Resin composition for damping material

Abstract

Provided is a vibration damping composite capable of providing a vibration damping material, at low cost, that exhibits a high vibration damping property in a wide temperature range and has excellent appearance. The present invention relates to a resin composition for vibration damping materials which contains a lignin and/or a lignin derivative. The present invention also relates to a vibration damping composite containing the resin composition for vibration damping materials and an inorganic pigment. The present invention also relates to a vibration damping material obtainable from the vibration damping composite.

Claims

1. A vibration damping composite comprising: a resin composition comprising: a lignin and/or a lignin derivative, a resin, and an aqueous solvent, in the resin composition, the resin being dispersed or dissolved in the aqueous solvent, the resin including at least one polymer selected from the group consisting of (meth)acrylic polymers, diene polymers, and vinyl acetate polymers; and an inorganic pigment, wherein the (meth)acrylic polymers are prepared by copolymerization of 0.1% to 5% by mass of (meth)acrylic acid monomer and 95% to 99.9% by mass of another copolymerizable unsaturated monomer, wherein said another copolymerizable unsaturated monomer is a (meth)acrylic monomer other than the (meth)acrylic acid monomer, or is an unsaturated monomer including an aromatic ring.

2. The vibration damping composite according to claim 1, wherein the (meth)acrylic polymer is a styrene-(meth)acrylic polymer obtained from a monomer component containing styrene.

3. The vibration damping composite according to claim 1, wherein the resin includes an emulsion prepared by emulsion polymerization of a monomer component.

4. The vibration damping composite according to claim 1, wherein the solids content of the (meth)acrylic polymer is 20% by mass or more of 100% by mass of the solids content of the resin composition for vibration damping materials.

5. The vibration damping composite according to claim 1, wherein the solids content of the (meth)acrylic polymer is 99% by mass or less of 100% by mass of the solids content of the resin composition for vibration damping materials.

6. The vibration damping composite according to claim 1, wherein the (meth)acrylic polymer has a weight average molecular weight of 20,000 to 800,000.

7. The vibration damping composite according to claim 1, wherein the (meth)acrylic polymer has a glass transition temperature of −20° C. to 40° C.

8. The vibration damping composite according to claim 3, wherein the emulsion contains emulsion particles having an average particle size of 80 to 450 nm.

9. The vibration damping composite according to claim 1, wherein the lignin is a lignin sulfonic acid (salt).

10. The vibration damping composite according to claim 1, wherein the lignin derivative has a structure represented by the following formula (1): ##STR00002## wherein R.sup.1 to R.sup.6 are the same as or different from one another, and each represent a hydrogen atom, a hydroxy group, an alkoxy group, an acyl group, an amino group, a sulfonic acid group, a sulfonate group, a carboxyl group-containing group, a (poly)alkylene glycol chain-containing group, a hydrocarbon group, a direct bond or a thioether bond to a structure derived from another phenylpropane skeleton; at least one of R.sup.1 to R.sup.6 represents a direct bond or a thioether bond to a structure derived from another phenylpropane skeleton; and at least one of R.sup.1 to R.sup.6 represent an alkoxy group, a carboxyl group-containing group, a (poly)alkylene glycol chain-containing group, or a hydrocarbon group.

11. The vibration damping composite according to claim 1, wherein the lignin and/or the lignin derivative have/has a weight average molecular weight of 100 to 40,000.

12. The vibration damping composite according to claim 1, wherein the amount of the lignin and/or the lignin derivative is 1% by mass or more of 100% by mass of the solids content of the resin composition for vibration damping materials.

13. The vibration damping composite according to claim 1, wherein the amount of the lignin and/or the lignin derivative is 80% by mass or less of 100% by mass of the solids content of the resin composition for vibration damping materials.

14. The vibration damping composite according to claim 1, wherein the amount of the aqueous solvent is 3% by mass or more of 100% by mass of the resin composition for vibration damping materials.

15. The vibration damping composite according to claim 1, wherein the amount of the aqueous solvent is 97% by mass or less of 100% by mass of the resin composition for vibration damping materials.

16. The vibration damping composite of claim 1, wherein the vibration damping composite is a coating material.

17. The vibration damping composite of claim 1, wherein the resin composition comprises an emulsion prepared by emulsion polymerization.

