JP5586135B2 - Water-based drawing material - Google Patents

Description

  The present invention relates to a high-viscosity water-based drawing material containing a glittering material, and in particular, while drawing out from the opening at the tip of a tube-shaped container, a drawn line such as glittering characters and figures can be drawn on the substrate, At the time of drawing, the drawn line is a water-based drawing material having a thickness or swell, and in particular, when drawing, the glittering material does not flow out excessively from the opening at the tip of the tube-like container and is not used. Thus, the present invention relates to an aqueous drawing material having excellent storage stability.

  Conventionally, an aqueous drawing material containing a thickening agent, and an aqueous drawing material capable of drawing letters or figures on various base materials as a drawn line having a thickness or swell is already known. In general, polyacrylic acid having thixotropic properties is used (see Patent Document 1).

Thus, according to the aqueous drawing material using polyacrylic acid having thixotropy as a thickener, the glittering material is drawn when it is not used even if it has a sufficient static viscosity and includes a glittering material. It does not separate and settle in the material. However, the aqueous drawing material using polyacrylic acid having thixotropic properties as a thickener in this way does not have sufficient kinematic viscosity, and in some cases, the drawing material is squeezed out from the opening of the tubular container, When drawing, the drawing material may flow out excessively and accumulate on the substrate. As described above, when the drawing material flows out excessively and accumulates on the base material, for example, it is not possible to accurately draw a thin and thick drawn line.
JP 2007-284663 A

  As described above, the present invention has been made in order to solve the problems in the conventional water-based drawing material that can draw characters and figures on various base materials as a drawn line having a thickness or a height. At the time, the drawing material does not flow out from the opening of the tube-shaped container, and the glittering material does not settle in the drawing material when not in use, thus providing an aqueous drawing material with excellent storage stability. The purpose is to do.

  According to the present invention, it is an aqueous drawing material for drawing a thick glitter line on a substrate while squeezing from the opening at the tip of a tubular container, and at least water, an organic solvent, a glitter material, A resin emulsion and a thickener are included, and as the above thickener, a Newtonian thickener is included together with a thixotropic thickener composed of alkali-swelling polyacrylic acid, and Newtonian with respect to 100 parts by weight of the thixotropic thickener. The thickener is contained in the range of 3 to 1500 parts by weight, and based on the drawing material, the thixotropic thickener is contained in the range of 0.15 to 0.6% by weight, and the Newtonian thickener is 0.01. It is characterized by having a static viscosity in the range of 8000-200000 mPa · s and a kinematic viscosity in the range of 1000-20000 mPa · s at a temperature of 20 ° C. Aqueous drawing material is provided.

  According to the present invention, the Newtonian thickener is preferably an associative urethane resin, and the resin emulsion is preferably an acrylic resin emulsion.

  According to the present invention, the organic solvent is preferably at least one selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, monoalkyl ethers and monoalkyl ether acetates thereof. Furthermore, the aqueous drawing material according to the present invention may contain a colorant.

  According to the aqueous drawing material of the present invention, an excessive amount of drawing material can be prevented from flowing out when squeezing from the opening at the tip of the tube-like container, and thus an appropriate amount of drawing material is squeezed out from the tube-like container. Thus, it is possible to draw on the base material, and accordingly, it is possible to accurately draw a thin and thick line, that is, a raised drawing line.

  An aqueous drawing material according to the present invention is an aqueous drawing material for drawing a thick glitter line on a substrate while squeezing from the opening at the tip of a tube-shaped container, and includes at least water, an organic solvent, and a glitter. Material, resin emulsion and thickener, and as the above thickener, a thixotropic thickener composed of alkali-swelling polyacrylic acid together with a Newtonian thickener, and 100 parts by weight of the thixotropic thickener In the range of 3 to 1500 parts by weight of the Newtonian thickener and in the range of 0.15 to 0.6% by weight of the thixotropic thickener based on the drawing material, the Newtonian thickener is 0. In the range of 0.01 to 2.0% by weight, and having a static viscosity in the range of 8000 to 200000 mPa · s and a kinematic viscosity in the range of 1000 to 20000 mPa · s at a temperature of 20 ° C. A.

  In the aqueous drawing material according to the present invention, water and an organic solvent are used in combination as the solvent. Water as the solvent is mainly used for the purpose of adjusting the concentration of the resin emulsion, that is, for the purpose of stabilization, and the organic solvent as the solvent is mainly the tip of the tubular container as described above for the aqueous drawing material according to the present invention. This is used to prevent the drawing material from being dried at the opening of the container when drawing on the drawing surface while being squeezed out from the opening, and to improve the wettability of the surface of the hydrophobic glittering material.

