WO2016170857A1 - Dissolving pulp composition and method for producing viscose rayon - Google Patents

Abstract

The purpose of the present invention is to provide a dissolving pulp composition which can undergo a mercerization reaction in an accelerated manner. The present invention is a dissolving pulp composition characterized by comprising: a mercerization accelerator that contains a surfactant (A) having an HLB value (Oda method) of 12 to 19 as an essential component; and dissolving pulp. The mercerization accelerator preferably contains at least one component selected from the group consisting of a polyoxyalkylene compound (A1), a compound (A2) that has at least one group selected from a sulfo group, a sulfoxy group and a phosphono group, and an amphoteric surfactant (A3).

Description

Dissolving pulp composition and method for producing viscose rayon

The present invention relates to a dissolving pulp composition and a method for producing a viscose rayon.

When a viscose rayon is produced through a step of preparing a cellulose cellulose by mercerizing (arcelerizing) the dissolving pulp in an alkaline solution, "a) 0.05-1" An alkylene oxide adduct of a weight percent alkyl branched alcohol having the formula R ₁ O (PO) m (CH ₂ CH ₂ O) nH (wherein R ₁ is branched having 8 to 12 carbon atoms). An alkylene oxide adduct having an alkyl group, PO is a propyleneoxy group, m is a number from 0 to 3, and n is a number from 2 to 7) b) 0.15 to 2% by weight Alkali hydroxide and / or alkaline complexing agent c) 0.025 to 1.75% by weight of hexyl glycoside and / or octyliminodipropionate d) 0.025 to 1.25% by weight of Includes a second surface active nonionic alkylene oxide adduct having at least 6.4 HLB value according to the scan (Davies), said second non-ionic alkylene oxide adduct has the formula _R 2 O _(C 2 H ₄ O) x (AO) yH (wherein R ₂ is an alkyl group containing 9 to 20 carbon atoms, AO is an alkyleneoxy group having 3 to 4 carbon atoms, and x is It is known to use a transparent and uniform aqueous composition having a number of 5 to 100 and y being a number of 0 to 4 (Patent Document 1).

Japanese Patent No. 4870555 (corresponding international patent application: WO2004 / 099355A1)

Even when a conventional aqueous composition is used, there is a problem that the mercerization reaction does not proceed sufficiently.
An object of the present invention is to provide a dissolving pulp composition capable of promoting a mercerization reaction.

The feature of the dissolving pulp composition of the present invention is that it contains a mercerization accelerator comprising a surfactant (A) having an HLB of 12 to 19 as an essential component and dissolving pulp.

The feature of the method for producing the viscose rayon of the present invention is summarized as including a step of obtaining alkali cellulose by subjecting the above dissolving pulp composition to mercerization (arcelization) reaction.

The dissolving pulp composition of the present invention can accelerate the mercerization reaction. Therefore, when the dissolving pulp composition of the present invention is used, the mercerization reaction can be advanced efficiently (in a short time) uniformly.

Since the viscose rayon production method of the present invention uses the above-described dissolving pulp composition, the mercerization reaction can be promoted and alkali cellulose can be obtained efficiently. Therefore, according to the viscose rayon manufacturing method of the present invention, the productivity of viscose rayon can be greatly improved.

The raw material chip of the dissolving pulp may be any of wood {coniferous and hardwood, etc.} and non-wood {plants (kenaf, bagasse, bamboo, etc.)} and is not particularly limited, but considering production efficiency Wood having a high bulk weight is preferably used. Applicable broad-leaved trees include eucalyptus globulas, eucalyptus grandis, eucalyptus eurograndis, eucalyptus perita, eucalyptus camaldrensis, eucalyptus brushana and acacia melanci. Applicable conifers include radiata pine, caribbean pine, Douglas fir, hemlock, redwood and larch. Needless to say, broad-leaved trees, coniferous trees, and non-woods can be used alone or in combination, and the combination is not limited.

The dissolving pulp may be produced by any method such as acidic sulfite cooking method or alkali cooking method (craft cooking, polysulfide cooking, soda cooking, alkali sulfite cooking, etc.), and is not particularly limited. Considering the quality of dissolving pulp, energy efficiency, etc., the kraft cooking method is preferably used. Below, although the manufacturing method of the dissolving pulp by a kraft cooking method is demonstrated, of course, it is not limited to this.

In order to produce dissolving pulp by kraft cooking, wood and other chips are heated in the presence of water and pre-hydrolyzed. The strength of the prehydrolysis is preferably 200 to 1000 as the P factor, the temperature is preferably 160 to 170 ° C., and the treatment temperature is determined according to the treatment time. The P factor is calculated from the temperature and time during the prehydrolysis. The apparatus used in the prehydrolysis step is not particularly limited, but a general-purpose continuous digester, batch kettle, or the like is preferably used.

