JP4916832B2 - Sanitary paper - Google Patents

Description

  The present invention relates to sanitary paper.

Sanitary paper such as tissue paper and toilet paper is usually used for wiping the skin, sniffing the nose, etc., and since it will rub against the skin during such use, it has been required to be soft and comfortable to the touch.
Therefore, for example, in order to increase the softness and feel of sanitary paper, oily substances such as liquid paraffin and surfactants are coated on the front and back surfaces of sanitary paper (external addition), or added to raw pulp and mixed. To do (internal), things have been done.
In recent years, for example, antibacterial properties are required for pulp sheets that come into contact with the skin because of high interest in hygienic environments. For example, Patent Document 1 discloses the use of titanium oxide as an example of a filler, which is a highly oil-absorbing cosmetic oil-removing paper, and includes sanitary paper according to the present invention containing a paper softener and a moisturizing component. is not.
JP 2003-38248 A

  Then, the main subject of this invention is providing the sanitary paper which shows the outstanding antimicrobial property. Another problem is to provide a sanitary paper exhibiting an excellent touch feeling (so-called “smooth feeling”) based on new knowledge.

The present invention that has solved the above problems is as follows.
<Invention of Claim 1>
A two-ply tissue paper,
The basis weight per ply is 10 to 35 g / m ² , the thickness at 2 plies is 100 to 300 μm,
The base paper is provided with a chemical agent containing titanium oxide having an average particle size (D50) of 0.05 to 30 μm, a softener for paper, and a moisturizing component, based on a laser diffraction scattering particle size distribution,
Sanitary paper, wherein the titanium oxide is contained in an amount of 10 to 30% by weight based on the base paper.

(Function and effect)
In the present invention, since it contains a moisturizing component, it gives a moist feeling. Paper softeners provide a softening effect. In the present invention, titanium oxide is also used. Titanium oxide exhibits antibacterial properties. It also has a deodorizing effect.
Furthermore, surprisingly, in the composition system of the present invention in which titanium oxide is used in combination with a softening agent for paper and a moisturizing component such as glycerin, an excellent “smooth feeling” rather than a smooth feeling is exhibited. .
In the present invention, since titanium oxide having an average particle diameter in a predetermined range is used in particular, it does not become rough and does not separate from the paper and transfer to the skin.
If the average particle size is excessively large, it becomes rough. On the other hand, if it is too small, the amount of separation from the paper increases, which tends to make the user uncomfortable. The average particle diameter of the present invention is 0.05 to 30 μm.
In addition, the titanium oxide of the present invention is measured using “SALD-2000” manufactured by Shimadzu Corporation as a laser diffraction particle size distribution measuring device for measuring the average particle size (D50) by laser diffraction scattering particle size distribution. It is a thing.

<Invention of Claim 2>
The sanitary paper according to claim 1, further comprising a paper strength agent.

(Function and effect)
By including a paper strength agent, particularly a wet strength paper strength, it is possible to suppress a decrease in wet strength due to the addition of a moisturizing component.

<Invention of Claim 3>
The sanitary paper according to claim 2, wherein the paper strength agent is selected from the group consisting of saponified rosin, natural reinforced rosin, alkyl ketene dimer, alkenyl succinic anhydride and stearic anhydride.

  As described above, according to the present invention, there are advantages such as excellent softness, paper strength, deodorization and antibacterial properties, and so-called “smooth feeling”.

Hereinafter, embodiments of the present invention will be described in detail.
As the base paper of the thin paper of the present invention, known ones can be used without limitation, but the NBKP blending ratio (JIS P 8120) in the pulp raw material is 30.0 to 80.0%, particularly 40.0 to 70. What is 0% is suitable. As for the rice tsubo (JIS P 8124), 10.0 to 35.0 g / m ² per ply is desirable. The paper thickness (measured with a Peacock manufactured by Ozaki Mfg. Co., Ltd.) is desirably 2 plies (two stacked), 100 to 300 [mu] m, and half for one ply. The crepe rate (((peripheral speed of the dryer during paper manufacture) − (reel peripheral speed)) / (peripheral speed of the dryer during paper manufacture) × 100) is desirably 15.0 to 26.0.

