CN107108964B - Dissolving pulp composition and viscose fiber manufacturing method - Google Patents
Dissolving pulp composition and viscose fiber manufacturing method Download PDFInfo
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- CN107108964B CN107108964B CN201680004692.4A CN201680004692A CN107108964B CN 107108964 B CN107108964 B CN 107108964B CN 201680004692 A CN201680004692 A CN 201680004692A CN 107108964 B CN107108964 B CN 107108964B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B9/00—Cellulose xanthate; Viscose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/08—Synthetic cellulose fibres from regenerated cellulose
Abstract
The object of the present invention is to provide a dissolving pulp composition which can promote mercerization reaction. The dissolving pulp composition is characterized by comprising dissolving pulp and a mercerization accelerator which takes a surfactant (A) with HLB (hydrophile-lipophile balance) of 12-19 as an essential constituent. The mercerizing accelerator preferably contains at least 1 selected from the group consisting of a polyoxyalkylene compound (a1), a compound (a2) having at least 1 of a sulfo group, a sulfoxy group, or a phosphono group, and an amphoteric surfactant (A3).
Description
Technical Field
The present invention relates to a dissolving pulp composition and a method for producing viscose rayon.
Background
In order to promote mercerization of dissolving pulp in the production of viscose by the step of preparing alkali cellulose through mercerization (alkali cellularization) of dissolving pulp in an alkali solution, it is known to use "a transparent and uniform aqueous composition containing:
a)0.05 to 1% by weight of an alkylene oxide adduct of an alkyl branched alcohol and having the formula R1O(PO)m(CH2CH2O)nH (here, R)1Is a branched alkyl group having 8 to 12 carbon atoms; PO is propyleneoxy; m is a number of 0 to 3 and n is a number of 2 to 7);
b) 0.15-2 wt% of alkali metal hydroxide and/or an alkali complexing agent;
c)0.025 to 1.75% by weight of hexyl glucoside and/or octyl imido dipropionate;
d)0.025 to 1.25% by weight of a2 nd surface active nonionic alkylene oxide adduct having an HLB value of at least 6.4 according to the Davies (Davies) method,
the 2 nd surface-active nonionic alkylene oxide adduct has the formula R2O(C2H4O)x(AO)yH (wherein, R2Is an alkyl group having 9 to 20 carbon atoms; AO is an alkyleneoxy group having 3 to 4 carbon atoms; x is a number of 5 to 100 and y is a number of 0 to 4) "(patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4870555 (corresponding international patent application: WO2004/099355A1)
Disclosure of Invention
Problems to be solved by the invention
Even when a conventional aqueous composition is used, there is a problem that the mercerization reaction does not proceed sufficiently.
The object of the present invention is to provide a dissolving pulp composition which can promote mercerization reaction.
Means for solving the problems
The dissolving pulp composition of the present invention is characterized by containing dissolving pulp and a mercerization accelerator containing a surfactant (A) having HLB of 12 to 19 as an essential component.
The method for producing viscose rayon according to the present invention is characterized by comprising a step of obtaining alkali cellulose by mercerizing (alkali cellularization) reaction of the dissolving pulp composition.
ADVANTAGEOUS EFFECTS OF INVENTION
The dissolving pulp composition of the present invention can promote mercerization reaction. Therefore, when the dissolving pulp composition of the present invention is used, the mercerizing reaction can be efficiently (in a short time) and uniformly performed.
In the method for producing viscose rayon of the present invention, the dissolving pulp composition is used, so that the mercerization reaction is promoted and the alkali cellulose can be efficiently obtained. Therefore, the productivity of the viscose yarn can be greatly improved by the method for producing the viscose yarn of the present invention.
Detailed Description
The raw material sheet for dissolving pulp may be any of wood { coniferous trees, broadleaf trees, and the like }, and non-wood { herbs (kenaf, bagasse, bamboo, and the like) }, and is not particularly limited, and wood having a high volume weight may be suitably used in consideration of production efficiency. Examples of the broad-leaved tree include: eucalyptus globulus, Eucalyptus grandis (Eucalyptus grandis), Eucalyptus urophylla (Eucalyptus urodera dis), Eucalyptus robusta (Eucalyptus pellita), Eucalyptus erythrinae (Eucalyptus camaldulensis), Eucalyptus globulus (Eucalyptus brassiana), and Acacia mearnsii (Acacia mearnsii). Examples of the coniferous tree include: radiata pine, caribbean pine (Pinus caribaea), Douglas fir (Douglas fir), hemlock, Redwood, Larch (Larch), and the like. Needless to say, coniferous trees, broadleaf trees, and nonwood may be used alone or in combination, and the combination is not particularly limited.
The dissolving pulp can be produced by any of acid sulfite cooking, alkali cooking (kraft cooking, polysulfide cooking, soda cooking, alkali sulfite cooking), and the like, and is not particularly limited. The kraft cooking method can be suitably used in consideration of the quality of dissolving pulp, energy efficiency, and the like. The following describes a method for producing dissolving pulp by the kraft cooking method, but the method is not limited thereto.
In order to produce dissolving pulp by the kraft cooking method, sheets of wood or the like are heated in the presence of water to be subjected to prehydrolysis treatment. The pre-hydrolysis strength is preferably 200 to 1000 in the form of P factor, the temperature is preferably 160 to 170 ℃, and the treatment temperature is determined according to the treatment time. It should be noted that the P factor is calculated from the temperature and time of the prehydrolysis. The apparatus used in the pre-hydrolysis step is not particularly limited, and a general-purpose continuous digester, batch cooker (Batchkettle), or the like can be suitably used.