チ ッ プ Chips such as wood after the pre-hydrolysis treatment are sent to the alkali cooking process. The apparatus used for alkaline cooking is not particularly limited, but a general-purpose continuous cooking kettle, batch kettle or the like is preferably used. When kraft cooking wood, the sulfation degree of the kraft cooking liquid is preferably 20 to 35%, the effective alkali addition rate is preferably 10 to 25% by weight per the dry wood weight, the cooking temperature is 140 to 170 ° C. A cooking method in which the liquid is added in portions may be used, and the method is not particularly limited.

The kappa number of unbleached pulp obtained by alkali digestion is not particularly limited. However, considering the quality of the dissolved pulp and the subsequent bleaching property, when hardwood is used as the raw material, the kappa number is 6-18. Preferably, when softwood is used as a raw material, the kappa number is preferably 20 to 35.

The unbleached pulp is subjected to washing, rough selection, and selection processes, and is preferably delignified by a known oxygen delignification method and then bleached by a known bleaching method (a bleached pulp is obtained). In the bleaching process, a multi-stage bleaching process in which bleaching stages such as chlorine dioxide, alkali, oxygen, hydrogen peroxide, and ozone are combined is generally used, and unbleached pulp finally has a whiteness of 87 to 92% ISO, preferably 89 to Bleaching to 92% ISO gives a dissolving pulp.

The main components of bleached pulp are cellulose and hemicellulose, which contain impurities such as lignin and resin. Of the bleached pulp, the dissolving pulp is composed of 95 to 99% by weight of cellulose and 1 to 5% by weight of hemicellulose, and the pulp for papermaking is about 85% by weight of cellulose and about 15% by weight of hemicellulose. On the other hand, cotton is 99% by weight or more of cellulose and less than 1% by weight of hemicellulose.

The HLB (Oda method) of the surfactant (A), which is an essential component of the mercerization accelerator, is 12 to 19, preferably 13 to 18, particularly preferably 14 to 17. Within this range, the mercerization reaction can be further promoted.

HLB represents a balance between organic and inorganic, and is an abbreviation for Hydrophile-Lipophile Balance. HLB is a numerical value based on the Oda method, and is a numerical value calculated from the organic value and the inorganic value by the following formula (Oda, Teramura, “Synthesis and application of surfactants”, page 501; 1957; Takemoto Fujimoto, “Introduction to New Surfactants”, 197-198, Sanyo Chemical Industries, 1985; Corresponding English book “New Introduction to Suface Active Agents”, 196-197, 1985) .
(HLB) = (inorganic value) ÷ (organic value) × 10

The surfactant (A) having an HLB in the above range includes known surfactants, and is a compound having at least one of a polyoxyalkylene compound (A1), a sulfo group, a sulfooxy group, or a phosphono group (A2 And at least one selected from the group consisting of amphoteric surfactants (A3) is preferred. Of these, the polyoxyalkylene compound (A1), the compound (A2) having at least one of a sulfo group, a sulfooxy group or a phosphono group are preferable, more preferably a polyoxyalkylene compound (A1), particularly preferably a general formula ( It is a compound represented by 1).

R ¹ [(—OA) _n —OR ² ] _m (1)

R ¹ is 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, or a reaction residue obtained by removing m hydroxyl groups from a polyhydric alcohol, R ² Is 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 is an oxyalkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100 , M represents an integer of 1-6.

Of the reaction residue (R ¹ ) obtained by removing m hydroxyl groups from 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, or a polyhydric alcohol As the alkyl group having 1 to 30 carbon atoms, a linear alkyl group and a branched alkyl group can be used.

Linear alkyl groups 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, heptacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and triaconsil.

Examples of the branched alkyl group include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, isotridecyl, isotetradecyl, isooctadecyl, isotriaconyl, 2-ethylhexyl, 8-methyl-1-nonyl, 2 -Propylheptyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl, 2-dodecylhexadecyl, 3,5,5-trimethylhexyl and 3, 7,11-trimethyldodecyl and the like.

In R ¹ , as the alkenyl group having 2 to 30 carbon atoms, a linear alkenyl group, a branched alkenyl group, or the like can be used.

Linear alkenyl groups include vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexosenyl, , Tetracocenyl, pentacocenyl, hexaxenyl, heptacocenyl, octacocenyl, triaconenyl and the like.

Examples of the branched alkenyl group include isobutenyl, isopentenyl, neopentenyl, isohexenyl, isotridecenyl, isooctadecenyl and isotriacontenyl.

In R ¹ , a saturated aliphatic acyl group, an unsaturated aliphatic acyl group, an alicyclic acyl group, an aromatic acyl group, or the like can be used as the acyl group having 2 to 30 carbon atoms.

Saturated aliphatic acyl groups include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, isotridecanoyl, myristoyl, palmitoyl And octadecanoyl.