18. The vibration damping composite of claim 1, wherein the lignin and/or lignin derivative is present in an amount of 7% by mass or more of 100% by mass of the solids content of the resin composition for vibration damping materials.

19. The vibration damping composite of claim 1, wherein the inorganic pigment is present in an amount within a range from 300 to 800 parts by mass per 100 parts by mass of the solids content of the resin.

Description

DESCRIPTION OF EMBODIMENTS

(1) The following description is offered to demonstrate the present invention based on embodiments of the present invention. The embodiments should not be construed as limiting the present invention. Unless otherwise mentioned, the term “part(s)” means “part(s) by weight” and “%” means “% by mass”.

(2) The properties were evaluated as follows in the production examples.

(3) <Average Particle Size>

(4) The average particle size of emulsion particles was measured by dynamic light scattering using a particle size distribution analyzer (FPAR-1000, Otsuka Electronics Co., Ltd.).

(5) <Nonvolatile Content (N.V.)>

(6) About 1 g of an obtained emulsion was weighed, and dried in a hot air dryer at 150° C. for one hour. The residue amount after drying was measured as the nonvolatile content and expressed as % by mass relative to the mass before drying.

(7) <pH>

(8) The pH at 25° C. was measured using a pH meter (“F-23” produced by Horiba, Ltd.).

(9) <Viscosity>

(10) The viscosity was measured at 25° C. and 20 rpm using a B type rotary viscometer (“VISCOMETER TUB-10” produced by Toki Sangyo Co., Ltd.).

(11) <Weight Average Molecular Weight>

(12) The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.

(13) Measuring equipment: HLC-8120GPC (trade name, produced by Tosoh Corporation)

(14) Molecular-weight column: TSK-GEL GMHXL-L and TSK-GEL G5000HXL (both produced by Tosoh Corporation) connected in series

(15) Eluent: Tetrahydrofuran (THF)

(16) Calibration curve reference material: Polystyrene (produced by Tosoh Corporation)

(17) Measuring method: A measurement object was dissolved in THF to a solids content of about 0.2% by mass, and the resulting solution was filtered through a filter. The filtrate was used as a measurement sample, and the molecular weight thereof was measured.

(18) <Glass Transition Temperature (Tg) of Polymer>

(19) The Tg of the polymer was calculated from the following formula (1) based on the compositions of the monomers used in the stages.

(20) $\begin{array}{cc}\frac{1}{T{g}^{\prime }}=\left[\frac{W_1^{\prime }}{T_1}+\frac{W_2^{\prime }}{T_2}+\mathrm{.Math.}+\frac{W_n^{\prime }}{T_n}\right]& \left(1\right)\end{array}$

(21) In the equation, Tg′ represents Tg (absolute temperature) of a polymer; W.sub.1′, W.sub.2′, . . . , and Wn′ each represent a mass fraction of each monomer relative to the entire monomer component; and T.sub.1, T.sub.2, . . . , and Tn each represent a glass transition temperature (absolute temperature) of the homopolymer of each monomer.

(22) The Tg calculated from the compositions of the monomers in all the stages was expressed as “total Tg”. The following shows the glass transition temperatures (Tg) of the homopolymers of the respective polymerizable monomers which were used to calculate the Tg based on the formula (1).

(23) Methyl methacrylate (MMA): 105° C.

(24) 2-Ethylhexyl acrylate (2EHA): −70° C.

(25) Butyl acrylate (BA): −56° C.

(26) Acrylic acid (AA): 95° C.

(27) Styrene (St): 100° C.

