JP6592704B2 - Powder viscoelasticity modifier - Google Patents

Description

  The present invention relates to a powder viscoelasticity adjusting agent.

  Conventionally, carboxymethylcellulose-based and acrylic acid-based synthetic products are known as viscoelasticity modifiers (Patent Document 1).

JP 2001-261419 A

The above-mentioned conventional synthetic product is a synthetic chemical substance when applied to, for example, excavation in the construction of building foundations and underground structures, mining of natural resources, and the like, there is a problem that adverse effects on the environment are concerned .
That is, an object of the present invention is to provide a powder viscoelasticity modifier that can impart excellent viscoelasticity without adversely affecting the environment.

The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems.
That is, the powder viscoelasticity adjusting agent of the present invention is characterized by containing a dried leaf pulverized product (A) of jute (Corchorus capsularis) ,
Alkali total content of the metal atoms and alkaline earth metal atom (wt%) is summarized as points Ru 1-20 der based on the weight of the dried leaves pulverized (A).

  The feature of the drilling mud according to the present invention is that it contains the above-mentioned powder viscoelasticity adjusting agent.

A feature of the production method of the present invention is a method for producing the above powder viscoelasticity modifier,
The gist of the present invention is to include a step of obtaining a dried leaf pulverized product (A) by drying and then pulverizing the leaves of Kouma (Corchorus capsularis).

The powder viscoelasticity adjusting agent of the present invention does not adversely affect the environment and can impart excellent viscoelasticity (particularly high thixotropy).
Furthermore, since the powder viscoelasticity adjusting agent of the present invention uses the leaves of the horses that have been discarded in the past, it contributes to a reduction in disposal costs and environmental pollution.

  Since the drilling mud of the present invention contains the above-mentioned powder viscoelasticity adjusting agent, it exhibits excellent viscoelasticity and can impart high excavation performance.

  According to the production method of the present invention, the above powder viscoelasticity modifier can be produced efficiently. Therefore, a powder viscoelasticity modifier that can impart excellent viscoelasticity (particularly high thixotropy) without adversely affecting the environment can be easily prepared by the production method of the present invention.

  Kouma (Corchorus capsularis) is an annual herb and is cultivated in tropical and subtropical regions to collect fiber from its stem, and its leaves are usually discarded. The present inventors have found that this dried leaf pulverized product (A) can impart excellent viscoelasticity.

  The dried leaf pulverized product (A) is composed of polysaccharides, proteins, nucleic acids, fibers and the like, and is dispersed in water. However, the detailed chemical structure has not been elucidated.

  The shape of the dried leaf pulverized product (A) is not particularly limited, but at least 50 (preferably 60, more preferably 70, particularly preferably 80)% by weight of the dried leaf pulverized product (A) is JIS Z8801-1: It is preferable to pass through a metal net sieve having an opening of 600 μm as defined in 2006.

  The water content (% by weight) of the dried leaf pulverized product (A) is preferably 15 or less, more preferably 13 or less, particularly preferably 12 or less, and most preferably 11 from the viewpoints of workability (reducing stickiness) and spoilage. It is as follows. The moisture content is calculated from the weight of the measurement sample before and after 1 to 1.5 g of the measurement sample is dried by heating at 160 ° C. for 30 minutes.

  The dried leaf pulverized product (A) contains an alkali metal (such as sodium and potassium) atom and an alkaline earth metal (such as magnesium and calcium) atom. The alkali metal atom and the alkaline earth metal atom may be ionically bonded to the polysaccharide in the dried leaf pulverized product, or may form a mixture with the polysaccharide as another compound.

  The total content (% by weight) of alkali metal atoms and alkaline earth metal atoms is preferably 1-20, more preferably 5-15, particularly preferably 7-based on the weight of the dried leaf pulverized product (A). 12. Within this range, further excellent viscoelasticity is exhibited.

  The content of alkali metal atoms and alkaline earth metal atoms is measured according to JIS K0116: 2014, “General Rules for Emission Spectroscopic Analysis”.

