JP5410026B2 - Sanitary tissue paper - Google Patents

Description

  The present invention relates to a sanitary thin paper having improved smoothness in addition to flexibility.

Sanitary thin paper such as tissue paper is used in various applications as an inexpensive disposable article. In particular, it is often used for wiping applications such as nose bites and mouth wipes, such as facial applications.
And since this type of sanitary thin paper is used for such applications, for example, the time of pollinosis, the problem that sebum is taken away frequently when biting the nose, the nose becomes red, etc. When wiping a weak part of the skin, there is a problem that it may hurt the skin by friction. Therefore, in this type of sanitary thin paper, it is important to be soft in order to reduce the influence on the skin due to friction, and efforts have been made to improve it.
However, it has been found that the above-mentioned problems with the skin cannot be improved only by increasing the flexibility, and that smooth touch is also an important factor.
Such smoothness can be improved by adding a large amount of a softening agent to the base paper. However, if a large amount of softening agent is used to increase flexibility, foaming of excess softening agent or surplus softening agent is used. There is a risk that operational troubles may occur due to the generation of debris due to flocculation or the like, and the paper strength may be reduced.
JP 2006-307403 A Japanese Patent No. 3322735

  Therefore, a main object of the present invention is to provide a sanitary thin paper that has a feeling of smoothness in addition to softness, and that can solve problems in production without lowering paper strength.

前記柔軟剤定着補助剤が、
ポリアミド・エピクロロヒドリン樹脂であり、
前記柔軟剤と柔軟剤定着補助剤の質量比が２．８：２．５〜１０：１であり、
かつ、柔軟剤の含有量が０．７〜２．８ｋｇ／ｔであり、柔軟剤定着補助剤の含有量が０．１〜２．５ｋｇ／ｔであり、
ＪＩＳ Ｐ ８１１３に規定される乾燥引張強度が、縦方向２００〜３５０ｃＮ／２５ｍｍ、横方向９０〜１４０ｃＮ／２５ｍｍであり、かつ、
澱粉、カチオン性澱粉、カチオン性変成澱粉、カルボキシメチルセルロース若しくはその塩であるカルボキシメチルセルロースナトリウム、カルボキシメチルセルロースカルシウム、カルボキシメチルセルロース亜鉛が含有されていない、
ことを特徴とする衛生用薄葉紙。 The present invention that has solved the above problems is as follows.
<Invention of Claim 1>
A sanitary thin paper containing a thin paper treating agent for a base paper,
The tissue paper treating agent includes a softening agent and a softening agent fixing aid,
The softener is
A nonionic surfactant having an alkyl group and / or alkenyl group (component A) and a cationic surfactant having an alkyl group and / or alkenyl group (component B), and the solid content weight ratio thereof is A component / B component = 100 / 0.5 to 100/20,
The component A is at least one compound represented by the following general formulas (1), (2) and (3),
R ¹ -A ^1- (EO) _m (PO) _n -CO-R ² (1)
R ¹ —O— (EO) _m (PO) _n —R ² (2)
R ¹ -A ^1- (EO) _m (PO) _n H (3)
(In the formula, —A ¹ — represents —O— or —COO—, R ¹ and R ² represent an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, and R ¹ and R ² may be the same or different, E represents an ethylene group, P represents a propylene group, and the sum of m and n is 1 to 60, where m and n are average additions Number of moles.)
The B component is a quaternary ammonium salt having an imidazoline ring having an alkyl group and / or an alkenyl group, or a compound represented by the following general formula (4):

The softener fixing auxiliary agent is
A polyamide / epichlorohydrin resin,
The mass ratio of the softener and softener fixing aid is 2.8: 2.5-10: 1;
And content of a softening agent is 0.7-2 . 8 kg / t, the content of the softener fixing auxiliary is 0.1 to 2.5 kg / t,
The dry tensile strength defined in JIS P 8113 is 200 to 350 cN / 25 mm in the longitudinal direction, 90 to 140 cN / 25 mm in the transverse direction, and
Contains no starch, cationic starch, cationic modified starch, carboxymethylcellulose or its salt, carboxymethylcellulose sodium, carboxymethylcellulose calcium, carboxymethylcellulose zinc,
Hygienic thin paper characterized by that.

  According to the present invention described above, a thin paper that can be produced without any trouble and that has improved smoothness in addition to softness is provided.

