Dispersant

Abstract

The present invention provides a hydrolysate of a lignocellulosic material, and specifically a method of using a hydrolysis treatment liquid obtained by a hydrolysis treatment of a lignocellulosic material before kraft cooking in order to obtain dissolving pulp for uses other than use of a fuel. Specifically, the present invention provides a dispersant containing the hydrolysate obtained by hydrolysis treatment of the lignocellulosic material. The dispersant of the present invention has excellent dispersibility for a substance such as an inorganic substance and an organic substance without limitation of powder, particulate, granular, fiber, and flat plane shapes.

Claims

1. A dispersant, comprising: a hydrolysate of a lignocellulosic material; and at least one selected from the group consisting of: (A) at least one of a sodium a poly(meth)acrylate, sodium gluconate, and a partially neutralized metal salt of a poly(meth)acrylic acid, (B) a compound having an acid group and a polyalkylene glycol chain, and (C) a compound having a sulfonic acid group, a salt thereof, or both, wherein: the hydrolysate comprises an oligosaccharide, a polysaccharide, or both, and a lignin; a contained amount of the oligosaccharide, the polysaccharide, or both, in the hydrolysate is 50% by weight to 80% by weight relative to a solid content of a hydrolysate; and a contained amount of the lignin in the hydrolysate is 1 to 10% by weight relative to the solid content of the hydrolysate.

2. The dispersant according to claim 1, wherein the hydrolysate has a weight average molecular weight of 1,000 to 5,000.

3. The dispersant according to claim 1, comprising at least one selected from the group consisting of: (A) the at least one of the sodium a poly(meth)acrylate, the sodium gluconate, and the partially neutralized metal salt of a poly(meth)acrylic acid; (B) at least one of: a copolymer of a (poly)oxyethylene methacrylate and (meth)acrylic acid, a copolymer of a (poly)oxyethylene allyl ether and (meth)acrylic acid, a copolymer of a (poly)oxyethylene allyl ether and maleic anhydride, a copolymer of a (poly)oxyethylene adduct of 3-methyl-3-buten-1-ol and (meth)acrylic acid, a copolymer of a (poly)oxyethylene adduct of 3-methyl-3-buten-1-ol and maleic anhydride, and salts thereof; and (C) the compound having a sulfonic acid group, a salt thereof, or both.

4. The dispersant according to claim 1, which is adapted to function as a dispersant for an inorganic substance.

5. The dispersant according to claim 1, which is adapted to function as a dispersant for an organic substance.

6. The dispersant according to claim 1, which is adapted to function as a dispersant for a cement.

7. A composition, comprising; the dispersant according to claim 1; a substance to be dispersed; and a dispersion medium.

8. The composition according to claim 7, wherein the substance to be dispersed is a hydraulic material.

9. The composition according to claim 8, wherein the hydraulic material comprises a cement.

10. A hydraulic composition, comprising: the dispersant according to claim 1; and a hydraulic material.

11. A cement composition, comprising: the dispersant according to claim 1; and a cement.

12. A method of producing a dispersion composition, the method comprising: dispersing a substance to be dispersed and a dispersion medium in the presence of the dispersant according to claim 1.

13. A dispersion composition, comprising a substance dispersed in a dispersion medium in the presence of the dispersant according to claim 1.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described specifically with reference to Examples, but is not limited to these Examples. In Examples, % represents % by weight, and part(s) represents part(s) by weight, unless otherwise noted.

Production Example 1

Production of Hydrolysis Treatment Liquid 1

(2) Hardwood chips in an absolute dry amount of 300 g were placed in a 2.4-L rotation-type autoclave, and water was added so that the liquid ratio was 2 L/kg. The mixture was held at 170 C. for 30 minutes, and hydrolyzed at a pH of 3.5. A neutralization liquid was added, resulting in neutralization at 155 C. for 15 minutes. The neutralization liquid was prepared by mixing sodium hydroxide and sodium sulfide so that the active alkali was 11% (relative to the weight of the chips), the sulfidity was 25%, and the liquid ratio was 2.5 L/kg. After the neutralization, the liquid was taken from the autoclave, and concentrated using a rotary evaporator so that the solid content was 20% by weight. Thus, a hydrolysis treatment liquid 1 having a weight average molecular weight of 2,700 was obtained. Chemical components of the hydrolysis treatment liquid 1 are shown in Table 1.

(3) A chemical composition of the hydrolysis treatment liquid 1 is shown in Table 1. Each component in each Production Example, and measurement conditions of weight average molecular weight are as follows.