  The organic solvent is not particularly limited, but at least one selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, these monoalkyl ethers and monoalkyl ether acetates is preferably used. Specific examples include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether and the like. Can be mentioned.

  Among the above organic solvents, relatively high boiling point glycols and monoethers thereof, such as dipropylene glycol mono n-propyl ether and monoether acetates, are film-forming aids for resin emulsions described later, That is, it also functions to lower the minimum film forming temperature of the resin emulsion.

  In the aqueous drawing material according to the present invention, the amount of water is usually 5 to 50% by weight, preferably 20 to 40% by weight, including the water in the resin emulsion described later, and the amount of the organic solvent. Is usually in the range of 5-30% by weight, preferably 10-20% by weight.

  The aqueous drawing material according to the present invention contains a glittering material, whereby a drawn line rich in decorativeness and design having glitter can be drawn on the substrate. The glittering material is not particularly limited as long as it is conventionally known. For example, glass flakes coated with metal or metal oxide, inorganic particles, pearl pigments, and crushed resin films A bright material such as is preferably used. The bright material is usually used in the range of 0.05 to 5% by weight, preferably in the range of 0.1 to 3% by weight, based on the drawing material.

  If necessary, the drawing material may contain a pigment as well as such a bright material. The pigment is not limited at all, and conventionally known inorganic and organic pigments are appropriately used.

  In the present invention, the substrate is not particularly limited, but usually, paper, fabric, glass, wood, metal and the like can be mentioned.

  The aqueous drawing material according to the present invention preferably has a minimum film-forming temperature in the range of −25 to 30 ° C., preferably −10 to 10 in order to form a glossy and thick drawn line on such a substrate. The resin emulsion in the range of ° C. is usually contained in the range of 20 to 50% by weight, preferably 30 to 50% by weight in terms of solid content based on the drawing material. When the amount of the resin emulsion in the drawing material is less than 20% by weight in terms of solid content, the resulting drawn line is poor in thickness and gloss. However, when the amount of the resin emulsion in the drawing material is more than 50% by weight in terms of solid content, it is difficult to squeeze the drawing material out of the container.

  In the present invention, the resin emulsion is not particularly limited, but an acrylic resin emulsion, a urethane resin emulsion, a vinyl acetate resin emulsion, or the like is preferably used.

  According to the present invention, depending on the resin emulsion used, for example, when the resin emulsion is an acrylic resin emulsion, the aqueous drawing material is basic together with the resin emulsion in order to neutralize the resin and stabilize the emulsion. It may contain a substance. Examples of such basic substances include ammonia, trimethylamine, propylamine, diethylamine, tripropylamine, dibutylamine, 1-amino-2-propanol, 2-propylaminoethanol, ethoxypropylamine, and the like. These basic substances are usually used in the range of 0.1 to 5% by weight based on the drawing material.

  The aqueous drawing material according to the present invention contains a thixotropic thickener so as to have thixotropy in a low shear region and a Newtonian thickener so as to have a Newton property in a high shear region.

  A thixotropic thickener dissolves in a dispersion medium, and when stress is applied, the viscosity decreases and the fluidity increases, and if left untreated, the viscosity increases again to increase the viscosity. The Newtonian thickener is a thickener that dissolves in a dispersion medium and gives the dispersion medium a viscosity that exhibits a strain rate proportional to the stress during flow.

  In the present invention, alkali-swelling polyacrylic acid is preferably used as the thixotropic thickener. Alkali-swelling polyacrylic acid is neutralized with an alkali in a dispersion medium, swells, spreads throughout the dispersion medium while molecules are entangled with each other, and thickens the dispersion medium. In the present invention, commercially available products can be used as such an alkali-swelling polyacrylic acid thickener. Examples of commercially available products include Carbopol 940, Carbopol 941, Carbopol manufactured by Nikko Chemicals Co., Ltd. 980, etc., and ASE60 manufactured by Rohm and Haas Japan Co., Ltd. can be mentioned.

  On the other hand, in the present invention, the Newtonian thickener is not particularly limited, and any can be used as long as it is a thickener that functions as a Newtonian thickener. Can be mentioned. Such an associative resin has a hydrophobic group and a hydrophilic group in the resin molecule, the hydrophobic group is hydrophobically bonded to the hydrophobic particles in the dispersion medium, and the hydrophilic group is associated with each other. , Spreads throughout the dispersion medium and thickens the dispersion medium.