  When the content of alkali metal atoms and alkaline earth metal atoms exceeds the upper limit of the above range, (1) a method of washing the Koma leaves with water before drying the Kouma leaves, (2) drying the Kouma leaves A method of washing with water later can be applied. In addition, it does not fall below the lower limit of the above range.

  The viscosity (η1; 25 ° C., Pa · s) of the 2% by weight dispersion of the powder viscoelasticity adjusting agent of the present invention is preferably 30 to 500, more preferably 40 to 400, particularly preferably 45 to 300, and most preferably. Is 50-250.

  Viscosity (η1) is a single-cylinder rotational viscometer [for example, a B-type viscometer (TVB-20L, Tokimec Co., Ltd.) according to JIS Z8803: 2011 for a 2% by weight aqueous dispersion of a powder viscoelasticity modifier. ] And viscosity at 60 rpm at 25 ° C.

  The TI value [(viscosity (η2)) / (viscosity (η1))] of a 2% by weight dispersion of the powder viscoelasticity adjusting agent of the present invention is preferably 1.5 to 4.0, more preferably 1.7. To 3.5, particularly preferably 1.8 to 3.0, and most preferably 2.0 to 2.8.

  The viscosity (η2) is a value measured in the same manner as the viscosity (η1) except that the rotation speed is changed from 60 rpm to 6 rpm.

  The powder viscoelasticity adjusting agent of the present invention preferably contains a compound having a polyoxyalkylene chain. Examples of the oxyalkylene group that can form a polyoxyalkylene chain include oxyalkylene (oxyethylene, oxypropylene, and oxybutylene) groups having 2 to 4 carbon atoms.

  The polyoxyalkylene chain may be composed of one kind of oxyalkylene group or may be composed of two or more kinds of oxyalkylene groups. When composed of two or more kinds of oxyalkylene groups, the bonding mode may be any of block, random and a mixture thereof.

  As the compound having such a polyoxyalkylene chain, the polyoxyalkylene compound (B) represented by the general formula (1) is preferable.

R- (OA) n-OR '(1)

  R is an acyl group having 2 to 30 carbon atoms, an alkyl or alkenyl group having 1 to 30 carbon atoms, or a hydrogen atom, R ′ is a hydrogen atom or an acyl group having 2 to 30 carbon atoms, and OA is an oxy having 2 to 4 carbon atoms. An alkylene group, n represents an integer of 2 to 100;

The acyl group having 2 to 30 carbon atoms includes a saturated acyl group and an unsaturated acyl group.
Saturated acyl groups include acetyl (ethanoyl), propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, octadecanoyl , Nonadecanoyl, icosanoyl, eicosanoyl, heicosanoyl, henecosanoyl, docosanoyl, tricosanoyl, tetracosanoyl, pentacosanoyl, hexacosanoyl, heptacosanoyl, octacosanoyl, nonacosanoyl and triacontanoyl.

  Unsaturated acyl groups include acryloyl, methacryloyl, crotonoyl, isocrotonoyl, butenoyl, butadienoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, cyclodecinoyl, oleroyl, cyclopentyl Heptanoyl, methylcyclopentanoyl, methylcyclohexanoyl, methylcycloheptanoyl, cyclopentenoyl, 2,4-cyclopentadenoyl, cyclohexenoyl, 2,4-cyclohexadenoyl, cycloheptenoyl, methyl Examples include cyclopentenoyl, methylcyclohexenoyl, and methylcycloheptenoyl.

  As a C1-C30 alkyl group and an alkenyl group, a C1-C30 linear alkyl group, a C5-C10 cyclic alkyl group, a C3-C30 branched alkyl group, C2-C2 30 linear alkenyl groups, cyclic alkenyl groups having 5 to 10 carbon atoms, and branched alkenyl groups having 3 to 30 carbon atoms are included.

  Examples of the linear alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl , Icosyl, henicosyl, docosyl, tricosyl, tetracosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and the like.

