JP2008007926A - Tissue paper treatment agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tissue paper treatment agent giving tissue paper good in skin touch including smoothness, moist feeling and softness, and also good in liquid stability. <P>SOLUTION: The tissue paper treatment agent comprises (A) an ester-type quaternary ammonium salt, (B) an ester of a 8-22C fatty acid and a polyethylene oxide addition sorbitan and (C) a polyhydric alcohol in the mass ratio A/B of 0.1-19.0. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thin paper treating agent.

Soft paper is required for thin paper such as toilet paper and tissue. As a method of giving a soft feel to the thin paper, it has been attempted to apply a treatment agent for improving the texture to the surface of the paper. For example, a technique for suppressing fuzz by applying a hydrophilic component such as glycerin or saccharide to thin paper is widely known. However, the method of applying a hydrophilic component such as glycerin or saccharide gives a moist feeling and softness and reduces the rough feeling, but has a drawback that the sticky feeling becomes stronger.
Therefore, a thin paper treatment in which the hydrophilic component is combined with a lipophilic compound such as a mineral oil such as paraffin (Patent Document 1), an animal and vegetable oil (Patent Document 2), an alkylene oxide adduct of lanolin or castor oil (Patent Document 3). There has been proposed a method of imparting smoothness to thin paper by using an agent and suppressing stickiness.

Furthermore, there is also a method of further improving the touch (texture) such as smoothness, moist feeling, and softness by treating the thin paper with a thin paper treatment agent combined with a third component such as an amphoteric surfactant or an amine compound. It has been proposed (Patent Document 4).
Moreover, by using a quaternary ammonium salt having an ester bond in a biodegradable molecule as a softening agent and a polyhydric alcohol compound such as glycerin as a humectant, flexibility and water absorption are imparted to the thin paper. A thin paper treating agent that can be used has been proposed (Patent Document 5).
JP-A-5-156596 (Claims, Examples, etc.) JP-A-7-82662 (Claims, Examples, etc.) JP 2006-118089 A (Claims, Examples, etc.) JP-A-9-296389 (Claims, Examples, etc.) JP-T-8-51169 (Claims, Examples, etc.)

However, even with these conventionally proposed thin paper treatment agents, the effect of improving the touch (texture) such as smoothness, moist feeling, and softness is not sufficient.
In addition, a thin paper treatment agent containing a lipophilic compound or a surfactant has a problem in storage stability (liquid stability).
Usually, since a thin paper processing agent is stored and transported after production, a time lag occurs between the production of the thin paper processing agent and the application to the thin paper. That is, it is an important issue to improve the liquid stability in consideration of the transfer period from the manufacturing site of the thin paper treatment agent to the factory where the coating operation is performed, the storage period in the warehouse, and the temperature conditions at that time. In particular, in a thin paper treatment agent containing a lipophilic compound having a low specific gravity and a very high lipophilicity, it is difficult to stably maintain a liquid state in which the lipophilic compound is uniformly dissolved or dispersed in the thin paper treatment agent.

  The present invention has been made in view of the above circumstances, and provides a thin paper treatment agent that provides a thin paper with a good texture (texture) such as smoothness, moist feeling, and softness, and a good liquid stability. Objective.

In order to solve the above-mentioned problems, the thin paper treating agent of the present invention contains the following components (A), (B) and (C), and is represented by (A) / (B). The mass ratio of the component and the component (B) is 0.1 to 19.0.
(A) Quaternary ammonium salt having an ester bond, (B) a fatty acid having 8 to 22 carbon atoms and an ester of polyethylene oxide-added sorbitan, (C) a polyhydric alcohol.
The thin paper treating agent of the present invention preferably further contains one or more compounds (D) selected from the group consisting of an alkylene oxide adduct of glycerin and an alkylene oxide adduct of polyglycerin.
The thin paper treating agent of the present invention preferably further contains one or more oily components (E) selected from the group consisting of fatty acids, aliphatic alcohols, esters of fatty acids and aliphatic alcohols, and paraffins.

  The thin paper treating agent of the present invention has good liquid stability, and when applied to thin paper, a thin paper having a good feeling (feel) such as moist feeling and softness can be obtained.

"(A) component"
The component (A) is a quaternary ammonium salt having an ester bond in the molecule (hereinafter sometimes referred to as an ester-type quaternary ammonium salt), specifically represented by the following general formula (I). Triester type quaternary ammonium salt (component (a-1)), diester type quaternary ammonium salt represented by general formula (II) (component (a-2)), and general formula (III) It is a mixture of the monoester type | mold quaternary ammonium salt ((a-3) component) represented by these. The proportion of each component of (a-1), (a-2) and (a-3) in the mixture is the condensation of long-chain fatty acids and trialkanolamine in the synthesis process of the ester type quaternary ammonium salt described later. It varies depending on the reaction molar ratio of long chain fatty acids to trialkanolamine in the reaction (long chain fatty acids / trialkanolamine).