As such an association type resin, for example , a urethane resin is known and can be obtained as a commercial product. Examples of such commercially available products include Adecanol UH manufactured by Asahi Denka Kogyo Co., Ltd., BERMODOL PUR manufactured by Akzo Nobel, Primal RM-2020NPR manufactured by Rohm and Haas Japan Co., Ltd., and Primal RM-6000. And Primal RM-5000.

  The aqueous drawing material according to the present invention has a Newtonian thickening agent in the range of 3 to 1500 parts by weight with respect to 100 parts by weight of the thixotropic thickening agent, and the thixotropic thickening agent has a concentration of 0. 15 to 0.6% by weight, Newtonian thickener in the range of 0.01 to 2.0% by weight, and a static viscosity in the range of 8000 to 200,000 mPa · s at a temperature of 20 ° C. It has a kinematic viscosity in the range of 20000 mPa · s.

  When the amount of thixotropic thickener is less than 0.15% by weight based on the drawing material, the resulting drawing material does not have a sufficient static viscosity, and therefore the glittering material is not used when the drawing material is not used. Separate and settle. On the other hand, when the amount of the thixotropic thickener is more than 0.6% by weight, the viscosity of the drawing material is too high and it is difficult to squeeze out from the container. Also, when the amount of Newtonian thickener is less than 0.01% by weight based on the drawing material, the resulting drawing material does not have sufficient kinematic viscosity, so the drawing material flows out of the container in an excessive amount. It is easy to do, and a thin and thick drawn line cannot be drawn on the substrate. However, when the amount of Newtonian thickener is more than 2.0% by weight, the viscosity of the drawing material is too high, and it is difficult to squeeze the drawing material out of the container.

  The drawing material according to the present invention includes the above-described thixotropic thickener and Newtonian thickener in the above-described ratio, and based on the drawing material, each in the above-described range, At room temperature (20 ° C.), it is necessary to have a static viscosity in the range of 8000 to 200000 mPa · sec and a kinematic viscosity in the range of 1000 to 20000 mPa · sec. Thus, according to the present invention, the tip of the tubular container It is possible to draw on the substrate while suppressing an excessive amount of the drawing material when the drawing material is squeezed out from the opening and squeezing an appropriate amount of the drawing material from the container, and therefore, it is thin and thick, that is, The raised stroke can be accurately drawn.

  Even with only the Newtonian thickener, the static viscosity and kinematic viscosity of the resulting drawing material can be made within the ranges specified in the present invention by appropriately adjusting the amount of use. In this case, an excessive amount of the drawing material can be prevented from flowing out when the drawing material is squeezed out of the container, so that it is possible to draw on the base material while squeezing an appropriate amount of the drawing material from the container. Settles over time. Only with the Newtonian thickener, the glittering material cannot be stably dispersed in the drawing material so as not to settle over time.

  Furthermore, the aqueous drawing material according to the present invention may appropriately contain a preservative, an antifungal agent, a wetting agent, an antifoaming agent, and the like as necessary.

EXAMPLES The present invention will be described below with reference to comparative examples together with examples of the present invention, but the present invention is not limited to these examples. Solvents, plasticizers, pigments, resins and gelling agents used in the following are as follows.

Organic solvent 1: Ethylene glycol Organic solvent 2: Dipropylene glycol n-propyl ether resin emulsion: Rohm and Haas acrylic resin emulsion, Primal RHA-691, solid content 62%
Thixotropic thickener: alkali-swelling polyacrylic acid made of luprisol, carbopol 940
Newtonian thickener: Rohm and Haas associative urethane resin, Primal RM-6000
Bright material: Rainbow Flakes II No. 501 SNo. 7
Antiseptic: Proxel XL-2 manufactured by Arch Chemicals
Antifungal agent: Coatside H manufactured by Nippon Enbiochemicals Co., Ltd.

Example 1
All the components listed in Table 1 were put into a container and stirred and degassed using a propeller under reduced pressure to obtain an aqueous drawing material.

Examples 2-5 and Comparative Examples 1-4
A drawing material was obtained in the same manner as in Example 1.

Evaluation of performance of drawing material Each drawing material obtained as described above was measured for kinematic viscosity and static viscosity and evaluated for drawing performance as follows.

Viscosity measurement Using a C35 / 1 ° cone as a sensor at a temperature of 20 ° C. with a rheometer (Hake rheostress RS75), the viscosity at a rotational speed of 1 / second is obtained as a static viscosity, The viscosity was determined as kinematic viscosity. The results are shown in Table 1.