Hereinafter, embodiments of the present invention will be described in detail.
The sanitary thin paper of the present invention contains a thin paper treating agent relative to the base paper.
[Base paper]
The number of plies of the base paper is not limited and can be appropriately selected according to the use of sanitary thin paper.
However, it is desirable that the rice tsubo per ply (JIS P 8124) is 10.0 to 25.0 g / m ² . When the rice tsubo is smaller than 10.0 g / m ² , sufficient strength cannot be maintained, and it is torn at the time of manufacture, causing paper breakage or the like. On the other hand, if the rice tsubo is larger than 25.0 g / m ² , not only the paper strength cannot be lowered, but also the effect when the softening agent is added becomes difficult to understand.

  On the other hand, the base paper of the sanitary thin paper of the present invention can be obtained by making a known papermaking raw material by a known papermaking technique within the range of the basis weight. A blending ratio (JIS P 8120) of 30.0 to 80.0%, particularly 40.0 to 70.0% is preferred.

  Further, the paper strength of the base paper can be adjusted by adjusting the starch for papermaking and the freeness in addition to the rice tsubo. The freeness (freeness) when raw pulp is not beaten is about 500 to 700 CC based on the Canadian standard freeness test method according to JIS P8121. By setting the freeness down width to about 0 to 50 CC by unbeating or beating this, the softening agent and smoothness can be maintained and the strength of the base paper can be given.

[Thin paper treatment agent]
On the other hand, the thin paper treating agent includes a softening agent and a softening agent fixing auxiliary agent.
(Softener)
The softener according to the present invention contains a nonionic surfactant having an alkyl group and / or alkenyl group (component A) and a cationic surfactant having an alkyl group and / or alkenyl group (component B). .

  First, the nonionic surfactant (component A) will be described. This nonionic surfactant (component A) has an alkyl group and / or alkenyl group, and has an alkyl group having 6 to 24 carbon atoms and / or an alkenyl group having 6 to 24 carbon atoms as a hydrophobic portion. preferable.

  In the present invention, if the carbon number of the component A is less than 6, the flexibility effect may not be enhanced, and if the carbon number exceeds 24, the dispersibility when added to the papermaking system may deteriorate. Therefore, the carbon number of the component A according to the present invention is preferably in the range of 6-24.

  As such a nonionic surfactant, a nonionic surfactant in which an oxyalkylene group is added to a higher alcohol or higher fatty acid, an ester of a polyhydric alcohol and a fatty acid, and the following general formulas (1) and (2) ) (Hereinafter referred to as Compound I). These may be used alone or in combination of two or more.

Examples of the nonionic surfactant in which an oxyalkylene group is added to a higher alcohol or a higher fatty acid include compounds represented by the following general formula (3).
R1-A1- (EO) m (PO) n-CO-R2 (1)
R1-O- (EO m (PO) n-R2 (2)
R1-A1- (EO) m (PO) nH (3)
(However, in the formula, -A1- represents -O- or -COO-, and R1 and R2 represent an alkyl group having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms, or 6 to 24 carbon atoms, preferably 10 to 10 carbon atoms. 22 represents an alkenyl group, and R1 and R2 may be the same or different, E represents an ethylene group, P represents a propylene group, and the sum of m and n is 1 to 60, preferably 2 to 40, where m and n are the average number of moles added.)

   Of the nonionic surfactants represented by the general formulas (1) to (3), the nonionic surfactants represented by the general formulas (1) and (2) are preferable, and the general formula (1) is more preferable. It is a nonionic surfactant shown by these.

  The compound represented by the general formula (1) is, for example, an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 alcohols or 7 to 27 carbon atoms, preferably 1 to 23 moles of fatty acids having 11 to 23 carbon atoms, and After addition of propylene oxide, it can be obtained by esterification with 1 mol of a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms. The addition form of ethylene oxide and / or propylene oxide may be random or block, and is an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms or 1 mol of fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms. 1 to 60 mol, preferably 2 to 40 mol. When it exceeds 60 mol, the softening effect may be lowered.

  The compound represented by the general formula (2) has, for example, 6 to 24 carbon atoms, preferably 6 to 22 carbon atoms after adding ethylene oxide and / or propylene oxide to 1 mole of alcohol having 10 to 22 carbon atoms. It can be obtained by etherification with 24, preferably 10 to 22 alcohols or 1 mole of alkyl halide with 6 to 24, preferably 10 to 22 carbon atoms. The addition form of ethylene oxide and / or propylene oxide may be random or block, and a ratio of 1 to 60 mol, preferably 2 to 40 mol, per 1 mol of alcohol having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms. It is added with. When it exceeds 60 mol, the softening effect may be lowered.