In general formulas (I) to (III), R _{1 to} R ₃ and R _{5 to} R ₇ are each an alkyl or alkenyl group having 9 to 23 carbon atoms, preferably 13 to 19 carbon atoms. When it is 9 or more, a soft texture can be imparted when applied to thin paper, and when it is 23 or less, a thin paper treating agent with high liquid stability can be obtained.
In addition, R _{1 to} R ₃ and R _{5 to} R ₇ in the molecule of each component of (a-1) to (a-3) are portions corresponding to residues obtained by removing a carboxy group from a raw long-chain fatty acid. is there. From the viewpoint of imparting a texture, it is desirable that 50% by mass or more of the “residue obtained by removing a carboxy group from a long-chain fatty acid” present in component (A) has 17 or more carbon atoms. The proportion of the “residue obtained by removing a carboxy group from a long-chain fatty acid” having 17 or more carbon atoms is more preferably 65% by mass or more, and particularly preferably 75% by mass or more.
R _{1 to} R ₃ present in one molecule or R _{5 to} R ₇ present in one molecule are each a residue obtained by removing a carboxy group from a saturated higher fatty acid (hereinafter sometimes referred to as a saturated residue) or Only one of the residues obtained by removing the carboxy group from the unsaturated higher fatty acid (hereinafter sometimes referred to as an unsaturated residue) may be present, or both may coexist. The ratio of the saturated residue / unsaturated residue in the “residue obtained by removing the carboxy group from the long-chain fatty acid” present in the component (A) is within the range of 10/0 to 1/9 by mass ratio. Desirably, it is preferably 10/0 to 3/7, particularly preferably 10/0 to 5/5 from the viewpoint of imparting a texture. When an unsaturated residue is present, the stereoisomer structure thereof may be either a cis isomer or a trans isomer, or both may be present together, and there is no particular limitation. However, from the economical viewpoint in view of the synthesis efficiency, it is desirable that the ratio of the cis isomer / trans isomer in the unsaturated residue is in the range of 25/75 to 100/0 by mass ratio.

In general formulas (I) to (III), R ₄ is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a hydroxyethyl group. A methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
In general formula (I)-(III), p is an integer of 2-4, Preferably it is 2 or 3, Comprising: 2 is especially preferable. when p is _3, -C _{p H 2p} - group represented by the isopropylene group is preferred.
In general formulas (I) to (III), n is an integer of 2 to 4, preferably 2. M is an integer of 0 to 3, preferably 0 or 1, and particularly preferably 0. Each n, m, and p in one molecule may be the same as each other or different from each other.

X ^- is denotes an anion, chlorine, bromine, halogen ion and methyl sulfate, alkyl sulfate ion such as ethyl sulfate, methyl carbonate ion preferably such as iodine, chlorine ion, bromine ion, methyl sulfate ion, an ethyl sulfate ion and more preferably Furthermore, methyl sulfate ion and ethyl sulfate ion are preferable. In particular, methyl sulfate ion is preferable from a practical viewpoint such as the corrosiveness of equipment.

The ester-type quaternary ammonium salt is obtained by, for example, condensing a long-chain fatty acid (long-chain fatty acid or a lower alcohol ester thereof) with a trialkanolamine, and then converting the resulting ester amine with a quaternizing agent such as dialkyl sulfuric acid. It can be obtained by grading. In the condensation reaction of long chain fatty acids and trialkanolamine, the reaction molar ratio of long chain fatty acids to trialkanolamine (long chain fatty acids / trialkanolamine) is preferably in the range of 1.3 to 2.2. .5 to 2.0 is more preferable. As needed, you may mix and use the multiple types of composition obtained by performing the said condensation reaction by mutually different reaction molar ratio. When the reaction molar ratio of the long-chain fatty acids to the trialkanolamine is 1.3 or more, the amount of unreacted trialkanolamine in esterification can be reduced. Conversely, if it is 2.2 or less, the amount of triester-type quaternary ammonium salt produced can be suppressed, which is preferable from the viewpoint of texture and stability.
Specific examples of long-chain fatty acids that can be used for the synthesis of ester-type quaternary ammonium salts include unsaturated higher fatty acids such as oleic acid, elaidic acid, linoleic acid, and linolenic acid; stearic acid, palmitic acid, myristic acid, lauric acid Saturated higher fatty acids such as acids; and their lower alcohol esters. In particular, derived from animal and vegetable oils such as fatty acids obtained by decomposing and refining natural fats such as beef tallow, lard, palm oil, soybean oil, rapeseed oil, safflower oil, sunflower oil, olive oil, coconut oil and palm kernel oil Of these fatty acids or their methyl esters. The long-chain fatty acids may be hydrogenated before or after decomposition of fats and oils.