(28) <Production Examples of Polymer Emulsion, and so Forth>

Production Example 1

(29) A polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel was charged with deionized water (180.3 parts). Then, the internal temperature was increased to 75° C. under stirring and nitrogen flow. The dropping funnel was charged with a monomer emulsion composed of methyl methacrylate (505 parts), 2-ethylhexyl acrylate (135.0 parts), butyl acrylate (350 parts), acrylic acid (10.0 parts), t-dodecyl mercaptan (4.0 parts) as a polymerization chain transfer agent, NEWCOL 707SF (trade name, ammonium polyoxyethylene polycyclic phenyl ether sulfate: produced by Nippon Nyukazai Co., Ltd.) (180.0 parts) adjusted to a 20% aqueous solution in advance, and deionized water (164.0 parts). While the internal temperature of the polymerization vessel was maintained at 75° C., a 27.0-part portion of the monomer emulsion, a 5% potassium persulfate aqueous solution (5 parts), and a 2% sodium hydrogen sulfite aqueous solution (10 parts) as a polymerization initiator (oxidant) were added to start initial polymerization. After 40 minutes, the rest of the monomer emulsion was uniformly added dropwise over 210 minutes with the reaction system being maintained at 80° C. Simultaneously, a 5% potassium persulfate aqueous solution (95 parts) and a 2% sodium hydrogen sulfite aqueous solution (90 parts) were uniformly added dropwise over 210 minutes. After the completion of the dropwise addition, the temperature was maintained for 60 minutes to complete the polymerization.

(30) The resulting reaction solution was cooled to room temperature, and 2-dimethylethanolamine (16.7 parts) was added. Thus, acrylic emulsion particles 1 which had a nonvolatile content of 60.1%, a pH of 8.1, a viscosity of 2,600 mPa.Math.s, an average particle size of 260 nm (particle size distribution 24%), and a weight average molecular weight of 49,000 were obtained.

Production Example 2

(31) A polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel was charged with deionized water (180.3 parts). Then, the internal temperature was increased to 75° C. under stirring and nitrogen flow. The dropping funnel was charged with a monomer emulsion composed of styrene (170 parts), methyl methacrylate (343 parts), 2-ethylhexyl acrylate (170 parts), butyl acrylate (307 parts), acrylic acid (10.0 parts), t-dodecyl mercaptan (4.0 parts) as a polymerization chain transfer agent, NEWCOL 707SF (trade name, ammonium polyoxyethylene polycyclic phenyl ether sulfate: produced by Nippon Nyukazai Co., Ltd.) (180.0 parts) adjusted to a 20% aqueous solution in advance, and deionized water (164.0 parts). While the internal temperature of the polymerization vessel was maintained at 75° C., a 27.0-part portion of the monomer emulsion, a 5% potassium persulfate aqueous solution (5 parts), and a 2% sodium hydrogen sulfite aqueous solution (10 parts) as a polymerization initiator (oxidant) were added to start initial polymerization. After 40 minutes, the rest of the monomer emulsion was uniformly added dropwise over 210 minutes with the reaction system being maintained at 80° C. Simultaneously, a 5% potassium persulfate aqueous solution (95 parts) and a 2% sodium hydrogen sulfite aqueous solution (90 parts) were uniformly added dropwise over 210 minutes. After the completion of the dropwise addition, the temperature was maintained for 60 minutes to complete the polymerization.

(32) The resulting reaction solution was cooled to room temperature, and 2-dimethylethanolamine (16.7 parts) was added. Thus, acrylic emulsion particles 2 which had a nonvolatile content of 59.9%, a pH of 8.0, a viscosity of 1,800 mPa.Math.s, an average particle size of 240 nm (particle size distribution 27%), and a weight average molecular weight of 48,000 were obtained.

