JP2010084273A - Modifier and paper product containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modifier imparting a paper product with pliancy and surface smoothness simultaneosuly, and to provide such a paper product containing the same. <P>SOLUTION: The modifier includes, as active ingredients, one or more compounds selected from each specific a sorbitan fatty acid ester, pentaerythritol fatty acid exter, dipentaerythritol fatty acid exter, olyoxyethylene sorbitan fatty acid ester, sodium dialkylsulfosucciniate, sodium alkyloleylsulfosuccinate, and sodium dioleylsulfosuccinate. The paper product containing the modifier is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a modifier for imparting flexibility and surface smoothness to a paper product, and a paper product including the same.

  In recent years, the standard of living has risen, and household paper products such as toilet paper, tissue paper, paper diapers and paper towels are required not only to function but also to feel when they come into contact with the skin. In general, a smooth use feeling that is soft and does not feel caught on the skin is required. In addition, products that are soft and smooth on the skin as described above are hygienic for patients with hay fever and rhinitis, and have a function of eliminating discomfort and inflammation when biting the nose.

  As described above, many products in which flexibility or the like is imparted to toilet paper or tissue paper are known, and it is common to use a softening agent during production. As the softening agent, polyhydric alcohol, fatty acid ester, paraffin emulsion, wax emulsion, quaternary ammonium salt compound and the like are used. For example, in the presence or absence of a polyhydric alcohol wetting agent, a polyglycerin fatty acid ester (the degree of polymerization of the glycerin moiety is 15 or less, the number of carbon atoms of the fatty acid moiety is 8 to 24, and the degree of esterification is 3). A tissue paper containing 0.05 to 5% of a smoothing agent / wetting agent selected from the group consisting of mol and less per weight of tissue web dry pulp fiber and a method for producing the same are disclosed (Patent Document 1). Or, for example, petrolatum or petrolatum plus alkyl ethoxylate emollient, sorbitan stearate or N-cocoyl, N-methylglucamide as an immobilizing agent that immobilizes the emollient on the surface of the paper web, Further, a lotion composition for treating toilet paper (Patent Document 2) containing a hydrophilic surfactant that improves wettability as required, and palm oil and / or palm kernel oil, which are vegetable oils, are mainly used as an interface. A composition for tissue paper obtained by adding a nonionic surfactant, an anionic surfactant and an antibacterial agent to a blend of an active agent and a divalent and trivalent water-soluble polyhydric alcohol with a slight amount of water ( Patent Document 3) is disclosed. Further, it contains one or more oil substances among hydrocarbons, vegetable oils, waxes, higher alcohols, and water-soluble wax, and further contains humectants, fatty acids, silicones and surfactants as necessary. A paper product (Patent Document 4) containing a chemical softening composition comprising a combination of a quaternary ammonium compound and glycerin, and polyethylene glycol and polypropylene glycol having a weight average molecular weight of about 200 to 4000 (Patent Document 5) Is also disclosed. Further, among humectants, glycerin, diglycerin, polyethylene glycol having an average molecular weight within a predetermined range, sorbit, propylene glycol, 1,3-butylene glycol, glycine betaine, pyrrolidone carboxylic acid, pyrrolidone carboxylate, maltitol, sodium lactate And one or more components of sodium carboxymethylcellulose, starch, modified starch, guar gum, polyvinyl alcohol, and polyacrylamide as a dry paper strength enhancer, or in addition, water-soluble Hydrolytic paper (Patent Document 6) containing polyethylene glycol having an average molecular weight in a predetermined range is also known as a conductive wax.

By applying such a softening agent or the like to a paper product, the feel of the paper product is significantly improved. When the polyhydric alcohol penetrates into the paper pulp fiber, the pulp fiber itself becomes supple and the paper product becomes soft. Fatty acid esters, paraffin emulsions, and wax emulsions have a lipophilic layer on the paper surface, thereby improving surface slippage and providing a smooth feel. A quaternary ammonium salt compound also forms a smooth surface by being oriented on the paper surface. However, it has been difficult to impart flexibility and surface smoothness simultaneously with these softeners. Polyhydric alcohol, which is a conventional technique, penetrates into pulp fibers and improves the water retention effect of the pulp fibers themselves, but the hydrophilic layer is thin and has a low water retention capability. Further, if the outer layer is covered with a fatty acid ester, a paraffin emulsion, or a wax emulsion, the water retention ability is significantly reduced. Moreover, the cationic surfactant represented by the quaternary ammonium salt compound forms a hydrophilic layer on the surface of the paper product by orienting a hydrophilic group on the pulp fiber surface and an outer lipophilic group. To form a lipophilic layer. However, when the cationic group is strongly bonded to the surface of the pulp fiber charged to the anion, the hydrophilic layer becomes thin and does not exhibit a sufficient effect on the softness. Further, the hydrophobicity of the outer layer may cause a reduction in water absorption, which is the original function of tissue paper and toilet paper.
JP-A-7-109694 Japanese National Patent Publication No. 9-506682 Japanese Patent Laid-Open No. 10-23988 Japanese Patent Laid-Open No. 10-226986 JP-T 8-502557 Japanese Patent Laid-Open No. 9-154664