  The compound represented by the general formula (3) is, for example, an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 alcohols or 7 to 25 carbon atoms, preferably 1 to 23 moles of fatty acids having 11 to 23 carbon atoms, and / Or it can be obtained by adding propylene oxide. The addition form of ethylene oxide and / or propylene oxide may be random or block, and is an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms, or 1 mol of fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms. 1 to 60 mol, preferably 2 to 40 mol. When it exceeds 60 mol, the softening effect may be lowered.

  The alcohol having 6 to 24 carbon atoms may be any of linear alcohol, branched chain alcohol, saturated alcohol, and unsaturated alcohol. Among these various alcohols, alcohols having 10 to 22 carbon atoms are preferable, and lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol are particularly preferable. These may be used alone or in combination of two or more.

  The fatty acid having 7 to 25 carbon atoms may be any of linear fatty acid, fatty acid having a branched chain, saturated fatty acid, and unsaturated fatty acid. Among these various fatty acids, fatty acids having 10 to 22 carbon atoms are preferable, and lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid are particularly preferable. These may be used alone or in combination of two or more.

  On the other hand, examples of the cationic surfactant (component B) include primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. These may be used alone or in combination of two or more. In particular, a quaternary ammonium salt is preferable.

As primary amines, compounds represented by the following general formula: R8-NH2 (6)
(In the formula, R8 represents one selected from an alkyl group having 6 to 24 carbon atoms and an alkenyl group having 6 to 24 carbon atoms.) Specific examples include oleylamine, laurylamine, and stearylamine.

Secondary amines are compounds represented by the following general formula: R9R10-NH (7)
(In the formula, R9 represents one selected from an alkyl group having 6 to 24 carbon atoms and an alkenyl group having 6 to 24 carbon atoms, and R10 is (EO) m (PO) nH, 1 to 24 carbon atoms). 1 is selected from an alkyl group having 1 to 24 carbon atoms, E is an ethylene group, P is a propylene group, and the sum of m and n is 1 to 60. , M and n are the average number of moles added.)
Specific examples include dioleylamine and monooleyl monomethylamine.

Tertiary amines are compounds represented by the following general formula: R11R12R13N (8)
(In the formula, R11 represents one selected from an alkyl group having 6 to 24 carbon atoms and an alkenyl group having 6 to 24 carbon atoms, and R12 and R13 are (EO) m (PO) nH, carbon number) 1 type | mold chosen from a C1-C24 alkyl group and a C1-C24 alkenyl group, and R12 and R13 may be the same or different, Said E shows an ethylene group, P 1 represents a propylene group, and the sum of m and n is 1 to 60, where m and n are the average number of moles added.
Specific examples of the tertiary amines include polyoxyalkylene dioleyl amine, polyoxyalkylene ethylene glycol lauryl amine, dimethyl monooleyl amine, and monomethyl dioleyl amine.

（ 但し、式中、Ｒ３は炭素数６〜２４のアルキル基又は炭素数６〜２４のアルケニル基を、Ｒ４とＲ５とは（ＥＯ）ｍ（ＰＯ）ｎＨ、炭素数１〜２４のアルキル基、及び炭素数１〜２４のアルケニル基から選ばれる１種を示し、かつＲ４とＲ５とは同一又は相異していてもよく、Ｘ−は陰イオンであり、前記Ｅはエチレン基を示し、前記Ｐはプロピレン基を示し、ｍとｎとの合計は１〜６０である。エチレンオキサイド、及び／ 又はプロピレンオキサイドの付加形態はランダムでもブロックでも良い。なお、ｍ及びｎは平均付加モル数である。）
上記一般式（４）で表される第４ 級アンモニウム塩としては、具体的にはトリメチルモノラウリルアンモニウムクロライド、トリメチルモノセチルアンモニウムクロライド、トリメチルモノパルミチルアンモニウムクロライド、トリメチルモノステアリルアンモニウムクロライド、トリメチルモノオレイルアンモニウムクロライド、トリメチルモノベヘニルアンモニウムクロライド、ジメチルジラウリルアンモニウムクロライド、ジメチルジセチルアンモニウムクロライド、ジメチルジパルミチルアンモニウムクロライド、ジメチルジステアリルアンモニウムクロライド、ジメチルジオレイルアンモニウムクロライド、ジメチルジベヘニルアンモニウムクロライド、ポリアルキレンオキシモノメチルジオレイルアンモニウムクロライド、ビス（ ポリアルキレンオキシ） モノメチルモノオレイルアンモニウムクロライドが挙げられる。
このなかでもトリメチルモノステアリルアンモニウムクロライド、トリメチルモノオレイルアンモニウムクロライド、ジメチルジラウリルアンモニウムクロライド、ジメチルジオレイルアンモニウムクロライド、ポリアルキレンオキシモノメチルジオレイルアンモニウムクロライド、ビス（ ポリアルキレンオキシ） モノメチルモノオレイルアンモニウムクロライドが好ましい。 Examples of the quaternary ammonium salt include a compound represented by the following general formula (4) and a quaternary salt having an imidazoline ring represented by the following general formula (5). These may be used alone or in combination of two or more.

