is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, per 100 parts by mass of the polyvinyl chloride resin. The content of the biomass-derived filler may be, for example, 100 parts by mass or less, preferably 70 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the polyvinyl chloride resin. Content within such numerical ranges is preferable for improving the biomass content and improving the mechanical strength of the coating film obtained from the ink composition.

[0055] (2)-4 Colorants The biomass ink composition of the present invention may contain a colorant for coloring, decoration, and coating. Either a pigment or a dye may be used as the colorant. Specific examples of colorants are given below, but are not limited thereto. Furthermore, one or more colorants can be mixed in any combination to achieve a desired color.

[0056] The aforementioned pigment may be either an organic pigment or an inorganic pigment. Examples of the organic pigment include azo pigments, disazo pigments, bisazo pigments, phthalocyanine pigments, polycyclic pigments, and underglaze lake pigments. Examples of the polycyclic pigment include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, dioxysazine pigments, thioindico pigments, anthraquinone pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, and diketopyrrolopyrrole pigments. Examples of the inorganic pigments include natural inorganic pigments such as clay, barite, mica, and yellow ochre; synthetic inorganic pigments such as titanium dioxide, zinc yellow, barium sulfate, zinc oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, and carbon black; and metal powders such as aluminum powder and zinc powder.

[0057] Examples of the aforementioned dyes include azo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoneimine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phatocyanine dyes, metal phthalocyanine dyes, and oil-soluble dyes.

[0058] The coloring agent may be a mixture containing the pigment. For example, a mixture of an organic pigment, a plasticizer, and a polyvinyl chloride resin can be used.

[0059] The content of the coloring agent is, for example, 1 part by mass or more, preferably 2.5 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the polyvinyl chloride resin. The content of the coloring agent may be, for example, 80 parts by mass or less, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less, per 100 parts by mass of the polyvinyl chloride resin. Content within such numerical ranges is preferred in order for the biomass ink composition to have excellent color development properties.

[0060] (2)-5 Other additives In addition to the components described above, the biomass ink composition of the present invention may contain various additives, provided that these additives do not impair its properties. As additives, for example, fillers other than biomass-derived fillers, plasticizers other than plant-derived plasticizers, stabilizers, foam stabilizers, surfactants, flame retardants, viscosity control agents such as thickeners or devisers, dispersants, hygroscopic agents such as calcium oxide, antioxidants, foaming agents, defoaming agents, diluents, anti-blocking agents, leveling agents, coupling agents, and UV absorbers may be added as needed.

[0061] [Fillers other than biomass-derived fillers] Examples of fillers other than the biomass-derived fillers mentioned above include, for example, wet silica, dry silica, glass spheres, hollow spheres, plastic spheres, fiberglass, talc, diatomaceous earth, calcium carbonate, barium carbonate, barium sulfate, kaolin, mica, acid clay, activated clay, bentonite, and zeolite.

[0062] [Stabilizer] The aforementioned stabilizers may be added to improve the processability and product characteristics of the polyvinyl chloride resin in the biomass ink composition of the present invention. Examples of such stabilizers include organotin-based stabilizers, calcium-zinc-based stabilizers, barium-zinc-based stabilizers, and the like.

[0063] (3) Ink for screen printing The biomass ink composition of the present invention can be used as an ink for screen printing. The properties of the biomass ink composition of the present invention make it suitable as an ink for screen printing from the viewpoint of viscosity, operability, color development, and pigment dispersibility.

[0064] (4) Screen printing method of the biomass ink composition of the present invention The screen printing method using the biomass ink composition of the present invention may include, but is not limited to, the method described below.

[0065] A screen printing method using the biomass ink composition of the present invention may include, for example, the following steps. (4)-1 Installation process for setting the screen printing plate on the target fabric; and, (4)-2 A filling step of filling the mesh holes on the screen printing plate that are not covered by the photosensitive material by spreading the biomass ink composition; and, (4)-3 A transfer process in which the biomass ink composition is pressed onto the fabric using a squeegee from the edge of the screen printing plate to transfer the ink; and, (4)-4 A curing process for curing the printed pattern of the biomass ink composition that has been transferred to the fabric. The following provides a detailed explanation of each step.