  The base paper of the present invention has a dry tensile strength (hereinafter also referred to as dry paper strength) specified in JIS P 8113 of 2 plies in a longitudinal direction of 130 cN / 25 mm or more, particularly 280 to 310 cN / 25 mm, and a transverse direction of 40 cN / 25 mm. As described above, it is particularly preferable to use one having a thickness of 60 to 100 cN / 25 mm. When the dry paper strength of the base paper is too low, troubles such as tearing and elongation are likely to occur during production, and when it is too high, the touch becomes stiff when used.

  These paper strengths can be adjusted by a known method. For example, a paper strength agent is internally added (added to a stage before the dryer part, for example, pulp slurry), and pulp freeness is reduced (for example, about 30 to 40 ml is reduced). It is possible to appropriately combine several methods such as increasing the NBKP blending ratio (for example, 50% or more).

  As the paper strength, it is important to secure a wet strength. As the wet strength, the strength of the saponified rosin, natural reinforced rosin, alkyl ketene dimer, alkenyl succinic anhydride and stearic anhydride. You can use one selected from the group. If necessary, polyamide / epichlorohydrin resin, urea resin, acid colloid / melamine resin, thermal crosslinkability imparting PAM and the like can also be used. When the wet paper strength agent is internally added, the addition amount can be about 5 to 20 kg / t in weight ratio to the pulp slurry.

In the present invention, a chemical is contained in the base paper. The chemical content in the thin paper is preferably 5 to 35% by weight with respect to the base paper. A particularly preferred range is 20 to 30% by weight. If the content of the chemical solution is too small, not only will the effect be poor, but the amount applied to the base paper will not be stable, and if it is too much, it will become sticky, impairing the softness and touch feeling. As a method for containing the chemical solution, a known application method such as spray coating, roll coating, or immersion can be used.
The chemical solution may be composed of about 60 to 100% by weight, particularly about 80 to 95% by weight of an active ingredient, and about 0 to 40% by weight, especially about 5 to 20% by weight of an ineffective ingredient such as moisture. it can.

In the present invention, titanium oxide having an average particle diameter (D50) by laser diffraction scattering particle size distribution of 0.05 to 30 μm (particularly desirably 0.05 to 15 μm) is used as the main component in the active ingredient. Is preferably 1 to 35% by weight, more preferably 10 to 30% by weight, and particularly preferably 12 to 20% by weight based on the base paper. The titanium oxide is roughly classified into a rutile type and an anatase type. In the present invention, these may be used alone or in combination, and are not particularly limited. Absent.
Moreover, what contains 3-18 weight% of paper softeners and 60-80% of a moisturizing component is desirable in the active ingredients.

The titanium oxide can be used in combination with other powders (particularly preferably in the form of granules) having an average particle size of 1 to 30 μm, particularly 3 to 15 μm. Talc is suitable as another powder to be used in combination, and the talc is preferably less than 50% by weight with respect to titanium oxide.
Moreover, when there is too much titanium oxide regarding the compounding ratio of titanium oxide and other powders to be used in combination, and the amount of other powders to be used in combination is too small, the touch feeling is improved, but the soft feeling is poor. On the other hand, when the amount of titanium oxide is too small and the amount of other powders used in combination is too large, the soft feeling is improved, but the touch feeling is poor.

  Furthermore, when there is too much titanium oxide content in a chemical | medical solution, the fluidity | liquidity of a chemical | medical solution will fall and the permeability and fixing property to a base paper will worsen. Moreover, when there is too little titanium oxide content, the effect by powder addition will become scarce.

