WO2011018933A1 - Synthetic fiber treating agent for papermaking, method for producing synthetic fiber for papermaking, and method for producing paper-made nonwoven fabric - Google Patents

Synthetic fiber treating agent for papermaking, method for producing synthetic fiber for papermaking, and method for producing paper-made nonwoven fabric Download PDF

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Publication number
WO2011018933A1
WO2011018933A1 PCT/JP2010/062197 JP2010062197W WO2011018933A1 WO 2011018933 A1 WO2011018933 A1 WO 2011018933A1 JP 2010062197 W JP2010062197 W JP 2010062197W WO 2011018933 A1 WO2011018933 A1 WO 2011018933A1
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Prior art keywords
papermaking
synthetic fiber
component
carbon atoms
group
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PCT/JP2010/062197
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French (fr)
Japanese (ja)
Inventor
俊彦 菊田
裕志 小南
英利 北口
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松本油脂製薬株式会社
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Application filed by 松本油脂製薬株式会社 filed Critical 松本油脂製薬株式会社
Priority to KR1020127003862A priority Critical patent/KR101684864B1/en
Priority to JP2010539654A priority patent/JP4709327B2/en
Priority to CN201080034116.7A priority patent/CN102471994B/en
Publication of WO2011018933A1 publication Critical patent/WO2011018933A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/419—Amides having nitrogen atoms of amide groups substituted by hydroxyalkyl or by etherified or esterified hydroxyalkyl groups
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel

Definitions

  • the present invention relates to a synthetic fiber treating agent for papermaking, a method for producing a synthetic fiber for papermaking, and a method for producing a papermaking nonwoven fabric.
  • Patent Document 1 discloses a polyester polyether block copolymer as a synthetic fiber treatment agent for papermaking.
  • the processing agent according to Patent Document 1 has poor low-shear dispersibility, and as a result, the uniform dispersion of the synthetic fiber bundle in the dispersion bath is insufficient.
  • Patent Document 2 discloses a mixture comprising a polyethylene glycol fatty acid monoester and a fatty acid soap.
  • the treatment agent according to Patent Document 2 has a problem that the foaming in the papermaking process is much and the generated bubbles adhere to the fibers, so that uniform dispersion in the dispersion bath is insufficient.
  • the antifoaming properties, defoaming properties, and low shear dispersibility required for the current synthetic fibers for papermaking are at an insufficient level, and a high-quality nonwoven fabric cannot be obtained. Therefore, in the nonwoven fabric manufactured by the papermaking method, a processing agent having all the required characteristics is desired for the synthetic fiber processing agent for papermaking because of the high quality of the nonwoven fabric.
  • the object of the present invention is to improve the dispersibility at a low share with respect to the synthetic fiber for papermaking used in the papermaking nonwoven fabric, to reduce the generation of bubbles in the papermaking process, and to provide excellent fiber dispersibility. It is to provide a synthetic fiber treating agent for papermaking, a method for producing a synthetic fiber for papermaking, and a method for producing a papermaking nonwoven fabric.
  • the present inventors have intensively studied. As a result, the present inventors have found that the above-mentioned problems can be solved by using a synthetic fiber treatment agent for papermaking containing a specific component as an essential component. .
  • the synthetic fiber treating agent for papermaking of the present invention comprises at least one dicarboxylic acid (derivative) selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 22 carbon atoms, and ester-forming derivatives thereof, and alkylene.
  • a component A which is a polyester compound obtained by polycondensation of glycol with polyalkylene glycol or a derivative thereof and a component B which is a condensate of a fatty acid and an alkanolamine are contained as essential components.
  • the proportion of the A component in the nonvolatile content of the treatment agent is 40 to 90% by weight and the proportion of the B component is 5 to 30% by weight.
  • the component A is a polycondensation of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof, an alkylene glycol represented by the following chemical formula (1), and a polyalkylene glycol represented by the following chemical formula (2) or a derivative thereof. It is preferable to be a polyester compound.
  • R 1 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 2 to 8 carbon atoms.
  • R 2 is an alkylene group having 2 to 4 carbon atoms
  • n is an integer of 20 to 200
  • R 3 is a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group.
  • the component B is preferably a compound represented by the following general formula (3).
  • R 4 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms
  • R 5 is a hydroxyalkyl group having 1 to 4 carbon atoms
  • R 6 is a hydrogen atom, and has 1 to 4 carbon atoms. It is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms.
  • the synthetic fiber treating agent for papermaking of the present invention preferably further contains a C component which is a fatty acid soap having 8 to 22 carbon atoms.
  • a C component which is a fatty acid soap having 8 to 22 carbon atoms.
  • the proportion of the A component in the nonvolatile content of the treatment agent is 40 to 90% by weight
  • the proportion of the B component is 5 to 30% by weight
  • the proportion of the C component is 5 to 30% by weight.
  • the treatment agent is an aqueous liquid further containing water, and the ratio of the nonvolatile content in the whole treatment agent is preferably 0.05 to 50% by weight. .
  • the manufacturing method of the synthetic fiber for papermaking of this invention includes the process of processing said synthetic fiber processing agent for papermaking to raw material synthetic fiber.
  • the paper manufacturing method of the present invention includes a step of making paper by dispersing the synthetic fiber for paper making treated with the above-mentioned synthetic fiber treating agent for paper making in water.
  • the synthetic fiber treatment agent for papermaking of the present invention can improve the dispersibility at a low share with respect to the synthetic fiber for papermaking used in papermaking, reduce the generation of bubbles in the papermaking process, and excellent fiber dispersion Can give sex.
  • the method for producing a synthetic fiber for papermaking according to the present invention can provide a synthetic fiber for papermaking that has good dispersibility at a low share, reduces the generation of bubbles in the papermaking process, and has excellent dispersibility.
  • the method for producing a papermaking nonwoven fabric according to the present invention can provide a papermaking nonwoven fabric having high productivity and uniform and good texture.
  • the synthetic fiber treating agent for papermaking of the present invention contains A component and B component as essential components.
  • each component which comprises the synthetic fiber processing agent for papermaking of this invention is demonstrated.
  • Component A includes at least one dicarboxylic acid (derivative) selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 22 carbon atoms, and ester-forming derivatives thereof, alkylene glycols, and polyalkylene glycols or derivatives thereof. Is a polyester compound obtained by polycondensation.
  • a component has strong affinity for synthetic fibers for papermaking, has low fiber / fiber friction when wet, and also has foam suppression when dissolved in water. Good dispersibility and foam suppression can be imparted.
  • An ester-forming derivative is a derivative of a carboxylic acid and can form a carboxylic acid ester with a hydroxyl group-containing compound by an esterification reaction or an ester substitution reaction.
  • Specific examples of the ester-forming derivative include aromatic dicarboxylic acids and esters of aliphatic dicarboxylic acids having 4 to 22 carbon atoms, acid anhydrides and amides.
  • the dicarboxylic acid is not particularly limited.
  • aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid
  • oxalic acid glutaric acid, adipic acid, pimelic acid
  • C4-C22 aliphatic dicarboxylic acid such as sebacic acid
  • aromatic dicarboxylic acid ester such as dimethyl terephthalate, dimethyl 5-sulfoisophthalate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl adipate, etc. 22 ester-forming derivatives of aliphatic dicarboxylic acids.
  • dicarboxylic acids may be used alone or in combination of two or more.
  • aromatic dicarboxylic acids are preferred, terephthalic acid and isophthalic acid are more preferred, and combined use of terephthalic acid and isophthalic acid is particularly preferred.
  • alkylene glycol represented by the said Chemical formula (1) is preferable.
  • R 1 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 2 to 8 carbon atoms.
  • Specific examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol and the like. These alkylene glycols may be used alone or in combination of two or more.
  • ethylene glycol, propylene glycol, and butylene glycol are preferable, and ethylene glycol is more preferable.
  • the polyalkylene glycol or its derivative is not particularly limited, but the polyalkylene glycol represented by the above chemical formula (2) or its derivative is preferable.
  • the polyalkylene glycol or derivative thereof may be composed of one kind or two or more kinds.
  • the derivative of polyalkylene glycol means one in which one of the two terminal hydroxyl groups of the polyalkylene glycol molecule is blocked with an organic group.
  • R 2 is an alkylene group having 2 to 4 carbon atoms. That is, the (OR 2 ) moiety is an oxyalkylene group, which is an oxyethylene group if it has 2 carbon atoms, an oxypropylene group if it has 3 carbon atoms, and an oxybutylene group if it has 4 carbon atoms. These oxyalkylene groups may be used alone or in combination of two or more.
  • the (H (OR 2 ) n O) moiety is a polyalkylene glycol moiety, but the bonding form when two or more oxyalkylenes are used in combination may be random or block.
  • R 3 is a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group.
  • the aliphatic hydrocarbon group may be linear or branched, and may be saturated or unsaturated.
  • Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 22 (preferably 1 to 12) carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a lauryl group, a stearyl group, and a behenyl group.
  • the aromatic group in R 3 of the general formula (2) means an organic group containing an aromatic hydrocarbon such as benzene, naphthalene, anthracene, and the number of the aromatic hydrocarbons contained is one. It is sufficient if there are two or more.
  • R 3 is an aromatic group
  • the R site bonded to the oxygen atom in the general formula (2) may or may not be an aromatic hydrocarbon moiety.
  • aromatic group for example, phenyl group, toluyl group, xylyl group, styrenated phenyl group, phenylethyl group, distyrenated phenyl group, tristyrenated phenyl group, benzyl group, benzylated phenyl group, dibenzylated phenyl group, Examples thereof include a tribenzylated phenyl group.
  • R 3 in the general formula (2) is preferably an alkyl group or an aromatic group.
  • n is an integer of 20 to 200, preferably 40 to 150, and more preferably 50 to 100. If n is less than 20, the hydrophilicity is insufficient, making it difficult to disperse in water and making it difficult to lubricate the fibers uniformly. On the other hand, if n is more than 200, affinity for synthetic fibers In some cases, the fiber / fiber friction at the time of wetting becomes high and good dispersibility cannot be imparted.
  • Specific examples of the polyalkylene glycol derivative include polyethylene glycol monophenyl ether (average molecular weight: 3000), polyethylene glycol (average molecular weight 2000), polyethylene glycol monomethyl ether (average molecular weight: 1000), and the like.
  • the ratio (molar ratio) of [dicarboxylic acid (derivative) / alkylene glycol] with respect to the ratio (molar ratio) of dicarboxylic acid (derivative), alkylene glycol and polyalkylene glycol or derivative thereof when producing the above-mentioned polyester compound as component A ) Is preferably in the range of 20/80 to 60/40, more preferably 30/70 to 50/50, and even more preferably 40/60 to 50/50.
  • the ratio of the dicarboxylic acid (derivative) and the alkylene glycol is within this range, the reaction can easily proceed and the amount of unreacted material after the reaction is reduced.
  • the ratio (molar ratio) of [dicarboxylic acid (derivative) / polyalkylene glycol or derivative thereof] is preferably in the range of 100/2 to 100/100, more preferably 100/2 to 100/50, More preferably, it is 100/2 to 100/20.
  • the ratio of the dicarboxylic acid (derivative) to the polyalkylene glycol or derivative thereof is within this range, it can be easily dispersed in water, the handling property is good, the affinity for synthetic fibers is good, and the wetness is good. The fiber / fiber friction is reduced, and good dispersibility can be imparted.
  • the reaction for producing the polyester compound can be carried out by appropriately selecting methods and conditions known in the art. Moreover, about reaction pressure, you may carry out by a normal pressure and you may carry out by pressure reduction.
  • the proportion of the component A in the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is 40 to 90% by weight, preferably 50 to 90% by weight, more preferably 70 to 90% by weight.
  • the non-volatile content of the synthetic fiber treatment agent for papermaking of the present invention means a component in the synthetic fiber treatment agent for papermaking that remains on the fiber surface even after the heat drying step for removing moisture, etc. Means a component that remains without volatilization under heat treatment conditions of 110 ° C. for 30 minutes.
  • [B component] B component is a condensate obtained by condensing a fatty acid and an alkanolamine.
  • the fatty acid constituting the component B is a fatty acid having 8 to 22 carbon atoms, preferably a fatty acid having 12 to 22 carbon atoms, and more preferably a fatty acid having 16 to 22 carbon atoms.
  • the B component can impart good dispersibility and foam suppression properties when used in combination with the component A, and can impart good foam suppression properties and antifoaming properties particularly in the paper making process.
  • the carbon number of 8 to 22 means that the fatty acid constituting the B component has 8 to 22 carbon atoms.
  • the fatty acid constituting the component B include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and behenic acid.
  • the fatty acid constituting the component B is stearic acid, oleic acid, or ricinoleic acid in terms of good balance between foam suppression, antifoaming properties and water solubility.
  • the fatty acid which comprises B component may be comprised from 1 type, and may be comprised from 2 or more types.
  • alkanolamine constituting the component B examples include monomethanolamine, dimethanolamine, monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, monoisopropanolamine and the like. Of these alkanolamines, diethylamine is preferred because it has a good balance between foam suppression, antifoaming and water solubility.
  • the alkanolamine constituting the component B may be composed of one kind or two or more kinds.
  • Examples of the component B include fatty acid amides represented by the above chemical formula (3).
  • R 4 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms
  • R 5 is a hydroxyalkyl group having 1 to 4 carbon atoms
  • R 6 is a hydrogen atom, and has 1 to 4 carbon atoms.
  • R 4 has 7 to 21 carbon atoms, preferably 11 to 21 and particularly preferably 15 to 21. If the carbon number of R 4 is less than 7, sufficient foam suppression and defoaming properties may not be exhibited in the paper making process, and in this case, good dispersibility may not be obtained.
  • R 4 when the carbon number of R 4 is more than 21, water solubility in water may be deteriorated, handling properties may be impaired, and further, the cost is increased and it is not suitable for practical use.
  • R 4 may be linear or branched and may be saturated or unsaturated. Examples of R 4 include an enanthyl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, margaryl group, pristane group, cis-9-heptadecenyl group, and the like.
  • R 4 an undecyl group, a tridecyl group, a pentadecyl group, a margaryl group, and a pristane group are preferable, and a margaryl group is particularly preferable.
  • the hydroxyalkyl group for R 5 may be linear or branched.
  • the number of carbon atoms of the hydroxyalkyl group of R 5 is preferably 1 to 3, more preferably 1 to 2. When the carbon number of R 5 is more than 4, the condensation reactivity is low, and the recovery rate of the condensate may be deteriorated.