[0066] (4)-1 Installation process A screen printing plate is placed on the target fabric. Note that a conventionally used screen printing plate can be used for the biomass ink composition of the present invention. The screen mesh used in the aforementioned screen printing plate can be appropriately selected depending on the target fabric and the type of biomass ink. Examples of screen mesh materials include polyester, nylon, polyarylate, and metal. The wire diameter of the screen mesh can be, for example, 20 to 150 μm. The opening ratio of the screen mesh can be, for example, 20 to 70%, but is not limited to this and can be appropriately selected depending on the printing method.

[0067] In the biomass ink composition of the present invention, for example, a screen mesh (100 mesh, manufactured by Toyo Corporation) made from Tetron mesh can be used as the screen mesh.

[0068] (4)-2 Filling process The biomass ink composition is spread onto the pores of the screen mesh on the screen printing plate that are not blocked by the photosensitive material, thereby filling them with ink. The filling step may be carried out under conditions based on methods known in the art.

[0069] The filling conditions may include, for example, placing the biomass ink composition on the upper edge of the printing area of ​​the screen printing plate, setting the clearance between the fabric (100% cotton) and the screen mask to 3-7 mm, and spreading it using a squeegee (square, 9 mm thick, hardness 70±5 (Type A)) at an angle of 45-80° and a transfer speed of 50-200 mm / min.

[0070] (4)-3 Transcription process The ink is transferred to the fabric by pressing the biomass ink composition onto the fabric from the edge of the screen printing plate using a squeegee. The transfer conditions may be those based on methods known in the art.

[0071] The transfer conditions may include, for example, a clearance of 3 to 7 mm between the screen printing plate and the fabric, a squeegee angle of 45 to 80 degrees, and a transfer speed of 50 to 200 mm / min.

[0072] (4)-4 Curing process The printed pattern of the biomass ink composition transferred to the fabric is cured. The method for curing the ink may be carried out under conditions based on methods known in the art, as described above.

[0073] The curing apparatus for the biomass ink composition can be appropriately selected depending on the type of ink and the size of the printing surface. Examples include, but are not limited to, conveyor dryers, spot dryers, heating guns, gear ovens, IR ovens, and hot presses.

[0074] For example, a gear oven can be used with respect to the biomass ink composition of the present invention.

[0075] (5) Fabric to which the biomass ink composition of the present invention may be applied The biomass ink composition of the present invention can be applied to, but is not limited to, fabrics, paper, plastics, glass, ceramics, and metal fabrics. Examples of fabrics include woven fabrics, knitted fabrics, felt, nonwoven fabrics, leather, and artificial leather. Examples of yarns used to form the fabrics include natural fibers such as cotton, silk, linen, and wool, regenerated fibers such as acetate and rayon, and synthetic fibers such as nylon, polyester, and polyurethane. Furthermore, the biomass ink composition can also be applied as an overlay to a cured ink coating. Therefore, a cured coating applied to the fabric can also be given as an example of an object to which the biomass ink composition can be applied.

[0076] (6) Clothing and fashion accessories containing a cured product of the biomass ink composition of the present invention The biomass ink composition of the present invention can be applied to clothing and fashion accessories. Examples of clothing include Western clothing, fabrics, dress shirts, blouses, shirts, T-shirts, sweaters, furs, underwear, socks, stockings, tights, handkerchiefs, hats, gloves, scarves, mufflers, ties, ribbons, kimono fabrics, bolts of cloth, yukata, bedding, bedding items, mats, and towels. Examples of fashion accessories include, but are not limited to, shoes, accessories, ties, handbags, bags, belts, wallets, leather goods, umbrellas, travel goods, sewing supplies, smoking accessories, kimonos, and Japanese clothing accessories.

[0077] (7) Method for producing biomass ink composition The method for producing the biomass ink composition of the present invention can be, but is not limited to, the method shown below.