The chips (chips) of the above-mentioned hydrolyzed wood and the like are sent to an alkali cooking step. The apparatus used for the alkali cooking is not particularly limited, and a general-purpose continuous cooker, batch cooker, or the like can be suitably used. When the wood is steamed by the sulfate method, the degree of vulcanization of the sulfate method steaming liquid is preferably 20 to 35%, the effective alkali addition rate per absolute dry weight of the wood is preferably 10 to 25% by weight, the steaming temperature is 140 to 170 ℃, the steaming method can be a steaming method in which the steaming white liquid is added in batches, and the mode is not particularly limited.
The kappa number of the unbleached pulp obtained by the alkali cooking is not particularly limited, and considering the quality of the dissolving pulp and the subsequent bleaching property, the kappa number is preferably 6 to 18 when broad-leaved trees are used as the raw material, and is preferably 20 to 35 when coniferous trees are used as the raw material.
The unbleached pulp is subjected to washing, rougher dressing and cleaner steps, preferably to a delignification treatment by a known oxygen delignification process, and then to a bleaching treatment by a known bleaching process (to obtain a bleached pulp). The bleaching step is usually a multi-stage bleaching step combining bleaching stages of chlorine dioxide, alkali, oxygen, hydrogen peroxide and ozone, and unbleached pulp is finally bleached to a whiteness degree of 87 to 92% ISO, preferably 89 to 92% ISO, to obtain a dissolving pulp.
The main components of bleached pulp are cellulose and hemicellulose, and impurities such as lignin and resin components are contained. In addition, in the bleached pulp, the dissolving pulp contains 95-99 wt% of cellulose and 1-5 wt% of hemicellulose, and the paper pulp for paper making contains about 85 wt% of cellulose and about 15 wt% of hemicellulose. On the other hand, cotton is more than 99% by weight cellulose and hemicellulose is less than 1% by weight.
The surfactant (A) which is an essential constituent of the mercerizing accelerator has an HLB (hydrophile lipophile balance) of 12 to 19, preferably 13 to 18, and particularly preferably 14 to 17. When the amount is within this range, the mercerizing reaction can be further promoted.
HLB denotes the Balance of organic and inorganic properties, and is an abbreviation for Hydrophile-Lipophile Balance. The HLB is a value obtained by the Tankian method, and is a value calculated from an organic value and an inorganic value by the following formula (Sedan, Temple, book "Synthesis and application of surfactant", page 501, book Omaki, 1957; Tanbian Wuyan & gt, New surfactant, Yongmen, pp 197-198, Sanyo chemical Industrial Co., Ltd., 1985; corresponding English book "New Integrated Circuit to surface Active Agents", page 196-197, 1985).
(HLB) — (inorganic value) ÷ (organic value) × 10
The surfactant (a) having HLB within the above range includes known surfactants, and is suitably at least 1 selected from the group consisting of a polyoxyalkylene compound (a1), a compound (a2) having at least 1 of a sulfo group, a sulfoxy group, or a phosphono group, and an amphoteric surfactant (A3). Among these, preferred is a polyoxyalkylene compound (A1) having a sulfo group,
The compound (a2) having at least 1 of a sulfoxy group or a phosphono group, more preferably the polyoxyalkylene compound (a1), and particularly preferably the compound represented by the general formula (1).
R1[(-OA)n-OR2]m(1)
R1Represents hydrogenAn atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms or a reaction residue obtained by removing m hydroxyl groups from a polyhydric alcohol; r2Represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an acyl group having 2 to 30 carbon atoms; OA represents an oxyalkylene group having 2 to 4 carbon atoms; n represents an integer of 2 to 100; m represents an integer of 1 to 6.
A hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms, a reaction residue (R) obtained by removing m hydroxyl groups from a polyhydric alcohol1) In the alkyl group having 1 to 30 carbon atoms, a straight-chain alkyl group, a branched-chain alkyl group, or the like can be used.
Examples of the straight-chain alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups, and the like.
As the branched alkyl group, there can be exemplified: isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, isotridecyl, isotetradecyl, isooctadecyl, isotridecyl, 2-ethylhexyl, 8-methyl-1-nonyl, 2-propylheptyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl (2-butyltetradecyl), 2-dodecylhexadecyl, 3, 5, 5-trimethylhexyl, and 3, 7, 11-trimethyldodecyl, and the like.
In addition, R1Among them, as the alkenyl group having 2 to 30 carbon atoms, a linear alkenyl group, a branched alkenyl group, and the like can be used.
As the linear alkenyl group, there may be mentioned: vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl and triacontenyl, and the like.
As the branched alkenyl group, there may be mentioned: isobutenyl, isopentenyl, neopentynyl, isohexenyl, isotridecyl, isostearyl, and isotridecyl, and the like.
In addition, R1Among them, as the acyl group having 2 to 30 carbon atoms, a saturated aliphatic acyl group, an unsaturated aliphatic acyl group, an alicyclic acyl group, an aromatic acyl group, and the like can be used.
Examples of the saturated aliphatic acyl group include: acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, isotridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl and the like.
Examples of the unsaturated aliphatic acyl group include: acryloyl, methacryloyl, crotonyl, isocrotonyl, crotonyl, butadienoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, tetradecenoyl, oleoyl, elaidoyl, and the like.