  An object of the present invention is to provide a modifier that simultaneously imparts flexibility and surface smoothness to a paper product and a paper product including the same.

  In order to achieve the above-described problems, the present inventors have intensively studied to find a compound that can simultaneously provide flexibility and surface smoothness to paper products and the combination of the components thereof. As a result, the paper products have flexibility and surface smoothness. In order to provide the thickness at the same time, a thick hydrophilic layer from the inside to the surface of the pulp fiber of the paper product is formed, and a thin lipophilic layer is formed on the outer layer, and the present invention has been completed. . Therefore, the compound most suitable for the present invention needs to have an anionic and / or nonionic hydrophilic group in order to form a thick hydrophilic layer, and a short hydrocarbon chain to form a thin lipophilic layer. However, if the hydrocarbon chain is too short, a sufficient lipophilic layer is not formed, and smoothness cannot be obtained. Therefore, the optimum range of the hydrocarbon chain length for obtaining a sufficiently thin lipophilic layer is determined.

  That is, in the invention of claim 1, the fatty acid has 12 to 18 carbon atoms, sorbitan fatty acid ester, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and alkyl group having 12 to 12 carbon atoms. A modifier for imparting flexibility and surface smoothness to paper products, comprising at least one selected from sodium dialkylsulfosuccinate, sodium alkyloleyl sulfosuccinate and dioleyl sodium sulfosuccinate as an active ingredient, is there.

  The sorbitan fatty acid ester, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and alkyl group having 12 to 18 carbon atoms, wherein the fatty acid has 12 to 18 carbon atoms. Certain sodium dialkylsulfosuccinates, alkyloleyl sodium sulfosuccinates and dioleyl sodium sulfosuccinates have anionic and / or nonionic hydrophilic groups, which are directly or water-bonded by hydrogen bonding with pulp fibers of paper products. Bonding through molecules forms a molecular layer of water. Further, the compound further increases the thickness of the hydrophilic layer when oxygen groups and hydroxyl groups that do not participate in bonding with the paper surface contain water molecules.

  On the other hand, the carbon number of the fatty acid and the carbon number of the alkyl group according to claim 1 are related to the thickness of the lipophilic layer formed in the outer layer of the hydrophilic layer of the paper product. That is, if the carbon number is 10 or less, a sufficient lipophilic layer is not formed, and the surface is rough. If the carbon number is 22 or more, the surface is smooth, but by pressing the lower hydrophilic layer, The layer becomes thinner and less flexible. Further, from the viewpoint of foamability, the carbon number desirably has a wide distribution in the range of 12-18. That is, if the carbon number distribution is narrow, the foaming property becomes high, and when a solution containing the modifier is applied to the paper previously made by a paper machine in the secondary process, the coating of the modifier is caused by the generated foam. Troubles such as unevenness of work are likely to occur. Further, sodium dialkylsulfosuccinate and dipentaerythritol fatty acid ester are more preferred because they have two hydrocarbon chains and thus have a high foam breaking effect.

  The invention according to claim 2 is characterized in that the modifier is an emulsified preparation, and the blending ratio is 1 to 30% by weight of the active ingredient and 1.0 to 15.0% by weight of the emulsifier. It is. In the state where the paper product is water-containing or pulp slurry, in order to quickly and uniformly adsorb and orient the modifier of the present invention on the surface of paper and paper product, the modifier is an O / W type emulsifier. It is desirable to be in the form of a preparation, and the blending ratio of the active ingredient is desirably 1 to 30% by weight. When the above-mentioned active ingredient is 30% by weight or more, the viscosity of the emulsified preparation becomes high, so that it becomes difficult to spray-coat on paper previously made by a paper machine, and when it is 1% by weight or less, the coating efficiency is deteriorated. As for the compounding quantity of the emulsifier in this emulsion formulation, 1.0-15.0 weight% is desirable. When the amount is 15.0% by weight or more, foaming trouble occurs. When the amount is 1.0% by weight or less, emulsification becomes unstable.