[0078] The method for producing the biomass ink composition of the present invention may include, for example, a kneading step. The biomass ink composition is obtained, for example, by kneading a polyvinyl chloride resin, a plant-derived plasticizer, and a biomass-derived filler. In addition, the above-mentioned additives may be added as needed.

[0079] The mixing method for the biomass ink composition can be any conventional mixing method, as long as it is possible to exert a high shear force on a mixture containing a high proportion of solid components such as fillers and pigments. Preferably, the mixing device for the biomass ink composition uses a mixing apparatus having a stirring tank and stirring blades. This method allows mixing even when the solid component concentration and viscosity are high. Examples of the mixing apparatus include dissolvers, single-screw extruders, twin-screw extruders, kneaders, Banbury mixers, planetary mixers, open rolls, two-roll mills, and three-roll mills. Alternatively, commercially available mixing apparatuses may be used, such as Trimix (manufactured by Inoue Seisakusho Co., Ltd.). From the viewpoint of high shear force, dispersion stability, and reduction of coarse particles, dissolvers, kneaders, planetary mixers, two-roll mills, and three-roll mills are preferred for the mixing apparatus of the biomass ink composition of the present invention. Multiple of the above-mentioned mixing apparatuses may be used in combination in the mixing method. Furthermore, the kneading process can generally be carried out at room temperature (20-30°C), but is not limited to this range.

[0080] (8) Physical properties of biomass ink composition The biomass ink composition of the present invention possesses excellent film strength due to the tensile strength described above, as well as excellent curability and viscosity. This curability and viscosity can be evaluated by the following physical properties.

[0081] (8)-1 Curability Curability is used as an indicator to evaluate the performance of the biomass ink composition, particularly the strength and workability of the coating film.

[0082] The curability of the biomass ink composition of the present invention is evaluated by the following method.

[0083] The biomass ink composition is printed onto 100% cotton fabric in a 70 x 40 mm rectangle using a screen printing plate. The print is then dried at 150°C, 160°C, 170°C, and 180°C for 30 seconds each to create test specimens for each curing temperature. After air-cooling the test specimens at 20-29°C for 5 minutes, the specimens are stretched and visually inspected to ensure there are no cracks or peeling in the printed pattern and that it conforms to the fabric. The stretching method involves first holding the centers of the opposing long sides of the rectangle in the printed pattern. Then, a force is applied outward from each center, parallel to the short side, to create tension. The same method is used to stretch the opposing short sides. This series of evaluations is performed by changing the curing temperature at regular intervals to identify the minimum curing temperature at which cracking and peeling do not occur.

[0084] Regarding the curing performance evaluation, the lowest temperature at which cracking and peeling do not occur in a test specimen of the biomass ink composition of the present invention may be, for example, 210°C or lower, preferably 200°C or lower, and more preferably 190°C or lower. By setting the temperature below this level, it becomes possible to obtain a cured coating film with excellent strength from the biomass ink composition at a relatively low temperature and in a short time.

[0085] (8)-2 Viscosity Viscosity is used as an indicator to evaluate the performance of the biomass ink, particularly its dispersion stability and workability.

[0086] The viscosity of the biomass ink composition of the present invention is, for example, 5 Pa·s or more, preferably 10 Pa·s or more, and more preferably 30 Pa·s or more. The viscosity of the biomass ink composition may be, for example, 200 Pa·s or less, preferably 190 Pa·s or less, and even more preferably 180 Pa·s or less. Here, the viscosity is the viscosity measured by 20 rotations of a BH-type rotational viscometer at 23°C. Having a viscosity within such a numerical range prevents the visibility of the printed material from being impaired by ink dripping, enlargement of the printed pattern, and bleeding during printing when the viscosity is less than 5 Pa·s. Furthermore, when the viscosity exceeds 200 Pa·s, the ink does not adequately follow the fabric during printing, preventing poor leveling of the printed pattern, uneven printing, and missing prints.