Further, as the trialkanolamine, triethanolamine and triisopropanolamine are preferable, and these may be used alone or in combination. Of these, triethanolamine is more preferred.
In addition, when an alkylene oxide is added to ammonia to synthesize a trialkanolamine, an adduct in which an alkylene oxide — (C _n H _2n O) — is added is generated. When the trialkanolamine from which the adduct has been removed is used, m in the above general formulas (I) to (III) is all 0, and when it is used without removing the adduct, the m is 1 or more. .

The quaternization reaction may be performed either without a solvent or in the presence of a solvent such as ethanol. When the reaction is performed without a solvent, a solvent may be added after the reaction. As the quaternizing agent, methyl halides such as methyl chloride, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate are preferable, and methyl chloride, dimethyl sulfate and diethyl sulfate are preferable, and dimethyl sulfate and diethyl are preferable because of high reactivity. Sulfuric acid is particularly preferred. The molar ratio of the quaternizing agent to the ester amine (quaternizing agent / ester amine) is preferably 0.90 to 1.5, more preferably 0.95 to 1.1, but when dialkyl sulfuric acid is used. From the viewpoint of safety, 0.90 to 1.0 is preferable, and 0.94 to 0.99 is more preferable. The temperature of the quaternization reaction is preferably 40 ° C to 120 ° C, more preferably 60 ° C to 100 ° C.
(A) A component can be used 1 type or in mixture of 2 or more types.

"(B) component"
The component (B) is a fatty acid having 8 to 22 carbon atoms and an ester of polyethylene oxide-added sorbitan. The structure of the ester of fatty acid and polyoxyethylene-added sorbitan is represented by the general formula (IV) and is also known as tweens or polysorbates.
R in the general formula (IV) corresponds to a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms, and is an alkyl or alkenyl group having 7 to 21 carbon atoms. When the carbon number of R is smaller than 7, the intended texture improving effect cannot be obtained and the stability of the liquid is also lowered. When the carbon number of R is larger than 21, the desired texture improving effect cannot be obtained, and the stability of the liquid is also lowered. 11-19 are preferable and 11-17 are more preferable from a viewpoint of a texture improvement effect and liquid stability. Specifically, R is a residue derived from an unsaturated higher fatty acid such as oleic acid, elaidic acid, linoleic acid or linolenic acid, or a saturated higher fatty acid such as stearic acid, palmitic acid, myristic acid or lauric acid. Residues are preferred.
In the general formula (IV), a, b and c represent the number of moles of oxyethylene added. The sum of a to c in one molecule is 5 to 100. By setting it to the lower limit or more, gelation and thickening effects can be obtained by combined use with the component (A). It is possible to prevent the handling property from deteriorating in the process of applying to paper. The total of a to c is preferably 10 to 50, more preferably 15 to 30 in that a better thickening effect can be obtained.
(B) A component can be used 1 type or in mixture of 2 or more types.

  By making the mass ratio ((A) component / (B) component) of the blending amount of the component (A) and the component (B) within the range of 0.1 to 19.0, the ester type quaternary ammonium salt And gelation and thickening due to the combined effect of polyoxyethylene-added sorbitan ester of fatty acid occur, and the desired texture-improving effect such as sliminess and moist feeling is obtained, and the liquid stability is also improved. The blending ratio of the component (A) and the component (B) is preferably 0.2 to 10.0 in that the combined effect of both is higher, and particularly preferably 0.4 to 4.0. preferable.

"(C) component"
Component (C) is a polyhydric alcohol. The component (C) is a hydrophilic component and mainly functions as a base. Moreover, the texture of thin paper improves also by mix | blending (C) component.
The component (C) can be used without particular limitation as long as it is a dihydric or higher alcohol. Among these, a divalent alcohol is preferable, and a trivalent alcohol is particularly preferable. Further, the carbon number is preferably 2 to 10 because water retention is improved by ensuring appropriate hydrophilicity and texture is improved.
Specific examples include glycerin, diglycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyglycerin, polyethylene glycol, polypropylene glycol, sorbitol, xylitol, erythritol and the like. Among them, glycerin, propylene glycol, 1, 3-butylene glycol is preferred, and glycerin is particularly preferred.

(C) component can be used 1 type or in mixture of 2 or more types.
In particular, from the viewpoint of liquid stability, it is preferable to use glycerin and another polyhydric alcohol in combination. The other polyhydric alcohol is preferably a dihydric alcohol such as propylene glycol or 1,3-butylene glycol, or sorbitol.
When using together, it is preferable that the compounding quantity of glycerol is 40 mass% or more in (C) component, It is especially preferable that it is 60 mass% or more. By setting it to 40% by mass or more, moisture retention of the thin paper is improved, and moist feeling and softness are improved.