Unsaturated aliphatic acyl groups include acryloyl, methacryloyl, crotonoyl, isocrotonoyl, butenoyl, butadenoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, oleoyl and oleoyl.

Cyclopentanoyl, cyclohexanoyl, cycloheptanoyl, methylcyclopentanoyl, methylcyclohexanoyl, methylcycloheptanoyl, cyclopentenoyl, 2,4-cyclopentadienoyl, cyclohexene Noyl, 2,4-cyclohexadienoyl, cycloheptenoyl, methylcyclopentenoyl, methylcyclohexenoyl, methylcycloheptenoyl and the like.

Examples of the aromatic acyl group include benzoyl, toluoyl, cinnamoyl and naphthoyl.

In addition, among R ¹ , polyhydric alcohols that can constitute a reaction residue obtained by removing m hydroxyl groups from polyhydric alcohols are dihydric alcohols (aliphatic diols, alicyclic diols and aromatic diols), trivalents. Alcohol (aliphatic triol, alicyclic triol and aromatic triol), tetravalent alcohol (aliphatic tetraol, alicyclic tetraol and aromatic tetraol), pentavalent alcohol (aliphatic pentaol, alicyclic pentaol) All and aromatic pentaols) and hexavalent alcohols (aliphatic hexaols, alicyclic hexaols and aromatic hexaols).

Aliphatic diols include aliphatic diols having 2 to 18 carbon atoms, such as ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, diethylpropanediol, hydroxyoctadecenyl alcohol, diethylene glycol, triethylene. Examples include glycol, tetraethylene glycol, trimethylpentanediol, and di (hydroxyethyl) thioether.

Examples of the alicyclic diol include alicyclic diols having 8 to 15 carbon atoms, such as 1,4-cyclohexanedimethanol, 4,4'-dihydroxydicyclohexane, and dihydroxydicyclohexyldimethylmethane.

The aromatic diol includes aromatic diols having 6 to 15 carbon atoms, and examples thereof include catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, and 1,4-dihydroxynaphthalene.

Aliphatic triols include aliphatic triols having 3 to 11 carbon atoms, and examples include glycerin, trimethylolethane, trimethylolpropane, trimethyloloctane, and hexanetriol.

Alicyclic triols include alicyclic triols having 6 to 15 carbon atoms, and examples include trihydroxycyclohexane, trihydroxydicyclohexane, and trihydroxydicyclohexyldimethylmethane.

Examples of the aromatic triol include aromatic triols having 6 to 15 carbon atoms, and examples include trihydroxybenzene, trihydroxybiphenyl, and trihydroxydiphenyldimethylmethane.

Aliphatic tetraols include aliphatic tetraols having 5 to 12 carbon atoms, and include diglycerin, pentaerythritol, trimethylolpentane, and ditrimethylolpropane.

Alicyclic tetraols include alicyclic tetraols having 6 to 15 carbon atoms, and examples include tetrahydroxycyclohexane, tetrahydroxydicyclohexane, sorbitan, and tetrahydroxydicyclohexyldimethylmethane.

The aromatic tetraol includes aromatic tetraol having 6 to 15 carbon atoms, and examples thereof include tetrahydroxybenzene, tetrahydroxybiphenyl, and tetrahydroxydiphenyldimethylmethane.

Aliphatic pentaols include aliphatic pentaols having 5 to 9 carbon atoms such as triglycerin and xylitol.

Alicyclic pentaols include alicyclic pentaols having 6 to 12 carbon atoms, such as pentahydroxycyclohexane, pentahydroxydicyclohexane, pentahydroxydicyclohexyldimethylmethane and hydroquinone-β-D-glucoside. Etc.

The aromatic pentaol includes aromatic pentaol having 6 to 15 carbon atoms, and examples thereof include pentahydroxybenzene, pentahydroxybiphenyl, and pentahydroxydiphenyldimethylmethane.

Aliphatic hexaols include aliphatic hexaols having 6 to 12 carbon atoms, and include sorbitol, tetraglycerin, dipentaerythritol and the like.

Alicyclic hexaols include alicyclic hexaols having 6 to 15 carbon atoms, and include hexahydroxycyclohexane, hexahydroxydicyclohexane, hexahydroxydicyclohexyldimethylmethane, and the like.

The aromatic hexaol includes aromatic hexaol having 6 to 15 carbon atoms, and examples thereof include hexahydroxybenzene, hexahydroxybiphenyl and hexahydroxydiphenyldimethylmethane.

These reaction residues excluding m hydroxyl groups do not necessarily mean reaction residues from which all hydroxyl groups of the polyhydric alcohol have been removed, but some hydroxyl groups remain in the reaction residues. Is also included. Therefore, the number of hydroxyl groups of the polyhydric alcohol does not necessarily match the value of m. That is, the relationship between the number of hydroxyl groups (s) in the polyhydric alcohol and the number of hydroxyl groups removed (m) is s ≧ m.