[0087] Furthermore, the thixotropic index (TI value) of the biomass ink composition of the present invention may be, for example, 2.0 or higher, preferably 2.5 or higher, and more preferably 3.0 or higher. The TI value of the biomass ink composition may be, for example, 10.0 or lower, preferably 9.0 or lower, and more preferably 8.0 or lower. Having a TI value within such a numerical range prevents the occurrence of ink dripping and enlargement of the printed pattern over time after printing, which can occur when the TI value is less than 2.0. Also, when the TI value is greater than 10, it prevents bleeding and chipping that can occur as a result of excessive ink discharge from the screen printing plate, preventing the acquisition of an appropriate printed pattern. Furthermore, it prevents leveling problems due to poor flowability over time.

[0088] In the biomass ink composition of the present invention, the TI value refers to the viscosity value V2 obtained after 2 rotations of a BH-type rotational viscometer at 23°C, and the viscosity value V after 20 rotations. 20 It is expressed as a ratio to . That is, the TI value is expressed by the following formula 4.

[0089]

number

[0090] The viscosity and TI value of the biomass ink composition are measured using a BH-type rotational viscometer.

[0091] The present invention will be described in more detail below based on experimental examples. Note that the experimental examples described below are representative examples of the present invention, and the scope of the present invention is not limited to these.

[0092] 1. Preparation of biomass ink composition

[0093] (Experimental Example 1) Biomass ink composition 1 was obtained by kneading 80 parts by mass of O-130S (biomass content 92.3%, manufactured by ADEKA Corporation) as a plant-derived plasticizer, 70 parts by mass of PCH-12 (vinyl chloride / vinyl acetate copolymer, manufactured by Kaneka Corporation) and 30 parts by mass of PS-300K (polyvinyl chloride, manufactured by Kaneka Corporation) as polyvinyl chloride resins, 1 part by mass of Adeka Stab 38 (manufactured by ADEKA Corporation) as a stabilizer, 30 parts by mass of GT-26 (eggshell powder, biomass content 99% or more (99% was used for calculating biomass content), manufactured by Green Techno 21 Corporation) as a biomass-derived filler, 30 parts by mass of SP-60 (colloidal calcium carbonate, manufactured by Takehara Chemical Co., Ltd.) as a filler, and 15 parts by mass of a coloring agent (manufactured by Nikko Bix Co., Ltd.) using a planetary mixer and a three-roll mill. The biomass content of the biomass ink composition 1 was 40.4%.

[0094] (Experimental Example 2) Biomass ink composition 2 was obtained using the same method as in Experimental Example 1, except that 30 parts by mass of GT-26 (manufactured by Green Techno 21 Co., Ltd.), which was added as a biomass-derived filler, were removed. The biomass content of biomass ink composition 2 was 32.7%.

[0095] (Experimental Example 3) Biomass ink composition 3 was obtained in the same manner as in Experimental Example 1, except that 30 parts by mass of Softon #1200 (ultrafine particle heavy calcium carbonate, manufactured by Bihoku Funka Kogyo Co., Ltd.) was added as a filler instead of 30 parts by mass of GT-26 (manufactured by Green Techno 21 Co., Ltd.) which was added as a biomass-derived filler. The biomass content of biomass ink composition 3 was 28.8%.

[0096] (Experimental Example 4) Biomass ink composition 4 was obtained in the same manner as in Experimental Example 1, except that 80 parts by mass of DINP (diisosinyl phthalate, manufactured by J-Plus Co., Ltd.), a general-purpose plasticizer, was added instead of 80 parts by mass of O-130S (biomass content 92.3%, manufactured by ADEKA Corporation), which was added as a plant-derived plasticizer. The biomass content of biomass ink composition 4 was 11.6%.

[0097] (Experimental Example 5) O-130S (biomass content 92.3%, ADEKA Corporation), added as a plant-derived plasticizer. Biomass ink composition 5 was obtained in the same manner as in Experimental Example 1, except that 80 parts by mass of DOTP (bis(2-ethylhexyl) terephthalate, manufactured by J-Plus Co., Ltd.), a general-purpose plasticizer, was added instead of 80 parts by mass of (manufactured by J-Plus Co., Ltd.). The biomass content of biomass ink composition 5 was 11.6%.