Examples of the alicyclic acyl group include: cyclopentoyl, cyclohexoyl, cycloheptoyl, methylcyclopentanoyl, methylcyclohexoyl, methylcyclocycloheptoyl, cyclopentenoyl, 2, 4-cyclopentadienoyl, cyclohexenoyl, 2, 4-cyclohexadieneacyl, cycloheptenoyl, methylcyclopentenoyl, methylcyclohexenoyl, and methylcycloheptenoyl, and the like.
As the aromatic acyl group, there may be mentioned: benzoyl, methylbenzoyl, cinnamoyl, naphthoyl, and the like.
In addition, R1Among them, the polyol which can constitute a reaction residue obtained by removing m hydroxyl groups from the polyol includes: dihydric alcohols (aliphatic diols, alicyclic diols and aromatic diols),Trihydric alcohols (aliphatic triol, alicyclic triol, and aromatic triol), tetrahydric alcohols (aliphatic tetraol, alicyclic tetraol, and aromatic tetraol), pentahydric alcohols (aliphatic pentahydric alcohol, alicyclic pentahydric alcohol, and aromatic pentahydric alcohol), and hexahydric alcohols (aliphatic hexahydric alcohol, alicyclic hexahydric alcohol, and aromatic hexahydric alcohol).
The aliphatic diol includes aliphatic diols having 2 to 18 carbon atoms, and examples thereof include: ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, diethyl propylene glycol, hydroxyoctadecenol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylpentanediol, bis (hydroxyethyl) sulfide and the like.
The alicyclic diol includes alicyclic diols having 8 to 15 carbon atoms, and examples thereof include: 1, 4-cyclohexanedimethanol, 4' -dihydroxybicyclohexane, dihydroxydicyclohexyldimethylmethane, and the like.
The aromatic diol includes aromatic diols having 6 to 15 carbon atoms, and examples thereof include: catechol, hydroquinone, bisphenol a, bisphenol F, bisphenol S, 1, 4-dihydroxynaphthalene, and the like.
The aliphatic triol includes aliphatic triols having 3 to 11 carbon atoms, and examples thereof include: glycerin, trimethylolethane, trimethylolpropane, trimethyloloctane, hexanetriol, and the like.
The alicyclic triol includes alicyclic triols having 6 to 15 carbon atoms, and examples thereof include: trihydroxycyclohexane, trihydroxydicyclohexyl and trihydroxydicyclohexyldimethylmethane.
The aromatic triol includes an aromatic triol having 6 to 15 carbon atoms, and includes: trihydroxybenzene, trihydroxybiphenyl, trihydroxydiphenyldimethylmethane, etc.
The aliphatic tetraol includes aliphatic tetraols having 5 to 12 carbon atoms, and includes: diglycerin, pentaerythritol, trimethylol pentane, di (trimethylol) pentane, and the like.
The alicyclic tetrol includes alicyclic tetrols having 6 to 15 carbon atoms, and includes: tetrahydroxycyclohexane, tetrahydroxybicyclohexane, sorbitan, tetrahydroxydicyclohexyldimethylmethane, and the like.
The aromatic tetraol includes aromatic tetraols having 6 to 15 carbon atoms, and includes: tetrahydroxybenzene, tetrahydroxybiphenyl, tetrahydroxydiphenyldimethylmethane, and the like.
The aliphatic pentaol includes aliphatic pentaols having 5 to 9 carbon atoms, and examples thereof include: triglycerol, xylitol, and the like.
The alicyclic pentaol includes alicyclic pentaols having 6 to 12 carbon atoms, and examples thereof include pentahydroxycyclohexane, pentahydroxybicyclohexane, pentahydroxydicyclohexyldimethylmethane, and hydroquinone- β -D-glycoside.
The aromatic pentaol includes aromatic pentaols having 6 to 15 carbon atoms, and examples thereof include: pentahydroxybenzene, pentahydroxybiphenyl, pentahydroxydiphenyldimethylmethane, and the like.
The aliphatic hexaol includes aliphatic hexaols having 6 to 12 carbon atoms, and examples thereof include: sorbitol, tetraglycerol, dipentaerythritol, and the like.
The alicyclic hexaol includes alicyclic hexaols having 6 to 15 carbon atoms, and examples thereof include: hexahydroxycyclohexane, hexahydroxydicyclohexyl, and hexahydroxydicyclohexyldimethylmethane.
The aromatic hexaol includes aromatic hexaols having 6 to 15 carbon atoms, and examples thereof include: hexahydroxybenzene, hexahydroxybiphenyl, hexahydroxydiphenyldimethylmethane, and the like.
These reaction residues obtained by removing m hydroxyl groups do not necessarily mean reaction residues obtained by removing all hydroxyl groups of the polyol, and include cases where some of the hydroxyl groups remain in the reaction residues. Therefore, the number of hydroxyl groups of the polyol does not always match the value of m. That is, the relationship between the number(s) of hydroxyl groups in the polyol and the number (m) of hydroxyl groups removed is s.gtoreq.m.
R1Among them, from the viewpoint of promoting the mercerizing reaction, preferred are an alkyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an acyl group having 2 to 22 carbon atoms and a reaction residue obtained by removing m hydroxyl groups from a polyhydric alcohol, more preferred are an alkyl group having 3 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an acyl group having 12 to 18 carbon atoms and a reaction residue obtained by removing m hydroxyl groups from a2 to 6-membered alcohol, particularly preferred are an alkyl group having 3 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms and an acyl group having 12 to 18 carbon atoms, and most preferred are a dodecanyl group, a decadecanoyl group and a decadecanoyl groupDialkyl, dodecenyl, 2-ethylhexyl, and 8-methyl-1-nonyl.
A hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms (R)2) And R1Are the same as those of (a). R2Among them, from the viewpoint of promoting the mercerizing reaction, a hydrogen atom, an alkyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, and an acyl group having 2 to 22 carbon atoms are preferable, a hydrogen atom, an alkyl group having 3 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, and an acyl group having 3 to 18 carbon atoms are more preferable, and a hydrogen atom, a dodecanoyl group, an octadecanoyl group, an oleoyl group, a dodecyl group, an octadecyl group, a dodecenyl group, and an octadecenyl group are particularly preferable.
The oxyalkylene group (OA) having 2 to 4 carbon atoms includes oxyethylene group, oxypropylene group and oxybutylene group. Among these, oxyethylene and oxypropylene are preferable from the viewpoint of promoting the mercerizing reaction.
(-OA)nWhen the compound is composed of 2 or more oxyalkylene groups, the bonding system of n oxyalkylene groups may be block or random or a combination thereof. In addition, m (-OA)n-O-R2May be the same or different.
n is preferably an integer of 2 to 100, more preferably an integer of 4 to 80, particularly preferably an integer of 6 to 60, and most preferably an integer of 8 to 50. When the amount is within this range, the mercerizing reaction can be further promoted.
m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3. When the amount is within this range, the mercerizing reaction can be further promoted.
The polyoxyalkylene compound (A1) can be produced by a known method (Japanese patent application laid-open Nos. 2003-268291 and 9-117607).
Examples of the polyoxyalkylene compound (a1) include: 10 mol ethylene oxide adduct of 2-ethylhexanol (HLB 14), 30 mol ethylene oxide adduct of 2-ethylhexanol (HLB 17), 11 mol ethylene oxide/1 mol propylene oxide block adduct of 2-ethylhexanol (HLB 14), 60 mol ethylene oxide/20 mol propylene oxide block adduct of 2-ethylhexanol (HLB 14), 12 mol ethylene oxide adduct of 8-methyl-1-nonanol (HLB 14), 15 mol ethylene oxide adduct of 8-methyl-1-nonanol (HLB 14), 40 mol ethylene oxide adduct of 8-methyl-1-nonanol (HLB 17), 1 mol propylene oxide/14 mol ethylene oxide block adduct of 8-methyl-1-nonanol (HLB 14), 20 mol of propylene oxide per 60 mol of ethylene oxide of 8-methyl-1-nonanol (HLB 14), 12 mol of ethylene oxide of 1-dodecanol (HLB 14), 21 mol of ethylene oxide of 1-dodecanol (HLB15), 40 mol of ethylene oxide per 3 mol of propylene oxide of 1-dodecanol (HLB 14), 45 mol of ethylene oxide of 1-dodecanol (HLB 17), 1 mol of propylene oxide per 20 mol of ethylene oxide of 1-dodecanol (HLB 14), 20 mol of propylene oxide per 60 mol of ethylene oxide of 1-dodecanol (HLB 14), 18 mol of ethylene oxide of dodecenol (HLB 14), 45 mol of ethylene oxide of dodecenol (HLB 17), A block adduct of 1 mol of propylene oxide/16 mol of ethylene oxide of dodecenol (HLB 14), a block adduct of 20 mol of propylene oxide/60 mol of ethylene oxide of dodecenol (HLB 14), a lauric diester of polyoxyethylene glycol (number average molecular weight 2000) (HLB15), a stearic acid monoester of polyoxyethylene glycol (number average molecular weight 1000) (HLB 14), a lauric acid ester of a block adduct of 1 mol of propylene oxide/30 mol of ethylene oxide of 2-ethylhexanol (HLB 14), a block adduct of 25 mol of ethylene oxide/3 mol of propylene oxide of 2-ethylhexanol (HLB15), a block adduct of 30 mol of ethylene oxide/3 mol of propylene oxide of 2-ethylhexanol (HLB16), a stearic acid ester of a block adduct of 1 mol of propylene oxide/14 mol of ethylene oxide of 8-methyl-1-nonanol (HLB 14), and mixtures thereof, Lauric acid diester (HLB15) of polyoxyethylene glycol (number average molecular weight 2000), ethylene oxide 30 mol adduct (HLB15) of glycerin, propylene oxide 3 mol/ethylene oxide 9 mol block adduct (HLB 14) of glycerin, stearic acid monoester (HLB15) of ethylene oxide 30 mol adduct of glycerin, ethylene oxide 16 mol/propylene oxide 4 mol block adduct (HLB15) of tetrahydroxycyclohexane, and the like.
Among the polyoxyalkylene compounds (a1), examples of compounds other than the compound represented by the general formula (1) include: oxyalkylene adducts of castor oil and oxyalkylene adducts of sucrose, and the like.
Examples of the compound (A2) having at least 1 of sulfo, sulfoxy or phosphono groups include α -olefin sulfonate, alkylbenzene sulfonic acid and its salt { for example, sodium dodecylbenzenesulfonate (HLB 14) }, naphthalenesulfonate-formaldehyde condensate, N-acylalkyltaurates, alkyl sulfate ester salts, alkyl ether sulfate ester salts { for example, sodium salt (HLB15) of lauryl alcohol ethylene oxide 3 mol adduct sulfate ester, alkyl sulfosuccinate, alkyl phosphate and polyoxyethylene alkyl ether phosphate.
As the amphoteric surfactant (a3), there can be mentioned: higher alkyl aminopropionates, higher alkyl dimethyl betaines, and the like.
The mercerizing accelerator may be composed of only 1 kind of surfactant, or may be composed of a plurality of kinds of surfactants, as long as the surfactant (a) is an essential constituent component.