(4) <Quantitative Determination of Constituent Saccharides>

(5) Among constituent saccharides, monosaccharides were detected by an ELSD-HPLC method. To a polysaccharide and an oligosaccharide, 1 M TFA was added in an amount two times the weight of solid content of the hydrolysis treatment liquid, and the mixture was heated at 105 C. for 3 hours resulting in complete hydrolysis. After that, the amounts of the polysaccharide and the oligosaccharide were determined as monosaccharides by HPLC.

(6) <Lignin>

(7) Lignin was measured in accordance with a method for measuring a methoxyl group on the basis of Method of Viebock and Schwappach (see Methods in lignin chemistry, pp. 336 to 340, 1994, Uni Press Co.). As the amount of lignin, the amount of the methoxyl group was used.

(8) <Organic Acid>

(9) An organic acid was measured by an ion-exclusion HPLC post-column chromatography reaction visible light detection method.

(10) <Oils>

(11) The amount of n-hexane extract was calculated in accordance with JIS-K0102, and noted as oils.

(12) <Furan>

(13) Furan was measured by an HPLC-UV method.

(14) <Ash Content>

(15) A sample was weighed in an ashing vessel, moisture was removed by an electric heater, and the sample was measured in accordance with JIS-P8002.

(16) <Weight Average Molecular Weight (Mw)>

(17) High performance liquid chromatography of GPC mode was performed using the following column and mobile phase, and a molecular weight-retention time standard curve was formed using a pullulan having a known molecular weight. The weight average molecular weight of the sample was measured with reference to the curve.

(18) Column: combination of OH pak SB806HQ+SB804HQ+SB802.5HQ (all columns were manufactured by Showa Denko K.K.)

(19) Mobile phase: aqueous sodium tetraborate (0.05 M) solution Standard substance: pullulan having a known molecular weight

(20) Device: high performance liquid chromatography device of GPC mode

(21) TABLE-US-00001 TABLE 1 CHEMICAL COMPOSITION OF HYDROLYSIS TREATMENT LIQUID 1 COMPONENT RATIO (%) GLUCOSE 2.6 MANNOSE 5.8 ARABINOSE 3.4 XYLOSE 7.4 GALACTOSE 6.2 POLYSACCHARIDE AND OLIGOSACCHARIDE 64.3 (TOTAL) (GLUCOMANNAN) 7.7 (GLUCURONOXYLAN) 44.9 LIGNIN 4.3 ORGANIC ACID 1.1 OILS 0.1 FURAN 0.3 ASH CONTENT 2.8 OTHER 1.7

Production Example 2

Production of Hydrolysis Treatment Liquid 2

(22) Softwood chips in an absolute dry amount of 300 g were placed in a 2.4-L rotation-type autoclave, and water was added so that the liquid ratio was 3.2 L/kg. The mixture was held at 170 C. for 30 minutes, and hydrolyzed at a pH of 3.8. A neutralization liquid was added, resulting in neutralization at 155 C. for 15 minutes. The neutralization liquid was prepared by mixing sodium hydroxide and sodium sulfide so that the active alkali was 11% (relative to the weight of the chips), the sulfidity was 25%, and the liquid ratio was 3.2 L/kg. After the neutralization, the liquid was taken from the autoclave, and concentrated using a rotary evaporator so that the solid content was 20% by weight. Thus, a hydrolysis treatment liquid 2 having a weight average molecular weight of 2,100 was obtained. A chemical composition of the hydrolysis treatment liquid 2 is shown in Table 2.

(23) TABLE-US-00002 TABLE 2 CHEMICAL COMPOSITION OF HYDROLYSIS TREATMENT LIQUID 2 COMPONENT RATIO (%) GLUCOSE 2.1 MANNOSE 6.6 ARABINOSE 4.1 XYLOSE 4.9 GALACTOSE 6.6 POLYSACCHARIDE AND OLIGOSACCHARIDE (total) 66.9 (GLUCOMANNAN) 40.7 (GALACTAN) 8.9 (ARABINOXYLAN) 1.7 LIGNIN 3.5 ORGANIC ACID 0.7 OILS 0.1 FURAN 0.1 ASH CONTENT 1.9 OTHER 2.5

Production Example 3

Production of Hydrolysis Treatment Liquid 3

(24) The hydrolysis treatment liquid 1 was subjected to ultrafiltration to prepare a 3-times concentrated liquid. Thus, a hydrolysis treatment liquid 3 having a weight average molecular weight of 4,500 was obtained. For the ultrafiltration, a flat membrane test machine UHP-76 (molecular weight cutoff: 110.sup.3) manufactured by Toyo Roshi Kaisha, Ltd., was used. A chemical composition of the hydrolysis treatment liquid 3 is shown in Table 3.