[0098] (Experimental Example 6) O-130S (biomass content 92.3%, ADEKA Corporation), added as a plant-derived plasticizer. Biomass ink composition 6 was obtained by the same method as in Experimental Example 1, except that 80 parts by mass of ATBC (tributyl acetylcitrate, manufactured by Taoka Chemical Co., Ltd.), a general-purpose plasticizer, was added instead of 80 parts by mass of (manufactured by Taoka Chemical Co., Ltd.). The biomass content of biomass ink composition 6 was 11.6%.

[0099] (Experimental Example 7) Ink composition 7 was obtained in the same manner as in Experimental Example 4, except that 30 parts by mass of Softon #1200 (ultrafine particle heavy calcium carbonate, manufactured by Bihoku Funka Kogyo Co., Ltd.) was added as a filler instead of 30 parts by mass of GT-26 (manufactured by Green Techno 21 Co., Ltd.), which was added as a biomass-derived filler. The biomass content of ink composition 7 was 0%.

[0100] The biomass ink compositions 1-6 and ink composition 7 obtained in experimental examples 1-7 were evaluated as follows.

[0101] 2. Evaluation of the tensile strength of cured coatings of biomass ink compositions.

[0102] (1) Preparation of samples for tensile testing The biomass ink compositions 1 to 6 and ink composition 7 were applied to a glass plate to a thickness of 0.45 ± 0.10 mm, and heated at 180°C for 10 minutes to obtain sheets 1 to 7 with uniform thickness. The sheets 1 to 7 were peeled from the glass plate and punched out into a dumbbell shape (type 2, compliant with JIS K6251). These were then left to stand for 24 to 48 hours in an environment of 23 ± 2°C and 50 ± 5% humidity to form test pieces 1 to 7.

[0103] (2) Evaluation by tensile test Tensile tests were performed on the aforementioned test specimens 1 to 7 using a benchtop precision tensile testing machine (Shimadzu Autograph AGS-X series, manufactured by Shimadzu Corporation) under conditions of 23±2°C and 50±5% humidity. The tensile strength (MPa) and elongation at break (%) were measured. The test speed was 200 mm / min.

[0104] 3. Evaluation of the curing properties of the biomass ink composition coating film.

[0105] (1) Preparation of samples for hardening evaluation tests First, biomass ink compositions 1-6 and ink composition 7 were placed on the upper edge of the printing area of ​​a screen printing plate (Tetron material, 100 mesh, manufactured by Toyo Corporation), and the clearance between the fabric (100% cotton) and the screen mask was set to 3-7 mm. Then, a squeegee (square, 9 mm thick, hardness 70±5 (Type A)) was set to an angle of 45-80° and a transfer speed of 50-200 mm / min, and the biomass ink compositions 1-7 were spread onto the screen printing plate. Then, printing was performed under the same transfer conditions as above, while applying pressure just enough to keep the screen printing plate and the fabric in contact. The printed pattern was a rectangle of 70 x 40 mm. Subsequently, each sample was dried in a gear oven (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 150°C, 160°C, 170°C, and 180°C for 30 seconds to obtain test pieces 1 to 7.

[0106] (2) Evaluation of curing properties After cooling test specimens 1-7 at 20-29°C for 5 minutes, they were stretched in the longitudinal and transverse directions. At that time, the curing properties were visually evaluated using the following two-stage evaluation to determine whether the printed pattern did not crack or peel and whether it conformed to the fabric. A: No cracks or peeling. B: Cracks or peeling present

[0107] 4. Evaluation of the viscosity of biomass ink compositions

[0108] For the biomass ink compositions 1 to 6 and ink composition 7, the viscosity values ​​were measured at 2 rotations and 20 rotations using a BH-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.), and the ratio (TI value) was calculated.

[0109] The composition of each experimental example and the results of each evaluation are shown in Table 1.

[0110] [Table 1]

[0111] As shown in the results of Experimental Examples 1-3 and Experimental Example 7, it was found that polyvinyl chloride-based resin ink compositions can be obtained that have a high biomass content of 20% or more and can form cured products with tensile properties comparable to or better than those of ink compositions that do not contain biomass materials.