  • R 6 is preferably a hydroxyalkyl group having 1 to 4 carbon atoms, and more preferably a hydroxyalkyl group having 1 to 2 carbon atoms. When R 6 has more than 4 carbon atoms, the condensation reactivity is low, and the recovery rate of the condensate may be deteriorated.
  • the reaction for producing the component B can be carried out by appropriately selecting methods and conditions known in the art. Moreover, about reaction pressure, you may carry out by a normal pressure and you may carry out by pressure reduction.
  • the proportion of the B component in the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is 5 to 30% by weight, preferably 5 to 25% by weight, and more preferably 5 to 15% by weight.
  • the ratio of the B component is within this range, sufficient foam suppression and defoaming can be imparted in the paper making process, and the friction between the fibers / fibers when wet can be reduced, and therefore, good dispersibility can be imparted. .
  • the synthetic fiber treating agent for papermaking of the present invention preferably further contains a C component which is a fatty acid soap having 8 to 22 carbon atoms in addition to the above A component and B component.
  • the component C is obtained by neutralizing a fatty acid with a base.
  • Component C is a fatty acid soap having 8 to 22 carbon atoms, preferably a fatty acid soap having 12 to 22 carbon atoms, and more preferably a fatty acid soap having 16 to 22 carbon atoms.
  • the carbon number means the carbon number of the fatty acid constituting the fatty acid soap.
  • the fatty acid constituting the component C include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and behenic acid.
  • the fatty acid constituting the component C is stearic acid, oleic acid, or ricinoleic acid because the balance between dispersibility and water solubility is good.
  • the fatty acid which comprises C component may be comprised from 1 type of these fatty acids, and may be comprised from 2 or more types.
  • the fatty acid soap shown by following Chemical formula (4) is mentioned, for example.
  • R 7 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms, M n + is a cation, and n is an integer of 1 or more.
  • examples of M n + include alkali metals such as sodium, potassium and lithium, and alkaline earth metals such as calcium and magnesium. Of these, preferred are alkali metals, and more preferred are sodium and potassium.
  • R 7 has 7 to 21 carbon atoms, preferably 11 to 21 carbon atoms, particularly preferably 15 to 21 carbon atoms. If the carbon number of R 7 is less than 7, good dispersibility may not be obtained because bubbles are generated in the paper making process. On the other hand, if the carbon number of R 7 is more than 21, wettability and dispersibility with a low share may be deteriorated. Furthermore, the cost is increased and it is not suitable for practical use. R 7 may be linear or branched and may be saturated or unsaturated.
  • R 7 examples include an enantyl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, margaryl group, pristane group, cis-9-heptadecenyl group, and the like.
  • an undecyl group, a tridecyl group, a pentadecyl group, a margaryl group, and a pristane group are preferable, and a margaryl group is particularly preferable.
  • the proportion of the C component in the nonvolatile content of the synthetic fiber treating agent for papermaking of the present invention is 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 15% by weight. It is. When the proportion of component C is in this range, good low shear dispersibility can be imparted in the paper making process.
  • component C is not particularly limited, and can be produced, for example, by neutralizing a fatty acid having 8 to 22 carbon atoms with a base.
  • the synthetic fiber treating agent for papermaking of the present invention is preferably an aqueous liquid containing water in which the aforementioned components are dispersed or emulsified.
  • the water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.
  • the proportion of the nonvolatile content in the entire treatment agent is preferably 0.05 to 50% by weight, more preferably 0.5 to 40% by weight, and further preferably 1 to 30% by weight.
  • the synthetic fiber treating agent for papermaking of the present invention can be supplemented with an additive in order to obtain an aqueous liquid in which the above-mentioned components are dispersed or emulsified and to improve the wettability at the time of adhesion.
  • additives that can be used for this purpose include nonionic surfactants such as polyoxyethylene-polyoxypropylene copolymer derivatives, polyoxyethylene (hereinafter abbreviated as POE) alkyl ethers, and POE alkyl esters.
  • anionic surfactants such as alkyl sulfates (salts), alkyl sulfonates (salts), and alkyl phosphates (salts).
  • An organic solvent can be appropriately used in preparing the aqueous liquid of the treatment agent of the present invention, including the case where these additives are used in combination.
  • the proportion of these additives in the non-volatile content of the synthetic fiber treatment agent for papermaking is not particularly limited, but is preferably less than 50% by weight, more preferably less than 20% by weight, and even more preferably less than 10% by weight.
  • the synthetic fiber treatment agent for papermaking of the present invention may further contain an antibacterial agent, an antioxidant, a preservative, a matting agent, a pigment, a rust preventive, a fragrance and the like, if necessary. .
  • the water emulsion in which the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is adjusted to 1% is preferably an emulsion that does not produce precipitates when heated to 40 ° C. Moreover, it is preferable not to contain an anionic surfactant and a cationic surfactant simultaneously.
  • the synthetic fiber treating agent for papermaking of the present invention can be produced by mixing the A component and the B component, and optionally the C component, and optionally mixing other components.
  • the order of mixing the components is not particularly limited, and these components may be mixed at room temperature (20 to 25 ° C.) or may be mixed by heating (20 ° C. to 80 ° C.).
  • the form of component A includes an aqueous liquid, a paste, a powder, and a block, but an aqueous liquid is preferable from the viewpoint of handleability.
  • the form of the component B includes an aqueous liquid, a powder form, a block form, etc., but an aqueous liquid is preferable from the viewpoint of handling.
  • the form of component C includes an aqueous liquid, a powder form, a block form, and the like, but an aqueous liquid is preferable from the viewpoint of handling. Therefore, the synthetic fiber treating agent for papermaking of the present invention mixes an aqueous liquid containing the A component and an aqueous liquid containing the B component, and optionally an aqueous liquid containing the C component, and optionally other components. It is preferable to manufacture.
  • the concentration of the aqueous liquid containing component A is, for example, 10 to 40% by weight
  • the concentration of the aqueous liquid containing component B is, for example, 20 to 100% by weight
  • the concentration of the aqueous liquid containing component C is, for example, For example, 20 to 50% by weight.
  • Each component constituting the synthetic fiber treating agent for papermaking of the present invention is such that an aqueous liquid (at least 10% by weight or more) is heated in water at room temperature (20 to 25 ° C.) or as necessary (20 ° C. to 80 ° C.). And dissolved and mixed to form a uniform and stable emulsion. Therefore, in manufacturing sites where synthetic fiber treatment agents for papermaking are applied to synthetic fibers, aqueous solutions of each component are dissolved or mixed at room temperature or heated to prepare synthetic fiber treatment agents for papermaking that are stable emulsions. You can also
  • the obtained composition for papermaking of the present invention can be obtained even if the A component and the B component, and in some cases, the C component coexist.
  • the product stability of the fiber treatment agent is good and there is no problem.
  • the A component, the B component, and the C component may be separated separately without mixing.
  • the manufacturing method of the synthetic fiber for papermaking of this invention includes the process of processing the synthetic fiber processing agent for papermaking of this invention to raw material synthetic fiber.
  • the raw material synthetic fiber refers to a synthetic fiber that has not been treated with the synthetic fiber treating agent for papermaking.
  • the synthetic fiber for papermaking means a short fiber cut into a predetermined length so that it can be used in the papermaking process. Since the synthetic fiber for papermaking obtained by the method for producing synthetic fiber for papermaking of the present invention is a short fiber treated with the synthetic fiber treating agent for papermaking of the present invention, water is produced in the process of papermaking during the production of papermaking. Are dispersed with a low share, and bubbles are suppressed.
  • the synthetic fiber is not particularly limited.
  • polyester fiber, polyamide fiber, polyolefin fiber, polyphenylene sulfide (PPS) fiber, polyacrylonitrile fiber, polypropylene fiber, or two or more of these polymers were used.
  • a composite synthetic fiber etc. can be mentioned.
  • the synthetic fiber is preferably a polyester fiber in terms of high affinity between the synthetic fiber treating agent for papermaking of the present invention and the fiber, and more preferably a polyethylene terephthalate (PET) fiber.
  • PET polyethylene terephthalate
  • the single yarn fineness of the fiber is preferably 0.01 to 2 dtex, and the fiber length is preferably 0.5 to 25 mm.
  • Polyester fiber is not only polyethylene terephthalate fiber, but also polylactic acid (PLA) fiber, polytrimethylene terephthalate (PTT) fiber, polybutylene terephthalate (PBT) fiber, polyethylene naphthalate (PEN) fiber, polyarylate fiber, etc. It means a fiber made of a polymer condensed by a reaction for forming a bond.
  • the process for treating the raw synthetic fiber with the synthetic fiber treating agent for papermaking is not particularly limited as long as it is processed before the paper making process using the synthetic fiber for papermaking.
  • synthetic fibers for papermaking are manufactured through a spinning process, a drawing process, a finishing process, a crimping process, and a cutting process. Further, it may be processed in at least one process selected from a stretching process and a finishing process, and may be processed in a crimping process and before and after, a cutting process, and before and after that.
  • a processing method oil supply method
  • a well-known method is employable. For example, when processing in a spinning process, a drawing process, and a finishing process, it can be performed by a normal processing method (oil supply method) such as a roller touch method, a spray method, or a dipping method.
  • the amount of non-volatile matter attached to the synthetic fiber treatment agent for papermaking is preferably 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, based on the synthetic fiber for papermaking.
  • adhesion amount is less than 0.05% by weight, dispersibility may be insufficient, and when it exceeds 2% by weight, foaming in the dispersion tank may increase in the paper making process.
  • the method for producing a papermaking nonwoven fabric of the present invention includes a step of making paper by dispersing the synthetic fiber for papermaking treated with the synthetic fiber treating agent of the present invention in water (sometimes referred to as a papermaking step).
  • the synthetic fiber for papermaking is not easily entangled with each other during stirring and dispersion, quickly disperses into a single fiber, and has good stable dispersibility.
  • a conventional wet papermaking process can be employed.
  • the papermaking synthetic fiber (short fiber) treated with the papermaking synthetic fiber treating agent in the above step is put into a pulper, stirred and dispersed in water, and suspended.
  • the netting net is generally a circular net or a short net, but may be a long net, a rotoformer, a hydroformer, a perchformer, or the like.
  • the drying process may be a plurality of rotary heating roller type (multi-cylinder type) or Yankee drum type.
  • the raw synthetic fiber or the synthetic fiber for papermaking may be dispersed in water containing the above-mentioned synthetic fiber treating agent for papermaking to make paper.
  • the method for producing a papermaking nonwoven fabric of the present invention it is possible to improve dispersibility at a low share with respect to synthetic fibers for papermaking, to reduce the generation of bubbles in the papermaking process, and to provide excellent fiber dispersibility. Therefore, not only the production speed is increased and the cost is reduced, but also a papermaking nonwoven fabric having a uniform and good texture can be obtained.
  • the papermaking nonwoven fabric obtained by the production method of the present invention is used in various known fields. Particularly suitable as wipers, air filters, liquid filters, battery separators, artificial leather fabrics, disposable diapers, tea bags, and packaging materials.
  • Table 1 All the numerical values in Table 1 are the proportions of non-volatile components contained in the synthetic fiber treating agent for papermaking (component A1, component A2 and component A3 are obtained as respective aqueous dispersions as shown below. Table 1 shows the ratio of each non-volatile content excluding).
  • Component A1 A mixture of dimethyl terephthalate and dimethyl isophthalate in a molar ratio of 80:20, a total of 25 parts by weight, 20 parts by weight of ethylene glycol and 55 parts by weight of polyethylene glycol monophenyl ether (average molecular weight: 3000), and a small amount as a catalyst Zinc acetate and titanium tetrabutoxide were added and reacted at 175 to 200 ° C. under atmospheric pressure for 180 minutes, and the theoretical amount of methanol was distilled off to complete the transesterification reaction. Next, the temperature was raised to 230 ° C.
  • the obtained polymer (average molecular weight 7000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A1.
  • the concentration of component A1 in the obtained aqueous dispersion was 20% by weight.
  • Component A2 Dimethyl terephthalate, dimethyl isophthalate, and dimethyl 5-sulfoisophthalate in a molar ratio of 75: 20: 5, a total of 25 parts by weight, ethylene glycol 10 parts by weight, diethylene glycol 20 parts by weight, and polyethylene glycol (average molecular weight 2000) 55 parts by weight
  • a small amount of zinc acetate and titanium tetrabutoxide were added as a catalyst, and the mixture was reacted at 175 to 200 ° C. under atmospheric pressure for 180 minutes. The theoretical amount of methanol was distilled off to complete the transesterification reaction. . Next, the temperature was raised to 230 ° C.
  • the obtained polymer (average molecular weight 5000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A2.
  • the concentration of component A2 in the obtained aqueous dispersion was 20% by weight.
  • Component A3 Dimethyl terephthalate and dimethyl isophthalate in a molar ratio of 80:20 were mixed in a total of 28 parts by weight, 7 parts by weight of ethylene glycol and 65 parts by weight of polyethylene glycol monomethyl ether (average molecular weight: 1000). Zinc acetate and titanium tetrabutoxide were added, and the mixture was reacted at 175 to 200 ° C. for 180 minutes under normal pressure, and the theoretical amount of methanol was distilled off to complete the transesterification reaction. Next, the temperature was raised to 230 ° C. and allowed to react for about 1 hour, and then the pressure was reduced to 0.5 mmHg at 230 to 260 ° C.
  • the obtained polymer (average molecular weight 7000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A3.
  • the concentration of Component A3 in the obtained aqueous dispersion was 20% by weight.
  • Component B1 Condensate of lauric acid and diethanolamine
  • Component B2 Condensate of stearic acid and diethanolamine
  • Component B3 Condensate of myristic acid and diethanolamine
  • Component C1 Potassium laurate component
  • C2 Sodium stearate component
  • C3 Oleic acid
  • C4 Sodium behenate component
  • D1 POE palmitic acid monoester MW: 2500
  • Examples 1 to 16 and Comparative Examples 1 to 7 (1) Preparation of Emulsions Each of the components shown in Table 1 and water were mixed, and Examples 1 to 16 and Comparative Examples 1 to 7 in which the non-volatile content in the total synthetic fiber treating agent for papermaking was 20% by weight. Synthetic fiber treatment agents for papermaking were prepared. The obtained synthetic fiber treating agent for papermaking was diluted with water so that each non-volatile component had a concentration of 0.4% by weight with warm water of 25 to 60 ° C. to prepare an emulsion. Using the obtained emulsion, it was evaluated according to (2) of the following evaluation method. The results are shown in Table 2.