Production Example 3

(33) A polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel was charged with deionized water (174.1 parts). Then, the internal temperature was increased to 75° C. under stirring and nitrogen flow. The dropping funnel was charged with a monomer emulsion of a first step which was composed of styrene (165 parts), methyl methacrylate (160 parts), 2-ethylhexyl acrylate (165 parts), acrylic acid (10 parts), t-dodecyl mercaptan (3 parts) as a polymerization chain transfer agent, LEVENOL WZ (trade name, produced by Kao Corporation) (90.0 parts) adjusted to a 20% aqueous solution in advance, and deionized water (82 parts). While the internal temperature of the polymerization vessel was maintained at 80° C., a 8-part portion of the monomer emulsion, a 5% potassium persulfate aqueous solution (5 parts), and a 2% sodium hydrogen sulfite aqueous solution (10 parts) as a polymerization initiator (oxidant) were added to start initial polymerization. After 20 minutes, the rest of the monomer emulsion was uniformly added dropwise over 120 minutes with the reaction system being maintained at 80° C. Simultaneously, a 5% potassium persulfate aqueous solution (50 parts) and a 2% sodium hydrogen sulfite aqueous solution (50 parts) were uniformly added dropwise over 120 minutes. After the completion of the dropwise addition, the temperature was maintained for 60 minutes. The dropping funnel was then charged with a monomer emulsion of a second step which was composed of styrene (100 parts), methyl methacrylate (100 parts), butyl acrylate (205 parts), 2-ethylhexyl acrylate (85 parts), acrylic acid (10 parts), t-dodecyl mercaptan (3 parts), LEVENOL WZ (trade name, produced by Kao Corporation) (90.0 parts) adjusted to a 20% aqueous solution in advance, and deionized water (82 parts). The monomer emulsion was uniformly added dropwise into the reaction solution over 120 minutes. Simultaneously, a 5% potassium persulfate aqueous solution (50 parts) and a 2% sodium hydrogen sulfite aqueous solution (50 parts) were uniformly added dropwise over 120 minutes. After the completion of the dropwise addition, the temperature was maintained for 90 minutes to complete the polymerization. The resulting reaction solution was cooled to room temperature, and 25% ammonia water (10 parts) was added. Thus, acrylic emulsion 3 which had a nonvolatile content of 59.8%, a pH of 8.0, a viscosity of 3,000 mPa.Math.s, an average particle size of 260 nm, a weight average molecular weight of 65,000, a Tg of the first step of 20.1° C., a Tg of the second step of −13° C., and a total Tg of 1.6° C. was obtained.

(34) The following shows the trade names and details of the polymer emulsions used in the below described Examples 11 and 12 and Comparative Examples 4 and 5.

(35) <SBR>

(36) SR-110 (produced by Nippon A&L Inc., styrene-butadiene resin, Tg: −20° C., nonvolatile content: 50%, SP value: 8.7)

(37) <Vinyl Acetate>

(38) Polysol for adhesion-1000J (produced by Showa Denko K.K., vinyl acetate resin, nonvolatile content: 51%)

(39) <Production Examples of a Lignin>

(40) (KP Liquor)

(41) Kraft pulp waste liquor was condensed so that the solids concentration was adjusted to 30% by mass.

(42) (SP Liquor)

(43) Sulfite pulp waste liquor was condensed so that the solids concentration was adjusted to 30% by mass.

(44) (Sodium Lignosulfonate Liquid)

(45) PEARLLEX NP (produced by Nippon Paper Industries Co., Ltd.) was dissolved in water so that the solids concentration was adjusted to 30% by mass.

(46) (Magnesium Lignosulfonate Liquid)

(47) San X P321 (produced by Nippon Paper Industries Co., Ltd.) was dissolved in water so that the solids concentration was adjusted to 30% by mass.

(48) (Calcium Lignosulfonate Liquid)

(49) PEARLLEX CP (Nippon Paper Industries Co., Ltd.) was dissolved in water so that the solids concentration was adjusted to 30% by mass.

(50) <Production Example of Lignin Derivative>

Production Example 4

(51) A glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping device was charged with water (300 parts), methoxypolyethylene glycol acrylate (Light acrylate 130A, produced by Kyoeisha Chemical Co., Ltd.) (40 g), acrylic acid (15 g), PEARLLEX NP (sodium lignosulfonate, produced by Nippon Paper Chemicals Co., Ltd.) (144 g), and t-dodecylmercaptan (0.5 g), and the temperature of the solution was increased to 100° C. under a nitrogen atmosphere. After the contents were stirred for 30 minutes, a 20% hydrogen peroxide aqueous solution (2 g) was continually added dropwise to the reaction vessel over 10 minutes. Immediately thereafter, dropwise addition of an aqueous solution (20 g) containing L-ascorbic acid (0.2 g) was started. The contents were reacted for one hour while the temperature was maintained at 100° C., and the reaction product was then mixed with water (147 g) and stirred. Thus, an aqueous solution of a lignin derivative with a solids content of 30% was obtained.

Examples 1 to 13, Comparative Examples 1 to 5

Example 1

(52) The emulsion 1 (80 parts) obtained in Production Example 1 was mixed with a lignin (KP liquor) (20 parts) and deionized water (20 parts) to prepare an emulsion-lignin blend (resin composition) 1 with a solids concentration of 45% by mass.