[0112] Furthermore, based on the results of Experimental Examples 1-3 and 4-7, it was found that biomass ink compositions with a biomass content of 20% or more and a cured coating film elongation at break of 305% or more, as measured by a tensile test in accordance with the Japanese Industrial Standard JIS K 6251, have performance comparable to or better than inks that do not contain biomass materials.

[0113] In particular, based on the results of Experimental Examples 1-3 and 4-6, it was found that a biomass content of 20% or more, and an elongation at break of 305% or more as measured by tensile testing of the cured coating film, are important for obtaining excellent tensile strength, curability, and thixotropy. The results for each experimental example are shown below.

[0114] The biomass ink composition of Experimental Example 1 is the same as that of the ink composition of Experimental Example 7, but with the plasticizer replaced by a plant-derived plasticizer and the non-biomass-derived general-purpose filler replaced by a biomass-derived filler. Here, the biomass content of each experimental example is 40.4% and 0%, respectively. Compared to Experimental Example 7, Experimental Example 1 has higher values ​​for elongation at break and tensile strength, and thus higher tensile strength. Also, since the minimum curing temperature for both is 170°C, they have a similar degree of curability. Furthermore, the TI value, which indicates thixotropy, was within the range of values ​​considered desirable for both. From this, it is considered that the biomass ink composition of Experimental Example 1 has superior tensile strength, curability, and thixotropy compared to the ink composition that does not contain biomass material.

[0115] The biomass ink composition of Experimental Example 2 is derived from the ink composition of Experimental Example 7, but with the plasticizer replaced by a plant-derived plasticizer and the general-purpose filler, which is not derived from biomass, removed. The biomass content of the biomass ink composition of Experimental Example 2 is 32.7%, which is lower than that of Experimental Example 1. Compared to Experimental Example 1, Experimental Example 2 shows higher values ​​for elongation at break and tensile strength, indicating higher tensile strength. Furthermore, the minimum curing temperature was 160°C, and the ink composition of Experimental Example 2 cured sufficiently at a lower temperature than that of Experimental Example 1, demonstrating superior curability. In addition, the TI value, which indicates thixotropy, was the same for both. From this, it can be concluded that the biomass ink composition of Experimental Example 2 also has superior tensile strength, curability, and thixotropy compared to the ink composition that does not contain biomass materials.

[0116] The biomass ink composition of Experimental Example 3 is a modified version of the biomass ink composition of Experimental Example 1, in which the biomass-derived filler is replaced with a general-purpose, non-biomass-derived filler. Furthermore, the biomass content of the biomass ink composition of Experimental Example 3 is 28.8%, which is lower than that of the ink compositions of Experimental Examples 1 and 2. Compared to Experimental Example 1, Experimental Example 3 exhibits higher elongation at break and tensile strength, demonstrating higher tensile strength. Although the minimum curing temperature is 10°C higher, a cured product with sufficient strength can be obtained at a curing temperature of 180°C. Additionally, the TI value was within a desirable range. Therefore, it is considered that the biomass ink composition of Experimental Example 3 possesses tensile strength, curability, and thixotropy comparable to or better than ink compositions that do not contain biomass materials.

[0117] The biomass ink composition of Experimental Example 4 is a modified version of the ink composition of Experimental Example 7, in which the non-biomass-derived general-purpose filler is replaced with a biomass-derived filler. The biomass content of the biomass ink composition of Experimental Example 4 is 11.6%. Compared to Experimental Example 7, Experimental Example 4 exhibits lower elongation at break and tensile strength, indicating lower tensile strength. Furthermore, the minimum curing temperature was 160°C, and the biomass ink composition of Experimental Example 4 cured sufficiently at a lower temperature than that of Experimental Example 7, demonstrating superior curability. The TI value, which indicates thixotropy, was within a desirable range. Therefore, it is considered that the biomass ink composition of Experimental Example 4 cannot achieve the same excellent tensile strength as inks that do not contain biomass materials.