  • polyethylene terephthalate short fiber for papermaking evaluation In the production of oiled cotton, the synthetic fiber treatment agent for papermaking to be evaluated is used for 10 g of raw fiber (polyethylene terephthalate short fiber having a fineness of 1.3 dtex and a length of 5 mm).
  • the emulsion (5 g) prepared in (1) above was adhered by spraying so that the nonvolatile content was 0.2% by weight of the fiber after the adhesion treatment, and dried for 1 hour in a hot air dryer at 80 ° C.
  • the polyethylene terephthalate short fibers (synthetic fibers for papermaking) obtained after drying were adjusted according to the following evaluation methods (4) to (7) after adjusting the temperature and humidity under the evaluation environmental conditions. The results are shown in Table 2.
  • ⁇ Criteria> Double-circle: It is very favorable in the condition where there is no bubble.
  • ⁇ Good in a situation where the degree of foaming is very small and almost no foam is formed.
  • X Remarkably poor in a situation where foaming is intensely generated.
  • Dispersibility test 500 g of ion-exchanged water is collected in a 500 ml beaker, 1.00 g of test fiber is put therein, and the mixture is stirred for 10 minutes with a propeller stirrer (rotation speed: 1000 rpm). The dispersion state of the fibers after the stirring was stopped was visually determined according to the following criteria, and used as an index of dispersibility.
  • the synthetic fiber treating agent for papermaking of Examples 1 to 16 was lubricated as compared with the synthetic fiber for papermaking using the conventional synthetic fiber treating agent for papermaking of Comparative Examples 1 to 7.
  • Synthetic fiber bundles for papermaking are less likely to get entangled with each other because the friction between fibers / fibers when wet is low in the papermaking process when producing papermaking from synthetic fiber bundles.
  • it since it has good dispersibility with a low share, it disperses quickly into single fibers.
  • the foam suppressing property and defoaming property are good, the fiber has less foaming property and there are no bubbles adhering to the fiber, so that the stable dispersibility is also good.
  • this synthetic fiber treating agent for papermaking is added, synthetic fibers for papermaking suitable for the papermaking process in which high quality and high speed of the papermaking nonwoven fabric are required can be obtained. Moreover, by using synthetic fibers for papermaking, a papermaking nonwoven fabric having a uniform and good texture can be obtained.
  • the synthetic fiber treating agent for papermaking of the present invention is suitably used for obtaining synthetic fibers for papermaking having excellent dispersibility.
  • the method for producing a synthetic fiber for papermaking of the present invention is suitable for obtaining a synthetic fiber for papermaking having excellent dispersibility.
  • the manufacturing method of the papermaking nonwoven fabric of this invention is suitable when obtaining the papermaking nonwoven fabric which is uniform and favorable in formation.
  • Polyester filament 2-6 Pulley 7: U gauge 8: Recorder 9: Load (20 g)

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Abstract

Disclosed is a synthetic fiber treating agent for papermaking, which is capable of providing synthetic fibers for papermaking used for a paper-made nonwoven fabric with good dispersibility at low share, while suppressing the formation of air bubbles during a papermaking step. Consequently, the synthetic fiber treating agent for papermaking is capable of providing excellent fiber dispersibility. Specifically disclosed is a synthetic fiber treating agent for papermaking, which contains, as essential ingredients, a component A that is composed of a polyester compound obtained by polycondensing at least one dicarboxylic acid (derivative) selected from among aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4-22 carbon atoms and ester-forming derivatives thereof, and an alkylene glycol, a polyalkylene glycol or a derivative thereof, and a component B that is composed of a condensation product of a fatty acid and an alkanol amine.

Description

抄紙用合成繊維処理剤、抄紙用合成繊維の製造方法、および抄紙不織布の製造方法Synthetic fiber treatment agent for papermaking, method for producing papermaking synthetic fiber, and method for producing papermaking nonwoven fabric
　本発明は、抄紙用合成繊維処理剤、抄紙用合成繊維の製造方法、および抄紙不織布の製造方法に関する。 The present invention relates to a synthetic fiber treating agent for papermaking, a method for producing a synthetic fiber for papermaking, and a method for producing a papermaking nonwoven fabric.
　抄紙用合成繊維としては、従来から、ビニロン、レ－ヨン、天然セルロ－ス、ポリプロピレン、ポリアクリロニトリル系繊維がかなり広く使用されてきた。しかし近年は、要求性能の高度化という点において、独特の柔軟な風合を有し、寸法安定性、耐熱性があり、更にはコストも安い、ポリオレフィン繊維やポリエステル繊維等の疎水性の合成繊維を原料とする抄紙用合成繊維を抄紙して得られる抄紙不織布（単に抄紙ということもある）が脚光を浴びている。 Conventionally, vinylon, rayon, natural cellulose, polypropylene, and polyacrylonitrile fibers have been widely used as synthetic fibers for papermaking. In recent years, however, hydrophobic synthetic fibers such as polyolefin fibers and polyester fibers that have a unique and flexible texture, have dimensional stability, heat resistance, and cost are low in terms of sophistication of required performance. Papermaking nonwoven fabrics (simply referred to as papermaking) obtained by making papermaking synthetic fibers made from limelight are in the spotlight.
　しかし、実用化されている製品は、疎水性の合成繊維自身のもつ優れた性能が十分に生かされていないのが現状である。特に抄紙工程において、市場が要求する疎水性の合成繊維の分散性を向上させ、生産速度の向上をはかり、抑泡性を有し、疎水性の合成繊維の抄紙を与えるための抄紙用合成繊維処理剤は未だに見いだされていないのが現状である。 However, the products currently in practical use are not fully utilizing the superior performance of hydrophobic synthetic fibers themselves. Synthetic fibers for papermaking to improve the dispersibility of hydrophobic synthetic fibers demanded by the market, to improve production speed, and to produce foamed, hydrophobic synthetic fibers, especially in the papermaking process The present condition is that the processing agent has not yet been found.
　抄紙用合成繊維処理剤として、例えば、特許文献１では、ポリエステルポリエーテルブロック共重合体が開示されている。しかし、特許文献１にかかる処理剤では、低シェアの分散性が不良であり、結果的に合成繊維束の分散浴中における均一分散が不十分である。特許文献２では、ポリエチレングリコール脂肪酸モノエステル及び脂肪酸石鹸からなる混合物が開示されている。しかし、特許文献２にかかる処理剤では、抄紙工程での泡立ちが多く、発生した気泡が繊維に付着することから分散浴中における均一分散が不十分であることが問題である。 For example, Patent Document 1 discloses a polyester polyether block copolymer as a synthetic fiber treatment agent for papermaking. However, the processing agent according to Patent Document 1 has poor low-shear dispersibility, and as a result, the uniform dispersion of the synthetic fiber bundle in the dispersion bath is insufficient. Patent Document 2 discloses a mixture comprising a polyethylene glycol fatty acid monoester and a fatty acid soap. However, the treatment agent according to Patent Document 2 has a problem that the foaming in the papermaking process is much and the generated bubbles adhere to the fibers, so that uniform dispersion in the dispersion bath is insufficient.
特公昭５８－２０８５００号公報Japanese Patent Publication No.58-208500 特開２００４－２３８７６４号公報Japanese Patent Laid-Open No. 2004-238774
　このように、これらの処理剤では、現在の抄紙用合成繊維に要求される抑泡性、脱泡性、低シェアの分散性は不十分なレベルにあり、高品質の不織布が得られない。従って、抄紙法で製造する不織布において、不織布の高品質化から、抄紙用合成繊維処理剤には全ての要求特性を併せもつ処理剤が望まれている。 Thus, with these treatment agents, the antifoaming properties, defoaming properties, and low shear dispersibility required for the current synthetic fibers for papermaking are at an insufficient level, and a high-quality nonwoven fabric cannot be obtained. Therefore, in the nonwoven fabric manufactured by the papermaking method, a processing agent having all the required characteristics is desired for the synthetic fiber processing agent for papermaking because of the high quality of the nonwoven fabric.
　本発明の目的は、抄紙不織布に用いられる抄紙用合成繊維に対して、低シェアでの分散性を良好にでき、抄紙工程での気泡の発生を低下させ、優れた繊維の分散性を与えることができる抄紙用合成繊維処理剤、抄紙用合成繊維の製造方法、および抄紙不織布の製造方法を提供することにある。 The object of the present invention is to improve the dispersibility at a low share with respect to the synthetic fiber for papermaking used in the papermaking nonwoven fabric, to reduce the generation of bubbles in the papermaking process, and to provide excellent fiber dispersibility. It is to provide a synthetic fiber treating agent for papermaking, a method for producing a synthetic fiber for papermaking, and a method for producing a papermaking nonwoven fabric.
　上記課題を解決するために、本発明者は鋭意検討した結果、特定の成分を必須成分として含む抄紙用合成繊維処理剤であれば、上記課題を解決されることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, the present inventors have found that the above-mentioned problems can be solved by using a synthetic fiber treatment agent for papermaking containing a specific component as an essential component. .
　すなわち、本発明の抄紙用合成繊維処理剤は、芳香族ジカルボン酸、炭素数４～２２の脂肪族ジカルボン酸およびこれらのエステル形成性誘導体から選ばれる少なくとも１種のジカルボン酸（誘導体）と、アルキレングリコールと、ポリアルキレングリコールまたはその誘導体とを重縮合させたポリエステル化合物であるＡ成分と、脂肪酸とアルカノ－ルアミンとの縮合物であるＢ成分とを必須成分として含むものである。 That is, the synthetic fiber treating agent for papermaking of the present invention comprises at least one dicarboxylic acid (derivative) selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 22 carbon atoms, and ester-forming derivatives thereof, and alkylene. A component A which is a polyester compound obtained by polycondensation of glycol with polyalkylene glycol or a derivative thereof and a component B which is a condensate of a fatty acid and an alkanolamine are contained as essential components.
　前記処理剤の不揮発分に占めるＡ成分の割合が４０～９０重量％で、Ｂ成分の割合が５～３０重量％であることが好ましい。 It is preferable that the proportion of the A component in the nonvolatile content of the treatment agent is 40 to 90% by weight and the proportion of the B component is 5 to 30% by weight.
　前記Ａ成分は、芳香族ジカルボン酸および／またはそのエステル形成誘導体と、下記化学式（１）で表されるアルキレングリコールと、下記化学式（２）で表されるポリアルキレングリコールまたはその誘導体とを重縮合させたポリエステル化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000004
 （但し、式中、Ｒ１は炭素数２～８の脂肪族炭化水素基または炭素数２～８の脂環族炭化水素基である。）
Figure JPOXMLDOC01-appb-C000005
 （但し、式中、Ｒ２は炭素数２～４のアルキレン基であり、ｎは２０～２００の整数であり、Ｒ３は水素原子、脂肪族炭化水素基または芳香族基である。） The component A is a polycondensation of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof, an alkylene glycol represented by the following chemical formula (1), and a polyalkylene glycol represented by the following chemical formula (2) or a derivative thereof. It is preferable to be a polyester compound.
Figure JPOXMLDOC01-appb-C000004
 (In the formula, R 1 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 2 to 8 carbon atoms.)
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 2 is an alkylene group having 2 to 4 carbon atoms, n is an integer of 20 to 200, and R 3 is a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group.)
　前記Ｂ成分は、下記一般式（３）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000006
 （但し、式中、Ｒ４は炭素数７～２１の脂肪族炭化水素基であり、Ｒ５は炭素数１～４のヒドロキシアルキル基であり、Ｒ６は水素原子、炭素数１～４のアルキル基または炭素数１～４のヒドロキシアルキル基である。） The component B is preferably a compound represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R 4 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms, R 5 is a hydroxyalkyl group having 1 to 4 carbon atoms, R 6 is a hydrogen atom, and has 1 to 4 carbon atoms. It is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms.)
　また、本発明の抄紙用合成繊維処理剤は、炭素数が８～２２の脂肪酸石鹸であるＣ成分をさらに含むことが好ましい。また、前記処理剤の不揮発分に占めるＡ成分の割合が４０～９０重量％で、Ｂ成分の割合が５～３０重量％で、Ｃ成分の割合が５～３０重量％であることが好ましい。 In addition, the synthetic fiber treating agent for papermaking of the present invention preferably further contains a C component which is a fatty acid soap having 8 to 22 carbon atoms. Further, it is preferable that the proportion of the A component in the nonvolatile content of the treatment agent is 40 to 90% by weight, the proportion of the B component is 5 to 30% by weight, and the proportion of the C component is 5 to 30% by weight.
　また、本発明の抄紙用合成繊維処理剤は、前記処理剤が水をさらに含む水性液となっており、処理剤全体に占める不揮発分の割合が０．０５～５０重量％であることが好ましい。 In the synthetic fiber treatment agent for papermaking of the present invention, the treatment agent is an aqueous liquid further containing water, and the ratio of the nonvolatile content in the whole treatment agent is preferably 0.05 to 50% by weight. .
　本発明の抄紙用合成繊維の製造方法は、原料合成繊維に、上記の抄紙用合成繊維処理剤を処理する工程を含むものである。
　本発明の抄紙の製造方法は、上記の抄紙用合成繊維処理剤が処理された抄紙用合成繊維を水中に分散させて抄紙する工程を含むものである。 The manufacturing method of the synthetic fiber for papermaking of this invention includes the process of processing said synthetic fiber processing agent for papermaking to raw material synthetic fiber.
The paper manufacturing method of the present invention includes a step of making paper by dispersing the synthetic fiber for paper making treated with the above-mentioned synthetic fiber treating agent for paper making in water.
　本発明の抄紙用合成繊維処理剤は、抄紙に用いられる抄紙用合成繊維に対して、低シェアでの分散性を良好にでき、抄紙工程での気泡の発生を低下させ、優れた繊維の分散性を与えることができる。
　本発明の抄紙用合成繊維の製造方法は、低シェアでの分散性が良好で、抄紙工程での気泡の発生を低下させ、優れた分散性を有する抄紙用合成繊維を得ることができる。
　本発明の抄紙不織布の製造方法は、生産性が高く、また均一で地合いの良好な抄紙不織布を得ることができる。 The synthetic fiber treatment agent for papermaking of the present invention can improve the dispersibility at a low share with respect to the synthetic fiber for papermaking used in papermaking, reduce the generation of bubbles in the papermaking process, and excellent fiber dispersion Can give sex.