(25) TABLE-US-00003 TABLE 3 CHEMICAL COMPOSITION OF HYDROLYSIS TREATMENT LIQUID 3 COMPONENT RATIO (%) GLUCOSE 3.3 MANNOSE 5.6 ARABINOSE 5.8 XYLOSE 3.6 GALACTOSE 1.6 POLYSACCHARIDE AND OLIGOSACCHARIDE (total) 70.2 (GLUCOMANNAN) 55.7 (GALACTAN) 9.2 (ARABINOXYLAN) 1.8 LIGNIN 3.1 ORGANIC ACID 0.5 OILS 0.1 FURAN 0.1 ASH CONTENT 0.1 OTHER 6

(26) [Bottom Notes in Tables]

(27) The ratio of each component in Tables 1 to 3 is a ratio (%) by weight of the component relative to the total weight (solid content) of each hydrolysis treatment liquid except for moisture content.

Examples 1 to 4 and Comparative Examples 1 to 4

(28) A fine aggregate, cement, water, and a dispersant were charged into a mortar mixer, and mechanically kneaded by the mortar mixer to prepare a mortar. A chemical composition of the fine aggregate, cement, and water is shown in Table 4, and the amount of added dispersant is shown in Table 5. The mortar flow, setting time, and air content of the obtained mortar were evaluated.

(29) The mortar flow was evaluated by the following procedure. A hollow-cylindrical compact slump cone with a diameter of bottom face of 20 cm, a diameter of upper face of 10 cm, and a height of 30 cm was charged with the mortar. An average of diameters in two directions of the mortar that spread on a table during vertical lifting of the compact slump cone was taken as a mortar flow value. When the addition amount is smaller and the mortar flow value is larger, the performance of the dispersant is judged to be favorable. Each air content in the mortar using each dispersant was adjusted to the same air content using an AE agent and a defoamer, and a test was then performed. The results are shown in Table 4.

(30) The setting time was evaluated by the following procedure. The mortar was poured into a container covered with a heat insulating material. A change of mortar temperature with time was checked using a time-dependent temperature measurement device. The time at which the temperature reached a maximum temperature was taken as the setting time of the mortar. In general, when the setting time is shorter, the dispersant is judged to be good.

(31) The air content was evaluated by the following procedure. A cylindrical container was charged with the mortar, the weight of the charged mortar was measured, and the air content was calculated by the following (Expression 1).
Air content (%)=(weight of charged mortar/weight of mortar with air content of 0%)100(Expression 1)

(32) The specific gravity (calculated value) of the mortar was first calculated from the specific gravities of water, cement, and sand. The weight of mortar with an air content of 0% in (Expression 1) was then calculated by the following (Expression 2).
Weight of mortar with air content of 0%=specific gravity (calculated value) of mortarvolume of cylindrical container(Expression 2)

(33) TABLE-US-00004 TABLE 4 UNIT AMOUNT g W/C % WATER CEMENT LAND SAND 52.5 329 627 1756

(34) The used materials are as follows.

(35) Cement:

(36) ordinary portland cement (available from Ube-Mitsubishi Cement Corporation, specific gravity: 3.16)

(37) ordinary portland cement (available from Taiheiyo Cement Corporation, specific gravity: 3.16)

(38) ordinary portland cement (available from Tokuyama Corporation, specific gravity: 3.16)

(39) Water: tap water

(40) Land sand: land sand from Kakegawa-Shi, Shizuoka Prefecture (fine aggregate, specific gravity: 2.59)