The blending amount of the component (C) is preferably 55 to 99% by mass, more preferably 65 to 99% by mass, and further preferably 70 to 99% by mass in the total of the components (A), (B) and (C). . By setting it to be equal to or more than the lower limit of the above range, the moisture retention is improved, and the texture is improved in that the moist feeling is improved. By being below the upper limit, a preferable content of the component (A) and the component (B) can be relatively secured, and the texture is improved in terms of improving flexibility and smoothness.
Moreover, the total amount of the component (A), the component (B) and the component (C) in the thin paper treating agent is preferably 50 to 99.5% by mass, more preferably 70 to 99% by mass. More preferably, it is 85-98 mass%. The effect of this invention can fully be exhibited as it is more than the lower limit of the said range. When the amount is not more than the upper limit, water can be contained in addition to the components (A) to (C) to improve the liquid stability, and the blending amounts of the components (D) and (E) described later can be secured.

"(D) component"
The component (D) is one or more compounds selected from the group consisting of an alkylene oxide adduct (D1) of glycerol and an alkylene oxide adduct (D2) of polyglycerol.
The component (D) promotes gel formation by the components (A) and (B) in the polyhydric alcohol (C), further improves the moisturizing power, and has the effect of further improving the moist and slimy feeling. Have.
The component (D2) is a compound obtained by adding an alkylene oxide to a condensate (polyglycerin) of two or more molecules of glycerin. The degree of polymerization in the polyglycerin (the number of molecules of glycerin constituting one molecule of the condensate) is preferably from 2 to 20, and more preferably from 2 to 10.
10-100 are preferable with respect to 1 mol of glycerol or polyglycerol, and, as for the addition mole number of the alkylene oxide in (D1) component and (D2) component, 30-80 are more preferable.

  Specific examples include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide alone or mixed (block, random) to glycerol or polyglycerols such as diglycerol and triglycerol. The alkylene oxide to be added is preferably a random or block copolymer of propylene oxide and ethylene oxide because the effect of improving the texture becomes higher. It is preferable that the copolymerization ratio of ethylene oxide and propylene oxide (ethylene oxide / propylene oxide) is within the range of 5/95 to 95/5 on the basis of the number of moles because the effect of improving the texture is higher. Those within the range of / 10 are more preferable.

(D) component can be used 1 type or in mixture of 2 or more types.
(D) The compounding quantity of a component has preferable 0.5-15 mass% with respect to the sum total of (A), (B) and (C) component, and its 1-12 mass% is more preferable. By setting it to the lower limit value or more of the above range, it is possible to obtain the desired texture improving effect, and by setting the upper limit value or less to prevent excessive gel formation, it is possible to obtain good handling properties. Moreover, even if it mix | blends more than this upper limit, the texture improvement effect commensurate with the addition beyond it cannot be acquired.

"(E) component"
(E) A component is an oil-based component.
The thin paper treating agent of the present invention further comprises one or more oily components selected from the group consisting of fatty acids (E1), aliphatic alcohols (E2), esters of fatty acids and fatty alcohols (E3), and paraffins (E4) ( It is preferable to contain E). The component (E) improves smoothness. It is also effective in suppressing foaming in the paper coating process.

The fatty acid (E1) is preferably a fatty acid having 8 to 20 carbon atoms, and more preferably a fatty acid having 16 to 18 carbon atoms. Specific examples include isostearic acid and stearic acid.
The aliphatic alcohol (E2) is preferably a linear or branched higher alcohol having 8 to 20 carbon atoms, and more preferably a linear or branched higher alcohol having 16 to 18 carbon atoms. Specific examples include isostearyl alcohol and oleyl alcohol.
The ester of fatty acid and aliphatic alcohol (E3) is preferably an ester of fatty acid having 8 to 20 carbon atoms and aliphatic alcohol having 1 to 5 carbon atoms, and specific examples thereof include methyl oleate and methyl stearate.
Paraffin (E4) is preferably liquid paraffin having an average molecular weight of 200 to 800, more preferably 250 to 450, and specific examples thereof include Moresco White 55 and 200 (manufactured by Matsumura Oil).
Among the above, (E) component is preferably a higher alcohol having 16 to 18 carbon atoms or a fatty acid having 16 to 18 carbon atoms, particularly preferably isostearyl alcohol, oleyl alcohol, or isostearic acid.