  The invention of claim 3 is characterized in that the emulsifier comprises a higher alcohol sulfate ester salt, alkylbenzene sulfonate salt, α-olefin sulfonate salt, polyoxyethylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether, PEG fatty acid ester, The modifier according to claim 2, wherein the modifier is one or more selected from EO / PO adducts of higher alcohols. Any of the compounds described in claim 3 is compatible with the active ingredient described in claim 3, and the product stability of the emulsion preparation is maintained.

  The invention of claim 4 is a condensate of aminoethylethanolamine and a higher fatty acid and its urea reaction product, a condensate of diethylenetriamine and a higher fatty acid and its urea reaction product, a succinic acid condensate of a condensate of diethylenetriamine and a higher fatty acid, diethylenetriamine An acetic anhydride condensate of a condensate of a higher fatty acid and a condensate of triethylenetetramine and a higher fatty acid and a urea reaction product thereof contain 1 to 10% by weight. 3. The modifier according to any one of 3 above.

  The compound according to claim 4 has an action of weakly crosslinking the pulp of the paper product, and can maintain flexibility even during drying by preventing a decrease in the bulk of the paper product in the dry state. . It is desirable that the modifier of the present invention contains 1 to 10% by weight of one or more selected from the group of compounds according to claim 4. When the content is 1% by weight or less, the effect of preventing the decrease in the bulk is weak, and although the effect of being expected to be 10% by weight or more is obtained, the cost is increased, and the viscosity of the modifier is increased and spray coating is applied to paper. It becomes difficult to do.

  The invention of claim 5 is a paper product characterized in that the modifier according to any one of claims 1 to 4 is contained in an amount of 1 to 20% by weight based on the dry weight of the paper product.

  The invention according to claim 6 is the paper product according to claim 5, wherein the paper product is tissue paper or toilet paper.

  The paper of the “paper product” to be provided with flexibility and surface smoothness of the present invention may be either naturally derived or synthesized. As a paper product, it can be used suitably for tissue paper and toilet paper.

  Since the modifier of the present invention can simultaneously impart flexibility and surface smoothness to the paper product, the paper product containing the modifier can provide a comfortable feeling of use, and hay fever, rhinitis, etc. It is hygienic and can eliminate discomfort and irritation when blowing the nose.

  The sorbitan fatty acid ester, pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and alkyl group having 12 to 18 carbon atoms, wherein the fatty acid has 12 to 18 carbon atoms in the invention of claim 1. These are sodium dialkylsulfosuccinate, sodium alkyloleyl sulfosuccinate and dioleyl sodium sulfosuccinate, which are formulated to impart flexibility and smoothness to paper products.

  Examples of sorbitan fatty acid esters of fatty acids having 12 to 18 carbon atoms include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan sesquioleate, and And sorbitan trioleate.

  Examples of the pentaerythritol fatty acid ester whose fatty acid has 12 to 18 carbon atoms include pentaerythritol tetralaurate, pentaerythritol trilaurate, pentaerythritol dilaurate, pentaerythritol monolaurate, pentaerythritol tetrapalmitate, pentaerythritol tripalmitate Pentaerythritol dipalmitate, pentaerythritol monopalmitate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monostearate and the like.

  Examples of the dipentaerythritol fatty acid ester whose fatty acid has 12 to 18 carbon atoms include dipentaerythritol hexalaurate, dipentaerythritol tetralaurate, dipentaerythritol monolaurate, dipentaerythritol hexapalmitate, dipentaerythritol tetra There are palmitate, dipentaerythritol monopalmitate, pentaerythritol hexastearate, dipentaerythritol tetrastearate, dipentaerythritol monostearate, dipentaerythritol monooleate and the like.

  Examples of the polyoxyethylene sorbitan fatty acid ester having a fatty acid having 12 to 18 carbon atoms include coconut oil fatty acid polyoxyethylene (20 mol) sorbitan, polyoxyethylene monopalmitate (20 mol) sorbitan, polyoxyethylene monostearate ( 20 mol) sorbitan, polyoxyethylene (20 mol) sorbitan monoisostearate, polyoxyethylene (20 mol) sorbitan monooleate, polyoxyethylene (20 mol) sorbitan trioleate, and the like.