The mercerizing accelerator preferably contains a polyoxyalkylene compound (B) having an HLB (Tata-Korea) of 1 to 7 in addition to a surfactant (A) having an HLB (Tata-Korea) of 12 to 19.
The HLB of the polyoxyalkylene compound (B) is preferably 1 to 7, and more preferably 2 to 6. When the amount is within this range, the mercerizing reaction can be further promoted.
As the polyoxyalkylene compound (B), a polyoxyalkylene compound (B) having the same chemical structure as the compound represented by the general formula (1) and having HLB (kohlrabi) within the above range can be used.
The polyoxyalkylene compound (B) can be produced by a known method (Japanese patent application laid-open Nos. 2003-268291 and 9-117607).
Examples of the polyoxyalkylene compound (B) include: propylene oxide 4 mole adduct of butanol (HLB4), propylene oxide 5 mole adduct of butanol (HLB4), propylene oxide 50 mole adduct of butanol (HLB4), propylene oxide 5 mole adduct of octadecanol (HLB2), propylene oxide 8 mole adduct of octadecanol (HLB2), propylene oxide 50 mole adduct of octadecanol (HLB4), polyoxypropylene (number average molecular weight 400, HLB4), polyoxypropylene (number average molecular weight 4000, HLB4), propylene oxide 3 mole adduct of glycerol (HLB6), propylene oxide 69 mole adduct of glycerol (HLB4), ethylene oxide 5 mole/propylene oxide 30 mole block copolymer (HLB6), ethylene oxide 1 mole/propylene oxide 30 mole block adduct of 2-ethylhexanol (HLB4), ethylene oxide 5 mole/propylene oxide 30 mole block adduct of 2-ethylhexanol (HLB5), A block adduct of 1-dodecanol with 10 moles of ethylene oxide per 30 moles of propylene oxide (HLB6), a block adduct of 1-dodecanol with 1 mole of ethylene oxide per 30 moles of propylene oxide (HLB4), a block adduct of 1-dodecanol with 5 moles of ethylene oxide per 20 moles of propylene oxide (HLB6), a lauric acid monoester of a propylene oxide 3 mole adduct of glycerin (HLB4), a stearic acid diester of polyethylene glycol (number average molecular weight 200) (HLB5), and the like.
When the polyoxyalkylene compound (B) is contained, the content (% by weight) of the surfactant (A) is preferably 60 to 99, and more preferably 70 to 95 based on the weight of the surfactant (A) and the polyoxyalkylene compound (B). In this case, the content (% by weight) of the polyoxyalkylene compound (B) is preferably 1 to 40, more preferably 5 to 30, based on the weight of the surfactant (a) and the oxyalkylene compound (B).
The mercerizing accelerator may contain a solvent (C) and other additives (D).
The solvent (C) includes water or a mixed solvent of water and a hydrophilic organic solvent. As the hydrophilic organic solvent, there may be mentioned: esters having 4 to 8 carbon atoms { ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, etc. }, ethers having 4 to 8 carbon atoms { ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. }, ketones having 3 to 8 carbon atoms { acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. }, alcohols having 1 to 8 carbon atoms { methanol, ethanol, N-or isopropanol, N-or iso-tert-butanol, propylene glycol, dipropylene glycol, etc. }, and heterocyclic compounds having 5 to 8 carbon atoms { N-methylpyrrolidone, etc. }.
As other additives (D), there may be mentioned: known additives { dispersing agents, thickeners, fluidity improvers, antioxidants, ultraviolet absorbers, deodorants, perfumes, dyes, preservatives, and the like }.
When the mercerizing accelerator is composed of a plurality of components, the mercerizing accelerator can be obtained by uniformly mixing the plurality of components.
The content (% by weight) of the mercerizing accelerator is not particularly limited, and is preferably 0.01 to 1, more preferably 0.03 to 0.5, and particularly preferably 0.05 to 0.2 based on the absolute dry weight of the dissolving pulp. When the amount is within this range, the mercerizing reaction can be further promoted.
Absolute dry weight of dissolving pulp according to JIS P8203: 2010 (corresponding to international specification; ISO 638: 2008), at 105 ℃.
The dissolving pulp composition of the present invention is not particularly limited as long as it contains a mercerization accelerator and dissolving pulp, and the mercerization accelerator may be sprayed or applied to the dissolving pulp or the dissolving pulp may be immersed in the mercerization accelerator. From the viewpoint of simplicity of equipment design, it is preferable to spray or coat a mercerization accelerator onto the dissolving pulp. In such a production method, the mercerizing accelerator may be diluted with the solvent (C) or the like for use in view of workability.
The form of the dissolving pulp composition of the present invention is not limited, and the dissolving pulp composition may be formed into a sheet form. In the case of forming a sheet, the sheet may contain a surfactant as a whole, or at least one surface layer of the sheet may contain a surfactant. The method of adding the surfactant is not particularly limited. The surfactant may be added to the inside of the suspension containing the dissolving pulp and then formed into a sheet, or the surfactant may be added (impregnated, sprayed, or coated) to the outside of the dissolving pulp after formed into a sheet. By the external addition, the surface layer portion of the sheet can contain a surfactant. The sheet may be formed in a wound shape.
The method for producing viscose rayon of the present invention is not particularly limited as long as it comprises a step of mercerizing (alkali-cellularizing) the above-mentioned dissolving pulp composition to obtain alkali cellulose, and a known step may be combined.
In the mercerization reaction, a known mercerization treatment liquid (an alkaline solution or the like) can be used, and the temperature, time, and the like of the mercerization reaction can be applied in a known range.