  Examples of the cyclic alkyl group having 5 to 10 carbon atoms include cyclopentyl, cyclohexyl and cyclodecyl.

  Examples of the branched alkyl group having 3 to 30 carbon atoms include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2-ethylhexyl, isotridecyl, isooctadecyl, and isotriacosyl.

  Examples of the straight-chain alkenyl group having 2 to 30 carbon atoms include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, , Henicocenyl, dococenyl, tricocenyl, tetracocenyl, hexacocenyl, heptacocenyl, octacocenyl, nonacosenyl and the like.

  Examples of the cyclic alkenyl group having 5 to 10 carbon atoms include cyclopentenyl, cyclohexenyl, cyclodecenyl and the like.

  Examples of the branched alkenyl group having 3 to 30 carbon atoms include isopropenyl, isobutenyl, isopentenyl, isohexenyl, 2-ethylhexenyl, isotridecenyl, isooctadecenyl and isotriacocenyl.

  OA represents an oxyalkylene group having 2 to 4 carbon atoms, and includes oxyethylene, oxypropylene, and oxybutylene. Of these, oxyethylene and oxypropylene are preferred.

  OA may contain two or more oxyalkylene groups. When two or more kinds of oxyalkylene groups are contained, any of block, random and a mixture thereof may be used, but a block of oxyethylene and oxypropylene is preferable.

  n represents an integer of 2 to 100, preferably an integer of 2 to 99, more preferably an integer of 3 to 60, particularly preferably an integer of 4 to 50, and most preferably an integer of 5 to 40. Within this range, further excellent viscoelasticity is exhibited.

  When the polyoxyalkylene compound (B) is contained, the content (% by weight) of the dried leaf pulverized product (A) is 95 based on the weight of the dried leaf pulverized product (A) and the polyoxyalkylene compound (B). To 99.99, more preferably 96 to 99.98, particularly preferably 97 to 99.95, and most preferably 98 to 99.93. In this case, the content (% by weight) of the polyoxyalkylene compound (B) is preferably 0.01 to 5, based on the weight of the dried leaf pulverized product (A) and the polyoxyalkylene compound (B). More preferably, it is 0.02-4, Most preferably, it is 0.05-3, Most preferably, it is 0.07-2. Within this range, further excellent viscoelasticity is exhibited.

  The polyoxyalkylene compound (B) can be easily obtained from the market, and examples thereof include the following products.

<Polyoxyalkylene glycol monoalkyl ether>
Newpole (registered trademark) series (LB-65, LB-385, LB-625, LB-1145, LB-1715, LB-1800X, PP-200, PP-950, PP-1000, PP-2000, PP- 3000, PP-4000, PP-5000, etc.) {Sanyo Chemical Industries Co., Ltd.}; Emarumin (registered trademark) series (40, 70, 110, CO-50, CO-100, CC-100, etc.) {Sanyo Chemical Industries Ltd. Company}; NAROACTY (registered trademark) series (CL-40, CL-50, CL-70, CL-85, CL-95, CL-100, CL-120, CL-140, ID-40, ID-60, ID-70 etc.) {Sanyo Chemical Industry Co., Ltd.}

<Polyoxyethylene glycol>
PEG200, 300, 400, 600, 1000, 2000, 4000N, 4000S, 20000 {Sanyo Chemical Industries, Ltd.}

<Polyoxyethylene glycol mono- or di-fatty acid ester>
Ionette (registered trademark) series (DL-200, DO-400, DO-600, DO-1000, MS-400, MS-1000, MO-200, MO-400, MO-600, etc.) {Sanyo Chemical Industries, Ltd. }

<Polyoxyethylene polyoxypropylene glycol>
New Pole (registered trademark) series (PE-61, PE-62, PE-64, PE-68, PE-71, PE-74, PE-75, PE-78, PE-108, etc.) {Sanyo Chemical Industries Ltd. Company}