The method for producing a synthetic fiber for papermaking according to the present invention can provide a synthetic fiber for papermaking that has good dispersibility at a low share, reduces the generation of bubbles in the papermaking process, and has excellent dispersibility.
The method for producing a papermaking nonwoven fabric according to the present invention can provide a papermaking nonwoven fabric having high productivity and uniform and good texture.
湿潤時の繊維／繊維間摩擦を測定する方法の概略図。Schematic of the method of measuring the fiber / fiber friction when wet.
　本発明の抄紙用合成繊維処理剤は、Ａ成分およびＢ成分を必須成分として含むものである。以下、本発明の抄紙用合成繊維処理剤を構成する各成分を説明する。 The synthetic fiber treating agent for papermaking of the present invention contains A component and B component as essential components. Hereinafter, each component which comprises the synthetic fiber processing agent for papermaking of this invention is demonstrated.
〔Ａ成分〕
　Ａ成分は、芳香族ジカルボン酸、炭素数４～２２の脂肪族ジカルボン酸およびこれらのエステル形成性誘導体から選ばれる少なくとも１種のジカルボン酸（誘導体）と、アルキレングリコールと、ポリアルキレングリコールまたはその誘導体とを重縮合させたポリエステル化合物である。Ａ成分は、抄紙用合成繊維に対する親和性が強く、湿潤時の繊維／繊維間摩擦が低く、また水に溶かしたときの抑泡性も有しているので、Ｂ成分と併用することにより、良好な分散性および抑泡性を付与することができる。 [Component A]
Component A includes at least one dicarboxylic acid (derivative) selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 22 carbon atoms, and ester-forming derivatives thereof, alkylene glycols, and polyalkylene glycols or derivatives thereof. Is a polyester compound obtained by polycondensation. A component has strong affinity for synthetic fibers for papermaking, has low fiber / fiber friction when wet, and also has foam suppression when dissolved in water. Good dispersibility and foam suppression can be imparted.
　エステル形成性誘導体とは、カルボン酸の誘導体であって、エステル化反応やエステル置換反応等により水酸基含有化合物とカルボン酸エステルを形成できる誘導体である。エステル形成性誘導体の具体例としては、芳香族ジカルボン酸や炭素数４～２２の脂肪族ジカルボン酸のエステル、酸無水物、アミド等が挙げられる。 An ester-forming derivative is a derivative of a carboxylic acid and can form a carboxylic acid ester with a hydroxyl group-containing compound by an esterification reaction or an ester substitution reaction. Specific examples of the ester-forming derivative include aromatic dicarboxylic acids and esters of aliphatic dicarboxylic acids having 4 to 22 carbon atoms, acid anhydrides and amides.
　ジカルボン酸（誘導体）としては特に限定はないが、たとえば、フタル酸、テレフタル酸、イソフタル酸、２，６－ナフタレンジカルボン酸等の芳香族ジカルボン酸；琥珀酸、グルタル酸、アジピン酸、ピメリン酸、セバシン酸等の炭素数４～２２の脂肪族ジカルボン酸；テレフタル酸ジメチル、５－スルホイソフタル酸ジメチル、１，４－ナフタレンジカルボン酸ジメチル、アジピン酸ジメチル等の芳香族ジカルボン酸エステルや炭素数４～２２の脂肪族ジカルボン酸のエステル形成性誘導体等が挙げられる。これらのジカルボン酸（誘導体）は、１種または２種以上を併用してもよい。ジカルボン酸（誘導体）のうちでも、芳香族ジカルボン酸が好ましく、テレフタル酸やイソフタル酸がさらに好ましく、テレフタル酸およびイソフタル酸の併用が特に好ましい。 The dicarboxylic acid (derivative) is not particularly limited. For example, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; oxalic acid, glutaric acid, adipic acid, pimelic acid, C4-C22 aliphatic dicarboxylic acid such as sebacic acid; aromatic dicarboxylic acid ester such as dimethyl terephthalate, dimethyl 5-sulfoisophthalate, dimethyl 1,4-naphthalenedicarboxylate, dimethyl adipate, etc. 22 ester-forming derivatives of aliphatic dicarboxylic acids. These dicarboxylic acids (derivatives) may be used alone or in combination of two or more. Of the dicarboxylic acids (derivatives), aromatic dicarboxylic acids are preferred, terephthalic acid and isophthalic acid are more preferred, and combined use of terephthalic acid and isophthalic acid is particularly preferred.
　アルキレングリコールとしては特に限定はないが、上記化学式（１）で表されるアルキレングリコールが好ましい。化学式（１）において、Ｒ１は炭素数２～８の脂肪族炭化水素基または炭素数２～８の脂環族炭化水素基である。
　アルキレングリコールの具体例としては、エチレングリコール、プロピレングリコール、ブチレングリコール、ブチレングルコール、１，６－ヘキサンジオール、１，８－オクタンジオール、１，４－シクロヘキサンジメタノール等が挙げられる。これらのアルキレングリコールは、１種または２種以上を併用してもよい。
　アルキレングリコールのなかでも、エチレングリコール、プロピレングリコール、ブチレングリコールが好ましく、エチレングリコールがさらに好ましい。 Although there is no limitation in particular as alkylene glycol, The alkylene glycol represented by the said Chemical formula (1) is preferable. In the chemical formula (1), R 1 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 2 to 8 carbon atoms.
Specific examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol and the like. These alkylene glycols may be used alone or in combination of two or more.
Among the alkylene glycols, ethylene glycol, propylene glycol, and butylene glycol are preferable, and ethylene glycol is more preferable.
　ポリアルキレングリコールまたはその誘導体としては特に限定はないが、上記化学式（２）で表されるポリアルキレングリコールまたはその誘導体が好ましい。ポリアルキレングリコールまたはその誘導体は、１種から構成されていてもよく、２種以上から構成されていてもよい。ここで、ポリアルキレングリコールの誘導体とは、ポリアルキレングリコール分子の２つの末端水酸基のうち片一方が有機基で封鎖されたものをいう。 The polyalkylene glycol or its derivative is not particularly limited, but the polyalkylene glycol represented by the above chemical formula (2) or its derivative is preferable. The polyalkylene glycol or derivative thereof may be composed of one kind or two or more kinds. Here, the derivative of polyalkylene glycol means one in which one of the two terminal hydroxyl groups of the polyalkylene glycol molecule is blocked with an organic group.
　化学式（２）において、Ｒ２は炭素数２～４のアルキレン基である。即ち、（ＯＲ２）部分はオキシアルキレン基であり、炭素数２であればオキシエチレン基、炭素数３であればオキシプロピレン基、炭素数４であればオキシブチレン基である。これらのオキシアルキレン基は、１種または２種以上を併用してもよい。（Ｈ（ＯＲ２）ｎＯ）部分はポリアルキレングリコール部分であるが、２種以上のオキシアルキレンを併用する場合の結合形式は、ランダムであってもブロックであってもよい。また、ポリアルキレングリコール部分は、オキシエチレン基／オキシプロピレン基＝１００／０～４０／６０（モル比）の割合で結合したものが好ましく、オキシエチレン基だけが結合したものがより好ましい。 In the chemical formula (2), R 2 is an alkylene group having 2 to 4 carbon atoms. That is, the (OR 2 ) moiety is an oxyalkylene group, which is an oxyethylene group if it has 2 carbon atoms, an oxypropylene group if it has 3 carbon atoms, and an oxybutylene group if it has 4 carbon atoms. These oxyalkylene groups may be used alone or in combination of two or more. The (H (OR 2 ) n O) moiety is a polyalkylene glycol moiety, but the bonding form when two or more oxyalkylenes are used in combination may be random or block. In addition, the polyalkylene glycol moiety is preferably bonded at a ratio of oxyethylene group / oxypropylene group = 100/0 to 40/60 (molar ratio), more preferably only oxyethylene group is bonded.
　化学式（２）において、Ｒ３は水素原子、脂肪族炭化水素基または芳香族基である。
　脂肪族炭化水素基は直鎖状であっても分岐していてもよく、飽和であっても不飽和であってもよい。脂肪族炭化水素基としては、炭素数が１～２２（好ましくは１～１２）のアルキル基を挙げることができる。アルキル基としては、たとえば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ラウリル基、ステアリル基、ベヘニル基等を挙げることができる。
　一般式（２）のＲ３における芳香族基とは、本発明においては、ベンゼン、ナフタレン、アントラセン等の芳香族炭化水素を含有する有機基を意味し、含有する芳香族炭化水素の数は１つ以上であればよい。Ｒ３が芳香族基の場合、一般式（２）において酸素原子と結合するＲの部位は、芳香族炭化水素部分であってもよく、そうでなくてもよい。芳香族基としては、たとえば、フェニル基、トルイル基、キシリル基、スチレン化フェニル基、フェニルエチル基、ジスチレン化フェニル基、トリスチレン化フェニル基、ベンジル基、ベンジル化フェニル基、ジベンジル化フェニル基、トリベンジル化フェニル基等を挙げることができる。
　一般式（２）のＲ３としては、アルキル基または芳香族基が好ましい。 In the chemical formula (2), R 3 is a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group.
The aliphatic hydrocarbon group may be linear or branched, and may be saturated or unsaturated. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 22 (preferably 1 to 12) carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a lauryl group, a stearyl group, and a behenyl group.
In the present invention, the aromatic group in R 3 of the general formula (2) means an organic group containing an aromatic hydrocarbon such as benzene, naphthalene, anthracene, and the number of the aromatic hydrocarbons contained is one. It is sufficient if there are two or more. When R 3 is an aromatic group, the R site bonded to the oxygen atom in the general formula (2) may or may not be an aromatic hydrocarbon moiety. As the aromatic group, for example, phenyl group, toluyl group, xylyl group, styrenated phenyl group, phenylethyl group, distyrenated phenyl group, tristyrenated phenyl group, benzyl group, benzylated phenyl group, dibenzylated phenyl group, Examples thereof include a tribenzylated phenyl group.
R 3 in the general formula (2) is preferably an alkyl group or an aromatic group.
　化学式（２）において、ｎは２０～２００の整数であり、好ましくは４０～１５０であり、さらに好ましくは５０～１００である。ｎが２０未満であると、親水性が不足し、水に分散させることが困難になり繊維に均一に給油しにくくなることがある、一方、ｎが２００超であると、合成繊維への親和性が弱くなり、湿潤時の繊維／繊維間摩擦が高くなり、良好な分散性を付与できなくなることがある。ここで、ポリアルキレングリコールの誘導体の具体例としては、ポリエチレングリコールモノフェニルエーテル（平均分子量：３０００）、ポリエチレングリコール（平均分子量２０００）、ポリエチレングリコールモノメチルエーテル（平均分子量：１０００）などがあげられる。 In the chemical formula (2), n is an integer of 20 to 200, preferably 40 to 150, and more preferably 50 to 100. If n is less than 20, the hydrophilicity is insufficient, making it difficult to disperse in water and making it difficult to lubricate the fibers uniformly. On the other hand, if n is more than 200, affinity for synthetic fibers In some cases, the fiber / fiber friction at the time of wetting becomes high and good dispersibility cannot be imparted. Specific examples of the polyalkylene glycol derivative include polyethylene glycol monophenyl ether (average molecular weight: 3000), polyethylene glycol (average molecular weight 2000), polyethylene glycol monomethyl ether (average molecular weight: 1000), and the like.
　Ａ成分である上記ポリエステル化合物を製造する場合のジカルボン酸（誘導体）、アルキレングリコールおよびポリアルキレングリコールまたはその誘導体の比率（モル比）について、［ジカルボン酸（誘導体）／アルキレングリコール］の比率（モル比）は２０／８０～６０／４０の範囲内であるのが好ましく、３０／７０～５０／５０がより好ましく、４０／６０～５０／５０がさらに好ましい。ジカルボン酸（誘導体）とアルキレングリコールの比率がこの範囲であることにより、反応が進みやすくまた、反応後の未反応物が少なくなる。
　また、［ジカルボン酸（誘導体）／ポリアルキレングリコールまたはその誘導体］の比率（モル比）は１００／２～１００／１００の範囲内であることが好ましく、１００／２～１００／５０がより好ましく、１００／２～１００／２０がさらに好ましい。ジカルボン酸（誘導体）とポリアルキレングリコールまたはその誘導体の比率がこの範囲であることにより、容易に水に分散させることができ取扱性が良好で、合成繊維への親和性が良好で、湿潤時の繊維／繊維間摩擦が低くなり、良好な分散性を付与できる。 The ratio (molar ratio) of [dicarboxylic acid (derivative) / alkylene glycol] with respect to the ratio (molar ratio) of dicarboxylic acid (derivative), alkylene glycol and polyalkylene glycol or derivative thereof when producing the above-mentioned polyester compound as component A ) Is preferably in the range of 20/80 to 60/40, more preferably 30/70 to 50/50, and even more preferably 40/60 to 50/50. When the ratio of the dicarboxylic acid (derivative) and the alkylene glycol is within this range, the reaction can easily proceed and the amount of unreacted material after the reaction is reduced.
The ratio (molar ratio) of [dicarboxylic acid (derivative) / polyalkylene glycol or derivative thereof] is preferably in the range of 100/2 to 100/100, more preferably 100/2 to 100/50, More preferably, it is 100/2 to 100/20. When the ratio of the dicarboxylic acid (derivative) to the polyalkylene glycol or derivative thereof is within this range, it can be easily dispersed in water, the handling property is good, the affinity for synthetic fibers is good, and the wetness is good. The fiber / fiber friction is reduced, and good dispersibility can be imparted.
　ポリエステル化合物を製造する反応は、当該分野において公知の方法および条件を適宜選択して行うことができる。また、反応圧については、常圧で行ってもよく、減圧で行ってもよい。 The reaction for producing the polyester compound can be carried out by appropriately selecting methods and conditions known in the art. Moreover, about reaction pressure, you may carry out by a normal pressure and you may carry out by pressure reduction.