(E) A component can be used 1 type or in mixture of 2 or more types.
(E) The compounding quantity of component is 0.01-11 mass% with respect to the sum total of (A), (B) and (C) component, 0.02-8 mass% is more preferable, 0.1-0.1 mass% 6 mass% is more preferable. By setting it above the lower limit of the above range, it is possible to obtain the desired texture-improving effect and foaming suppression effect, and by setting it to the upper limit or less, the balance with the blended amount of the polyhydric alcohol of component (C) is good. Therefore, even when the component (E) that is poorly compatible with the component (C) is blended, the liquid stability can be maintained. Moreover, even if it mix | blends more than this upper limit, the texture improvement effect commensurate with the addition beyond it cannot be acquired.

"water"
The thin paper treating agent of the present invention preferably contains water. By adding water, the liquid stability is further improved.
For example, ion-exchanged water is preferably used as the water.
The blending amount of water is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more for the lower limit in the thin paper treating agent. About an upper limit, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 15 mass% or less. By being above the lower limit value, the liquid stability is improved, and by being below the upper limit value, it is possible to suppress the phenomenon in which foaming occurs in the coating process and wrinkles occur on the thin paper immediately after coating.

"Optional ingredients"
Moreover, other arbitrary components can be mix | blended with a thin paper processing agent.
For example, an antifoamer, a preservative, etc. are mentioned. In particular, since the composition of the present invention contains a surfactant component, it tends to foam during processing. Therefore, it is preferable to use an antifoaming agent.
Examples of the antifoaming agent include polysiloxane, inorganic filler compounded compound silicone or emulsion thereof, POE (polyoxyethylene) -modified silicone, amino-modified silicone, ethanol, higher alcohol, POE (polyoxyethylene) and / or POP (polyethylene). Adducts added with oxypropylene) can be used. Of these polysiloxanes, dimethyl silicone, hydroxy-modified silicone, amino-modified silicone These polysiloxanes may be used as they are, but those emulsified with water are preferably used.

Examples of the preservative include oxybenzoic acid preservatives such as benzoate, methylparaben, and ethylparaben; organic nitrogen preservatives represented by hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine Agents: 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazoline Organic nitrogen sulfur-based preservatives typified by N-butyl-1,2-benzisothiazolin-3-one; 1,2-bis (bromoacetoxy) ethane, 2,2-dibromo-3-nitrilopropionamide, Organic bromide preservatives such as bistribromomethylsulfone; represented by 4,5-dichloro-1,2-dithiol-3-one Organic sulfur preservative such UNA like.
The compounding amount of the preservative is preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass in the thin paper treating agent.

  Other optional components include saccharides such as fructose, glucose and oligosaccharides; antioxidants such as vitamin C and vitamin E; fragrances; deodorants; pigments;

The thin paper treating agent can be obtained by uniformly mixing the components.
The thin paper treating agent preferably has a pH of 2 to 9 at 20 ° C., more preferably 3 to 8. Therefore, an appropriate pH adjuster (for example, sodium hydroxide, sulfuric acid, etc.) can be added as necessary. When the pH is in the above range, the liquid stability is improved. Moreover, it becomes gentler and less irritating to the skin, which is preferable.

The tissue paper treating agent is applied to tissue paper. For example, by applying the thin paper treating agent of the present invention to a thin paper, a good thin paper such as a texture can be obtained.
The thin paper to be treated is not particularly limited, and paper obtained by a conventionally known paper making method can be used.
As a method for applying the thin paper treating agent to the thin paper, a conventionally known method such as a roll transfer method or a spray coating method can be adopted.
The coating amount of the thin paper treatment agent is an active ingredient equivalent mass excluding water, and is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to the dry mass of the thin paper. A texture improves by making it more than a lower limit. By setting it to the upper limit value or less, it is possible to suppress the tendency of wrinkles and the like to impair the appearance of the thin paper, and it is economically advantageous.

By using the thin paper treating agent of the present invention, a thin paper having a good feel (feel) such as a slimy feeling, smoothness, moist feeling, and softness can be obtained. The thin paper treating agent of the present invention has good liquid stability.
Although the mechanism of action in the present invention is not clear, it is considered that the ester type quaternary ammonium salt of the component (A) is adsorbed on the fiber surface of the thin paper and hydrophobized to express flexibility and smoothness. Also, the ester type quaternary ammonium salt of component (A) and the polyoxyethylene-added sorbitan ester of fatty acid of component (B) form a gel-like aggregate in the polyhydric alcohol of component (C). When touched with a finger, the feeling of the gel collapsing produces a slimy feeling and smoothness, and a moist feeling can be obtained by releasing moisture confined in the aggregate. Moreover, by forming such a gel state, the liquid stability is improved, and liquid separation during storage is suppressed. The formation of this gel state can be grasped by an increase in the viscosity of the thin paper treating agent.

As described above, according to the present invention, it is possible to provide a thin paper treating agent that can obtain a thin paper having a good touch (texture) such as smoothness, moist feeling, and softness and that has good liquid stability.
The tissue paper treating agent of the present invention is suitable for processing household tissue paper used at home.
The thin paper treatment agent of the present invention can be used for, for example, wipe products suitable for personal care and household goods cleaning, paper products such as tissue (thin paper), and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the unit of a compounding composition is the mass% (total 100 mass%).