  Examples of the alkyl group of sodium dialkylsulfosuccinate having 12 to 18 carbon atoms in the alkyl group and sodium alkyloleyl sulfosuccinate include lauryl group, myristyl group, palmityl group, stearyl group, and the like. Sodium dilaurylsulfosuccinate, dimyristyl Sodium sulfosuccinate, sodium dipalmityl sulfosuccinate, sodium distearyl sulfosuccinate, sodium lauryl oleyl sulfosuccinate, sodium myristyl oleyl sulfosuccinate, sodium palmityl oleyl sulfosuccinate, sodium stearyl oleyl sulfosuccinate, and other beef tallow and palm oil There is sodium sulfosuccinate having an alkyl group having a plurality of carbon atoms using a higher alcohol as a raw material.

  Further, as the sulfate ester of higher alcohol as the emulsifier used in the invention of claim 3, sulfate salt of 2-ethylhexyl alcohol, sulfate potassium salt of 2-ethylhexyl alcohol, sulfate sodium salt of dodecyl alcohol, dodecyl Alcohol sulfate potassium salt, cetyl alcohol sulfate sodium salt, cetyl alcohol sulfate potassium salt, oleyl alcohol sulfate sodium salt, oleyl alcohol sulfate potassium salt, stearyl alcohol sulfate sodium salt, stearyl alcohol Sulfate ester potassium salt.

  Examples of the alkyl benzene sulfonate include decyl benzene sulfonate, dodecyl benzene sulfonate, myristyl benzene sulfonate, and cetyl benzene sulfonate.

  As the α-olefin sulfonate, lauryl sulfosuccinate, lauryl sulfonate, C12 olefin sulfonate, lauroyl methyl taurate, lauroyl taurate, polyoxyethylene lauryl ether sulfosuccinate, isethionate laurate, Myristyl sulfosuccinate, myristyl sulfonate, C14 olefin sulfonate, myristoyl methyl taurate, myristoyl taurate, polyoxyethylene myristyl ether sulfosuccinate, isethionate myristate, cetyl sulfosuccinate, cetyl sulfonate , C16 olefin sulfonate, palmitoyl methyl taurate, palmitoyl taurate, polyoxyethylene cetyl ether sulfosuccinate, isethionic acid Palmitic acid ester salts, stearyl sulfosuccinate, stearyl sulfonate, and the like C18 olefin sulfonates.

  As the sulfate ester salt of polyoxyethylene alkyl ether, polyoxyethylene decyl ether sulfate ester salt, polyoxyethylene dodecyl ether sulfate ester salt, polyoxyethylene tridecyl ether sulfate ester salt, polyoxyethylene tetradecyl ether sulfate ester salt, Examples thereof include polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, and polyoxyethylene oleyl ether sulfate.

  The polyoxyalkylene alkyl ether is obtained by adding a polyalkylene oxide to a linear or branched, saturated or unsaturated alcohol having 8 to 30 carbon atoms. Specifically, polyoxyethylene (3 mol) octyl ether, polyoxyethylene (5 mol) dodecyl ether, polyoxyethylene (10 mol) oleyl ether, polyoxyethylene (15 mol) stearyl ether, polyoxyethylene (20 Mol) behenyl ether, polyoxyethylene (10 mol) polyoxypropylene (10 mol) decyl ether, polyoxyethylene (15 mol) polyoxypropylene (2 mol) isostearyl ether, polyoxyethylene (10 mol) cholestanol ether And polyoxyethylene (20 mol) polyoxypropylene (20 mol) hydrogenated lanolin.

  Examples of PEG fatty acid esters include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol dilaurate, polyethylene glycol dipalmitate, polyethylene glycol distearate, and polyethylene glycol dioleate.

  EO / PO adducts of higher alcohols include polyoxyethylene / polyoxypropylene decyl ether, polyoxyethylene / polyoxypropylene dodecyl ether, polyoxyethylene / polyoxypropylene tridecyl ether, polyoxyethylene / polyoxypropylene cetyl ether Examples include ethers, polyoxyethylene / polyoxypropylene stearyl ether, polyoxyethylene / polyoxypropylene oleyl ether, and EO / PO adducts of higher alcohols derived from beef tallow, palm oil, or palm oil.

  The higher fatty acid used in the invention of claim 4 is a linear or branched, saturated or unsaturated higher fatty acid, specifically capric acid, myristic acid, palmitic acid, palmitoyl acid, stearic acid. , Isostearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid and the like.