　本発明の抄紙用合成繊維処理剤の不揮発分に占めるＡ成分の割合は、４０～９０重量％であり、好ましくは５０～９０重量％、さらに好ましくは７０～９０重量％である。Ａ成分の割合がこの範囲であることにより、湿潤時の繊維／繊維間の摩擦を低くでき、良好な分散性を付与できる。なお、本発明の抄紙用合成繊維処理剤の不揮発分とは、水分などを除くための熱乾燥工程後においても繊維表面に残存する抄紙用合成繊維処理剤中の成分を意味し、一般的には１１０℃、３０分間の熱処理条件において揮発せずに残存した成分を意味する。 The proportion of the component A in the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is 40 to 90% by weight, preferably 50 to 90% by weight, more preferably 70 to 90% by weight. When the ratio of the component A is within this range, it is possible to reduce the fiber / fiber friction when wet and to impart good dispersibility. The non-volatile content of the synthetic fiber treatment agent for papermaking of the present invention means a component in the synthetic fiber treatment agent for papermaking that remains on the fiber surface even after the heat drying step for removing moisture, etc. Means a component that remains without volatilization under heat treatment conditions of 110 ° C. for 30 minutes.
〔Ｂ成分〕
　Ｂ成分は、脂肪酸とアルカノールアミンを縮合することによって得られる縮合物である。Ｂ成分を構成する脂肪酸は、炭素数８～２２の脂肪酸であり、好ましくは炭素数１２～２２の脂肪酸であり、さらに好ましくは炭素数１６～２２の脂肪酸である。Ｂ成分は、Ａ成分と併用することにより、良好な分散性および抑泡性を付与することができ、特に抄紙工程で良好な抑泡性、消泡性を付与できる。なお、ここで、炭素数８～２２とは、Ｂ成分を構成する脂肪酸の炭素数が８～２２であるという意味である。 [B component]
B component is a condensate obtained by condensing a fatty acid and an alkanolamine. The fatty acid constituting the component B is a fatty acid having 8 to 22 carbon atoms, preferably a fatty acid having 12 to 22 carbon atoms, and more preferably a fatty acid having 16 to 22 carbon atoms. The B component can impart good dispersibility and foam suppression properties when used in combination with the component A, and can impart good foam suppression properties and antifoaming properties particularly in the paper making process. Here, the carbon number of 8 to 22 means that the fatty acid constituting the B component has 8 to 22 carbon atoms.
　Ｂ成分を構成する脂肪酸の具体例としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、リノール酸、リノレン酸、リシノール酸およびベヘン酸などがあげられる。これらの脂肪酸のなかでも、Ｂ成分を構成する脂肪酸がステアリン酸、オレイン酸、リシノール酸であると、抑泡性、消泡性と水に対する水溶性のバランスが良いという点で好ましい。Ｂ成分を構成する脂肪酸は、１種から構成されていてもよく、２種以上から構成されていてもよい。
　Ｂ成分を構成するアルカノールアミンの具体例としては、モノメタノールアミン、ジメタノールアミン、モノエタノ－ルアミン、ジエタノ－ルアミン、モノプロパノールアミン、ジプロパノールアミン、モノイソプロパノ－ルアミン等が挙げられる。これらのアルカノールアミンのなかでもジエタノ－ルアミンであると、抑泡性、消泡性と水に対する水溶性のバランスが良いという点で好ましい。Ｂ成分を構成するアルカノールアミンは、１種から構成されていてもよく、２種以上から構成されていてもよい。 Specific examples of the fatty acid constituting the component B include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and behenic acid. Among these fatty acids, it is preferable that the fatty acid constituting the component B is stearic acid, oleic acid, or ricinoleic acid in terms of good balance between foam suppression, antifoaming properties and water solubility. The fatty acid which comprises B component may be comprised from 1 type, and may be comprised from 2 or more types.
Specific examples of the alkanolamine constituting the component B include monomethanolamine, dimethanolamine, monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, monoisopropanolamine and the like. Of these alkanolamines, diethylamine is preferred because it has a good balance between foam suppression, antifoaming and water solubility. The alkanolamine constituting the component B may be composed of one kind or two or more kinds.
　Ｂ成分としては、たとえば、上記化学式（３）で示される脂肪酸アミドが挙げられる。式（３）において、Ｒ４は炭素数７～２１の脂肪族炭化水素基であり、Ｒ５は炭素数１～４のヒドロキシアルキル基であり、Ｒ６は水素原子、炭素数１～４のアルキル基または炭素数１～４のヒドロキシアルキル基である。
　Ｒ４の炭素数は７～２１であり、１１～２１が好ましく、１５～２１が特に好ましい。Ｒ４の炭素数が７未満であると、抄紙工程で十分な抑泡性、消泡性を示さないことがあり、その場合良好な分散性が得られないことがある。一方、Ｒ４の炭素数が２１超であると、水に対する水溶性が悪くなり取扱い性が損なわれることがあり、さらにはコストアップになり実用に適さない。Ｒ４は直鎖状であっても分岐していてもよく、飽和であっても不飽和であってもよい。Ｒ４としては、たとえば、エナンチル基、ノニル基、ウンデシル基、トリデシル基、ペンタデシル基、マルガリル基、プリスタン基、ｃｉｓ－９－ヘプタデセニル基等を挙げることができる。これらのうちでも、Ｒ４としては、ウンデシル基、トリデシル基、ペンタデシル基、マルガリル基、プリスタン基が好ましく、マルガリル基が特に好ましい。 Examples of the component B include fatty acid amides represented by the above chemical formula (3). In the formula (3), R 4 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms, R 5 is a hydroxyalkyl group having 1 to 4 carbon atoms, R 6 is a hydrogen atom, and has 1 to 4 carbon atoms. An alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms.
R 4 has 7 to 21 carbon atoms, preferably 11 to 21 and particularly preferably 15 to 21. If the carbon number of R 4 is less than 7, sufficient foam suppression and defoaming properties may not be exhibited in the paper making process, and in this case, good dispersibility may not be obtained. On the other hand, when the carbon number of R 4 is more than 21, water solubility in water may be deteriorated, handling properties may be impaired, and further, the cost is increased and it is not suitable for practical use. R 4 may be linear or branched and may be saturated or unsaturated. Examples of R 4 include an enanthyl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, margaryl group, pristane group, cis-9-heptadecenyl group, and the like. Among these, as R 4 , an undecyl group, a tridecyl group, a pentadecyl group, a margaryl group, and a pristane group are preferable, and a margaryl group is particularly preferable.
　Ｒ５のヒドロキシアルキル基は、直鎖状であっても分岐していてもよい。Ｒ５のヒドロキシアルキル基の炭素数は、１～３が好ましく、１～２がさらに好ましい。Ｒ５の炭素数が４超であると縮合反応性が低く、縮合物の回収率が悪くなることがある。
　Ｒ６としては、炭素数１～４のヒドロキシアルキル基が好ましく、炭素数１～２のヒドロキシアルキル基がさらに好ましい。Ｒ６の炭素数が４超であると縮合反応性が低く、縮合物の回収率が悪くなることがある。 The hydroxyalkyl group for R 5 may be linear or branched. The number of carbon atoms of the hydroxyalkyl group of R 5 is preferably 1 to 3, more preferably 1 to 2. When the carbon number of R 5 is more than 4, the condensation reactivity is low, and the recovery rate of the condensate may be deteriorated.
R 6 is preferably a hydroxyalkyl group having 1 to 4 carbon atoms, and more preferably a hydroxyalkyl group having 1 to 2 carbon atoms. When R 6 has more than 4 carbon atoms, the condensation reactivity is low, and the recovery rate of the condensate may be deteriorated.
　上記Ｂ成分を製造する場合、脂肪酸及びアルカノールアミンの比率（モル比）は、脂肪酸／アルカノールアミン＝３／１～１／３の範囲内であるのが好ましい。
　上記Ｂ成分を製造する反応は、当該分野において公知の方法および条件を適宜選択して行うことができる。また、反応圧については、常圧で行ってもよく、減圧で行ってもよい。 When the component B is produced, the ratio (molar ratio) of fatty acid and alkanolamine is preferably in the range of fatty acid / alkanolamine = 3/1 to 1/3.
The reaction for producing the component B can be carried out by appropriately selecting methods and conditions known in the art. Moreover, about reaction pressure, you may carry out by a normal pressure and you may carry out by pressure reduction.
　本発明の抄紙用合成繊維処理剤の不揮発分に占めるＢ成分の割合は、５～３０重量％であり、好ましくは５～２５重量％、さらに好ましくは５～１５重量％である。Ｂ成分の割合がこの範囲であることにより、抄紙工程で十分な抑泡性、消泡性を付与でき、また湿潤時の繊維／繊維間の摩擦を低くでき、そのため良好な分散性を付与できる。 The proportion of the B component in the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is 5 to 30% by weight, preferably 5 to 25% by weight, and more preferably 5 to 15% by weight. When the ratio of the B component is within this range, sufficient foam suppression and defoaming can be imparted in the paper making process, and the friction between the fibers / fibers when wet can be reduced, and therefore, good dispersibility can be imparted. .
〔Ｃ成分〕
　本発明の抄紙用合成繊維処理剤は、上記のＡ成分およびＢ成分に加え、さらに炭素数が８～２２の脂肪酸石鹸であるＣ成分をさらに含むことが好ましい。Ｃ成分は、脂肪酸を塩基で中和することによって得られるものである。Ｃ成分を含むことにより、抄紙用合成繊維に対して、低シェアでさらに良好な分散性を付与できる。
　Ｃ成分は、炭素数８～２２の脂肪酸石鹸であり、好ましくは炭素数１２～２２の脂肪酸石鹸であり、さらに好ましくは炭素数１６～２２の脂肪酸石鹸である。なお、ここで、炭素数とは脂肪酸石鹸を構成する脂肪酸の炭素数を意味する。
　Ｃ成分を構成する脂肪酸の具体例としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、リノール酸、リノレン酸、リシノール酸およびベヘン酸などがあげられる。これらの脂肪酸のなかでも、Ｃ成分を構成する脂肪酸がステアリン酸、オレイン酸、リシノール酸であると、分散性と水に対する水溶性のバランスが良いという点で好ましい。Ｃ成分を構成する脂肪酸は、これらの脂肪酸のうちの１種から構成されていてもよく、２種以上から構成されていてもよい。Ｃ成分としては、たとえば、下記化学式（４）で示される脂肪酸石鹸が挙げられる。 [C component]
The synthetic fiber treating agent for papermaking of the present invention preferably further contains a C component which is a fatty acid soap having 8 to 22 carbon atoms in addition to the above A component and B component. The component C is obtained by neutralizing a fatty acid with a base. By including the C component, it is possible to impart a better dispersibility with a low share to the synthetic fiber for papermaking.
Component C is a fatty acid soap having 8 to 22 carbon atoms, preferably a fatty acid soap having 12 to 22 carbon atoms, and more preferably a fatty acid soap having 16 to 22 carbon atoms. Here, the carbon number means the carbon number of the fatty acid constituting the fatty acid soap.
Specific examples of the fatty acid constituting the component C include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and behenic acid. Among these fatty acids, it is preferable that the fatty acid constituting the component C is stearic acid, oleic acid, or ricinoleic acid because the balance between dispersibility and water solubility is good. The fatty acid which comprises C component may be comprised from 1 type of these fatty acids, and may be comprised from 2 or more types. As C component, the fatty acid soap shown by following Chemical formula (4) is mentioned, for example.
Figure JPOXMLDOC01-appb-C000007
 （但し、上記化学式（４）において、Ｒ７は炭素数７～２１の脂肪族炭化水素基であり、Ｍｎ＋は陽イオンであり、ｎは１以上の整数である。）
Figure JPOXMLDOC01-appb-C000007
 (In the above chemical formula (4), R 7 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms, M n + is a cation, and n is an integer of 1 or more.)
　上記化学式（４）において、Ｍｎ＋としては、ナトリウム、カリウム、リチウムなどのアルカリ金属やカルシウム、マグネシウムなどのアルカリ土類金属が挙げられる。これらのうちで、好ましくは、アルカリ金属であり、さらに好ましくはナトリウム、カリウムである。 In the above chemical formula (4), examples of M n + include alkali metals such as sodium, potassium and lithium, and alkaline earth metals such as calcium and magnesium. Of these, preferred are alkali metals, and more preferred are sodium and potassium.
　Ｒ７の炭素数は、７～２１であり、好ましくは１１～２１、特に好ましくは１５～２１である。Ｒ７の炭素数が７未満であると、抄紙工程で気泡が発生することから良好な分散性が得られないことがある。一方、Ｒ７の炭素数が２１超であると、濡れ性および低シェアでの分散性が悪くなることがある。さらには、コストアップになり実用に適さない。また、Ｒ７は直鎖状であっても分岐していてもよく、飽和であっても不飽和であってもよい。Ｒ７としては、たとえば、エナンチル基、ノニル基、ウンデシル基、トリデシル基、ペンタデシル基、マルガリル基、プリスタン基、ｃｉｓ－９－ヘプタデセニル基等を挙げることができる。これらのうちでも、Ｒ７としては、ウンデシル基、トリデシル基、ペンタデシル基、マルガリル基、プリスタン基が好ましく、マルガリル基が特に好ましい。 R 7 has 7 to 21 carbon atoms, preferably 11 to 21 carbon atoms, particularly preferably 15 to 21 carbon atoms. If the carbon number of R 7 is less than 7, good dispersibility may not be obtained because bubbles are generated in the paper making process. On the other hand, if the carbon number of R 7 is more than 21, wettability and dispersibility with a low share may be deteriorated. Furthermore, the cost is increased and it is not suitable for practical use. R 7 may be linear or branched and may be saturated or unsaturated. Examples of R 7 include an enantyl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, margaryl group, pristane group, cis-9-heptadecenyl group, and the like. Among these, as R 7 , an undecyl group, a tridecyl group, a pentadecyl group, a margaryl group, and a pristane group are preferable, and a margaryl group is particularly preferable.
　Ｃ成分を含む場合の本発明の抄紙用合成繊維処理剤の不揮発分に占めるＣ成分の割合は、５～３０重量％であり、好ましくは５～２５重量％、さらに好ましくは５～１５重量％である。Ｃ成分の割合がこの範囲にあることにより、抄紙工程で良好な低シェアの分散性を付与できる。 When the C component is contained, the proportion of the C component in the nonvolatile content of the synthetic fiber treating agent for papermaking of the present invention is 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 15% by weight. It is. When the proportion of component C is in this range, good low shear dispersibility can be imparted in the paper making process.
　Ｃ成分の製造方法については、特に限定はなく、たとえば、炭素数８～２２の脂肪酸を塩基で中和して製造できる。 The production method of component C is not particularly limited, and can be produced, for example, by neutralizing a fatty acid having 8 to 22 carbon atoms with a base.