The method for producing viscose rayon according to the present invention comprises a step of mixing alkali cellulose and carbon disulfide to obtain viscose (cellulose xanthate sodium salt) (the step of obtaining alkali cellulose and the step of obtaining viscose may be performed in parallel) after the step of obtaining alkali cellulose, and a spinning step of ejecting viscose from a fine hole into dilute sulfuric acid to obtain viscose rayon.
The viscose obtained by using the dissolving pulp composition of the present invention as a raw material has a high solubility, and is characterized in that an appropriate aqueous solution viscosity can be obtained, and viscose can be efficiently obtained by the high solubility, and viscose can be efficiently produced by preventing trouble in spinning due to low viscosity and reduction in spinning speed due to high viscosity, and viscose can be further obtained with an appropriate aqueous solution viscosity range, that is, an appropriate polymerization degree range, and thus can maintain necessary strength of rayon fiber.
Examples
Parts and% are parts by weight and% by weight, unless otherwise specified.
< example 1>
To a sheet formed of dissolving pulp (prepared from broadleaf tree, cellulose content 98%, weight per unit area 800 g/m)2) After spraying 5 parts of a diluted solution of 0.1 part of ethylene oxide 30 mol adduct of 2-ethylhexanol (HLB 17, BLANONEH-30, manufactured by Rauwolf oil and fat industries, Ltd.) as a mercerizing accelerator (1) and 4.9 parts of water, 100 parts thereof were mixed and the mixture was cooled to room temperature (25 to 30 ℃ C., the same applies hereinafter). ) Then, the resulting mixture was air-dried to obtain a dissolving pulp composition (1) of the present invention.
< example 2>
A dissolving pulp composition (2) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the ethylene oxide 30 mol adduct of { 2-ethylhexanol (HLB 17) } was changed to 0.1 part of the ethylene oxide 15 mol adduct of { 8-methyl-1-nonanol (HLB 14, noise SD-150, first industrial pharmaceutical company, "noise" is a registered trademark of this company) } of the mercerization accelerator (2).
< example 3>
A dissolving pulp composition (3) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the ethylene oxide 30 mol adduct of { 2-ethylhexanol (HLB 17) } as the mercerizing accelerator (1) was changed to 0.1 part of the ethylene oxide 21 mol adduct of { 1-dodecanol (HLB15, BLAUNON EL-1521, manufactured by Rauwolf oil and fat industries, Ltd.) }.
< example 4>
A dissolving pulp composition (4) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the mercerization accelerator (1) { 30 mol of ethylene oxide/3 mol of propylene oxide block adduct of 2-ethylhexanol (HLB16) } was changed to 0.1 part of the mercerization accelerator (4) { 2-ethylhexanol (HLB 17) }. Incidentally, a block adduct of 2-ethylhexanol with 30 moles of ethylene oxide/3 moles of propylene oxide was prepared by a well-known alkylene oxide addition reaction.
< example 5>
A dissolving pulp composition (5) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the mercerizing accelerator (1) { 30 mol of ethylene oxide adduct of 2-ethylhexanol (HLB 17) } was changed to 0.1 part of lauric acid ester of 40 mol of ethylene oxide/3 mol of propylene oxide block adduct of 1-dodecanol (HLB 14) } of the mercerizing accelerator (5). It is to be noted that the laurate of a block adduct of 1-dodecanol having 40 moles of ethylene oxide/3 moles of propylene oxide was prepared by the well-known alkylene oxide addition reaction and esterification reaction.
< example 6>
A dissolving pulp composition (6) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the mercerization accelerator (1) { 30 mol adduct of ethylene oxide (HLB 17) } of 2-ethylhexanol was changed to 0.1 part of the mercerization accelerator (6) { 10 mol adduct of ethylene oxide (HLB 14) } of 2-ethylhexanol. The ethylene oxide 10 mol adduct of 2-ethylhexanol was prepared by a known alkylene oxide addition reaction.
< example 7>
A dissolving pulp composition (7) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the ethylene oxide 30-mole adduct of { 2-ethylhexanol (HLB 17) } as a mercerizing accelerator (1) { sodium dodecylbenzenesulfonate (HLB 14, nepelex G-15, kawakaki co., ltd. "nepelex" is a registered trademark of this company) } was changed to 0.1 part of the mercerizing accelerator (7).
< example 8>
A dissolving pulp composition (8) of the present invention was obtained in the same manner as in example 1 except that 0.1 part of the ethylene oxide 30 mol adduct of { 2-ethylhexanol (HLB 17) } of the mercerizing accelerator (1) { 8) { 1-dodecanol ethylene oxide 21 mol adduct (HLB15, BLANON EL-1521, manufactured by Qingmu oil & fat industries Co., Ltd.) and 90 parts of a butanol propylene oxide 5 mol adduct (HLB4, Newpol LB-65, manufactured by Sanyo chemical industries, Ltd. "Newpol" is a registered trademark of the same Co., Ltd.) were uniformly mixed together to obtain }0.1 part of the dissolved pulp composition (8).
< example 9>
A dissolving pulp composition (9) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the mercerizing accelerator (1) { 30 mol of ethylene oxide adduct of 2-ethylhexanol (HLB 17) } was changed to 0.1 part of the mercerizing accelerator (9) { 25 mol of ethylene oxide/3 mol of propylene oxide block adduct of 2-ethylhexanol (HLB15) and 0.1 part of propylene oxide 8 mol adduct of stearyl alcohol (HLB2) which were uniformly mixed. It is to be noted that a block adduct of 2-ethylhexanol with 25 moles of ethylene oxide/3 moles of propylene oxide was prepared by a well-known alkylene oxide addition reaction.