(41) Dispersant (in terms of solid content): see Table 5

(42) TABLE-US-00005 TABLE 5 ADDITION AMOUNT WEIGHT WEIGHT OF AVERAGE DISPERSANT/ MORTAR SETTING AIR MOLECULAR WEIGHT FLOW TIME CONTENT WEIGHT Mw OF CEMENT % mm hr % EXAMPLE 1 HYDROLYSIS 2700 0.4 221 17 4.4 TREATMENT 0.7 231 48< 4.9 LIQUID 1 1 238 48< 4.6 EXAMPLE 2 HYDROLYSIS 2100 0.4 222 17.5 4.7 TREATMENT 0.7 233 48< 4.6 LIQUID 2 1 239 48< 4.7 EXAMPLE 3 HYDROLYSIS 4500 0.4 226 16.5 4.2 TREATMENT 0.7 235 48< 4.5 LIQUID 3 1 242 48< 4.5 EXAMPLE 4 HYDROLYSIS 4560 0.5 220 18 4.3 TREATMENT 0.8 239 35.5 4.2 LIQUID 1 + 1.1 232 48< 4.1 LIGNIN SULFONIC ACID (*1) 50/50 (BY WEIGHT) COMPAR- LIGNIN SULFONIC 12000 0.4 292 12 4.4 ATIVE ACID (*1) 0.7 205 16 4.5 EXAMPLE 1 1 217 19.5 4.9 COMPAR- SODIUM 218 0.4 210 20 4.4 ATIVE GLUCONATE (*2) 0.7 218 48< 4.2 EXAMPLE 2 1 225 48< 4.7 COMPAR- SOY 120000 0.4 168 17 4.3 ATIVE POLYSACCHARIDE 0.7 179 25 4.6 EXAMPLE 3 (*3) 1 186 29 4.3 COMPAR- DEXTRIN (*4) 1700 0.4 200 18.5 4.5 ATIVE 0.7 216 48< 4.8 EXAMPLE 4 1 221 48< 4.5 [Bottom Notes in Table 5] (*1) lignin sulfonic acid-based cement dispersant: trade name SUNFLO-RH available from Nippon Paper Industries Co., Ltd. (*2) sodium gluconate-based cement dispersant: trade name C-PARN available from Fuso Chemical Co., Ltd. (*3) soya polysaccharides: trade name SOYAFIBE S-DN available from Fuji Oil Co., Ltd. (*4) starch hydrolysate: trade name pinedex #2 available from Matsutani Chemical Industry Co., Ltd. <48 means that coagulation is not achieved in 48 hours.

Examples 5 to 7, and Comparative Example 5

(43) A fine aggregate, cement, water, and a dispersant were charged into a mortar mixer, and mechanically kneaded by the mortar mixer to prepare a mortar. A chemical composition of the fine aggregate, cement, and water is shown in Table 6, and the amount of added dispersant is shown in Table 7. The mortar flow, setting time, and air content of the obtained mortar were evaluated in the same manner as in Example 1.

(44) TABLE-US-00006 TABLE 6 UNIT AMOUNT g W/C % WATER CEMENT LAND SAND 45 312 693 1670

(45) The used materials are as follows.

(46) Cement:

(47) ordinary portland cement (available from Ube-Mitsubishi Cement Corporation, specific gravity: 3.16)

(48) ordinary portland cement (available from Taiheiyo Cement Corporation, specific gravity: 3.16)

(49) ordinary portland cement (available from Tokuyama Corporation, specific gravity: 3.16)

(50) Water: tap water

(51) Land sand: land sand from Kakegawa-Shi, Shizuoka Prefecture (fine aggregate, specific gravity: 2.59) Dispersant (in terms of solid content): see Table 7

(52) A polymer A was produced in the same manner as in Example 1 in Japanese Patent Application Laid-Open No. 2000-239595. Specifically, 173 g of pure water, 180 g (2.5 mol) of acrylic acid, and 174 g (1.35 mol) of an aqueous 31% NaOH solution were mixed and stirred to prepare a mixed liquid a. In a 1,000-mL flask equipped with a stirrer, a thermometer, and a reflux condenser, 163 g of pure water was placed, and heated to 80 C. with stirring. To the flask, the prepared mixed liquid a and 60.0 g of aqueous 12% by weight ammonium persulfate solution were each independently added dropwise simultaneously over 3 hours. After completion of the dropwise addition, the mixture was aged for 2 hours to obtain an aqueous solution of partially neutralized metal salt of polyacrylic acid (polymer A). The resulting aqueous solution was concentrated to 40% by weight. The weight average molecular weight of the polymer A was 14,000, and the pH was 5.0.

(53) A polymer B was produced in the same manner as in paragraph [0051] in Japanese Patent Application Laid-Open No. 2011-057459. Specifically, in a glass reaction container equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet tube, and a dropping device, 247 parts by weight of water, 578 parts by weight of polyethylene glycol monoallyl ether (average additional amount by mole of ethylene oxide: 10), and 8 parts by weight of a compound in which 3-position and 3-position of 4,4-dihydroxydiphenylsulfone were substituted with allyl were charged. Inside air of the reaction container was replaced with nitrogen gas while stirring, and the mixture was heated to 100 C. in a nitrogen gas atmosphere. After that, a monomer aqueous solution in which 130 parts by weight of acrylic acid and 618 parts by weight of water were mixed, and a mixed liquid of 14 parts by weight of ammonium persulfate and 186 parts by weight of water were each continuously added dropwise to the mixture in the reaction container over 1 hour while the temperature of reaction mixture was maintained at 100 C. The temperature of the resulting reaction mixture was further maintained at 100 C., and the reaction was caused for 1 hour to obtain an aqueous solution of a copolymer (polymer B). The contained amount of unsaturated polyethylene glycol alkenyl ether was 19% by weight. The pH of this liquid was adjusted to 7 by an aqueous 30% NaOH solution, to obtain an aqueous solution of the copolymer having a weight average molecular weight of 18,300.