〔その他の成分〕
　本発明の抄紙用合成繊維処理剤は、前述の成分を分散あるいは乳化した水を含む水性液であることが好ましい。本発明に使用する水としては、純水、蒸留水、精製水、軟水、イオン交換水、水道水等のいずれであってもよい。水を含有する水性液の場合、処理剤全体に占める不揮発分の割合は、０．０５～５０重量％が好ましく、０．５～４０重量％がより好ましく、１～３０重量％がさらに好ましい。 [Other ingredients]
The synthetic fiber treating agent for papermaking of the present invention is preferably an aqueous liquid containing water in which the aforementioned components are dispersed or emulsified. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like. In the case of an aqueous liquid containing water, the proportion of the nonvolatile content in the entire treatment agent is preferably 0.05 to 50% by weight, more preferably 0.5 to 40% by weight, and further preferably 1 to 30% by weight.
　本発明の抄紙用合成繊維処理剤は、前述の成分を分散あるいは乳化した水性液とするため、また付着時の濡れ特性を向上させるため、補助的に添加剤を併用することができる。かかる目的のために用いることのできる添加剤としては、ポリオキシエチレンとポリオキシプロピレンの共重合物誘導体、ポリオキシエチレン（以下ＰＯＥと略記する）アルキルエーテル、ＰＯＥアルキルエステル等の非イオン界面活性剤、アルキルサルフェート（塩）、アルキルスルホネート（塩）、アルキルホスフェート（塩）等のアニオン界面活性剤が挙げられる。これらの添加剤を併用する場合も含め、本発明の処理剤の水性液の作製に際しては適宜に有機溶媒を使用することもできる。また、抄紙用合成繊維処理剤の不揮発分に占めるこれらの添加剤の割合は特に限定はないが、５０重量％未満が好ましく、２０重量％未満がより好ましく、１０重量％未満がさらに好ましい。 The synthetic fiber treating agent for papermaking of the present invention can be supplemented with an additive in order to obtain an aqueous liquid in which the above-mentioned components are dispersed or emulsified and to improve the wettability at the time of adhesion. Examples of additives that can be used for this purpose include nonionic surfactants such as polyoxyethylene-polyoxypropylene copolymer derivatives, polyoxyethylene (hereinafter abbreviated as POE) alkyl ethers, and POE alkyl esters. And anionic surfactants such as alkyl sulfates (salts), alkyl sulfonates (salts), and alkyl phosphates (salts). An organic solvent can be appropriately used in preparing the aqueous liquid of the treatment agent of the present invention, including the case where these additives are used in combination. The proportion of these additives in the non-volatile content of the synthetic fiber treatment agent for papermaking is not particularly limited, but is preferably less than 50% by weight, more preferably less than 20% by weight, and even more preferably less than 10% by weight.
　また、本発明の抄紙用合成繊維処理剤には、必要に応じて、抗菌剤、酸化防止剤、防腐剤、艶消し剤、顔料、防錆剤、芳香剤等がさらに含まれていてもよい。 In addition, the synthetic fiber treatment agent for papermaking of the present invention may further contain an antibacterial agent, an antioxidant, a preservative, a matting agent, a pigment, a rust preventive, a fragrance and the like, if necessary. .
　本発明の抄紙用合成繊維処理剤の不揮発分濃度が１％に調整された水エマルションは、４０℃に加熱した場合に析出物が生じないエマルションであることが好ましい。また、アニオン界面活性剤およびカチオン界面活性剤を同時に含有しないことが好ましい。 The water emulsion in which the non-volatile content of the synthetic fiber treating agent for papermaking of the present invention is adjusted to 1% is preferably an emulsion that does not produce precipitates when heated to 40 ° C. Moreover, it is preferable not to contain an anionic surfactant and a cationic surfactant simultaneously.
〔抄紙用合成繊維処理剤の製造方法〕
　本発明の抄紙用合成繊維処理剤は、Ａ成分およびＢ成分、場合によってはさらにＣ成分を混合し、必要に応じてその他成分を混合することによって製造できる。それぞれの成分の混合順序については特に限定はなく、また、これら成分を室温（２０～２５℃）で混合してもよく、加温（２０℃～８０℃）して混合してもよい。
　Ａ成分の形態には水性液、ペースト状、粉体状およびブロック状等があるが、取り扱い性の上からは水性液が好ましい。Ｂ成分の形態には水性液、粉体状およびブロック状等があるが、取り扱い性の上からは水性液が好ましい。Ｃ成分の形態には水性液、粉体状およびブロック状等があるが、取り扱い性の上からは水性液が好ましい。したがって、本発明の抄紙用合成繊維処理剤は、Ａ成分を含む水性液およびＢ成分を含む水性液、場合によってはさらにＣ成分を含む水性液を混合し、必要に応じてその他成分を混合して製造することが好ましい。 [Method for producing synthetic fiber treating agent for papermaking]
The synthetic fiber treating agent for papermaking of the present invention can be produced by mixing the A component and the B component, and optionally the C component, and optionally mixing other components. The order of mixing the components is not particularly limited, and these components may be mixed at room temperature (20 to 25 ° C.) or may be mixed by heating (20 ° C. to 80 ° C.).
The form of component A includes an aqueous liquid, a paste, a powder, and a block, but an aqueous liquid is preferable from the viewpoint of handleability. The form of the component B includes an aqueous liquid, a powder form, a block form, etc., but an aqueous liquid is preferable from the viewpoint of handling. The form of component C includes an aqueous liquid, a powder form, a block form, and the like, but an aqueous liquid is preferable from the viewpoint of handling. Therefore, the synthetic fiber treating agent for papermaking of the present invention mixes an aqueous liquid containing the A component and an aqueous liquid containing the B component, and optionally an aqueous liquid containing the C component, and optionally other components. It is preferable to manufacture.
　Ａ成分を含む水性液の濃度としては、例えば１０～４０重量％であり、Ｂ成分を含む水性液の濃度としては、例えば２０～１００重量％であり、Ｃ成分を含む水性液の濃度としては、例えば２０～５０重量％である。
　本発明の抄紙用合成繊維処理剤を構成する各成分は、その水性液（少なくとも１０重量％以上）が水に室温（２０～２５℃）または必要に応じて加温（２０℃～８０℃）して溶解・混合し、均一安定なエマルションとなる成分である。従って、抄紙用合成繊維処理剤を合成繊維に付与するような製造現場において、各成分の水性液を室温または加温して溶解・混合し、安定なエマルションである抄紙用合成繊維処理剤を調製することもできる。 The concentration of the aqueous liquid containing component A is, for example, 10 to 40% by weight, the concentration of the aqueous liquid containing component B is, for example, 20 to 100% by weight, and the concentration of the aqueous liquid containing component C is, for example, For example, 20 to 50% by weight.
Each component constituting the synthetic fiber treating agent for papermaking of the present invention is such that an aqueous liquid (at least 10% by weight or more) is heated in water at room temperature (20 to 25 ° C.) or as necessary (20 ° C. to 80 ° C.). And dissolved and mixed to form a uniform and stable emulsion. Therefore, in manufacturing sites where synthetic fiber treatment agents for papermaking are applied to synthetic fibers, aqueous solutions of each component are dissolved or mixed at room temperature or heated to prepare synthetic fiber treatment agents for papermaking that are stable emulsions. You can also
　本発明の抄紙用合成繊維処理剤を製造するための原料を取扱、保管、運搬等する場合、Ａ成分およびＢ成分、場合によってはＣ成分を共存させても、得られる本発明の抄紙用合成繊維処理剤の製品安定性は良好であり問題はない。この場合、これら成分の配合品の高濃度品の水性液としては、具体的には５０重量％以下の水性液の調製が可能である。もちろん、Ａ成分、Ｂ成分、Ｃ成分を混合せずに、別々に分けておいてもよい。 When the raw material for producing the synthetic fiber treating agent for papermaking of the present invention is handled, stored, transported, etc., the obtained composition for papermaking of the present invention can be obtained even if the A component and the B component, and in some cases, the C component coexist. The product stability of the fiber treatment agent is good and there is no problem. In this case, it is possible to prepare an aqueous liquid having a concentration of 50% by weight or less as a high-concentration aqueous liquid. Of course, the A component, the B component, and the C component may be separated separately without mixing.
〔抄紙用合成繊維の製造方法〕
　本発明の抄紙用合成繊維の製造方法は、原料合成繊維に、本発明の抄紙用合成繊維処理剤を処理する工程を含むものである。ここで、原料合成繊維とは、抄紙用合成繊維処理剤が処理されていない合成繊維をいう。抄紙用合成繊維とは、抄紙工程で使用できるよう所定の長さに切断された短繊維をいう。本発明の抄紙用合成繊維の製造方法によって得られる抄紙用合成繊維は、本発明の抄紙用合成繊維処理剤が処理された短繊維であるので、抄紙を製造する際の抄紙する工程で、水に低シェアで分散され、気泡が抑制される。 [Method for producing synthetic fiber for papermaking]
The manufacturing method of the synthetic fiber for papermaking of this invention includes the process of processing the synthetic fiber processing agent for papermaking of this invention to raw material synthetic fiber. Here, the raw material synthetic fiber refers to a synthetic fiber that has not been treated with the synthetic fiber treating agent for papermaking. The synthetic fiber for papermaking means a short fiber cut into a predetermined length so that it can be used in the papermaking process. Since the synthetic fiber for papermaking obtained by the method for producing synthetic fiber for papermaking of the present invention is a short fiber treated with the synthetic fiber treating agent for papermaking of the present invention, water is produced in the process of papermaking during the production of papermaking. Are dispersed with a low share, and bubbles are suppressed.
　（原料）合成繊維については、特に限定はなく、たとえば、ポリエステル繊維、ポリアミド繊維、ポリオレフィン繊維、ポリフェニレンサルファイド（ＰＰＳ）繊維、ポリアクリロニトリル系繊維、ポリプロピレン系繊維、これらの２種以上のポリマーを用いた複合合成繊維等を挙げることができる。なかでも、合成繊維がポリエステル繊維であると、本発明の抄紙用合成繊維処理剤と繊維との親和性が高い点で好ましく、ポリエチレンテレフタレート（ＰＥＴ）繊維であるとさらに好ましい。繊維の単糸繊度は０．０１～２ｄｔｅｘが好ましく、繊維長は０．５～２５ｍｍが好ましい。とりわけ裁断された繊維長が５ｍｍ以上で繊度が１．０デニール以下の抄紙用ポリエステル系繊維に適用する場合に特に有効である。なお、ポリエステル繊維とはポリエチレンテレフタレート繊維のほかに、ポリ乳酸（ＰＬＡ）繊維、ポリトリメチレンテレフタレート（ＰＴＴ）繊維、ポリブチレンテレフタレート（ＰＢＴ）繊維、ポリエチレンナフタレート（ＰＥＮ）繊維、ポリアリレート繊維等エステル結合を形成する反応によって縮合させた高分子からなる繊維を意味する。 (Raw material) The synthetic fiber is not particularly limited. For example, polyester fiber, polyamide fiber, polyolefin fiber, polyphenylene sulfide (PPS) fiber, polyacrylonitrile fiber, polypropylene fiber, or two or more of these polymers were used. A composite synthetic fiber etc. can be mentioned. Among them, the synthetic fiber is preferably a polyester fiber in terms of high affinity between the synthetic fiber treating agent for papermaking of the present invention and the fiber, and more preferably a polyethylene terephthalate (PET) fiber. The single yarn fineness of the fiber is preferably 0.01 to 2 dtex, and the fiber length is preferably 0.5 to 25 mm. It is particularly effective when applied to a polyester fiber for papermaking having a cut fiber length of 5 mm or more and a fineness of 1.0 denier or less. Polyester fiber is not only polyethylene terephthalate fiber, but also polylactic acid (PLA) fiber, polytrimethylene terephthalate (PTT) fiber, polybutylene terephthalate (PBT) fiber, polyethylene naphthalate (PEN) fiber, polyarylate fiber, etc. It means a fiber made of a polymer condensed by a reaction for forming a bond.
　原料合成繊維に抄紙用合成繊維処理剤を処理する工程としては、抄紙用合成繊維を用いて抄紙する工程に入る前までに処理されていれば特に限定はない。一般に、抄紙用合成繊維（短繊維）は、紡糸工程、延伸工程、仕上工程、巻縮工程、切断工程を経て製造されるが、原料合成繊維に対して、抄紙用合成繊維処理剤を紡糸工程、延伸工程および仕上工程から選ばれる少なくとも１つの工程で処理してもよく、巻縮工程及びその前後、切断工程及びその前後等で処理してもよい。処理方法（給油方法）としては、特に限定は無く、公知の方法を採用できる。例えば、紡糸工程、延伸工程、仕上工程で処理する場合は、ローラータッチ法、スプレー法、浸漬法等の通常の処理方法（給油方法）で行うことができる。 The process for treating the raw synthetic fiber with the synthetic fiber treating agent for papermaking is not particularly limited as long as it is processed before the paper making process using the synthetic fiber for papermaking. Generally, synthetic fibers for papermaking (short fibers) are manufactured through a spinning process, a drawing process, a finishing process, a crimping process, and a cutting process. Further, it may be processed in at least one process selected from a stretching process and a finishing process, and may be processed in a crimping process and before and after, a cutting process, and before and after that. There is no limitation in particular as a processing method (oil supply method), A well-known method is employable. For example, when processing in a spinning process, a drawing process, and a finishing process, it can be performed by a normal processing method (oil supply method) such as a roller touch method, a spray method, or a dipping method.
　抄紙用合成繊維処理剤の不揮発分の付着量は、抄紙用合成繊維に対して、０．０５～２重量％が好ましく、０．１～１重量％がさらに好ましい。付着量が０．０５重量％未満では分散性が不十分となることがあり、２重量％を超えると抄紙工程で分散槽の泡立ちが増加することがある。 The amount of non-volatile matter attached to the synthetic fiber treatment agent for papermaking is preferably 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, based on the synthetic fiber for papermaking. When the adhesion amount is less than 0.05% by weight, dispersibility may be insufficient, and when it exceeds 2% by weight, foaming in the dispersion tank may increase in the paper making process.