(In the formula, R3 is an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, R4 and R5 are (EO) m (PO) nH, an alkyl group having 1 to 24 carbon atoms, And R4 and R5 may be the same or different from each other, X- is an anion, E represents an ethylene group, P represents a propylene group, and the total of m and n is 1 to 60. The addition form of ethylene oxide and / or propylene oxide may be random or block, where m and n are the average number of moles added. .)
Specific examples of the quaternary ammonium salt represented by the general formula (4) include trimethyl monolauryl ammonium chloride, trimethyl monocetyl ammonium chloride, trimethyl monopalmityl ammonium chloride, trimethyl monostearyl ammonium chloride, trimethyl monooleyl. Ammonium chloride, trimethyl monobehenyl ammonium chloride, dimethyl dilauryl ammonium chloride, dimethyl dicetyl ammonium chloride, dimethyl dipalmityl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl dibehenyl ammonium chloride, polyalkyleneoxy monomethyl Dioleyl ammonium chloride, bis (Polyalkyleneoxy) Monomethyl monooleyl ammonium chloride is exemplified.
Among these, trimethyl monostearyl ammonium chloride, trimethyl monooleyl ammonium chloride, dimethyl dilauryl ammonium chloride, dimethyl dioleyl ammonium chloride, polyalkyleneoxy monomethyl dioleyl ammonium chloride, and bis (polyalkyleneoxy) monomethyl monooleyl ammonium chloride are preferable.

（ 但し、式中、Ｒ６は炭素数６〜２４のアルキル基又は炭素数６〜２４のアルケニル基を、Ｒ７は炭素数１〜２４のアルキル基又は炭素数１〜２４のアルケニル基を示し、Ｘ− は陰イオンである。） Examples of the quaternary ammonium salt having an imidazoline ring include compounds represented by the following general formula (5). These may be used alone or in combination of two or more.

(In the formula, R6 represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, R7 represents an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 1 to 24 carbon atoms, and X -Is an anion.)

  In the present invention, when the hydrophobic part of the component B is an alkyl group and / or alkenyl group, if the carbon number is less than 6, sufficient surface activity may not be obtained. May be worse. Therefore, it is preferable that the carbon number of B component of this invention is the range of 6-24.

  Specific examples of the quaternary ammonium salt having an imidazoline ring represented by the general formula (5) include 1-hydroxyethyl-1-ethyl-2-oleylimidazoline ethyl sulfate, 1-hydroxyethyl-1 -Methyl-2-oleylimidazoline chloride, 1-hydroxyethyl-1-ethyl-2-laurylimidazoline ethyl sulfate and the like.

Examples of the B component other than the above include monomethyl ester quaternary salt, dimethyl diester quaternary salt, trimethyl diester quaternary salt, and ester amide type tertiary salt.
Examples of the monomethyl ester quaternary salt include those obtained by diesterifying triethanolamine with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23, for example, stearic acid and quaternizing with dimethyl sulfate. Examples of the salt include N-methyldiethanolamine that is diesterified with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23, for example, oleic acid, and quaternized with methyl chloride. As the trimethyl diester quaternary salt, Examples include 3-dimethylamino-1,2-propanediol, which is diesterified with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms, such as oleic acid, and quaternized with methyl chloride. Examples of the salt include N- (2-hydroxyethyl) -N-methyl-1,3-propa Diamine 7-25 carbon atoms, preferably fatty acids of 11 to 23, for example esterified with oleic acid, amidation, and the like those tertiary ammonium salt is neutralized with hydrochloric acid.

  The mass ratio of the A component and the B component in the present invention is usually A / B = 100 / 0.5 to 100/20, and preferably A / B = 100/2 to 100/10. If the B component is less than 0.5 parts by weight relative to 100 parts by weight of the A component, it may not be able to be sufficiently adsorbed to the paper stock, and if the B component exceeds 20 parts by weight, its stability over time May get worse.

The softening agent of this invention contains the said A component and the said B component in a solvent or under absence of solvent.
Examples of the solvent include water and alcohols such as isopropyl alcohol.

(Softener fixing aid)
On the other hand, the softener fixing auxiliary agent according to the present invention increases the fixing rate of the softening agent, and means all substances that improve the fixing rate of the softening agent to the base paper when added. Preferable examples include those containing a polyamide / epichlorohydrin resin as an active ingredient, and particularly a polyamide / epichlorohydrin resin.