  In the powder viscoelasticity adjusting agent of the present invention, in addition to the dried leaf pulverized product (A) and the polyoxyalkylene compound (B), other viscoelasticity adjusting agents and / or additives (an antifoaming agent, a dispersing agent, an emulsifier, Wetting agents, antioxidants, UV absorbers, deodorants, fragrances, anti-blocking agents, water-resistant agents, antiseptics and fungicides, etc.) and / or solvents {water, alcohols having 1 to 6 carbon atoms (methanol, Ethanol, ethylene glycol, diethylene glycol, etc.), C3-C6 ketones (methyl isobutyl ketone, acetone, etc.) and mixtures thereof, etc.}.

  Other viscoelastic modifiers include xanthan gum, locust bean gum, guar gum, carrageenan, alginic acid and its salts, starch, tragacanth gum, magnesium aluminum silicate, bentonite, polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, gelatin, agar and carboxyl groups Synthetic polymer type viscoelasticity modifiers (trade names such as SN thickener 636, SN thickener 641, SN thickener 617, etc .; San Nopco Corp.), associative thickeners containing polyoxyethylene chains (trade names such as , SN thickener 625N, SN thickener 665T, etc.) and viscoelasticity modifiers (extracted from the leaves of Kouma (Corchorus capsularis)) containing water-soluble polysaccharides extracted from the leaves of Kouma The extract (A) contains water-soluble polysaccharides, alkali metal atoms and alkaline earth metal atoms, and the total content of alkali metal atoms and alkaline earth metal atoms is extracted. Viscoelasticity adjusting agent characterized by 0.5 to 10% by weight based on the weight of the product (A); PCT / JP2015 / 078724) and the like.

  When other viscoelasticity adjusting agents and / or additives are contained, the total content (% by weight) is preferably 0.01 to 95, more preferably, based on the weight of the dried leaf pulverized product (A). Is 0.05 to 50, particularly preferably 0.1 to 30.

  When the solvent is contained, the content (% by weight) is preferably from 1 to 99.9, more preferably from 5 to 99.5, particularly preferably from 10 to 9, based on the weight of the dried leaf pulverized product (A). 99.

  There is no restriction | limiting in the form of the powder viscoelasticity regulator of this invention, When it consists only of dried leaf ground material (A), when it is a pulverized form and contains a polyoxyalkylene compound (B), an additive, and / or a solvent Depending on its content, it may be liquid.

  Although there is no restriction | limiting in particular as a manufacturing method of the powder viscoelasticity adjusting agent of this invention, Any may be sufficient as long as it includes the process of drying and grind | pulverizing a Kouma leaf. The raw Kouma leaf may be fresh or dry.

  It is preferable to dry the koma leaf (sun-drying or hot-air drying) and then crushing to obtain a dried pulverized product (A). Moreover, after crushing a leaf of a horse, you may dry (sun drying or warm air drying).

  For the pulverization, a known pulverizer such as a mortar, a juicer mixer, a homogenizer, a disk capitalization mixer, a colloid mill, a Henschel mixer, a coreless mixer, a high speed mixer, an attritor, a pin mill, a sand mill, or a ball mill can be used. Moreover, you may perform multi-order grinding | pulverization combining a grinder (multistage grinding | pulverization process).

  For the drying, a known method can be applied. For example, natural drying, hot air drying, freeze drying, or a drum drying method and a spray drying method may be applied.

  In the case where the powder viscoelasticity modifier of the present invention contains a polyoxyalkylene compound (B), an additive and / or a solvent, the production method is not limited as long as it is uniformly present together with the dried leaf pulverized product (A). The mixing method can be applied.

  The powder viscoelasticity adjusting agent of the present invention can be widely used as long as it is a liquid that requires adjustment of viscoelasticity, and is particularly effective for an aqueous solution or an aqueous dispersion. Application fields include, for example, fields such as chemical industry, food industry, petroleum industry, civil engineering and construction industry, textile industry, pulp and paper industry, paint and ink industry, metal industry, machine industry, ceramic industry or pharmaceutical industry. It is suitable in the construction industry field, and is particularly suitable as a powder viscoelasticity adjusting agent for application to excavation in the construction of building foundations and underground structures, mining of natural resources, and the like.