〔抄紙不織布の製造方法〕
　本発明の抄紙不織布の製造方法は、本発明の抄紙用合成繊維処理剤が処理された抄紙用合成繊維を水中に分散させて抄紙する工程（抄紙工程ということもある）を含むものである。該抄紙用合成繊維は、抄紙工程において、攪拌・分散時、繊維同士が絡みにくく、速やかに単繊維に分散し、安定分散性も良好である。
　抄紙工程としては、常法の湿式抄紙工程を採用できる。湿式抄紙工程としては、上記工程で抄紙用合成繊維処理剤が処理された抄紙用合成繊維（短繊維）をパルパーに投入して水中で攪拌・分散し、懸濁させる。この時、水に低シェアで分散され、気泡が抑制されるので、繊維が均一に分散することで、地合いの良好な抄紙を得ることができる。次に、抄き網に供給し、湿紙とする。そして、湿紙を乾燥させる乾燥工程を経て、ロール状に巻取り、湿式抄紙不織布を得る。抄き網は円網、短網が一般的であるが、長網、ロトフォーマー、ハイドロフォーマー、パーチフォーマーなどでも構わない。乾燥工程は複数の回転加熱ローラー式（多筒式）あるいはヤンキードラム式のいずれでも構わない。 [Method for producing paper nonwoven fabric]
The method for producing a papermaking nonwoven fabric of the present invention includes a step of making paper by dispersing the synthetic fiber for papermaking treated with the synthetic fiber treating agent of the present invention in water (sometimes referred to as a papermaking step). In the papermaking process, the synthetic fiber for papermaking is not easily entangled with each other during stirring and dispersion, quickly disperses into a single fiber, and has good stable dispersibility.
As the papermaking process, a conventional wet papermaking process can be employed. In the wet papermaking step, the papermaking synthetic fiber (short fiber) treated with the papermaking synthetic fiber treating agent in the above step is put into a pulper, stirred and dispersed in water, and suspended. At this time, since it is dispersed in water with a low share and air bubbles are suppressed, paper making with a good texture can be obtained by uniformly dispersing the fibers. Next, the paper is supplied to a paper net and used as wet paper. And after the drying process which dries a wet paper, it winds up in roll shape and obtains a wet papermaking nonwoven fabric. The netting net is generally a circular net or a short net, but may be a long net, a rotoformer, a hydroformer, a perchformer, or the like. The drying process may be a plurality of rotary heating roller type (multi-cylinder type) or Yankee drum type.
　また、本発明の抄紙不織布の製造方法は、抄紙工程で、原料合成繊維または抄紙用合成繊維を上記の抄紙用合成繊維処理剤を含む水中に分散させて抄紙してもよい。 Further, in the method for producing the papermaking nonwoven fabric of the present invention, in the papermaking step, the raw synthetic fiber or the synthetic fiber for papermaking may be dispersed in water containing the above-mentioned synthetic fiber treating agent for papermaking to make paper.
　本発明の抄紙不織布の製造方法によれば、抄紙用合成繊維に対して、低シェアでの分散性を良好にでき、抄紙工程での気泡の発生を低下させ、優れた繊維の分散性を与えることができることから、製造速度が速くなりコスト削減につながるだけでなく、均一で地合いの良好な抄紙不織布が得られる。 According to the method for producing a papermaking nonwoven fabric of the present invention, it is possible to improve dispersibility at a low share with respect to synthetic fibers for papermaking, to reduce the generation of bubbles in the papermaking process, and to provide excellent fiber dispersibility. Therefore, not only the production speed is increased and the cost is reduced, but also a papermaking nonwoven fabric having a uniform and good texture can be obtained.
　本発明の製造方法で得られる抄紙不織布は、周知の様々な分野に利用される。特にワイパー、エアーフィルター、液体フィルター、電池セパレーター、人工皮革用基布、紙おむつ、ティーバッグ、包装材料として最適である。 The papermaking nonwoven fabric obtained by the production method of the present invention is used in various known fields. Particularly suitable as wipers, air filters, liquid filters, battery separators, artificial leather fabrics, disposable diapers, tea bags, and packaging materials.
　以下に本発明を実施例によって説明するが、本発明はこれに限定されるものではない。なお、各実施例および比較例における評価項目と評価方法は以下の通りである。以下では、「％」はいずれも「重量％」を表す。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto. In addition, the evaluation items and the evaluation method in each example and comparative example are as follows. Hereinafter, “%” represents “% by weight”.
　表１中の数値はいずれも抄紙用合成繊維処理剤に含まれる不揮発分の割合（成分Ａ１、成分Ａ２および成分Ａ３では、下記に示すようにそれぞれの水分散液として得られているが、水を除いたそれぞれの不揮発分の割合を表１では示している）を示している。 All the numerical values in Table 1 are the proportions of non-volatile components contained in the synthetic fiber treating agent for papermaking (component A1, component A2 and component A3 are obtained as respective aqueous dispersions as shown below. Table 1 shows the ratio of each non-volatile content excluding).
　表１に記載した各成分は下記の通りである。
　成分Ａ１：ジメチルテレフタレートとジメチルイソフタレートとをモル比８０：２０で合計２５重量部、エチレングリコール２０重量部およびポリエチレングリコールモノフェニルエーテル（平均分子量：３０００）５５重量部とを混合し、触媒として少量の酢酸亜鉛とチタンテトラブトキシドを加えて、常圧下１７５～２００℃で１８０分間反応させて、ほぼ理論量のメタノールを留去し、エステル交換反応を完了させた。次いで、２３０℃に昇温して１時間ほど反応させた後、０．５ｍｍＨｇに減圧して２３０～２６０℃において２０分間、続いて０．１～０．５ｍｍＨｇで２７５℃において４０分間反応させ、得られた重合体（平均分子量７０００）を直ちに温水に撹絆しながら投入して成分Ａ１の水分散液を得た。得られた水分散液中の成分Ａ１の濃度は２０重量％であった。 Each component described in Table 1 is as follows.
Component A1: A mixture of dimethyl terephthalate and dimethyl isophthalate in a molar ratio of 80:20, a total of 25 parts by weight, 20 parts by weight of ethylene glycol and 55 parts by weight of polyethylene glycol monophenyl ether (average molecular weight: 3000), and a small amount as a catalyst Zinc acetate and titanium tetrabutoxide were added and reacted at 175 to 200 ° C. under atmospheric pressure for 180 minutes, and the theoretical amount of methanol was distilled off to complete the transesterification reaction. Next, the temperature was raised to 230 ° C. and allowed to react for about 1 hour, and then the pressure was reduced to 0.5 mmHg at 230 to 260 ° C. for 20 minutes, followed by reaction at 0.1 to 0.5 mmHg at 275 ° C. for 40 minutes. The obtained polymer (average molecular weight 7000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A1. The concentration of component A1 in the obtained aqueous dispersion was 20% by weight.
　成分Ａ２：ジメチルテレフタレートとジメチルイソフタレートと５－スルホイソフタル酸ジメチルをモル比７５：２０：５で合計２５重量部、エチレングリコール１０重量部、ジエチレングリコール２０重量部およびポリエチレングリコール（平均分子量２０００）５５重量部とを混合し、触媒として少量の酢酸亜鉛とチタンテトラブトキシドを加えて、常圧下１７５～２００℃において１８０分間反応させて、ほぼ理論量のメタノールを留去し、エステル交換反応を完了させた。次いで、２３０℃に昇温して１時間ほど反応させた後、０．５ｍｍＨｇに減圧して２３０～２６０℃において２０分間、続いて０．１～０．５ｍｍＨｇで２７５℃において４０分間反応させ、得られた重合体（平均分子量５０００）を直ちに温水に撹絆しながら投入して成分Ａ２の水分散液を得た。得られた水分散液中の成分Ａ２の濃度は２０重量％であった。 Component A2: Dimethyl terephthalate, dimethyl isophthalate, and dimethyl 5-sulfoisophthalate in a molar ratio of 75: 20: 5, a total of 25 parts by weight, ethylene glycol 10 parts by weight, diethylene glycol 20 parts by weight, and polyethylene glycol (average molecular weight 2000) 55 parts by weight A small amount of zinc acetate and titanium tetrabutoxide were added as a catalyst, and the mixture was reacted at 175 to 200 ° C. under atmospheric pressure for 180 minutes. The theoretical amount of methanol was distilled off to complete the transesterification reaction. . Next, the temperature was raised to 230 ° C. and allowed to react for about 1 hour, and then the pressure was reduced to 0.5 mmHg at 230 to 260 ° C. for 20 minutes, followed by reaction at 0.1 to 0.5 mmHg at 275 ° C. for 40 minutes. The obtained polymer (average molecular weight 5000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A2. The concentration of component A2 in the obtained aqueous dispersion was 20% by weight.
　成分Ａ３：ジメチルテレフタレートとジメチルイソフタレートとをモル比８０：２０で合計２８重量部、エチレングリコール７重量部およびポリエチレングリコールモノメチルエーテル（平均分子量：１０００）６５重量部とを混合し、触媒として少量の酢酸亜鉛とチタンテトラブトキシドを加えて、常圧下１７５～２００℃で１８０分間反応させて、ほぼ理論量のメタノールを留去し、エステル交換反応を完了させた。次いで、２３０℃に昇温して１時間ほど反応させた後、０．５ｍｍＨｇに減圧して２３０～２６０℃において２０分間、続いて０．１～０．５ｍｍＨｇで２７５℃において４０分間反応させ、得られた重合体（平均分子量７０００）を直ちに温水に撹絆しながら投入して成分Ａ３の水分散液を得た。得られた水分散液中の成分Ａ３の濃度は２０重量％であった。 Component A3: Dimethyl terephthalate and dimethyl isophthalate in a molar ratio of 80:20 were mixed in a total of 28 parts by weight, 7 parts by weight of ethylene glycol and 65 parts by weight of polyethylene glycol monomethyl ether (average molecular weight: 1000). Zinc acetate and titanium tetrabutoxide were added, and the mixture was reacted at 175 to 200 ° C. for 180 minutes under normal pressure, and the theoretical amount of methanol was distilled off to complete the transesterification reaction. Next, the temperature was raised to 230 ° C. and allowed to react for about 1 hour, and then the pressure was reduced to 0.5 mmHg at 230 to 260 ° C. for 20 minutes, followed by reaction at 0.1 to 0.5 mmHg at 275 ° C. for 40 minutes. The obtained polymer (average molecular weight 7000) was immediately added while stirring in warm water to obtain an aqueous dispersion of component A3. The concentration of Component A3 in the obtained aqueous dispersion was 20% by weight.
成分Ｂ１：ラウリン酸とジエタノールアミンとの縮合物
成分Ｂ２：ステアリン酸とジエタノールアミンとの縮合物
成分Ｂ３：ミリスチン酸とジエタノールアミンとの縮合物
成分Ｃ１：ラウリン酸カリウム
成分Ｃ２：ステアリン酸ナトリウム
成分Ｃ３：オレイン酸カリウム
成分Ｃ４：ベヘン酸ナトリウム
成分Ｄ１：ＰＯＥパルミチン酸モノエステル　ＭＷ：２５００ Component B1: Condensate of lauric acid and diethanolamine Component B2: Condensate of stearic acid and diethanolamine Component B3: Condensate of myristic acid and diethanolamine Component C1: Potassium laurate component C2: Sodium stearate component C3: Oleic acid Potassium component C4: Sodium behenate component D1: POE palmitic acid monoester MW: 2500
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
（実施例１～１６および比較例１～７）
（１）エマルションの調製
　表１に示す各成分および水を混合して、抄紙用合成繊維処理剤全体に占める不揮発分の重量割合が２０重量％の実施例１～１６、比較例１～７の抄紙用合成繊維処理剤をそれぞれ調製した。得られた抄紙用合成繊維処理剤をそれぞれ２５～６０℃の温水で不揮発分の重量割合が０．４重量％の濃度になるよう水で希釈してエマルションを調製した。得られたエマルションを用いて、下記評価方法の（２）に従って評価した。その結果を表２に示す。 (Examples 1 to 16 and Comparative Examples 1 to 7)
(1) Preparation of Emulsions Each of the components shown in Table 1 and water were mixed, and Examples 1 to 16 and Comparative Examples 1 to 7 in which the non-volatile content in the total synthetic fiber treating agent for papermaking was 20% by weight. Synthetic fiber treatment agents for papermaking were prepared. The obtained synthetic fiber treating agent for papermaking was diluted with water so that each non-volatile component had a concentration of 0.4% by weight with warm water of 25 to 60 ° C. to prepare an emulsion. Using the obtained emulsion, it was evaluated according to (2) of the following evaluation method. The results are shown in Table 2.
（２）湿潤時の繊維／繊維間摩擦（Ｆ／Ｆ摩擦）試験
　図１のように、カット直前のトウを脱脂したポリエステルフィラメント（１５０ｄ／４８ｆ）（１）をプーリー（２～６）に通して図１に示すようにセットした。Ｕゲージ（７）に結びつけたフィラメントの一端を３ｃｍ／ｍｉｎ．の速度で引っ張ることによって、上記（１）で作製したエマルションでフィラメントを浸し加撚部分の繊維間の最大摩擦力（ｇ）を測定した。測定の雰囲気は全て２０℃×６５％ＲＨとした。 (2) Fiber / fiber friction (F / F friction) test when wet As shown in FIG. 1, the polyester filament (150d / 48f) (1) from which the tow just before cutting was degreased was passed through the pulleys (2 to 6). Was set as shown in FIG. One end of the filament tied to the U gauge (7) is 3 cm / min. The filament was dipped with the emulsion prepared in (1) above, and the maximum frictional force (g) between the fibers in the twisted portion was measured. The measurement atmosphere was all 20 ° C. × 65% RH.
（３）抄紙性評価用ポリエチレンテレフタレート短繊維
　給油綿の作製においては、原料繊維（繊度１．３ｄｔｅｘ、長さ５ｍｍのポリエチレンテレフタレート短繊維）１０ｇに対して、評価対象の抄紙用合成繊維処理剤の不揮発分が付着処理後の繊維の０．２重量％になるように、上記（１）で調製したエマルション５ｇをスプレーで付着させ、８０℃の温風乾燥機の中で１時間乾燥した。乾燥後に得られたポリエチレンテレフタレート短繊維（抄紙用合成繊維）を、それぞれ、評価環境条件下で温湿度調節させた後、下記評価方法の（４）～（７）に従って評価した。その結果を表２に示す。 (3) Polyethylene terephthalate short fiber for papermaking evaluation In the production of oiled cotton, the synthetic fiber treatment agent for papermaking to be evaluated is used for 10 g of raw fiber (polyethylene terephthalate short fiber having a fineness of 1.3 dtex and a length of 5 mm). The emulsion (5 g) prepared in (1) above was adhered by spraying so that the nonvolatile content was 0.2% by weight of the fiber after the adhesion treatment, and dried for 1 hour in a hot air dryer at 80 ° C. The polyethylene terephthalate short fibers (synthetic fibers for papermaking) obtained after drying were adjusted according to the following evaluation methods (4) to (7) after adjusting the temperature and humidity under the evaluation environmental conditions. The results are shown in Table 2.