  This softener fixing auxiliary agent is preferably adjusted so that the active ingredient is contained in a solid content of 0.1 to 2.5 kg / t. Further, the softener fixing auxiliary agent is desirably ionic amphoteric, and if it is cationic, anionic, or nonionic, sufficient effects may not be obtained.

  In using the softener fixing auxiliary agent, an aqueous solvent such as water is used, and a viscosity adjusting agent, a pH adjusting agent, or the like is used as appropriate, and the viscosity is adjusted to be suitable for use.

  If the polyamide / epichlorohydrin resin is used, the molecular weight is preferably 100,000 or more and 1,000,000 or less, particularly preferably 600,000 or less. When the molecular weight is 100,000 or less, the fixing property when added is poor, and when it exceeds 1,000,000, the effect of increasing paper strength is strongly expressed, and the paper texture after papermaking is deteriorated.

  By using this softener fixing auxiliary in addition to the softener, the fixing ratio of the softener to the base paper is improved, the softness is improved without a decrease in paper strength, and the smoothness is also improved.

(Mixing ratio)
On the other hand, the blending ratio of the softening agent and the softening agent fixing auxiliary agent in the thin paper treatment agent includes at least the softening agent in a mass ratio, and preferably, the softening agent: softening agent fixing auxiliary agent = 2.8 by mass ratio. : 2.5 to 10: 1. When the amount of the softening aid is small relative to the softening agent, the fixing rate to the base paper is not sufficient, and the softness and smoothness are not sufficiently exhibited. When the amount of the softener fixing auxiliary agent is large, the paper strength is excessively increased, and the texture may be deteriorated.

(Content etc.)
On the other hand, in the sanitary thin paper of the present invention, it is desirable that the content of the softening agent is 0.1 to 2.8 kg / t. If it is less than 0.1 kg / t, the expression of flexibility, smoothness, and paper strength is not sufficient, and if it exceeds 2.8 kg / t, it is difficult to secure the paper strength necessary for wiping. It is necessary to take measures such as increasing the floor area. As a result, the texture tends to be hard. This content can be reliably achieved by the combined use of the softening agent fixing aid.

  On the other hand, the thin paper treating agent of the present invention may be used by adding to a papermaking raw material (pulp slurry), or may be used by coating on the surface of the base paper (that is, coating the surface).

  The thin paper treating agent of the present invention has a fixing ratio of the softening agent in the thin paper treating agent to the base paper exceeding 80% by mass, and can be extremely high as compared with the conventional about 60% by mass. In consideration of this, the addition amount is determined.

Furthermore, the thin paper treating agent of the present invention may be further applied to the surface of the base paper obtained by adding the thin paper treating agent of the present invention to the papermaking raw material, then papermaking and drying.
When the thin paper treating agent of the present invention is used by adding it to the papermaking raw material, the method of use is not particularly limited, and it can be diluted with industrial water or the like, or can be added as it is.

In any case, a method similar to a general paper manufacturing method can be adopted.
On the other hand, preferred methods for applying the paper softener of the present invention to surface coating include spray coating, flexo printing or gravure printing using a printing press, size press, gate roll coater, bill blade coater or Examples include coating with a calender and the like. In any case, a method similar to a general paper manufacturing method can be adopted except that the paper softener of the present invention is used.

[Structure and physical properties of sanitary thin paper]
On the other hand, the structure of the sanitary thin paper of the present invention may be 1 ply according to the base paper, 2 plies (a set of two stacked sheets), 3 plies, 4 plies or more plies. Also good. In the case of a plurality of plies, the chemical solution may be contained only in the base paper constituting the surface, or the chemical solution may be contained in all the base papers.

  In addition, the sanitary thin paper of the present invention is particularly suitable for toilet paper and tissue paper, and is preferably used for this purpose. It is easy to feel the effect of the present invention.

  On the other hand, the sanitary thin paper of the present invention preferably has an elongation of 7 to 15%. Most preferably, it is 8 to 13%. If the elongation is less than 7%, it is torn during production and troubles such as paper breakage occur. Also, paper with an elongation of more than 15% is not preferable because it needs to increase the number of irregularities on the surface of the paper such as increasing the crepe rate, and feels rough when rubbing the skin.

  This elongation rate is measured according to JIS P8113. Specifically, the dry tensile strength in the machine direction of the paper is measured, and the elongation percentage of the paper is calculated from the length of the paper immediately before the break and the length of the paper before the measurement. The measurement is performed with 2 plies for the final product, that is, a 2-ply product, and with 3 plies for a 3-ply product.