The liquid that requires adjustment of viscoelasticity may contain water-soluble substances (water-soluble alcohol, alkali metal ions, alkaline earth metal ions, etc.), earth and sand, and the like.
The addition amount of the powder viscoelasticity adjusting agent of the present invention is preferably such that the dried leaf pulverized product (A) is 1 to 50% by weight based on the weight of the liquid that needs to be adjusted for viscoelasticity.

Hereinafter, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
Put 100 parts of Kouma leaf (from Bangladesh) and 2000 parts of tap water into a stainless steel container, stir at 1000 rpm with a stirring motor for 15 minutes, then perform solid-liquid separation with a metal mesh sieve with an opening of 600 μm and wash. Leaves (Be1) were obtained.
The washed leaf (Be1) is spread on a stainless steel tray, dried at 70 ° C. for 5 hours in a smooth air dryer, and then pulverized in a mortar for 30 minutes to obtain a dried leaf pulverized product (a1) {metal mesh sieve having an opening of 600 μm. Passage: 80%, moisture content: 11%, total content of alkali metal atoms and alkaline earth metal atoms: 12%} was prepared and used as the powder viscoelasticity modifier (1) of the present invention.

<Example 2>
100 parts of Kouma leaf (from Bangladesh) and 2000 parts of ion-exchanged water were put into a stainless steel container, stirred at 1000 rpm with a stirring motor for 15 minutes, and then subjected to solid-liquid separation with a metal mesh sieve having an opening of 600 μm. Washed leaves (Be2) were obtained.
The washed leaf (Be2) is spread on a stainless steel tray, dried at 80 ° C. for 5 hours in a smooth air dryer, and then pulverized for 30 minutes with a high-speed mixer to obtain a dried leaf pulverized product (a2) {made of metal having an opening of 600 μm Screen sieve pass: 80%, moisture content: 10%, total content of alkali metal atoms and alkaline earth metal atoms: 10%} was prepared and used as the powder viscoelasticity modifier (2) of the present invention.

<Example 3>
99.9 parts of the dried leaf pulverized product (a2) was charged into a Henschel mixer, and the polyoxyalkylene compound (b1; polyoxyalkylene alkyl ether, NAROACTY CL-85, Sanyo Chemical Industries, Ltd.) 0. 01 parts were added, and it stirred for 30 minutes, and obtained the powder viscoelasticity modifier (3) of this invention.

<Example 4>
Koma leaves (from Bangladesh) were spread on a stainless steel tray, dried for 4 hours at 80 ° C. with a smooth air dryer, then ground for 30 minutes with a juicer mixer, and dried leaf ground product (a3) {opening 600 μm Metal mesh sieve passage: 85%, water content: 10%, total content of alkali metal atoms and alkaline earth metal atoms: 10%}, and this is used as the powder viscoelasticity modifier (4) of the present invention. did.

<Example 5>
99.9 parts of dried leaf pulverized product (a3) was put into a Henschel mixer, and while stirring this, 5 parts of a polyoxyalkylene compound (b2; polyoxyethylene glycol, PEG-600, Sanyo Chemical Industries, Ltd.), 30 The mixture was stirred for a while to obtain the powder viscoelasticity modifier (5) of the present invention.

<Example 6>
100 parts of Kouma leaf (from Bangladesh) and 3000 parts of ion-exchanged water were put into a stainless steel container, stirred at 1000 rpm with a stirring motor for 20 minutes, and then subjected to solid-liquid separation with a metal mesh sieve having an opening of 600 μm. Washed leaves (Be3) were obtained.
The washed leaves (Be3) were spread on a stainless steel tray, dried at 80 ° C. for 5 hours with a smooth air dryer, and then pulverized with a ball mill for 30 minutes to obtain a dried leaf pulverized product (a4) {metal mesh sieve with an opening of 600 μm. Passage: 90%, water content: 9%, total content of alkali metal atoms and alkaline earth metal atoms: 9%} was prepared and used as the powder viscoelasticity modifier (6) of the present invention.