Examples 2 to 13, Comparative Examples 1 to 5

(53) Emulsion-lignin blends 2 to 18 were obtained as in Example 1, except that the kind and/or the amount of emulsion, a lignin, a lignin derivative, and/or deionized water were/was changed according to Table 1. In Comparative Examples 1 to 5, neither a lignin nor a lignin derivative was blended.

(54) <Preparation of Vibration Damping Composite>

(55) The emulsion-lignin blends 1 to 13 in Examples 1 to 13 and the emulsion-lignin blends 14 to 18 in Comparative Examples 1 to 5 were each blended as described below, and thereby vibration damping composites were prepared. The properties were evaluated as follows. Table 1 shows the results. Emulsion-lignin blends 1 to 18: 359 parts Calcium carbonate NN#200.sup.*1: 620 parts Dispersant AQUALIC DL-40S.sup.*2: 6 parts Thickener ACRYSET WR-650.sup.*3: 4 parts
*1: Filler produced by Nitto Funka Kogyo K.K.
*2: Polycarboxylic acid-based dispersant (active component: 44%) produced by Nippon Shokubai Co., Ltd.
*3: Alkali-soluble acrylic thickener (active component: 30%) produced by Nippon Shokubai Co., Ltd.

(56) The following shows the methods for evaluation of the properties.

(57) Coatings formed from the vibration damping composites obtained in the examples and comparative examples were evaluated for their appearance and tested for their vibration damping properties by the following methods. Table 1 shows the results.

(58) <Evaluation of Appearance of Coating>

(59) Each vibration damping composite was applied to a steel plate (trade name: SPCC-SD, 75 mm in width×150 mm in length×0.8 mm in thickness, produced by Nippon Testpanel Co., Ltd.) so that the formulation had a thickness of 4 mm, and dried in a hot air dryer at 150° C. for 50 minutes. The condition of the surface of the resulting dry coating was evaluated using the following criteria.

(60) Good: No defect

(61) Fair: The coating was partly peeled from the base material or cracked.

(62) Bad: Peeling or cracking was observed throughout the coating.

(63) <Vibration Damping Property Test>

(64) Each vibration damping composite was applied to a cold rolled steel plate (trade name: SPCC, 15 mm in width×250 mm in length×1.5 mm in thickness, produced by Nippon Testpanel Co., Ltd.) so that the formulation had a thickness of 3 mm, and dried at 150° C. for 30 minutes. Thus, a vibration damping coating with a surface density of 4.0 kg/m.sup.2 was formed on the cold rolled steel plate.

(65) The vibration damping property was measured by evaluating the loss coefficients at particular temperatures (20° C., 30° C., 40° C., 50° C., and 60° C.) by a cantilever method (loss coefficient measurement system produced by Ono Sokki Co., Ltd.). The vibration damping property was evaluated based on the total loss coefficient (the sum of loss coefficients at 20° C., 30° C., 40° C., 50° C., and 60° C.). A larger total loss coefficient corresponds to a higher vibration damping property.