  The elongation rate has a large correlation with the crepe rate, and in order to suitably achieve the elongation rate, it is desirable that the crepe rate at the time of manufacturing the base paper is 12.0 to 20.0%. The crepe rate is a value calculated by the formula (((peripheral speed of the dryer during paper manufacture) − (peripheral speed of the reel)) / (peripheral speed of the dryer during paper manufacture) × 100).

On the other hand, the sanitary thin paper of the present invention has a dry tensile strength (hereinafter also referred to as dry paper strength) specified in JIS P 8113 of 200 to 350 cN / 25 mm in the longitudinal direction, more preferably 200 to 300 cN / 25 mm, and transverse direction. It is preferably 90 to 140 cN / 25 mm. If the dry paper strength is too low, it tends to break during manufacturing and troubles such as paper breakage occur, and if it is too high, the touch becomes stiff when used.
These dry paper strengths can be achieved in the present invention without the need for dry paper strength agents. Therefore, it is preferable that the sanitary thin paper of the present invention does not contain a dry paper strength agent.

  Dry paper strength agents that are not used include starch, cationic starch, cationic modified starch, carboxymethylcellulose sodium, carboxymethylcellulose calcium, and carboxymethylcellulose zinc, which are CMC (carboxymethylcellulose) or salts thereof. At least those listed here are not included.

  On the other hand, the paper thickness of the sanitary thin paper of the present invention (measured by a Peacock manufactured by Ozaki Seisakusho) is preferably 100 to 300 μm, particularly 110 to 200 μm, preferably 2 plies (two sheets stacked), It is desirable to be half.

  On the other hand, it is desirable that the sanitary thin paper of the present invention has an MMD value of 7 to 8.5. In addition, MMD here is the average deviation MMD of a friction coefficient measured on the conditions prescribed | regulated to JISP8111. The average deviation MMD of the friction coefficient can be measured using “Friction Sense Tester KES SE” manufactured by Kato Tech Co., Ltd. A larger MMD value means less smoothness.

  On the other hand, the sanitary thin paper of the present invention desirably has a touch test value based on MMD of 8.5 to 10.0. This touch test is performed by using an artificial leather (supplement: Idemitsu Techno Fine Co., Ltd.) on a base of a normal MMD tester, for example, a friction tester “KES SE” manufactured by Kato Tech Co., Ltd. as shown in FIGS. The measurement terminal is covered with artificial leather (Supplar: manufactured by Idemitsu Techno Fine Co., Ltd.), and the measurement surface of the measurement terminal is covered with artificial leather, and this is performed in the same manner as the MMD measurement procedure. . This touch test correlates with the smoothness felt when actually touching the skin.

  The details of the measurement will be further described. The contact plane made of artificial leather is formed by covering a silicon MMD measurement terminal having a measurement surface of approximately 10 mm square with the artificial leather.

The terminal is covered with artificial leather so that the artificial leather is in close contact with the measurement surface of the terminal so that a 10 mm square contact plane is formed, or with a slight tension. Can be achieved. When fixing the artificial leather to the terminal, make sure that the artificial leather and the internal terminal are not displaced when measuring, that is, when the paper sample is moved, so that the artificial leather and the contact plane are not distorted. is important. For example, after covering the terminal so that the contact plane is configured, the part that does not configure the contact plane is securely fixed to a part that does not affect the measurement of the device with a rubber band or the like, such as a support material for the terminal. To do. Also, artificial leather is laid on the base of the MMD testing machine and fixed with adhesive tape or the like. At this time, it is important to firmly fix the artificial leather to the base so as not to be distorted during measurement. The artificial leather laid on the base is the same as the artificial leather constituting the contact plane. In addition, the paper sample is cut into a 10 cm square and used, and is fixed to a base on which artificial leather is laid. At the time of measurement, a sample pressing weight (about 100 g) is pressed on a paper sample. Moreover, the load to the measurement terminal of a testing machine is performed as 15g. The measurement is performed three times in the vertical direction of the paper sample and three times in the horizontal direction for a total of six times, and the measured value (KES feel index) is the average value of the six times. In addition, in principle, two plies are used for a paper sample, and when one ply is assumed, two samples are stacked and measured. In this test, the average value of 6 times 10 times was adopted as the touch test value.
The sanitary thin paper of the present invention described above in detail has no advantage in paper strength, smoothness and softness are sufficiently improved as compared with conventional examples, and has excellent advantages in use.

  Subsequently, the result of having tested about the softness etc. of the Example of this invention and a comparative example is shown below as an Example.