<Synthesis Example 1: Synthesis of ester type quaternary ammonium salt (A-1)>
-Preparation of ester amine-
740 g (2.7 mol) of palm oil fatty acid as long chain fatty acids and 250 g (1.7 mol) of triethanolamine were equipped with a stirrer, a partial condenser, a cooler, a thermometer, and a nitrogen introduction tube. A 2 L 4-neck flask was charged. Next, nitrogen was allowed to flow at a rate of 0.4 L / min, and the reaction was performed for 10 hours after the temperature was raised to 190 ° C. at a rate of 1.5 ° C./min while distilling out by-product water. Reaction was stopped. Thus, an ester amine (alkanolamine ester) as an intermediate was prepared.

-Production of ester type quaternary ammonium salt-
300 g (0.53 mol) of the prepared esteramine was charged into a 1 L separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and 63.6 g (0.51 mol) of dimethyl sulfuric acid as a quaternizing agent was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 65 g of ethanol to prepare an ethanol solution having a solid content of 85% by mass. Thus, an ester type quaternary ammonium salt (A-1) was produced.

<Synthesis Example 2: Synthesis of ester type quaternary ammonium salt (A-2)>
-Preparation of ester alkanolamine ester-
788 g (2.7 mol) of a fatty acid methyl ester mixture derived from palm oil (produced by Lion Oleo Chemical Co., pastel M180, pastel M181, pastel M16) and 250 g (1.7 mol) of triethanolamine were mixed with an alkali catalyst. Was added to a 2 L four-necked flask equipped with a stirrer, a partial condenser, a cooler, a thermometer, and a nitrogen inlet tube. Next, nitrogen was allowed to flow in at a rate of 0.4 L / min, and by-produced methanol was distilled out of the system, while the temperature was raised to 190 ° C. at a rate of 1.5 ° C./min. Reaction was stopped. Thus, an ester amine as an intermediate was prepared.

-Production of ester type quaternary ammonium salt-
300 g (0.52 mol) of the prepared ester amine was charged into a 1 L separable flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 90 degreeC and 64.0 g (0.51 mol) of dimethyl sulfuric acid as a quaternizing agent was dripped over 2 hours. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 65 g of ethanol to prepare an ethanol solution having a solid content of 85% by mass. Thus, an ester type quaternary ammonium salt (A-2) was produced.

The properties of the ester type quaternary ammonium salts synthesized in Synthesis Examples 1 and 2 are shown in Table 1. The analysis method is as follows.
<Measurement of mono, di, triester composition ratio in ester type quaternary ammonium salt>
The ester amine obtained as the intermediate was diluted to about 10 mL of isopropanol and heated moderately to completely dissolve the ester amine. This was used as a measurement sample, analyzed by liquid chromatography under the following analysis conditions, and the composition ratio was measured from the area ratio of mono-, di-, and tri-fatty acid esters. The results are shown in Table 1. In Table 1, the measurement results of the composition ratio are the triester type quaternary ammonium salt (a-1), the diester type quaternary ammonium salt (a-2), and the monoester type quaternary ammonium salt (a- The total mass of 3) is defined as 100% by mass, and the respective ratios are represented by mass%.
-Analysis conditions-
Column: Nucleosil 5SB 4.6φ × 250 mm, eluent: 0.3% -sodium perchlorate / 0.175% monochloroacetic acid-methanol solution, flow rate: 1.0 mL / min, detector: RI (differential refractometer) Sample injection volume: 100 μL.

<Measurement of alkyl distribution>
The alkyl distribution of the ester-type quaternary ammonium salt is about 1% of a sample obtained by dissolving long-chain fatty acids (fatty acids in Synthesis Example 1 and a mixture of fatty acid methyl esters in Synthesis Example 2) used as a raw material for ester amine in isopropanol. Was prepared and analyzed by gas chromatography under the following analysis conditions, and the area ratio was determined. In the measurement of fatty acid, the sample was silylated with silylating agent BSTFA and then dissolved in isopropanol, and the fatty acid methyl ester was dissolved in isopropanol as it was to prepare a sample.
The results are shown in Table 1. In Table 1, the measurement result of the alkyl distribution shows that the total mass of long-chain fatty acids is 100% by mass, among which long-chain fatty acids (residues obtained by removing carboxy groups from long-chain fatty acids) have 15 carbon atoms ( C15), long-chain fatty acids having 17 carbon atoms and 0 unsaturated bond in the residue (C17F0), long-chain fatty acids having 17 carbon atoms and 1 unsaturated bond ( The ratios of C17F1), long-chain fatty acids having 17 carbon atoms and two unsaturated bonds (C17F1), and long-chain fatty acids having 19 carbon atoms are shown by mass%.
-Analysis conditions-
Model: Hitachi FID Gaschrom G-3000, Column: GL Science TC-70 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm).
Temperature: temperature rising from column 150 ° C. to 230 ° C., temperature rising rate 10 ° C./min, injector and detector 240 ° C., column pressure: 1.0 kgf / cm ² .