  Examples of powders other than the talc that can be used in combination include inorganic powders such as kaolin, clay, and calcium carbonate, metal soaps (aluminum stearate, magnesium stearate, calcium stearate, zinc stearate, lithium stearate, etc.), Organic powders such as corn starch, wheat flour, rice starch, potato starch, and wheat flour protein can be used singly or in combination. Among these, starch is optimal, and the effect is not remarkable in the other powders exemplified.

When titanium oxide is contained in the chemical, titanium oxide can be contained in a so-called lotion agent, and the lotion agent can be fixed to the paper by a transfer method.
When titanium oxide is included, an adhesive component can be used to fix the titanium oxide to the base paper, but the adhesive component inhibits the movement of titanium oxide, so when the skin comes into contact with the skin during use, the skin is damaged by the titanium oxide. There is a fear. In addition, since the paper becomes hard by containing an adhesive component, irritation to the skin increases. On the other hand, by not containing adhesive components, titanium oxide does not adhere firmly to paper, and titanium oxide added during use reduces skin irritation by rolling or sliding on the skin. Can do.

  In the present invention, a moisturizing agent is additionally contained as a main component of the active ingredient. As the humectant, polyhydric alcohols such as glycerin, diglycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, saccharides such as sorbitol, glucose, xylitol, maltose, maltitol, mannitol, trehalose, glycolic drugs, and the like Derivatives such as cetanol (cetyl alcohol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol and other higher alcohols (those belonging to aliphatic alcohols among higher alcohols), liquid paraffin, collagen, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed One or more of silk, hyaluronic acid or a salt thereof, ceramide and the like can be used in any combination. The humectant is preferably contained in the main component excluding the powder in an amount of 60 to 80% by weight, particularly 65 to 75% by weight.

It is particularly desirable to employ glycerin as a moisturizing agent and contain 60 to 80% by weight in the main component.
Another effective moisturizing agent is liquid paraffin, and the amount is desirably 10% or less, particularly 0.5 to 5% in the moisturizing component.

  Furthermore, as the humectant, an aliphatic alcohol having a linear or branched (preferably linear) alkyl or alkenyl group having 14 to 24 carbon atoms (preferably 18 to 22) is effective. . Preferred examples include myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol, and mixtures of aliphatic alcohols such as cetostearyl alcohol, which is a mixture of cetyl alcohol and stearyl alcohol. In particular, cetyl alcohol, cetostearyl alcohol, and stearyl alcohol are preferable. The amount of the aliphatic alcohol added is preferably 10% or less, particularly 0.5 to 5% in the moisturizing component.

  Further, as other active ingredients, an oily component, an emulsifying component, an antifungal component, an antifoaming component and the like can be contained in the chemical solution. These components are preferably 5% by weight or less. In particular, when there are too many oil components, the sticky feeling increases, and when there are too many emulsified components, foaming tends to occur, so that there is a problem of deterioration in texture and operability.

  Oily components include petroleum or mineral oil-derived components such as petrolatum, animal oil-derived components such as mink oil, lanolin oil, squalane, olive oil, jojoba oil, rosehip oil, almond oil, eucalyptus oil, avocado oil, camellia oil, large oil Plant-derived components such as bean oil, safflower oil, sesame oil, evening primrose oil, sunflower oil, silicone oil such as alkylmethyl silicone, and liquid paraffin can be used. Liquid paraffin is particularly suitable.

In the present invention, a paper softener is used. As the paper softener, it is desirable to use 3 to 18% by weight in the main component in the active ingredient.
As the paper softener, an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be appropriately selected and used. They also exhibit an antifoaming effect and contribute to emulsion stability.

  As the anionic surfactant, carboxylate, sulfonate, sulfate ester, phosphate ester, and the like can be used. An alkyl phosphate ester salt is particularly preferable.