(66) TABLE-US-00001 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Resin Production Example 1 80 80 — — — — — Production Example 2 — — 80 60 80 80 80 Production Example 3 — — — — — — — SER (SR-110) — — — — — — — Vinyl acetate — — — — — — — (Polysol 1000J) Lignin KP liquor 20 — 20 40 — — — SP liquor — 20 — — 20 — — Sodium — — — — — 20 — lignosulfonate liquid Magnesium — — — — — — 20 lignosulfonate liquid Calcium — — — — — — — lignosulfonate liquid Lignin derivative — — — — — — — (Production Example 4) Water 20 20 20 6.7 20 20 20 Appearance Good Good Good Good Good Good Good Vibration 20° C. 0.084 0.081 0.082 0.078 0.079 0.077 0.081 damping 30° C. 0.126 0.118 0.137 0.108 0.128 0.127 0.136 property 40° C. 0.088 0.096 0.081 0.128 0.091 0.093 0.097 50° C. 0.061 0.071 0.046 0.086 0.054 0.058 0.062 60° C. 0.024 0.028 0.019 0.042 0.026 0.031 0.034 Total 0.383 0.394 0.365 0.442 0.378 0.386 0.41 Example Example Example Example Example 8 Example 9 10 11 12 13 Resin Production Example 1 — — — — — — Production Example 2 60 80 — — 62.3 80 Production Example 3 — — 80 — — — SER (SR-110) — — — 96 — — Vinyl acetate — — — — 20.8 — (Polysol 1000J) Lignin KP liquor — — 20 20 20 — SP liquor — — — — — — Sodium — — — — — — lignosulfonate liquid Magnesium 40 — — — — — lignosulfonate liquid Calcium — 20 — — — — lignosulfonate liquid Lignin derivative — — — — — 20 (Production Example 4) Water 6.7 20 20 4 16.9 20 Appearance Good Good Good Fair Good Good Vibration 20° C. 0.08 0.078 0.071 0.068 0.064 0.076 damping 30° C. 0.139 0.126 0.119 0.062 0.114 0.117 property 40° C. 0.113 0.096 0.121 0.041 0.071 0.097 50° C. 0.076 0.061 0.069 0.022 0.035 0.066 60° C. 0.042 0.033 0.031 0.011 0.018 0.041 Total 0.45 0.394 0.411 0.204 0.302 0.397 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Resin Production Example 1 100 — — — — Production Example 2 — 100 — — 75 Production Example 3 — — 100 — — SER (SR-110) — — — 100 — Vinyl acetate — — — — 25 (Polysol 1000J) Lignin KP liquor — — — — — SP liquor — — — — — Sodium — — — — — lignosulfonate liquid Magnesium — — — — — lignosulfonate liquid Calcium — — — — — lignosulfonate liquid Lignin derivative — — — — — (Production Example 4) Water 33.3 33.3 33.3 13.3 26.3 Appearance Bad Fair Fair Bad Bad Vibration 20° C. 0.114 0.102 0.091 0.061 0.081 damping 30° C. 0.128 0.132 0.14 0.043 0.109 property 40° C. 0.068 0.061 0.092 0.022 0.051 50° C. 0.024 0.019 0.03 0.018 0.017 60° C. 0.019 0.011 0.016 0.009 0.011 Total 0.353 0.325 0.369 0.151 0.269

(67) The comparison of Examples 1 and 2 with Comparative Example 1 in which the emulsion obtained in Production Example 1 was used demonstrates that a higher vibration damping property and better appearance were obtained in Examples 1 and 2 because a KP liquor was used in Example 1 and a SP liquor was used in Example 2. The comparison of Examples 3 to 9 and 13 with Comparative Example 2 in which the emulsion obtained in Production Example 2 was used demonstrates that a higher vibration damping property and better appearance were obtained in Examples 3 to 9 and 13 because a KP liquor was used in Examples 3 and 4, a SP liquor was used in Example 5, each of the lignosulfonates was used in Examples 6 to 9, and a lignin derivative was used in Example 13. The comparison of Example 10 with Comparative Example 3 in which the emulsion obtained in Production Example 3 was used demonstrates that a higher vibration damping property and better appearance were obtained because a KP liquor was used in Example 10. The comparison of Example 11 with Comparative Example 4 in which a styrene-butadiene resin was used demonstrates that a higher vibration damping property and better appearance were obtained because a KP liquor was used in Example 11. The comparison of Example 12 with Comparative Example 5 in which the emulsion obtained in Production Example 2 and a vinyl acetate resin were used in combination demonstrates that a higher vibration damping property and better appearance were obtained in Example 12 because a KP liquor was used in Example 12.

(68) As described above, the comparisons of the examples with the corresponding comparative examples (in which the same resins as in the examples were used) demonstrate that a higher vibration damping property and better appearance were obtained in all the examples in which the vibration damping composite contains a lignin and/or a lignin derivative. In particular, the vibration damping material coatings in the examples have sufficiently good appearance in which generation of peeling and cracks is suppressed even without containing a foaming agent. This demonstrates remarkably high effects of improving the appearance of the present invention. Accordingly, the results of the examples show that the present invention can be employed in the entire technical field of the present invention and in the various embodiments disclosed herein, and can exhibit advantageous effects.