Among R ¹ , m hydroxyl groups are removed from 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 polyhydric alcohol from the viewpoint of promoting mercerization reaction. And more preferably, 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 m hydroxyl groups are removed from a divalent to hexavalent alcohol. Particularly preferably 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, most preferably dodecanoyl, dodecyl, 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, and an acyl group (R ² ) having 2 to 30 carbon atoms are the same as those for R ¹ . Of R ² , 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, and a hydrogen atom is more preferable, from the viewpoint of promoting the mercerization reaction. , 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, particularly preferably a hydrogen atom, dodecanoyl, octadecanoyl, oleoyl, dodecyl, octadecyl, dodecenyl and octadecenyl. is there.

Examples of the oxyalkylene group (OA) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, and oxybutylene. Of these, oxyethylene and oxypropylene are preferable from the viewpoint of promoting the mercerization reaction.

When (—OA) n is composed of two or more types of oxyalkylene groups, the bonding form of the n oxyalkylene groups may be block, random, or a combination thereof. In addition, m (—OA) n—O—R ² may 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. Within this range, the mercerization reaction is further promoted.

M is preferably an integer of 1 to 6, more preferably an integer of 1 to 3. Within this range, the mercerization reaction is further promoted.

The polyoxyalkylene compound (A1) can be produced by a known method (JP 2003-268291 A, JP 9-117607 A, etc.).

Examples of the polyoxyalkylene compound (A1) include 2-ethylhexanol ethylene oxide 10 mol adduct (HLB14), 2-ethylhexanol ethylene oxide 30 mol adduct (HLB17), 2-ethylhexanol ethylene oxide 11 mol / propylene oxide 1 Mole block adduct (HLB14), 2-ethylhexanol 60 mol ethylene oxide / propylene oxide 20 mol block adduct (HLB14), 8-methyl-1-nonanol ethylene oxide 12 mol adduct (HLB14), 8-methyl-1 -Nonanol ethylene oxide 15 mol adduct (HLB14), 8-methyl-1-nonanol ethylene oxide 40 mol adduct (HLB17), 8-methyl-1-nonanol propylene oxide 1 1 mol / ethylene oxide 14 mol block adduct (HLB14), propylene oxide 20 mol / methyl-1-nonanol 20 mol / ethylene oxide 60 mol block adduct (HLB14), 1-dodecanol ethylene oxide 12 mol adduct (HLB14), 1- Ethylene oxide 21 mol adduct of dodecanol (HLB15), ethylene oxide 40 mol of 1-dodecanol / propylene oxide 3 mol block adduct lauric acid ester (HLB14), ethylene oxide 45 mol adduct of 1-dodecanol (HLB17), 1-dodecanol Propylene oxide 1 mol / ethylene oxide 20 mol block adduct (HLB14), 1-dodecanol propylene oxide 20 mol / ethylene oxide 60 mol block adduct (H B14), ethylene oxide 18 mol adduct of dodecenol (HLB14), ethylene oxide 45 mol adduct of dodecenol (HLB17), propylene oxide 1 mol / ethylene oxide 16 mol block adduct (HLB14) of dodecenol, propylene oxide 20 mol / ethylene oxide of dodecenol 60 mol block adduct (HLB14), polyoxyethylene glycol (number average molecular weight 2000) lauric acid diester (HLB15), polyoxyethylene glycol (number average molecular weight 1000) stearic acid monoester (HLB14), 2-ethylhexanol 1 mol of propylene oxide / 30 mol of ethylene oxide block adduct, lauric acid ester (HLB14), ethyleneoxy of 2-ethylhexanol 25 mol / propylene oxide 3 mol block adduct (HLB15), 2-ethylhexanol 30 mol ethylene oxide / propylene oxide 3 mol block adduct (HLB16), 8-methyl-1-nonanol propylene oxide 1 mol / ethylene oxide 14 Mole block adduct stearate (HLB14), polyoxyethylene glycol (number average molecular weight 2000) lauric acid diester (HLB15), glycerin ethylene oxide 30 mol adduct (HLB15), glycerin propylene oxide 3 mol / ethylene oxide 9 Moleblock adduct (HLB14), stearic acid monoester of 30 mol adduct of glycerin ethylene oxide (HLB15) and ethylene hydroxy of tetrahydroxycyclohexane Sid 16 mol / propylene oxide 4 mol block adduct (HLB15), and the like.

Examples of the polyoxyalkylene compound (A1) other than the compound represented by the general formula (1) include an oxyalkylene adduct of castor oil and an oxyalkylene adduct of sucrose.