  Examples of condensates of aminoethylethanolamine and higher fatty acids and urea reaction products thereof include flexible bases NO190 and NO191 (produced by Ohara Palladium Chemical Co., Ltd.). Condensates of diethylenetriamine and higher fatty acids and urea reaction products thereof, succinic acid condensates of condensates of diethylenetriamine and higher fatty acids, and acetic anhydride condensates of condensates of diethylenetriamine and higher fatty acids include flexible bases NO130, NO131, NO132, NO133. (Ohara Palladium Chemical Co., Ltd.). Examples of condensates of triethylenetetramine and higher fatty acids and urea reaction products thereof include flexible bases NO80 and NO81 (manufactured by Ohara Palladium Chemical Co., Ltd.).

  Although the emulsification method of the modifier of the present invention is not particularly limited, for example, a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd .: a TK homomixer MARK II 2.5 type blade is attached to a main body TK robot mix) is used. A sorbitan fatty acid ester which is an active ingredient and an emulsified component according to claim 1, wherein the emulsifier of the present invention is added to water or an aqueous solvent at a liquid temperature of 60 to 90 ° C., and the homogenizer is rotated at 5000 rpm. Add one or more selected from pentaerythritol fatty acid ester, dipentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sodium dialkylsulfosuccinate, sodium alkyloleyl sulfosuccinate, dioleyl sodium sulfosuccinate and rotate for 1 to 3 minutes After maintaining, the homogenizer is stopped to complete the emulsification. Even when a plurality of compounds are selected from the above compounds as the emulsified component, the order of addition and the addition method are not particularly limited.

  In order to further enhance the effect of the present invention, the condensate of aminoethylethanolamine and higher fatty acid and its urea reaction product, the condensate of diethylenetriamine and higher fatty acid and the urea reaction product thereof, and the condensate of diethylenetriamine and higher fatty acid A succinic acid condensate, an acetic anhydride condensate of a condensate of diethylenetriamine and a higher fatty acid, a condensate of triethylenetetramine and a higher fatty acid, and a urea reaction product thereof may be blended. In that case, after completion of the emulsification, the selected compound according to claim 4 is added while maintaining the rotation of the homogenizer, and the rotation of the homogenizer is stopped after maintaining the rotation for 1 to 3 minutes. By this method, the emulsified modifier of the present invention can be obtained.

  Moreover, you may mix | blend various polyhydric alcohol and water-soluble polymer after completion | finish of emulsification as needed. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, polyethylene glycol, propylene oxide, propylene glycol, polypropylene glycol, 1, Examples include 3-butylene glycol, glycerin, diglycerin, polyglycerin, pentaerythritol, sorbitol, and mannitol. These 1 type (s) or 2 or more types can be used.

  The water-soluble polymer is, for example, a polysaccharide containing at least fucose, glucose, glucuronic acid, and rhamnose as a constituent monosaccharide, and preferably glucose, glucuronic acid, rhamnose represented by the following formula (Formula 1): There is a polysaccharide which consists of a main chain having a repeating structure consisting of 1 and a structure in which one fucose is branched to one glucose in the main chain.

  The polysaccharide of the above formula (Chemical Formula 1) can be obtained, for example, as a product of Alkaline Genus Lasus B-16 strain bacteria (FERM BP-2015), and Alcathylan (manufactured by Hakuto Co., Ltd.) can be obtained. Other water-soluble polymers include plant-based polymers such as gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, algae colloid, fucoidan, trant gum, locust bean gum, galactomannan; Microbial polymers such as xanthan gum, curdlan, gellan gum, fucogel, dextran, succinoglucan and pullulan; animal polymers such as chitosan, casein, albumin and gelatin; starches such as starch, carboxymethyl starch and methylhydroxypropyl starch Polymers: methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitro Cellulose polymers such as roulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate; polyvinyl methyl ether, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, etc. Vinyl polymers; polyoxyethylene polymers; polyoxyethylene polyoxypropylene copolymer polymers; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide; polyethyleneimine, cationic polymers, bentonite, Inorganic water-soluble polymers such as laponite and hectorite, dimethylbenzyl dodecyl ammonium montmorillonite clay, dimethyl geo And organic-modified clay minerals such as data decyl ammonium montmorillonite clay. These 1 type (s) or 2 or more types can be used. These water-soluble polymers are preliminarily prepared in an aqueous solution having an appropriate concentration, and are mixed with the modifier of the present invention. The term “appropriate concentration” as used herein refers to a concentration that does not significantly increase the viscosity of the modifier after blending with the modifier.

  As a mixing ratio, 1/10 to 10 times the amount of various polyhydric alcohols and / or aqueous solutions of water-soluble polymers are mixed with the modifier of the present invention. be able to.