[0118] The biomass ink composition of Experimental Example 5 is a modified version of the biomass ink composition of Experimental Example 4, in which the non-biomass-derived general-purpose filler is replaced with a different type of non-biomass-derived general-purpose filler. The biomass content of the biomass ink composition of Experimental Example 5 is 11.6%, the same as in Experimental Example 4. Compared to Experimental Example 7, Experimental Example 5 has lower values ​​for elongation at break and tensile strength, indicating lower tensile strength. Furthermore, the minimum curing temperature is 10°C higher, resulting in lower curability compared to Experimental Example 7. The TI value, which indicates thixotropy, was within the range of a desirable value. From this, it is considered that the biomass ink composition of Experimental Example 5 cannot obtain the same level of excellent tensile strength and curability as inks that do not contain biomass materials.

[0119] The biomass ink composition of Experimental Example 6 is a modified version of the biomass ink composition of Experimental Example 5, in which the non-biomass-derived general-purpose filler is replaced with a different type of non-biomass-derived general-purpose filler. The biomass content of the biomass ink composition of Experimental Example 6 is 11.6%, the same as in Experimental Examples 4 and 5. Compared to Experimental Example 7, Experimental Example 6 showed higher elongation at break and lower tensile strength. In terms of curability, the minimum curing temperature was 10°C lower, indicating that the biomass ink composition of Experimental Example 6 cured sufficiently at a lower temperature compared to Experimental Example 7, demonstrating superior curability. The TI value was also within a desirable range. However, it is considered that the biomass ink composition of Experimental Example 6 cannot achieve the same tensile strength as inks that do not contain biomass materials.

[0120] Furthermore, as shown in the results of Experimental Examples 1 and 4-6, it was found that plant-derived plasticizers are important for obtaining excellent tensile strength, curability, and thixotropy. The biomass ink compositions of Experimental Examples 4-6 are compositions in which the plant-derived plasticizer is replaced with a general-purpose, non-plant-derived plasticizer compared to Experimental Example 1. However, none of Experimental Examples 4-6 yielded good results. This also indicates that whether or not the plasticizer is plant-derived is more important than the type of general-purpose, non-plant-derived plasticizer in obtaining a biomass ink composition with superior performance.

Claims

1. A biomass ink composition for screen printing having a biomass content of 20% or more. It contains polyvinyl chloride resin and plant-derived plasticizers. The content of the polyvinyl chloride resin is 10 parts by mass or more and 70 parts by mass or less per 100 parts by mass of the biomass ink composition. The content of the plant-derived plasticizer is 40 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the polyvinyl chloride resin. The average degree of polymerization of the polyvinyl chloride resin is 800 or more and 2000 or less. The polyvinyl chloride resin is a polyvinyl chloride resin, a vinyl chloride / vinyl acetate copolymer, or a mixture of a polyvinyl chloride resin and a vinyl chloride / vinyl acetate copolymer. The aforementioned plant-derived plasticizer is an epoxidized ester derived from vegetable oil. The biomass ink composition wherein the elongation at break, as measured by the following hardening treatment and the following tensile test in accordance with the Japanese Industrial Standard JIS K 6251, is 305% or more. <Hardening treatment> The biomass ink composition is applied to a glass plate to a thickness of 0.45 ± 0.1 mm, and heated at 180°C for 10 minutes to obtain a sheet of uniform thickness. The sheet is peeled from the glass plate and punched out into a dumbbell shape (type 2, in accordance with JIS K6251). The resulting piece is left to stand for 24 to 48 hours in an environment of 23 ± 2°C and 50 ± 5% humidity to form a test specimen. <Tensile Test> Using a desktop precision tensile testing machine (Shimadzu Autograph AGS-X series, manufactured by Shimadzu Corporation), the test specimen is subjected to a tensile test under the conditions of a temperature of 23±2°C, a humidity of 50±5%, and a test speed of 200 mm / min.

2. The biomass ink composition according to claim 1, further comprising a biomass-derived filler.

3. A fabric to which the biomass ink composition according to claim 1 or 2 has been applied.

4. Clothing or fashion accessories comprising a cured product of the biomass ink composition according to claim 1 or 2.

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