Examples of the compound (A2) having at least one of sulfo group, sulfooxy group or phosphono group include α-olefin sulfonate, alkylbenzene sulfonic acid and its salt {for example, sodium dodecylbenzene sulfonate (HLB14)}, naphthalene sulfonic acid Salt-formaldehyde condensate, N-acylalkyl taurate salt, alkyl sulfate ester salt, alkyl ether sulfate ester {eg, sodium salt of lauryl alcohol ethylene oxide 3 mol adduct sulfate (HLB15)}, alkyl sulfosuccinate, alkyl Examples thereof include phosphates and polyoxyethylene alkyl ether phosphates.

Examples of the amphoteric surfactant (A3) include higher alkylaminopropionates and higher alkyldimethyl betanic acids.

The mercerization accelerator only needs to be composed of the surfactant (A) as an essential component, and may be composed of only one type of surfactant or a plurality of types of surfactant.

The mercerization accelerator preferably contains a polyoxyalkylene compound (B) having an HLB (Oda method) of 1 to 7 in addition to the surfactant (A) having an HLB (Oda method) of 12 to 19. .

The HLB of the polyoxyalkylene compound (B) is preferably 1 to 7, and more preferably 2 to 6. Within this range, the mercerization reaction is further promoted.

As the polyoxyalkylene compound (B), those having the same chemical structure as the compound represented by the general formula (1) and having an HLB (Oda method) in the above range can be used.

The polyoxyalkylene compound (B) can be produced by a known method (JP 2003-268291 A, JP 9-117607 A, etc.).

Examples of the polyoxyalkylene compound (B) include propanol oxide 4 mol adduct of butanol (HLB4), propylene oxide 5 mol adduct of butanol (HLB4), propylene oxide 50 mol adduct of butanol (HLB4), and octadecanol. Propylene oxide 5-mole adduct (HLB2), octadecanol propylene oxide 8-mole adduct (HLB2), octadecanol propylene oxide 50-mole adduct (HLB4), polyoxypropylene glycol (number average molecular weight 400, HLB4) , Polyoxypropylene glycol (number average molecular weight 4000, HLB4), propylene oxide 3 mol adduct (HLB6) of glycerol, propylene oxide 69 mol adduct (HLB4) of glycerol, ethylene oxide 5 mol Block copolymer of 30 mol of propylene oxide (HLB6), 1 mol of ethylene oxide of 2-ethylhexanol / 30 mol of propylene oxide block adduct (HLB4), 5 mol of ethylene oxide of 2-ethylhexanol / 30 mol of propylene oxide block adduct (HLB5), 1-dodecanol ethylene oxide 10 mol / propylene oxide 30 mol block adduct (HLB6), 1-dodecanol ethylene oxide 1 mol / propylene oxide 30 mol block adduct (HLB4), 1-dodecanol ethylene oxide 5 mol / Propylene oxide 20 mol block adduct (HLB6), Lauric acid monoester (HLB4) of propylene oxide 3 mol adduct of glycerin, polyoxyethylene glycol ( Diester stearate (HLB5) and having an average molecular weight 200) are mentioned.

When the polyoxyalkylene compound (B) is contained, the content (% by weight) of the surfactant (A) is 60 to 99 based on the weight of the surfactant (A) and the polyoxyalkylene compound (B). Preferably, it is 70-95. In this case, the content (% by weight) of the polyoxyalkylene compound (B) is preferably 1 to 40, more preferably 5 based on the weight of the surfactant (A) and the polyoxyalkylene compound (B). ~ 30.

The mercerization accelerator may contain a solvent (C) and other additives (D).

Solvent (C) includes water or a mixed solvent of water and a hydrophilic organic solvent. Examples of the hydrophilic organic solvent include esters having 4 to 8 carbon atoms {ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate}, ethers having 4 to 8 carbon atoms {ethyl cellosolve, butyl cellosolve and propylene glycol. Monomethyl ether, etc.}, ketones having 3 to 8 carbon atoms {acetone, methyl ethyl ketone and methyl isobutyl ketone, etc.}, alcohols having 1 to 8 carbon atoms {methanol, ethanol, n- or i-propanol, n-, i- or t- Butanol, propylene glycol, dipropylene glycol and the like}, and a heterocyclic compound having 5 to 8 carbon atoms {N-methylpyrrolidone and the like}.

As other additives (D), known additives {dispersants, thickeners, fluidity improvers, antioxidants, ultraviolet absorbers, deodorants, fragrances, dyes and / or preservatives, etc.}, etc. Is mentioned.

When the mercerization accelerator is composed of a plurality of components, the mercerization accelerator can be obtained by uniformly mixing a plurality of components.

The content (% by weight) of the mercerization accelerator is not particularly limited, but is preferably 0.01 to 1, more preferably 0.03 to 0.5, based on the absolute dry weight of the dissolving pulp. Particularly preferred is 0.05 to 0.2. Within this range, the mercerization reaction can be further promoted.

The absolute dry weight of the dissolving pulp is measured at 105 ° C. according to JIS P8203: 2010 (corresponding international standard: ISO638: 2008).