  When the modifier of the present invention is applied to paper products, there is a method of adding to the pulp slurry before paper making. Furthermore, it is also possible to directly spray-apply a solution diluted with water or the above-mentioned polyhydric alcohol as it is, in a step where the water content after paper formation in the paper making step is 20% or less. If the viscosity of the solution to be sprayed is too high, fine and uniform droplets cannot be obtained, so the solution viscosity at 25 ° C. is 100 mPa.s. S or less is preferable. In addition, there is a method in which a solution containing the modifier of the present invention is applied in a secondary process to paper previously made by a paper machine. This includes a coater or printing system. In coating with a coater or printing machine, the viscosity of the solution to be coated is 200 mPa.s. S (at 25 ° C) or less is desirable.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
(A) Components imparting flexibility and surface smoothness (1) Items to be blended in the examples A-1: NIKKOL SS-10V (manufactured by Nikko Chemical Co., Ltd .: sorbitan monostearate)
A-2: EXCEPARL PE-MO (manufactured by Kao Corporation: pentaerythritol monooleate)
A-3: Unistar H-676 (manufactured by NOF Corporation: dipentaerythritol fatty acid ester)
A-4: NIKKOL TP-10V (manufactured by Nikko Chemical Co., Ltd .: polyoxyethylene (20 mol) sorbitan monopalmitate)
A-5: Perex OT-P (manufactured by Kao Corporation: sodium dialkylsulfosuccinate)
(2) What is blended in the comparative example A-6: NIKKOL DGMS (manufactured by Nikko Chemical Co., Ltd .: diglyceryl monostearate)
A-7: Esocard O / 12 (manufactured by Lion Corporation: di (polyoxyethylene) oleylmethylammonium chloride (2EO))
(B) Emulsifier (1) Compounded in Examples B-1: Persoft EK (manufactured by NOF Corporation: sulfate ester of polyoxyethylene alkyl ether)
B-2: NIKKOL BC-20 (manufactured by Nikko Chemical Co., Ltd .: polyoxyethylene (20 mol) cetyl ether)
B-3: NIKKOL MYS-40V (manufactured by Nikko Chemical Co., Ltd .: PEG-40 stearate)
B-4: NIKKOL BWA-10 (manufactured by Nikko Chemical Co., Ltd .: polyoxyethylene (10 mol) lanolin alcohol)
B-5: Sinoline SP (manufactured by Shin Nippon Rika Co., Ltd .: sulfate ester of higher alcohol)
B-6: Lipolane PB-800 (manufactured by Lion Corporation: α-olefin sulfonate)
B-7: Neoperex G-15 (manufactured by Kao Corporation: sodium dodecylbenzenesulfonate (soft type))
(2) What is blended in the comparative example B-8: NIKKOL HCO-60 (manufactured by Nikko Chemical Co., Ltd .: polyoxyethylene (60 mol) hydrogenated castor oil)
(C) Compound C-1 of Invention of Claim 4: Flexible base NO190 (Ohara Palladium Chemical Co., Ltd .: condensate of aminoethylethanolamine and higher fatty acid)
C-2: Flexible base NO191 (Ohara Palladium Chemical Co., Ltd .: urea reaction product of condensate of aminoethylethanolamine and higher fatty acid)
C-3: Flexible base NO130 (produced by Ohara Palladium Chemical Co., Ltd .: condensate of diethylenetriamine and higher fatty acid)
C-4: Flexible base NO131 (Ohara Palladium Chemical Co., Ltd .: urea reaction product of condensate of diethylenetriamine and higher fatty acid)
C-5: Flexible base NO132 (Ohara Palladium Chemical Co., Ltd .: succinic acid condensate of diethylenetriamine and higher fatty acid condensate)
C-6: Flexible base NO133 (Ohara Palladium Chemical Co., Ltd .: Acetic anhydride condensate of diethylenetriamine and higher fatty acid condensate)
C-7: Flexible base NO80 (Ohara Palladium Chemical Co., Ltd .: condensate of triethylenetetramine and higher fatty acid)
C-8: Flexible base NO81 (manufactured by Ohara Palladium Chemical Co., Ltd .: urea reaction product of condensate of triethylenetetramine and higher fatty acid)

(Examples 1 to 10)
After adding 395 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 5 g of B-2 (polyoxyethylene (20 mol) cetyl ether) previously heated to 60 ° C. was added, and 100 g of A-1 (sorbitan monostearate) previously heated to 60 ° C. was added, The emulsification treatment was performed for 3 minutes. Subsequently, the obtained emulsion was cooled to room temperature to obtain Example 1 of the present modifier. Further, in the same manner, A-2 to A-5 were blended in place of A-1, and Examples 2 to 10 of the present invention modifiers shown in Table 1 were obtained.