(54) TABLE-US-00007 TABLE 7 ADDITION AMOUNT WEIGHT OF DISPERSANT/ AIR WEIGHT OF MORTAR SETTING CONTENT CEMENT % FLOW mm TIME hr % EXAMPLE 5 HYDROLYSIS 0.17 180 16 4.5 TREATMENT LIQUID 1 + 0.21 200 18 4.6 POLYMER A (*5) 0.23 223 20 4.7 50/50 (RATIO BY WEIGHT OF EACH SOLID CONTENT) EXAMPLE 6 HYDROLYSIS 0.17 170 14 4.5 TREATMENT LIQUID 1 + 0.21 190 15 4.6 POLYMER B (*6) 0.23 210 16 4.3 50/50 (RATIO BY WEIGHT OF EACH SOLID CONTENT) EXAMPLE 7 HYDROLYSIS 0.19 172 10 4.3 TREATMENT LIQUID 1 + 0.23 193 12 4.6 NAPHTHALENE 0.25 215 15 4.3 SULFONIC ACID (*7) 50/50 (RATIO BY WEIGHT OF EACH SOLID CONTENT) COMPARATIVE LIGNIN SULFONIC 2 221 30 4.4 EXAMPLE 5 ACID (*1) 2.5 223 48< 4.3 3 225 48< 4.5 [Bottom Notes in Table 7] (*1) lignin sulfonic acid-based cement dispersant: trade name SUNFLO-RH available from Nippon Paper Industries Co., Ltd. (*5) As the polymer A, a polymer described in Example 1 in Japanese Patent Application Laid-Open No. 2000-239595 was used. (*6) As the polymer B, A-1 described in Japanese Patent Application Laid-Open No. 2011-057459 was used. (*7) naphthalenesulfonic acid was a naphthalene sulfonate formaldehyde condensate-based dispersant (available from Flowric Co., Ltd. (product name: FLOWRIC PS)) <48 means that coagulation is not achieved in 48 hours.

(55) As apparent from Tables 5 and 7, even when the addition amount of the dispersant in the cement composition of each Example was small, the mortar flow that was the same as in each Comparative Example is obtained. Therefore, the cement composition of each Example has high performance. The setting time of the cement composition of the cement composition of each Example was shorter than that of each Comparative Example.

(56) The cement compositions of Examples 4 to 7 using the hydrolysis treatment liquid and the other component exhibited more excellent mortar flow values and setting time. In Example 4 using the hydrolysis treatment liquid and lignin sulfonic acid in combination, although the addition amount was small, high mortar flow was obtained as compared with Comparative Example 5 using lignin sulfonic acid alone. This shows that dispersibility is excellent. In Example 4, the setting time was shorter than that in Comparative Example 5. Among Examples 4 to 7, Example 6 using the polymer B in combination exhibited high cement dispersibility, and shorter setting time.

(57) These results show that the dispersant of the present invention exerts excellent dispersibility in cement, and the setting of the cement composition containing the dispersant can be controlled appropriately according to demands of uses and the like. These results show that the dispersant of the present invention can impart excellent dispersibility even when it is applied to another substance to be dispersed.

Example 8

(58) 5 g of titanium dioxide was weighted in a 50-mL measuring cylinder. Subsequently, the hydrolysis treatment liquid 1 produced in accordance with Production Example 1 and ion-exchanged water were added to prepare a dispersion composition so that the final concentration of solid content of the hydrolysis treatment liquid 1 in the dispersion composition was 0.1% by weight. This measuring cylinder was mounted in a shaker, and shaken at a rate of 350 rpm/min for 30 seconds. The cylinder was allowed to stand at room temperature for 24 hours, and the syneresis ratio was measured. The dispersibility was judged. As the syneresis ratio, a ratio of supernatant relative to the whole volume of the measuring cylinder was calculated. When the syneresis ratio is 5% or less, the dispersibility can be evaluated to be favorable.

Example 9

(59) Evaluation was performed in the same manner as in Example 8 except that calcium carbonate was used in place of titanium dioxide.

(60) The syneresis ratios in Examples 8 and 9 were 3% and 4%, respectively. These results show that the dispersant of the present invention can exert favorable dispersibility in a substance other than cement, such as an inorganic substance, and is useful as a dispersant for the inorganic substance.