The dissolving pulp composition of the present invention is not limited in its production method as long as the mercerization accelerator and the dissolving pulp are contained, and the mercerization accelerator may be sprayed or applied to the dissolving pulp, or the mercerization promotion is promoted. The dissolving pulp may be immersed in the agent. From the viewpoint of simplicity of equipment design, it is preferable to spray or apply a mercerization accelerator to dissolving pulp. In such a production method, from the viewpoint of workability, the mercerization accelerator may be diluted with a solvent (C) or the like.

There is no limitation on the form of the dissolving pulp composition of the present invention, and it can be formed into a sheet. In the case of forming a sheet, a surfactant can be contained in the entire sheet, or a surfactant can be contained in at least one surface layer portion of the sheet. The method for adding the surfactant is not particularly limited. A surfactant may be internally added to the suspension containing the dissolved pulp, and then formed into a sheet shape. After the dissolved pulp is formed into a sheet shape, the surfactant is externally added (immersion, spraying or coating). ) By adding externally, a surfactant can be contained in the surface layer portion of the sheet. Moreover, the said sheet | seat can also be made into the form of winding-up.

The method for producing the viscose rayon of the present invention can be combined with known steps without particular limitation as long as it includes a step of obtaining the alkali cellulose by subjecting the above dissolving pulp composition to mercerization (arcelization) reaction.
For the mercerization reaction, a known mercerization treatment solution (such as an alkali solution) can be used, and the temperature, time, etc. of the mercerization reaction can be within a known range.

In the method for producing viscose rayon of the present invention, subsequent to the step of obtaining alkali cellulose, the step of mixing alkali cellulose and carbon disulfide to obtain viscose (cellulose xanthate sodium) and the step of obtaining alkali cellulose The course obtaining step may be performed in parallel), and further includes a spinning step in which viscose is ejected from the pores into dilute sulfuric acid to obtain viscose rayon.

Viscose obtained using the dissolving pulp composition of the present invention as a raw material is characterized by high solubility and appropriate aqueous solution viscosity. Viscose can be obtained efficiently due to its high solubility. Moreover, since an appropriate aqueous solution viscosity is obtained, troubles during spinning due to low viscosity and a decrease in spinning speed due to high viscosity can be prevented in advance, and viscose rayon can be produced efficiently. Furthermore, since a viscose having an appropriate aqueous solution viscosity range, that is, an appropriate polymerization degree range is obtained, the strength required for the rayon fiber can be maintained. Since the dissolving pulp composition of the present invention has a high α-cellulose content, it is widely used as a raw material for various cellulosic derivatives such as general viscose rayon, special rayon, chemical, and medical applications. Can be used.

Parts and% mean parts by weight and% by weight unless otherwise specified.
<Example 1>
Mercerization accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17) to 100 parts of sheet made of dissolving pulp (prepared from hardwood, cellulose content 98%, basis weight 800 g / m ² ) , Brownon EH-30, Aoki Yushi Kogyo Co., Ltd.)} After spraying 5 parts of a dilute solution consisting of 0.1 parts and 4.9 parts of water, air-dry at room temperature (25-30 ° C., hereinafter the same). Thus, the dissolving pulp composition (1) of the present invention was obtained.

<Example 2>
Mercerization accelerator (1) 0.1 part of {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 part of mercerization accelerator (2) {8-methyl-1-nonanol ethylene oxide 15 mol adduct (HLB14, Neugen SD-150, Daiichi Kogyo Seiyaku Co., Ltd. “Neugen” is a registered trademark of the company.)} The dissolving pulp of the present invention was the same as Example 1 except that the content was changed to 0.1 part. A composition (2) was obtained.

<Example 3>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 part Mercerization Accelerator (3) {1-dodecanol ethylene oxide 21 mol adduct (HLB15, BROWNON EL-) 1521, Aoki Yushi Kogyo Co., Ltd.)} The dissolving pulp composition (3) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to 0.1 part.

<Example 4>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization Accelerator (4) {2-ethylhexanol 30 mol ethylene oxide / propylene oxide 3 mol block addition Body (HLB16)} The dissolving pulp composition (4) of the present invention was obtained in the same manner as in Example 1 except that the amount was changed to 0.1 part. An ethylene oxide 30 mol / propylene oxide 3 mol block adduct of 2-ethylhexanol was prepared by a known alkylene oxide addition reaction.

<Example 5>
Mercerization accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts mercerization accelerator (5) {1-dodecanol ethylene oxide 40 mol / propylene oxide 3 mol block adduct The lauric acid ester (HLB14)} was changed to 0.1 part, and the dissolving pulp composition (5) of the present invention was obtained in the same manner as in Example 1. The lauric acid ester of 1-dodecanol ethylene oxide 40 mol / propylene oxide 3 mol block adduct was prepared by known alkylene oxide addition reaction and esterification reaction.