(Examples 11 to 13)
After adding 470 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 25 g of B-2 (polyoxyethylene (20 mol) cetyl ether) previously heated to 60 ° C. was added, and 5 g of A-1 (sorbitan monostearate) previously heated to 60 ° C. was added. The emulsification treatment was performed for 3 minutes. Subsequently, the obtained emulsion was cooled to room temperature to obtain Example 11 of the present modifier. Furthermore, in the same manner, ion-exchanged water was replaced with 470 g, 400 g, B-2 was replaced with 25 g, 50 g, and A-1 was replaced with 5 g, and 50 g was added to obtain Example 12 of the present modifier. . Further, in the same manner, 275 g of ion-exchanged water was replaced with 275 g, 75 g of B-2 was replaced with 25 g, and 150 g of A-1 was replaced with 5 g to obtain Example 13 of the present modifier. . The formulation is shown in Table 1.

(Examples 14 to 19)
After adding 395 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 5 g of B-1 (sulfuric acid ester salt of polyoxyethylene alkyl ether) previously heated to 60 ° C. was added, and 100 g of A-1 (sorbitan monostearate) previously heated to 60 ° C. was added, The emulsification treatment was performed for 3 minutes. Subsequently, the obtained emulsion was cooled to room temperature to obtain Example 14 of the present modifier. Further, in the same manner, B-3 to B-7 were blended instead of B-1, and Examples 15 to 19 of the present modifier were obtained. The formulation is shown in Table 1.

(Examples 20 to 27)
After adding 345 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 5 g of B-2 (polyoxyethylene (20 mol) cetyl ether) that had been heated to 60 ° C. in advance was added, and 100 g of A-5 (sodium dialkylsulfosuccinate) that had been heated to 60 ° C. was added, The emulsification treatment was performed for 3 minutes. Further, 50 g of C-1 (condensation product of aminoethylethanolamine and higher fatty acid) was added and maintained for 1 minute, and then the obtained emulsion was cooled to room temperature to give Example 20 of the present modifier. Obtained. Further, in the same manner, C-2 to C-8 were blended instead of C-1, and Examples 21 to 27 of the present modifier were obtained. The formulation is shown in Table 2.

(Examples 28 and 29)
After adding 390 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 5 g of B-2 (polyoxyethylene (20 mol) cetyl ether) that had been heated to 60 ° C. in advance was added, and 100 g of A-5 (sodium dialkylsulfosuccinate) that had been heated to 60 ° C. was added, The emulsification treatment was performed for 3 minutes. Further, 5 g of C-1 (condensate of aminoethylethanolamine and higher fatty acid) was added and maintained for 1 minute, and then the obtained emulsion was cooled to room temperature, and Example 28 of the present modifier was changed. Obtained. Further, in the same manner, 370 g of ion-exchanged water was replaced with 370 g, and 25 g of C-1 was added instead of 5 g to obtain Example 29 of the present modifier. The formulation is shown in Table 2.

(Comparative Examples 1 and 2)
After adding 395 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 revolutions using a homomixer (manufactured by Special Machine Chemical Co., Ltd.). 5 g of B-2 (polyoxyethylene (20 mol) cetyl ether) previously heated to 60 ° C. was added, and 100 g of A-6 (diglyceryl monostearate) previously heated to 60 ° C. was added, The emulsification treatment was performed for 3 minutes. Subsequently, the obtained emulsion was cooled to room temperature to obtain Comparative Example 1. Further, in the same manner, A-7 was blended instead of A-6, and Comparative Example 2 was obtained.

(Comparative Examples 3 and 4)
After adding 395 g of ion-exchanged water to a beaker having a capacity of 1000 ml and heating to 60 ° C., T.W. K. Stirring was started at 5,000 revolutions using a homomixer (manufactured by Special Machine Chemical Co., Ltd.). Add 5 g of B-8 (polyoxyethylene (60 mol) hydrogenated castor oil) previously heated to 60 ° C., and add 100 g of A-1 (sorbitan monostearate) previously heated to 60 ° C. The emulsification treatment was performed for 3 minutes. Subsequently, the obtained emulsion was cooled to room temperature to obtain Comparative Example 3. Further, in the same manner, A-6 was blended instead of A-1, and Comparative Example 4 was obtained.