< example 10>
A dissolving pulp composition (10) of the present invention was obtained in the same manner as in example 1 except that 0.1 part of the mercerizing accelerator (1) { 30-mole ethylene oxide adduct of 2-ethylhexanol (HLB 17, BLAMINON EH-30, manufactured by Qingmu oil & fat industries, Ltd.) was changed to 0.1 part of the mercerizing accelerator (10) { 30-mole ethylene oxide adduct of 2-ethylhexanol (HLB 17, BLAMINON EH-30, manufactured by Qingmu oil and fat industries, Ltd.) and 5 parts of polyoxypropylene glycol (number average molecular weight 4000, HLB4, Newpol PP-4000, manufactured by Sanyo chemical industries, Ltd.) were uniformly mixed to obtain }0.1 part of the product.
< example 11>
A dissolving pulp composition (11) of the present invention was obtained in the same manner as in example 1 except that 0.1 part of the mercerizing accelerator (1) { 30 mol ethylene oxide adduct of 2-ethylhexanol (HLB 17) } was changed to 0.1 part of the mercerizing accelerator (11) { 21 mol ethylene oxide adduct of 1-dodecanol (HLB15, BLAUNON EL-1521, manufactured by Rauwolf oil and fat industries Co., Ltd.) and 0.1 part of the block ethylene oxide 5 mol of 1-dodecanol/20 mol propylene oxide adduct (HLB6) were uniformly mixed. It is to be noted that a block adduct of 1-dodecanol with 5 moles of ethylene oxide/20 moles of propylene oxide was prepared by a well-known alkylene oxide addition reaction.
< example 12>
A dissolving pulp composition (12) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the mercerizing accelerator (1) { 30 mol ethylene oxide adduct of 2-ethylhexanol (HLB 17) } was changed to 0.1 part of the mercerizing accelerator (12) { 21 mol ethylene oxide adduct of 1-dodecanol (HLB15, BLAUNON EL-1521, manufactured by Rauwolf oil and fat industries Co., Ltd.) and 0.1 part of the lauric acid monoester of 3 mol propylene oxide adduct of glycerin (HLB4) were uniformly mixed. The lauric acid monoester of the propylene oxide 3 mol adduct of glycerin is produced by a known alkylene oxide addition reaction and esterification reaction.
< example 13>
A dissolving pulp composition (13) of the present invention was obtained in the same manner as in example 1, except that 0.1 part of the ethylene oxide 30 molar adduct of { 2-ethylhexanol (HLB 17) } as the mercerizing accelerator (1) { 1-dodecanol (HLB15, BLAUNON EL-1521, manufactured by Rauwolf oil and fat industries Co., Ltd.) was changed to 0.1 part of the mixture of 90 parts of the ethylene oxide 21 molar adduct of the mercerizing accelerator (13) { 1-dodecanol (HLB15, Blaunon EL-1521, manufactured by Rauwolf oil and fat industries, Ltd.) and 10 parts of the stearic acid diester (HLB5) of polyethylene glycol (number average molecular weight 200. The stearic acid diester of polyoxyethylene glycol (number average molecular weight 200) is prepared by a known alkylene oxide addition reaction and esterification reaction.
< example 14>
To a sheet formed of dissolving pulp (prepared from broadleaf tree, cellulose content 98%, weight per unit area 800 g/m)2) After spraying 5 parts of a diluted solution composed of 0.05 part of ethylene oxide 30 molar adduct of 2-ethylhexanol (HLB 17) as a mercerizing accelerator (1) and 4.95 parts of water, 100 parts thereof were dried at room temperature to obtain a dissolved pulp composition (14) of the present invention.
< example 15>
To a sheet formed of dissolving pulp (prepared from broadleaf tree, cellulose content 98%, weight per unit area 800 g/m)2) After spraying 5 parts of a diluted solution composed of 0.2 part of ethylene oxide 30 mole adduct of 2-ethylhexanol (HLB 17) as a mercerizing accelerator (1) and 4.8 parts of water, 100 parts thereof were dried at room temperature to obtain a dissolved pulp composition (15) of the present invention.
< comparative example 1>
A comparative dissolving pulp composition (H1) was obtained in the same manner as in example 1, except that 0.1 part of the mercerizing accelerator (1) { 30-mole adduct of ethylene oxide (HLB 17) } of 2-ethylhexanol was changed to 0.1 part of water.
< evaluation of acceleration of mercerizing reaction >
For each of the dissolving pulp compositions prepared in examples 1 to 15 and comparative example 1, 361mL of a 13.7% aqueous sodium hydroxide solution was separated from each dissolving pulp composition (14.4 g in absolute dry weight) to obtain a pulp, 8mL of carbon disulfide was added thereto, and a mercerization reaction was performed for 3 hours with a constant temperature oscillator (170rpm) having an internal temperature of 20 ℃. Then, 250mL of the viscose solution was filled in a dedicated filter (stainless steel filter screen 1 ten thousand holes/cm)2) The filtrate (viscose solution) was recovered using a 250mL graduated cylinder. The filtration time of the filtrate from 25mL to 50mL (t1) and the filtration time of the filtrate from 125mL to 150mL (t2) were measured, respectively, and the time difference between them was determined (t2-t 1).The values are shown in table 1 according to the following criteria. It can be said that the smaller the time difference, the more the mercerizing reaction is accelerated.