<Example 6>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization accelerator (6) {2-ethylhexanol ethylene oxide 10 mol adduct (HLB14)} 0 The dissolving pulp composition (6) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to 1 part. An ethylene oxide 10 mol adduct of 2-ethylhexanol was prepared by a known alkylene oxide addition reaction.

<Example 7>
Mercerization accelerator (1) 0.1 part of {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 part of mercerization accelerator (7) {Sodium dodecylbenzenesulfonate (HLB14, Neoperex G-15, Kao) Co., Ltd. “Neopelex” is a registered trademark of the same company.)} The dissolving pulp composition (7) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to 0.1 part.

<Example 8>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 part Mercerization Accelerator (8) {1-dodecanol ethylene oxide 21 mol adduct (HLB15, BROWNON EL-) 1521, Aoki Yushi Kogyo Co., Ltd.) 90 parts and butanol propylene oxide 5-mole adduct (HLB4, New Pole LB-65, Sanyo Chemical Industries, Ltd., “New Pole” is a registered trademark of the same company) 10 parts The dissolving pulp composition (8) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to 0.1 part.

<Example 9>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 part Mercerization Accelerator (9) {2-ethylhexanol ethylene oxide 25 mol / propylene oxide 3 mol block addition 70 parts of body (HLB15) and 30 parts of octadecanol propylene oxide 8 mol adduct (HLB2) uniformly mixed} 0.1 parts except that the dissolved pulp of the present invention was changed to 0.1 parts A composition (9) was obtained. An ethylene oxide 25 mol / propylene oxide 3 mol block adduct of 2-ethylhexanol was prepared by a known alkylene oxide addition reaction.

<Example 10>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization Accelerator (10) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17, Braunon EH) -30, Aoki Yushi Kogyo Co., Ltd.) 95 parts and polyoxypropylene glycol (number average molecular weight 4000, HLB4, New Pole PP-4000, Sanyo Chemical Industries Co., Ltd.) 5 parts uniformly mixed} 0.1 parts Except having carried out, it carried out similarly to Example 1, and obtained the dissolving pulp composition (10) of this invention.

<Example 11>
Mercerization accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization accelerator (11) {1-dodecanol ethylene oxide 21 mol adduct (HLB15, BROWNON EL-) 1521, Aoki Yushi Kogyo Co., Ltd.) 90 parts and 1-dodecanol ethylene oxide 5 mol / propylene oxide 20 mol block adduct (HLB6) 10 parts uniformly mixed} 0.1 parts other than that changed to 0.1 part The dissolving pulp composition (11) of the present invention was obtained in the same manner as above. A 1-dodecanol ethylene oxide 5 mol / propylene oxide 20 mol block adduct was prepared by a known alkylene oxide addition reaction.

<Example 12>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization Accelerator (12) {1-dodecanol ethylene oxide 21 mol adduct (HLB15, BROWNON EL-) 1521, Aoki Yushi Kogyo Co., Ltd.) 90 parts and 10 parts of lauric acid monoester (HLB4) of propylene oxide 3 mol adduct of glycerin uniformly mixed} Same as Example 1 except for changing to 0.1 parts Thus, the dissolving pulp composition (12) of the present invention was obtained. In addition, lauric acid monoester of propylene oxide 3 mol adduct of glycerin was prepared by known alkylene oxide addition reaction and esterification reaction.

<Example 13>
Mercerization Accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} 0.1 parts Mercerization Accelerator (13) {1-dodecanol ethylene oxide 21 mol adduct (HLB15, BROWNON EL-) 1521, Aoki Yushi Kogyo Co., Ltd.) 90 parts and polyoxyethylene glycol (number average molecular weight 200) stearic acid diester (HLB5) 10 parts uniformly mixed} Except for changing to 0.1 part, Example 1 Similarly, the dissolving pulp composition (13) of the present invention was obtained. A stearic acid diester of polyoxyethylene glycol (number average molecular weight 200) was prepared by a known alkylene oxide addition reaction and esterification reaction.

<Example 14>
Mercerization accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17) to 100 parts of sheet made of dissolving pulp (prepared from hardwood, cellulose content 98%, basis weight 800 g / m ² ) )} After spraying 5 parts of a diluted solution consisting of 0.05 parts and 4.95 parts of water, it was air-dried at room temperature to obtain the dissolving pulp composition (14) of the present invention.

<Example 15>
Mercerization accelerator (1) {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17) to 100 parts of sheet made of dissolving pulp (prepared from hardwood, cellulose content 98%, basis weight 800 g / m ² ) )} After spraying 5 parts of a diluted solution consisting of 0.2 parts and 4.8 parts of water, it was air-dried at room temperature to obtain the dissolving pulp composition (15) of the present invention.

<Comparative Example 1>
Mercerization accelerator (1) Comparative dissolved pulp in the same manner as in Example 1 except that 0.1 part of {2-ethylhexanol ethylene oxide 30 mol adduct (HLB17)} was changed to 0.1 part of water. A composition (H1) was obtained.