  The following Tables 1 to 4 show the results of measuring the composition and physical properties of sanitary thin papers according to Examples and Comparative Examples of the present invention and the results of sensory evaluation for each example.

The sensory evaluation was performed as follows: “Softness”
A sensory evaluation of 30 subjects was performed. The evaluation was performed by scoring how the soft paper felt by touching the thin paper as a sample, hitting the face, biting the nose, etc. based on the reference example. The score is 1 point: the texture is clearly inferior to the reference example, 2 points: the texture is slightly inferior to the reference example, 3 points: the same as the reference example comparative example 1, 4 points: It can be seen that the texture is slightly better than the reference example. 5 points: It is clearly understood that the texture is superior to the reference example. The score in the table is the average of 30 people.

"Smoothness"
A sensory evaluation of 30 subjects was performed. The evaluation was performed by scoring how to feel the smoothness by touching the thin paper as a sample, hitting the face, biting the nose, etc., based on the reference example. The score is 1 point: the texture is clearly inferior to the reference example, 2 points: the texture is slightly inferior to the reference example, 3 points: the same as the reference example, 4 points: the reference example It can be seen that the texture is slightly superior when compared, 5 points: The texture is clearly superior when compared with the reference example. The score in the table is the average of 30 people.

"Soft feeling"
A sensory evaluation of 30 subjects was performed. The evaluation was performed by scoring how the soft paper feels by touching the thin paper as a sample, hitting the face, biting the nose, etc., based on the reference example. The score is 1 point: the texture is clearly inferior to the reference example, 2 points: the texture is slightly inferior to the reference example, 3 points: the same as the reference example, 4 points: the reference example It can be seen that the texture is slightly superior when compared, 5 points: The texture is clearly superior when compared with the reference example. The score in the table is the average of 30 people.

In addition, the reference examples in each sensory evaluation are those in which all sensory evaluation values are 3.0 in the table.
Moreover, what prepared the T-FS301 (made by Seiko PMC Co., Ltd.) and the main component molecular weight was used for the softening agent in a thin paper processing agent. Further, T-FS371 (manufactured by Seiko PMC Co., Ltd.) was used as the softener fixing auxiliary agent, and was used by being internally added to the papermaking raw material. Moreover, DD-4280 (made by Seiko PMC Co., Ltd.) was used as the starch.
Moreover, the measuring method concerning each test followed the measuring method demonstrated in the said detailed description, and softness was measured based on the handle ohm method according to JISL1096E method.

Table 1 shows the results of a test for confirming the effects of the softener and the softener fixing auxiliary agent of the present invention. From Table 11, from Examples 11 to 13 according to the present invention, the value of MMD which is an index of smoothness is less than 7.7, and the numerical value of the smoothness test is also 9.4, which is an index of softness. The softness is less than 1.7, and the paper thickness serving as an index of soft feeling is 135 μm or more. Sufficient value in use.
In Examples 11 and 12, the addition ratio of the softener fixing auxiliary agent is changed. In Example 13, starch was added as a dry paper strength enhancer.

  As a result of the test, it was confirmed that the examples of the present invention were higher in sensory evaluation, smoothness, and softness than Comparative Examples 11 and 12 in which only the softener was added and no softener was added.

In Examples 11 and 12, it can be confirmed that Example 11 has a more desirable value for the addition amount of the softener fixing auxiliary.
Examples 14 and 15 are examples in which the crepe rate was changed from Example 1. As a result, it was confirmed that lowering the crepe rate improved the smoothness and feel, and increasing the crepe rate reduced the smoothness and feel. This is presumed to have occurred because the unevenness of the paper surface was reduced by lowering the crepe rate. Therefore, it is desirable that the crepe rate is within an appropriate range.

  On the other hand, it can be understood from Examples 11 to 15 that the amount of fixing of the softening agent is improved by adding the softening agent fixing auxiliary agent. It has been confirmed that the use of the softening agent and softening agent fixing auxiliary agent according to the present invention improves the fixing rate of the softening agent.

  Comparative Example 13 contains a softening agent and a softening agent fixing auxiliary agent. However, the amount of the softening agent fixing auxiliary agent is larger than that of the softening agent. As a result, although the fixing amount of the softening agent has improved, the values of softness and paper thickness have decreased. From the results, it is presumed that when the amount of the softener fixing auxiliary added is larger than that of the softener, the effect of the softener is superior in reducing the surface properties of the softener fixing auxiliary itself, and good results are not exhibited. The

On the other hand, Table 2 shows the results of studies on differences in molecular weights of softener fixing aids. The sensory evaluation was carried out using Comparative Example 20 as a reference example. From Table 2, with respect to Examples 20 to 22, the value of MMD, which is an index of smoothness, is less than 7.9, and similarly, the numerical value of the smoothness test is also 1 for softness, which is an index of 9.4 softness. It is less than .65, and the paper thickness, which is an index of soft feeling, is 137 μm or more, which is a good result. Good enough results were obtained.
In Examples 23 and 24, no significant improvement in numerical value was observed.