[Modifier stability test]
After preparing the modifiers of Examples 1 to 29 and Comparative Examples 1 to 4, 100 ml was taken into a 100 ml measuring cylinder with a stopper, stoppered, and placed in a 45 ° C. incubator. Twelve weeks later, the separation of the modifier in the 100 ml stoppered measuring cylinder was visually measured. The results are shown in Table 3 according to the following evaluation criteria. All examples show good results.
(Stability evaluation criteria)
○: No separation / precipitation is observed by visual inspection.
X: Separation / precipitation is observed visually.

[Modification test of paper products]
(1) Coating method Bar coater No. 10 (manufactured by RD SPECIAL TIES INK), Examples 1 to 29 of the present modifier were uniformly coated on a commercially available plywood (length 200 mm × width 230 mm × plate thickness 12 mm). Next, a commercially available tissue paper weighed in advance was brought into close contact with the coated surface of the plywood, and the composition was absorbed into the tissue paper by lightly pressing from above. The coating amount was determined from the increase in coating weight. The above operation was repeated, and the coating weight was adjusted to 20% of the paper weight in terms of the modifier weight of the example. For the coating prototype, a plurality of tissue papers were stacked in the same direction and aged for 24 hours. Furthermore, a commercially available toilet paper was also coated in the same manner. Comparative examples 1 to 4 were similarly tested.
(2) Spraying method A commercially available tissue paper weighed in advance was spread on a flat plate, and Examples 1 to 29 of the modifier of the present invention were spray-coated from four sides of the tissue paper using a sprayer. The tissue paper after spraying was left overnight under conditions of an average room temperature of 25 ° C. and an average humidity of 65%, and the coating amount was determined from the increase in coating weight. The above operation was repeated, and the coating weight was adjusted to 20% of the paper weight in terms of the modifier weight of the example. Comparative examples 1 to 4 were similarly tested.

(3) Sensory test 1
About the coating prototype produced by the said method, the tactile sensation test by 14 panelists was done in the following procedure. As tactile sensation evaluation items, flexibility and surface smoothness were set. Each coating prototype was arranged randomly so that it could not be distinguished. Subsequently, a total of 10 panelists were selected, 2 from each age group from the 10s to the 50s, and each was touched with a finger to perform a sensory evaluation of “flexibility and surface smoothness”. Each evaluation standard was as follows. The results are shown in Table 4. All examples show good results.
Evaluation criteria ○: Eight or more of 10 people evaluated that there was a soft and smooth feel.
X: 7 or less of 10 people evaluated that there was a soft and smooth feel.

(4) Sensory test 2
In the above coating method, Example 13-1 was obtained by adjusting the coating weight of Example 13 of the present modifier so as to be 1% of the paper weight in terms of the weight of the modifier of Example 13. Similarly, Example 13-2 was obtained by adjusting the coating weight of Example 13 of the present invention modifier to 5% of the paper weight in terms of the modifier weight of Example 13. Similarly, Example 13-3 was obtained by adjusting the coating weight of Example 13 of the inventive modifier to 10% of the paper weight in terms of the modifier weight of Example 13. About Examples 13-1 to 13-3, the sensory test 2 similar to the said sensory test 1 was done. The results are shown in Table 5. All examples show good results.

Claims (6)

A sorbitan fatty acid ester, a pentaerythritol fatty acid ester, a dipentaerythritol fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, wherein the fatty acid has 12 to 18 carbon atoms, and a sodium dialkylsulfosuccinate whose alkyl group has 12 to 18 carbon atoms A modifier for imparting flexibility and surface smoothness to paper products, containing as an active ingredient at least one selected from alkyloleyl sodium sulfosuccinate and dioleyl sodium sulfosuccinate. The modifying agent according to claim 1, wherein the modifying agent is an emulsified preparation, and the blending ratio thereof is 1 to 30% by weight of the active ingredient and 1.0 to 15.0% by weight of an emulsifier. Addition of the above emulsifiers to higher alcohol sulfates, alkylbenzene sulfonates, α-olefin sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyalkylene alkyl ethers, PEG fatty acid esters, higher alcohol EO / PO addition The modifier according to claim 2, wherein the modifier is one or more selected from products. Condensates of aminoethylethanolamine and higher fatty acids and their urea reactants, condensates of diethylenetriamine and higher fatty acids and their urea reactants, succinic acid condensates of diethylenetriamine and higher fatty acid condensates, condensates of diethylenetriamine and higher fatty acids It contains 1 to 10% by weight of one or more selected from acetic anhydride condensate, triethylenetetramine and higher fatty acid condensate and urea reaction product thereof. Modifier. A paper product comprising 1 to 20% by weight of the modifier according to any one of claims 1 to 4 per dry weight of the paper product. The paper product according to claim 5, wherein the paper product is tissue paper or toilet paper.