<Acceleration evaluation of mercerization reaction>
For the dissolving pulp compositions prepared in Examples 1 to 15 and Comparative Example 1, each dissolving pulp composition (absolutely dry weight 14.4 g) and 361 mL of a 13.7% aqueous sodium hydroxide solution were disaggregated to obtain a pulp slurry. After being obtained, 8 mL of carbon disulfide was added thereto, and a mercerization reaction was performed for 3 hours on a constant temperature shaker (170 rpm) with an internal temperature of 20 ° C. to obtain a viscose solution (a mercerization reaction to obtain alkali cellulose The reaction of alkali cellulose and carbon disulfide to obtain a viscose solution was performed in parallel. Next, 250 mL of this viscose solution was filled into a special filter (stainless steel filter net 10,000 holes / cm ² ), and the filtrate (viscose solution) was collected with a 250 mL graduated cylinder. The filtration time (t1) when the filtrate was from 25 mL to 50 mL and the filtration time (t2) when the filtrate was from 125 mL to 150 mL were also measured, and the time difference (t2−t1) was determined. These values are shown in Table 1 according to the following criteria. It can be said that the mercerization reaction is promoted as the time difference decreases.

A: Time difference after filtration is 0 second or more and less than 5 seconds, and mercerization reactivity is particularly high.
○: The time difference after filtration is 5 seconds or more and less than 10 seconds, and the mercerization reactivity is very high.
□: Time difference after filtration is 10 seconds or more and less than 20 seconds, and mercerization reactivity is high.
(Triangle | delta): The time difference filtered is 20 seconds or more, and mercerization reactivity is bad.
X: Since the filtered viscose solution does not reach 150 mL even after 10 minutes, the mercerization reactivity is very poor.

<Comparative example 2>
Mercerization treatment solution described in Example 1 of Patent Document 1 {2-ethylhexanol ethylene oxide 4-mol adduct (HLB10, New Coal 1004 Nippon Emulsifier Co., Ltd.) 0.004 parts, sodium hydroxide 13.7 parts And 6.3 mL of water and 86.3 parts of water uniformly mixed with pulp pulp (dissolved pulp sheet (prepared from hardwood, cellulose content 98%, basis weight 800 g / m ² )) and dry weight 14.4 g. After obtaining the slurry, 8 mL of carbon disulfide was added thereto, and a mercerization reaction was performed for 3 hours with a constant temperature shaker (170 rpm) having an internal temperature of 20 ° C. to prepare a viscose solution. Next, 250 mL of this viscose solution was filled into a special filter (stainless steel filter net 10,000 holes / cm ² ), and the filtrate (viscose solution) was collected with a 250 mL graduated cylinder. The filtration time (t1) when the filtrate was from 25 mL to 50 mL and the filtration time (t2) when the filtrate was from 125 mL to 150 mL were also measured, and the time difference (t2−t1) was determined. This value is shown in Table 1 according to the above criteria.

As shown in Table 1, in the dissolving pulp composition of the present invention, the time difference (t2-t1) between the filtration time (t1) and the filtration time (t2) is small compared to the comparative example, and the mercerization reaction is not caused. Has been promoted.

Claims (6)

1. A dissolving pulp composition comprising a mercerization accelerator comprising a surfactant (A) having an HLB (Oda method) of 12 to 19 as an essential component and dissolving pulp.
2. The mercerization accelerator includes at least one selected from the group consisting of a polyoxyalkylene compound (A1), a compound (A2) having at least one of a sulfo group, a sulfooxy group or a phosphono group and an amphoteric surfactant (A3). The dissolving pulp composition according to claim 1.
3. Including a polyoxyalkylene compound (A1) as a mercerization accelerator,
   The dissolving pulp composition according to claim 1 or 2, wherein the polyoxyalkylene compound (A1) contains at least one compound represented by the general formula (1).
   
   R ¹ [(—OA) _n —OR ² ] _m (1)
   
   R ¹ is 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, or a reaction residue obtained by removing m hydroxyl groups from a polyhydric alcohol, R ² Is 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 is an oxyalkylene group having 2 to 4 carbon atoms, and n is an integer of 2 to 100 , M represents an integer of 1-6.
4. The dissolving pulp composition according to any one of claims 1 to 3, further comprising a polyoxyalkylene compound (B) having an HLB (Oda method) of 1 to 7.
5. The dissolving pulp composition according to any one of claims 1 to 4, wherein the content of the mercerization accelerator is 0.01 to 1% by weight based on the absolute dry weight of the dissolving pulp.
6. A method for producing viscose rayon, comprising a step of subjecting the dissolving pulp composition according to any one of claims 1 to 5 to mercerization (arcerylation) reaction to obtain alkali cellulose.