<Example 7>
100 parts of Kouma leaf (from Bangladesh) and 1000 parts of ion-exchanged water were put into a stainless steel container, stirred at 1000 rpm with a stirring motor for 10 minutes, and then subjected to solid-liquid separation with a metal mesh sieve having an opening of 600 μm. Washed leaves (Be4) were obtained.
The washed leaf (Be4) was spread on a stainless steel tray, dried at 80 ° C. for 3 hours with a smooth air dryer, and then ground with a ball mill for 60 minutes to obtain a dried leaf pulverized product (a5) {metal mesh sieve with an opening of 600 μm. Passage: 100%, water content: 7%, total content of alkali metal atoms and alkaline earth metal atoms: 7%} was prepared and used as the powder viscoelasticity modifier (7) of the present invention.

<Comparative Example 1>
Methyl cellulose (Marporose (registered trademark) 25, Matsumoto Yushi Seiyaku Co., Ltd.) was used as a comparative powder viscoelasticity modifier (H1).

<Comparative example 2>
Methyl cellulose (60SH-25, Shin-Etsu Chemical Co., Ltd.) was used as a comparative powder viscoelasticity modifier (H2).

  Using the powder viscoelasticity modifiers (1) to (5) and (H1) to (H2) obtained in Examples and Comparative Examples and ion-exchanged water, a 2% aqueous dispersion or 2% aqueous solution was prepared. One minute later, these aqueous dispersions or aqueous solutions were subjected to viscosity measurement at 6 rpm and 60 rpm using a B-type viscometer (TVB-20L, Tokimec Co., Ltd.). And TI value was computed from the following formula.

TI value = (viscosity at 6 rpm) / (viscosity at 60 rpm)

  As shown in Table 1, the powder viscoelasticity adjusting agent of the present invention had a high TI value and excellent viscoelasticity compared to the comparative powder viscoelasticity adjusting agent. Moreover, since the powder viscoelasticity adjusting agent of the present invention has a natural material as a main component, it has no influence on the human body and the environment due to chemicals and is environmentally friendly.

Claims (6)

Containing dried leaf grind (A) of jute (burlap, Corchorus capsularis) ,
Powder viscoelastic modifier, wherein 1 to 20 der isosamples based on the weight of the total content of alkali metal atoms and alkaline earth metal atom (wt%) of the dried leaves pulverized (A). The powder viscoelasticity adjusting agent according to claim 1, wherein at least 50% by weight of the dried leaf pulverized product (A) passes through a metal mesh screen having an opening of 600 µm. The powder viscoelasticity adjusting agent according to claim 1 or 2, wherein the dry leaf pulverized product (A) has a water content of 15 wt% or less. Furthermore, it contains the polyoxyalkylene compound (B) represented by the general formula (1), and based on the weight of the dry leaf pulverized product (A) and the polyoxyalkylene compound (B), The powder viscoelasticity adjusting agent according to any one of claims 1 to 3, wherein the content of A) is 95 to 99.99% by weight, and the content of the polyoxyalkylene compound (B) is 0.01 to 5% by weight. .

R- (OA) n-OR '(1)

R is an acyl group having 2 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or a hydrogen atom, R ′ is a hydrogen atom or an acyl group having 2 to 30 carbon atoms, and OA is carbon The oxyalkylene group of number 2-4, n represents the integer of 2-100. Drilling mud characterized by containing the powder viscoelasticity regulator as described in any one of Claims 1-4. A method for producing the powder viscoelasticity modifier according to any one of claims 1 to 4,
A production method comprising a step of obtaining a dried leaf pulverized product (A) by drying and crushing leaves of kouma (Corchorus capsularis).