（４）低シェア分散性試験
　５００ｍｌビーカーにイオン交換水５００ｇを採取し、その中に試験用繊維１．００ｇを入れ、プロペラ撹拌機（回転数１００ｒｐｍ）で１分間攪拌する。攪拌停止後、１分後の繊維の分散状態を次の判定基準で目視判定し、繊維の低シェア分散性の指標とした。
＜判定基準＞
　◎：低シェア分散性が非常に良好で、繊維が均一に分散している。
　○：低シェア分散性が良好であるが、繊維束が一部に認められる。
　△：低シェア分散性がやや良好で、繊維束が多く認められる。
　×：低シェア分散性が不良で、繊維束が著しく多く認められる。 (4) Low shear dispersibility test 500 g of ion-exchanged water is collected in a 500 ml beaker, and 1.00 g of test fiber is put therein and stirred with a propeller stirrer (rotation speed 100 rpm) for 1 minute. After the stirring was stopped, the fiber dispersion state after 1 minute was visually determined according to the following criteria, which was used as an index of the low shear dispersibility of the fiber.
<Criteria>
A: Low shear dispersibility is very good, and fibers are uniformly dispersed.
○: Low shear dispersibility is good, but some fiber bundles are observed.
(Triangle | delta): Low shear dispersibility is a little good and many fiber bundles are recognized.
X: Low shear dispersibility is poor, and remarkably many fiber bundles are observed.
（５）抑泡性試験
　５００ｍｌビーカーにイオン交換水５００ｇを採取し、その中に試験用繊維１．００ｇを入れ、プロペラ撹拌機（回転数１０００ｒｐｍ）で１０分間攪拌する。攪拌停止後の泡立ち状態を次の判定基準で目視判定し、抑泡性の指標とした。
＜判定基準＞
　◎：全く泡が立っていない状況で非常に良好である。
　○：泡立ちの程度が微量でほとんど泡が立っていない状況で良好である。
　△：泡立ちが発生している状況でやや良好である。
　×：泡立ちが激しく発生している状況で著しく不良である。 (5) Foam suppression test 500 g of ion-exchanged water is collected in a 500 ml beaker, 1.00 g of test fiber is put therein, and the mixture is stirred for 10 minutes with a propeller stirrer (rotation speed 1000 rpm). The foaming state after the stirring was stopped was visually determined according to the following criteria, and used as an index of foam suppression.
<Criteria>
(Double-circle): It is very favorable in the condition where there is no bubble.
◯: Good in a situation where the degree of foaming is very small and almost no foam is formed.
(Triangle | delta): It is a little good in the condition where foaming has generate | occur | produced.
X: Remarkably poor in a situation where foaming is intensely generated.
（６）脱泡性試験
　５００ｍｌビーカーにイオン交換水５００ｇを採取し、その中に試験用繊維１．００ｇを入れ、プロペラ撹拌機（回転数１０００ｒｐｍ）で１０分間攪拌する。攪拌停止後、再びプロペラ撹拌機（回転数１００ｒｐｍ）で１分間攪拌する。攪拌停止後、繊維に付着した気泡の状況を次の判定基準で目視判定し、脱泡性の指標とした。
＜判定基準＞
　◎：繊維に付着した気泡が全く認められない状況で非常に良好である。
　○：繊維に付着した気泡がほとんど認められない状況で良好である。
　△：繊維に付着した気泡が一部に認められやや良好である。
　×：繊維に付着した気泡が明らかに認められ著しく不良である。 (6) Defoaming test 500 g of ion-exchanged water is collected in a 500 ml beaker, 1.00 g of test fiber is put therein, and the mixture is stirred for 10 minutes with a propeller stirrer (rotation speed 1000 rpm). After the stirring is stopped, the mixture is again stirred for 1 minute with a propeller stirrer (rotation speed: 100 rpm). After the stirring was stopped, the state of bubbles adhering to the fibers was visually determined according to the following criteria, and used as an index for defoaming.
<Criteria>
(Double-circle): It is very favorable in the situation where the bubble adhering to the fiber is not recognized at all.
○: Good in a situation where almost no bubbles attached to the fiber are observed.
(Triangle | delta): The bubble adhering to the fiber is recognized partially, and is somewhat favorable.
X: The bubble adhering to a fiber is recognized clearly and it is remarkably bad.
（７）分散性試験
　５００ｍｌビーカーにイオン交換水５００ｇを採取し、その中に試験用繊維１．００ｇを入れ、プロペラ撹拌機（回転数１０００ｒｐｍ）で１０分間攪拌する。攪拌停止後の繊維の分散状況を次の判定基準で目視判定し、分散性の指標とした。
＜判定基準＞
　◎：分散性が非常に良好で、繊維が均一に分散している。
　○：分散性が良好であるが、繊維束が一部に認められる。
　△：分散性がやや良好で、繊維束が多く認められる。
　×：分散性が不良で、繊維束が著しく多く認められる。 (7) Dispersibility test 500 g of ion-exchanged water is collected in a 500 ml beaker, 1.00 g of test fiber is put therein, and the mixture is stirred for 10 minutes with a propeller stirrer (rotation speed: 1000 rpm). The dispersion state of the fibers after the stirring was stopped was visually determined according to the following criteria, and used as an index of dispersibility.
<Criteria>
A: Dispersibility is very good, and fibers are uniformly dispersed.
○: Dispersibility is good, but some fiber bundles are observed.
Δ: Dispersibility is slightly good, and many fiber bundles are observed.
X: Dispersibility is poor, and remarkably many fiber bundles are observed.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表２から明らかなように、比較例１～７の従来の抄紙用合成繊維処理剤を用いた抄紙用合成繊維に比べ、実施例１～１６の本発明の抄紙用合成繊維処理剤を給油した抄紙用合成繊維束は、合成繊維束から抄紙を製造する際の抄紙工程において、湿潤時の繊維／繊維間の摩擦が低いことから、繊維同士が絡みにくい。また、低シェアでの分散性が良好なことから、速やかに単繊維に分散する。さらに、抑泡性、脱泡性が良好であることから、繊維に起泡性が少なく、繊維に付着する気泡がないので、安定分散性も良好である。この抄紙用合成繊維処理剤を付与すれば、抄紙不織布の高品質化及び高速化が求められている抄紙工程に好適な抄紙用合成繊維を得ることができる。また、抄紙用合成繊維を用いることにより、均一で地合いの良好な抄紙不織布を得ることができる。 As is apparent from Table 2, the synthetic fiber treating agent for papermaking of Examples 1 to 16 was lubricated as compared with the synthetic fiber for papermaking using the conventional synthetic fiber treating agent for papermaking of Comparative Examples 1 to 7. Synthetic fiber bundles for papermaking are less likely to get entangled with each other because the friction between fibers / fibers when wet is low in the papermaking process when producing papermaking from synthetic fiber bundles. In addition, since it has good dispersibility with a low share, it disperses quickly into single fibers. Furthermore, since the foam suppressing property and defoaming property are good, the fiber has less foaming property and there are no bubbles adhering to the fiber, so that the stable dispersibility is also good. If this synthetic fiber treating agent for papermaking is added, synthetic fibers for papermaking suitable for the papermaking process in which high quality and high speed of the papermaking nonwoven fabric are required can be obtained. Moreover, by using synthetic fibers for papermaking, a papermaking nonwoven fabric having a uniform and good texture can be obtained.
　本発明の抄紙用合成繊維処理剤は、優れた分散性を有する抄紙用合成繊維を得るときに好適に用いられる。本発明の抄紙用合成繊維の製造方法は、優れた分散性を有する抄紙用合成繊維を得るときに好適である。本発明の抄紙不織布の製造方法は、均一で地合の良好な抄紙不織布を得るときに好適である。 The synthetic fiber treating agent for papermaking of the present invention is suitably used for obtaining synthetic fibers for papermaking having excellent dispersibility. The method for producing a synthetic fiber for papermaking of the present invention is suitable for obtaining a synthetic fiber for papermaking having excellent dispersibility. The manufacturing method of the papermaking nonwoven fabric of this invention is suitable when obtaining the papermaking nonwoven fabric which is uniform and favorable in formation.
　１：ポリエステルフィラメント
　２～６：プーリー
　７：Ｕゲージ
　８：記録計
　９：荷重（２０ｇ） 1: Polyester filament 2-6: Pulley 7: U gauge 8: Recorder 9: Load (20 g)

Claims (9)

  1. 　芳香族ジカルボン酸、炭素数４～２２の脂肪族ジカルボン酸およびこれらのエステル形成性誘導体から選ばれる少なくとも１種のジカルボン酸（誘導体）と、アルキレングリコールと、ポリアルキレングリコールまたはその誘導体とを重縮合させたポリエステル化合物であるＡ成分と、脂肪酸とアルカノ－ルアミンとの縮合物であるＢ成分とを必須成分として含む、抄紙用合成繊維処理剤。 Polycondensation of at least one dicarboxylic acid (derivative) selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 22 carbon atoms and ester-forming derivatives thereof, alkylene glycol, and polyalkylene glycol or derivatives thereof A synthetic fiber treating agent for papermaking, comprising as an essential component a component A as a polyester compound and a component B as a condensate of a fatty acid and an alkanolamine.
  2. 　前記処理剤の不揮発分に占めるＡ成分の割合が４０～９０重量％で、Ｂ成分の割合が５～３０重量％である、請求項１に記載の抄紙用合成繊維処理剤。 The synthetic fiber treating agent for papermaking according to claim 1, wherein the proportion of the A component in the non-volatile content of the treating agent is 40 to 90% by weight and the proportion of the B component is 5 to 30% by weight.
  3. 　前記Ａ成分が、芳香族ジカルボン酸および／またはそのエステル形成誘導体と、下記化学式（１）で表されるアルキレングリコールと、下記化学式（２）で表されるポリアルキレングリコールまたはその誘導体とを重縮合させたポリエステル化合物である、請求項１または２に記載の抄紙用合成繊維処理剤。
    Figure JPOXMLDOC01-appb-C000001
     （但し、式中、Ｒ１は炭素数２～８の脂肪族炭化水素基または炭素数２～８の脂環族炭化水素基である。）
    Figure JPOXMLDOC01-appb-C000002
     （但し、式中、Ｒ２は炭素数２～４のアルキレン基であり、ｎは２０～２００の整数であり、Ｒ３は水素原子、脂肪族炭化水素基または芳香族基である。）     The component A is a polycondensation of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof, an alkylene glycol represented by the following chemical formula (1), and a polyalkylene glycol represented by the following chemical formula (2) or a derivative thereof. The synthetic fiber processing agent for papermaking of Claim 1 or 2 which is the made polyester compound.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or an alicyclic hydrocarbon group having 2 to 8 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 2 is an alkylene group having 2 to 4 carbon atoms, n is an integer of 20 to 200, and R 3 is a hydrogen atom, an aliphatic hydrocarbon group or an aromatic group.)
  4. 　前記Ｂ成分が、下記一般式（３）で表される化合物である、請求項１～３のいずれかに記載の抄紙用合成繊維処理剤。
    Figure JPOXMLDOC01-appb-C000003
     （但し、式中、Ｒ４は炭素数７～２１の脂肪族炭化水素基であり、Ｒ５は炭素数１～４のヒドロキシアルキル基であり、Ｒ６は水素原子、炭素数１～４のアルキル基または炭素数１～４のヒドロキシアルキル基である。）     The synthetic fiber treating agent for papermaking according to any one of claims 1 to 3, wherein the component B is a compound represented by the following general formula (3).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 4 is an aliphatic hydrocarbon group having 7 to 21 carbon atoms, R 5 is a hydroxyalkyl group having 1 to 4 carbon atoms, R 6 is a hydrogen atom, and has 1 to 4 carbon atoms. It is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms.)
  5. 　炭素数が８～２２の脂肪酸石鹸であるＣ成分をさらに含む、請求項１～４のいずれかに記載の抄紙用合成繊維処理剤。 The synthetic fiber treating agent for papermaking according to any one of claims 1 to 4, further comprising a C component which is a fatty acid soap having 8 to 22 carbon atoms.
  6. 　前記処理剤の不揮発分に占めるＡ成分の割合が４０～９０重量％で、Ｂ成分の割合が５～３０重量％で、Ｃ成分の割合が５～３０重量％である、請求項５に記載の抄紙用合成繊維処理剤。 The proportion of the A component in the non-volatile content of the treatment agent is 40 to 90% by weight, the proportion of the B component is 5 to 30% by weight, and the proportion of the C component is 5 to 30% by weight. Synthetic fiber treatment agent for papermaking.
  7. 　前記処理剤が水をさらに含む水性液となっており、処理剤全体に占める不揮発分の割合が０．０５～５０重量％である、請求項１～６のいずれかに記載の抄紙用合成繊維処理剤。 The synthetic fiber for papermaking according to any one of claims 1 to 6, wherein the treatment agent is an aqueous liquid further containing water, and a ratio of a non-volatile content in the whole treatment agent is 0.05 to 50% by weight. Processing agent.
  8. 　原料合成繊維に、請求項１～７のいずれかに記載の抄紙用合成繊維処理剤を処理する工程を含む、抄紙用合成繊維の製造方法。 A method for producing a synthetic fiber for papermaking, comprising a step of treating the raw synthetic fiber with the synthetic fiber treatment agent for papermaking according to any one of claims 1 to 7.
  9. 　請求項１～７のいずれかに記載の抄紙用合成繊維処理剤が処理された抄紙用合成繊維を水中に分散させて抄紙する工程を含む、抄紙不織布の製造方法。 A method for producing a papermaking nonwoven fabric, comprising a step of dispersing the papermaking synthetic fiber treated with the papermaking synthetic fiber treating agent according to any one of claims 1 to 7 in water.
PCT/JP2010/062197 2009-08-11 2010-07-21 Synthetic fiber treating agent for papermaking, method for producing synthetic fiber for papermaking, and method for producing paper-made nonwoven fabric WO2011018933A1 (en)

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