Writing quality (drawability)
The drawing material was filled into a tube-shaped container made of polyethylene resin having an opening with a diameter of 0.6 mm at the tip. As the base material, four 1.0 cm square, 1.5 cm square, and 3.0 cm square frames were connected on a cardboard to form a drawing surface. Four Hiragana characters selected in advance in each of the four frames of the three types were drawn while drawing material from the opening at the tip of the container. When drawing, the drawing material does not collect on the drawing surface, a certain amount flows out of the container, and when the character can be drawn accurately, the drawing material may collect on the drawing surface. △ When a certain amount flows out of the container and characters can be drawn almost accurately, when drawing material overflows from the container and accumulates excessively on the drawing surface and characters can not be drawn accurately Was marked with x. The results are shown in Table 1 .

Storage stability The drawing material was stored in a glass bottle at a temperature of 50 ° C. for 2 weeks, and it was examined whether or not the glittering material had settled in the drawing material. The case where it did not settle was marked with ◯, and the time when it settled was marked with ×. The results are shown in Table 1.

  As seen in Comparative Examples 1 and 2, using only an alkali-swelling polyacrylic acid thickener that is thixotropic, and increasing the amount, the resulting drawing material has no settling of glittering material and is stable in storage. However, since the kinematic viscosity is too small, an excessive amount of the drawing material flows out of the container and accumulates on the drawing surface during drawing, resulting in poor drawing performance. On the other hand, as seen in Comparative Examples 3 and 4, when only the associative urethane resin thickener that is Newtonian thickener is used, if the amount is increased, sufficient kinematic viscosity can be obtained, The resulting drawing material is excellent in drawing performance, but as seen in Comparative Example 4, the drawing material does not contain the thixotropic thickener, although the drawing material has a sufficiently high kinematic viscosity. Therefore, the glitter material settles in the drawing material with the passage of time, and is inferior in storage stability.

  That is, the thixotropic alkali-swelling polyacrylic acid thickener swells in the drawing material and spreads throughout the drawing material to increase the viscosity of the drawing material. Can be held while being stably dispersed. In contrast, Newtonian associative urethane resin thickeners are hydrophobically bonded to the surface of the glitter material by their hydrophobic groups and spread across the entire rendering material. Unbonded hydrophilic groups are associated with each other in the drawing material. Thus, since the surface of the glittering material is covered with the hydrophobic group of the Newtonian thickener, It cannot be dispersed and settles in the drawing material over time.

On the other hand, according to the present invention, in the aqueous drawing material, a thixotropic thickener and a Newtonian thickener are used in combination, and the thixotropic thickener and Newtonian thickener are in a predetermined ratio, and the drawing material. The drawing material is squeezed out from the container by having a static viscosity in the range of 8000-200000 mPa · s and a kinematic viscosity in the range of 1000-20000 mPa · s at a temperature of 20 ° C. Therefore, it is possible to draw on the substrate while squeezing an appropriate amount of drawing material from the tube-like container, so that the drawing line is thin and thick, i.e., raised. Can be drawn accurately.

Claims (8)

  A water-based drawing material for drawing a thick bright line on a substrate while squeezing from the opening at the tip of a tube-shaped container, and at least water, an organic solvent, a bright material, a resin emulsion, and a thickener A thixotropic thickener made of alkali-swelling polyacrylic acid together with a Newtonian thickener, and a Newtonian thickener 3 to 100 parts by weight of the thixotropic thickener. In the range of 1500 parts by weight and based on the drawing material, it contains a thixotropic thickener in the range of 0.15 to 0.6% by weight, and a Newtonian thickener in the range of 0.01 to 2.0% by weight. An aqueous drawing material having a static viscosity in the range of 8000 to 200000 mPa · s and a kinematic viscosity in the range of 1000 to 20000 mPa · s at a temperature of 20 ° C.   The aqueous drawing material according to claim 1, wherein the Newtonian thickener is an associative urethane resin.   The aqueous drawing material according to claim 1, wherein the resin emulsion is an acrylic resin emulsion.   The aqueous drawing material according to claim 1, wherein the organic solvent is at least one selected from ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, monoalkyl ethers and monoalkyl ether acetates thereof.   The aqueous drawing material according to claim 1, comprising a colorant. The aqueous drawing material according to claim 1, comprising a resin emulsion in a range of 20 to 50% by weight in terms of solid content. The water-based drawing material according to claim 1, comprising a bright material in a range of 0.05 to 5% by weight. The aqueous drawing material according to claim 1, comprising water in a range of 5 to 50% by weight and an organic solvent in a range of 5 to 30% by weight.