<Synthesis Example 3: Synthesis of glycerin alkylene oxide adduct (D)>
A predetermined amount of 285 g of propylene oxide (PO) and 2 g of potassium hydroxide catalyst were added to 22 g of glycerin and added under pressure to obtain an intermediate having a molecular weight of 1300. Next, 552 g of PO and 140 g of ethylene oxide (EO) were randomly added so that the total number of moles added per mole of glycerin was finally 74 moles and the ratio of EO / PO added was 13/60. Finally, potassium content was removed using 1 g of silicate (trade name: KYOWARD 600, manufactured by Kyowa Chemical), and then dehydrated under reduced pressure to obtain a “glycerin EO / PO (13/60) adduct”.

[Examples and Comparative Examples]
In the following Examples and Comparative Examples, the ester-type quaternary ammonium salts (A-1) and (A-2) obtained in Synthesis Examples 1 and 2 and the glycerin EO / PO obtained in Synthesis Example 3 (13/60) ) Adducts and the following compounds were used.
-Polyoxyethylene (EO20) sorbitan monolaurate: trade name LT221, manufactured by NOF Corporation.
-Polyoxyethylene (EO10) sorbitan monolaurate: trade name Nonion LT210, manufactured by NOF Corporation.
-Polyoxyethylene (EO80) sorbitan monolaurate: trade name Nonion LT280, manufactured by NOF Corporation.
-Monooleic acid polyoxyethylene (EO20) sorbitan: Trade name Nonion OT220, manufactured by NOF Corporation.
・ Polyoxyethylene monostearate (EO20) sorbitan: Trade name Nonion ST220, manufactured by NOF Corporation.
Glycerin: Lion, food-added glycerin, viscosity at 25 ° C. of 420 mPa · s.
-Sorbitol: Trade name Sorbit D-70, manufactured by Towa Kasei.
-Isostearic acid: trade name isostearic acid EX, manufactured by Higher Alcohol Industry.
Isostearyl alcohol: trade name Isostearyl alcohol EX, manufactured by Higher Alcohol Industry
・ Oleyl alcohol: Trade name oleyl alcohol, manufactured by Higher Alcohol Industry.
・ Di-cured tallow methylammonium chloride: Product name Arcard 2HT, manufactured by Lion Akzo.
Castor oil EO 40 mol adduct: Trade name HCO-40, manufactured by Aoki Oils and Fats.
-Dimethyl silicone: Trade name KF-70, manufactured by Shin-Etsu Chemical Co., Ltd., emulsion type (effective portion 25%).

<Preparation of thin paper treatment agent>
(Examples 1-10, Comparative Examples 3-6)
Thin paper treatment agents were prepared with the formulations shown in Tables 2, 3, and 4.
First, a predetermined amount of (C) component, ion-exchanged water, (B) component, and (A) component was taken in a 200 mL beaker in order, heated to 50 ° C. in an oil bath, and stirred and mixed. After becoming uniform, dimethyl silicone was added, and the mixture was further stirred and mixed at room temperature for 5 minutes. Thereafter, a predetermined amount of glycerin was added and further stirred until a uniform and transparent state was obtained. At this time, when the pH was outside the range of 5 to 6, the pH was adjusted to 5 to 6 using 1N sodium hydroxide or sulfuric acid to obtain the intended thin paper treatment agent.
The pH was measured using a glass electrode pH meter (trade name: F-21, manufactured by HORIBA, Ltd.) at 25 ° C.

(Comparative Examples 1 and 2)
A thin paper treating agent having the composition shown in Table 3 was prepared as follows.
That is, in Examples 1 and 2, instead of the component (B), castor oil polyoxyethylene adduct, which is a lipophilic compound used in a conventional thin paper treating agent (for example, Patent Document 3), was used. Except for this, the desired thin paper treating agent was obtained in the same procedure as in Example 1.

(Comparative Example 7)
A thin paper treating agent having the composition shown in Table 3 was prepared as follows.
That is, instead of the component (A) in Example 1, dicured tallow methylammonium chloride, which is a general cationic surfactant and a quaternary ammonium salt having no ester bond in the molecule, was used. The target thin paper treating agent was obtained by the same procedure as in Example 1 except for.