◎ the difference in filtration time is more than 0 second and less than 5 seconds, and the mercerizing reactivity is particularly high.
○ the difference in filtration time is more than 5 seconds and less than 10 seconds and the mercerizing reactivity is very high.
□: the difference in filtration time is 10 seconds or more and less than 20 seconds, and the mercerizing reactivity is high.
△ the difference in filtration time is 20 seconds or more, and the mercerizing reactivity is poor.
X: the filtered viscose solution did not reach 150mL even after 10 minutes, and thus, the mercerizing reactivity was very poor.
< comparative example 2>
0.004 part of ethylene oxide 4 mol adduct of { 2-ethylhexanol (HLB 10, Newcol 1004 Nippon emulsifier Co., Ltd.) as a mercerizing liquid described in example 1 of patent document 1, 13.7 parts of sodium hydroxide and 86.3 parts of water were uniformly mixed to obtain }361mL and a dissolving pulp sheet (prepared from broadleaf tree, having a cellulose content of 98% and a weight per unit area of 800 g/m)2) After separating 14.4g of the absolute dry weight to obtain pulp, 8mL of carbon disulfide was added thereto, and a mercerization reaction was performed for 3 hours with a constant temperature oscillator (170rpm) having an internal temperature of 20 ℃ to prepare a viscose solution. Then, 250mL of the viscose solution was filled in a dedicated filter (stainless steel filter screen 1 ten thousand holes/cm)2) The filtrate (viscose solution) was recovered using a 250mL graduated cylinder. The filtration time of the filtrate from 25mL to 50mL (t1) and the filtration time of the filtrate from 125mL to 150mL (t2) were measured, respectively, and the time difference between them was determined (t2-t 1). The values are shown in table 1 according to the above criteria.
TABLE 1
As shown in table 1, the difference between the filtration time (t1) and the filtration time (t2) (t2 to t1) of the dissolving pulp composition of the present invention was small as compared with the comparative examples, and the mercerization reaction was accelerated.
Claims (5)
1. A dissolving pulp composition characterized by comprising dissolving pulp and a mercerization accelerator comprising a surfactant A having an HLB, as measured by the Korea method, of 12 to 19 as an essential constituent,
the mercerizing accelerator comprises an accelerator selected from the group consisting of: polyoxyalkylene compound A1, and dodecylbenzene sulfonate, at least 1,
the polyoxyalkylene compound A1 contains at least 1 kind of the compound represented by the general formula (1),
R1[(-OA)n-OR2]m(1)
in the formula, R1Represents an alkyl group having 8 to 30 carbon atoms; r2Represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an acyl group having 2 to 30 carbon atoms; OA represents an oxyalkylene group having 2 to 4 carbon atoms; n represents an integer of 2 to 100; m represents 1.
2. The dissolving pulp composition according to claim 1, wherein the mercerizing accelerator comprises a polyoxyalkylene compound a 1.
3. The dissolving pulp composition according to claim 1 or 2, further comprising a polyoxyalkylene compound B having HLB of 1 to 7 as measured by the Paddy field method.
4. The dissolving pulp composition according to claim 1 or 2, wherein the content of the mercerizing accelerator per absolute dry weight of the dissolving pulp is 0.01-1 wt%.
5. A method for producing viscose rayon, comprising a step of mercerizing the dissolving pulp composition of any one of claims 1 to 4, i.e., an alkali cellulose conversion reaction, to obtain alkali cellulose.
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| SE540778C2 (en) * | 2016-12-23 | 2018-11-06 | Soedra Skogsaegarna Ekonomisk Foerening | A method of manufacturing dissolving pulp using coniferous wood material |
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| JPS5975902A (en) * | 1982-10-22 | 1984-04-28 | Daicel Chem Ind Ltd | Production of hydroxyethylcellulose |
| JP2622924B2 (en) * | 1993-02-02 | 1997-06-25 | 本州製紙株式会社 | Method for producing renewable release paper |
| SE511842C2 (en) * | 1997-04-18 | 1999-12-06 | Akzo Nobel Surface Chem | Ways to prepare a viscous solution |
| US7390566B2 (en) * | 2006-06-30 | 2008-06-24 | Weyerhaeuser Company | Viscose product |
| WO2008023493A1 (en) * | 2006-08-22 | 2008-02-28 | Nicca Chemical Co., Ltd. | In-bath quality enhancing agent for fiber processing and method of processing |
| JP2011149129A (en) * | 2010-01-22 | 2011-08-04 | Oji Paper Co Ltd | Production method for pulp |
| CN101979753B (en) * | 2010-09-28 | 2013-03-27 | 绍兴文理学院 | High-efficiency mercerization method of pure cotton woven fabrics |
| DE102010043113A1 (en) * | 2010-10-29 | 2012-05-03 | Evonik Stockhausen Gmbh | Process for the preparation of improved absorbent polymers by cryogenic milling |
| CN102230297B (en) * | 2011-06-13 | 2013-01-09 | 东北林业大学 | Plant paper pulp fiber modifying method, and filter paper and preparation method thereof |
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| AU2013249725B2 (en) * | 2012-04-18 | 2017-04-20 | Gp Cellulose Gmbh | The use of surfactant to treat pulp and improve the incorporation of kraft pulp into fiber for the production of viscose and other secondary fiber products |
| JP6346400B2 (en) * | 2012-08-15 | 2018-06-20 | 日本製紙株式会社 | Dissolving pulp |
| JP6417502B2 (en) * | 2015-04-23 | 2018-11-07 | サンノプコ株式会社 | Mercerization accelerator and method for producing viscose rayon |
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