  From the above results, in the case of 23, the molecular weight of the softening agent fixing auxiliary agent is small, so that the softening agent fixing amount as in Example 20 is not seen, so it is presumed that the numerical value was not improved. In Example 24, since the softener fixing auxiliary agent has a large molecular weight, the effect of the softener as a fixing agent can be seen. However, since the adhesiveness was developed, it was estimated that the paper thickness and softness were not improved. To do.

  In Table 3, the addition amount of the softening agent was examined. From Example 30 and Comparative Examples 31 and 32, it can be seen that the quality greatly changes by changing the softener addition amount. In Comparative Example 32, the softener fixing amount is larger than in Comparative Example 31, and the numerical values of MMD, smoothness test, paper thickness, and softness tend to be slightly improved. However, the effect does not reach Example 30 where the fixing amount of the softening agent is large. Therefore, it was confirmed that the flexibility was increased by fixing the softener of the present invention.

  In Comparative Examples 33 and 34, as a result of adding the softening agent from Example 31, paper strength could not be maintained and papermaking could not be performed. Although the paper strength can be adjusted by adding starch, beating, etc., it was not carried out because numerical values such as softness and paper thickness could not be maintained within a suitable range.

Table 4 tested the operability. Mainly, it is a study on the tsubo and crepe rate of the target thin paper (base paper sheet). From Table 4, it was confirmed that an excessively low basis weight and a high basis weight are not suitable as the thin paper of the present invention. Specifically, with respect to rice tsubo, at least 9 g / m ² or less and 27 g / m ² or more, the operation may be difficult, and if the crepe rate is 12, the operation may be difficult. It was confirmed that there is. Therefore, it is desirable to design the thin paper (base paper sheet) according to the present invention in consideration of the range.

  Summarizing the results shown in Tables 1 to 4 above, the sanitary thin paper according to the present invention is excellent in softness and smoothness, can be produced without any operational trouble, and has sufficient paper strength. It can be said.

  The present invention is applicable to sanitary thin paper such as tissue paper, toilet paper, kitchen paper, and crepe paper.

It is a 1st figure for demonstrating the touch test based on MMD. It is a 2nd figure for demonstrating the touch test based on MMD. It is a 3rd figure for demonstrating the touch test based on MMD.

  X1 ... Testing machine for MMD-based touch test

Claims (1)

A sanitary thin paper containing a thin paper treating agent for a base paper,
The tissue paper treating agent includes a softening agent and a softening agent fixing aid,
The softener is
A nonionic surfactant having an alkyl group and / or alkenyl group (component A) and a cationic surfactant having an alkyl group and / or alkenyl group (component B), and the solid content weight ratio thereof is A component / B component = 100 / 0.5 to 100/20,
The component A is at least one compound represented by the following general formulas (1), (2) and (3),
R ¹ -A ^1- (EO) _m (PO) _n -CO-R ² (1)
R ¹ —O— (EO) _m (PO) _n —R ² (2)
R ¹ -A ^1- (EO) _m (PO) _n H (3)
(In the formula, —A ¹ — represents —O— or —COO—, R ¹ and R ² represent an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, and R ¹ and R ² may be the same or different, E represents an ethylene group, P represents a propylene group, and the sum of m and n is 1 to 60, where m and n are average additions Number of moles.)
The B component is a quaternary ammonium salt having an imidazoline ring having an alkyl group and / or an alkenyl group, or a compound represented by the following general formula (4):

The softener fixing auxiliary agent is
A polyamide / epichlorohydrin resin,
The mass ratio of the softener and softener fixing aid is 2.8: 2.5-10: 1;
And content of a softening agent is 0.7-2 . 8 kg / t, the content of the softener fixing auxiliary is 0.1 to 2.5 kg / t,
The dry tensile strength defined in JIS P 8113 is 200 to 350 cN / 25 mm in the longitudinal direction, 90 to 140 cN / 25 mm in the transverse direction, and
Contains no starch, cationic starch, cationic modified starch, carboxymethylcellulose or its salt, carboxymethylcellulose sodium, carboxymethylcellulose calcium, carboxymethylcellulose zinc,
Hygienic thin paper characterized by that.

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