(Examples 11-14)
A thin paper treating agent having the composition shown in Table 5 was prepared as follows.
In Example 2, (D) component and / or (E) component were added after (A) component, and it heated to 50 degreeC in the oil bath, and stirred and mixed. After becoming uniform, dimethyl silicone was added and stirred and mixed at room temperature for 5 minutes. Thereafter, the intended thin paper treating agent was obtained in the same procedure as in Example 2.

The following evaluation was performed about each thin paper processing agent obtained above. The evaluation results are shown in Tables 2-5.
"viscosity"
100 g of the prepared thin paper treating agent was put in a 100 mL sample bottle, and the temperature was adjusted in a thermostatic bath at 25 ° C. for 2 hours. Then, using a B-type viscometer (manufactured by TOKIMEC), a No. 2 rotor was used for less than 1000 mPa · s, a No. 3 rotor was used for 1000 to 4000 mPa · s, and a No. 4 rotor was used for 4000 to 10000 mPa · s, after 30 seconds at 30 rpm. Read the value. The measured values (unit: mPa · s) are shown in the table.
Here, it is desirable that the flowability at normal temperature is good as the handling property of the processing agent.
The standard is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, and further preferably 2500 mPa · s.

"Evaluation of texture"
About the thin paper processed by the method shown below using the thin paper processing agent, the texture was evaluated as follows.
<Method of processing thin paper>
In this test, in order to apply to spray coating, the thin paper treatment agents obtained in the above Examples and Comparative Examples were each diluted with ion-exchanged water so as to be 20% by mass in terms of active ingredients (components excluding water). The secondary treatment agent used was used.
Next, this secondary treatment agent is spray-applied uniformly to an untreated tissue paper so that the coating amount after the drying treatment is 25% by mass with respect to the tissue, and a constant temperature and humidity chamber (temperature 25 ° C./humidity). 65% RH) for 24 hours and dried. The texture of the treated tissue paper thus obtained was evaluated.
The evaluation of the texture was performed by a method of comprehensive sensory evaluation by comparing with a target panel the moist, soft, slimy and smoothness of the treated tissue paper by a specialized panel. As the target product, tissue paper treated in the same manner was used in place of the secondary treatment agent, except that an aqueous solution of 25% by mass of glycerin (manufactured by Lion, glycerin for food addition) was used. The evaluation criteria were as follows.
(Evaluation criteria)
Very good compared to the target product: ◎.
Good compared to the target product: ○.
Slightly better than the target product: △.
Less than or equal to the target product: ×.

"Liquid stability"
The thin paper treating agent was stored at 25 ° C. for 2 months, and the presence or absence of separation was visually determined and evaluated according to the following criteria.
A: Transparent and uniform with no separation.
○: Slightly turbid and no separation.
Δ: Slight separation is observed.
X: Completely separated.

From the results shown in Tables 2 to 5, the thin paper treatment agents obtained in the examples according to the present invention have excellent liquid stability because the liquid is difficult to separate, and the texture of the thin paper treated with the thin paper treatment agent is good. Met.
On the other hand, Comparative Examples 1 and 2 using castor oil polyoxyethylene adduct instead of the component (B) had a lower viscosity than Examples 1 and 2, respectively, and the texture and liquid of the treated thin paper Poor separation and foaming.
In Comparative Example 3 in which the component (A) was not used, the viscosity was low and the liquid was difficult to separate, but a good texture of the thin paper was not obtained.
In Comparative Example 4 in which the component (B) was not used, the viscosity was low, the liquid was easily separated, and the texture of the thin paper was inferior.
The comparative example 5 containing the component (A) and the component (B) but the mass ratio of (A) / (B) is too large is inferior in liquid separability and texture of the thin paper, and (A) / (B) In Comparative Example 6 in which the mass ratio is too small, the liquid is difficult to separate but the texture of the thin paper is inferior.
Comparative Example 7 using di-cured beef tallow methylammonium chloride instead of the component (A) has a lower viscosity than Examples 1 and 2, and is inferior in texture, liquid separability, and foaming of the treated thin paper.

Claims (3)

The following (A) component, (B) component, and (C) component are contained, The mass ratio of the said (A) component represented by (A) / (B) and (B) component is 0.1-19. A thin paper treating agent characterized by being zero.
(A) a quaternary ammonium salt having an ester bond,
(B) a fatty acid having 8 to 22 carbon atoms and an ester of polyethylene oxide-added sorbitan,
(C) Polyhydric alcohol.   Furthermore, the thin paper processing agent of Claim 1 containing 1 or more types of compounds (D) chosen from the group which consists of alkylene oxide adduct of glycerol and the alkylene oxide adduct of polyglycerol.   Furthermore, the thin paper processing agent of Claim 1 or 2 containing 1 or more types of oil-based components (E) chosen from the group which consists of fatty acid, fatty alcohol, ester of fatty acid and fatty alcohol, and paraffin.