  Examples of nonionic surfactants include sorbitan fatty acid esters, diethylene glycol monostearate, diethylene glycol monooleate, glyceryl monostearate, glyceryl monooleate, and polyhydric alcohol monofatty acid esters such as N- (3- Oleiroshiki-2-hydroxypropyl) diethanolamine, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan beeswax, polyoxyethylene sorbitan sesquistearate, polyoxyethylene monooleate, polyoxyethylene monolaurate, polyoxyethylene cetyl ether Polyoxyethylene lauryl ether can be used.

  As the cationic surfactant, a quaternary ammonium salt, an amine salt, an amine, or the like can be used.

  In addition, as the zwitterionic surfactant, an aliphatic derivative of a secondary or tertiary amine containing carboxy, sulfonate, sulfate, an aliphatic derivative of a heterocyclic secondary or tertiary amine, or the like is used. be able to.

（式中、Ｒ¹は、炭素数６〜２４の直鎖もしくは分岐鎖のアルキル基もしくはアルケニル基又はＲ³−Ｏ−Ｒ⁴−を示し、Ｒ²は、炭素数１〜６の直鎖もしくは分岐鎖のアルキル基又は炭素数１〜３のヒドロキシアルキル基を示し、それぞれ異なっていても良い。Ｒ³は炭素数６〜２４の直鎖もしくは分岐鎖のアルキル基もしくはアルケニル基、Ｒ⁴は炭素数１〜６の直鎖のアルキレン基を示す。Ｘ^-は陰イオンを示す。） Among the foregoing, cationic surfactants have a high softening effect. In particular, a quaternary ammonium salt, particularly a compound represented by the following general formula (A) (component (A)) is optimal.

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms or R ³ —O—R ⁴ —, and R ² represents a straight chain having 1 to 6 carbon atoms or A branched alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, which may be different from each other, R ³ is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ⁴ is carbon. Represents a linear alkylene group of 1 to 6. X ⁻ represents an anion.)

In the component (A), R ¹ and R ² are preferably shown below from the viewpoint of paper softness.
In the above Formula (A), the R ^1, a 6 to 24 carbon atoms, preferably from 12 to 24, more preferably from 16 to 22, more preferably 20 to 22. R ¹ is a linear or branched alkyl group or alkenyl group or R ³ —O—R ⁴ —, and R ¹ and R ³ are preferably linear, and are preferably alkyl groups. The group is particularly preferred. R ² is a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and may be different from each other. R ² is preferably a linear alkyl group. R ⁴ is a linear alkylene group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.

X ⁻ is an anion, a halogen ion such as fluorine ion, chlorine ion, bromine ion or iodine ion, or an organic anion such as acetate ion, citrate ion, lactate ion, glycolate, phosphate ion or nitrate ion. Sulphonate ions, sulfate ions, and alkyl sulfate ions such as methyl sulfate ions and ethyl sulfate ions. Halogen ions or alkyl sulfate ions are preferable, and chlorine ions, methyl sulfate ions, or ethyl sulfate ions are particularly preferable.

As a compound of the general formula (A), monoalkyltrimethylammonium salt, N-alkyl-N, N-dihydroxyethyl-N-methylammonium salt, monoalkyltriethylammonium salt, monoalkenyltrimethylammonium salt, oxyhydroalkylenetrimethyl chloride And ammonium salts. Specifically, monoalkyltrimethylammonium bromide such as dodecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, hydrogenated tallow alkyltrimethylammonium chloride, chlorinated hardened palm oil alkyltrimethylammonium chloride, cetyltrimethyl chloride Examples thereof include monoalkyltrimethylammonium chlorides such as ammonium, stearyltrimethylammonium chloride and behenyltrimethylammonium chloride, and monoalkyltrimethylammonium sulfates such as ethyl behenyltrimethylammonium sulfate. In addition, monoalkenyltrimethylammonium chloride such as oleyltrimethylammonium chloride, hydrocarbon oxyalkylenetrimethylammonium chloride such as octadecyloxypropyltrimethylammonium chloride, and the like (here, “hydrocarbonoxyalkylene” refers to the group “R ³ -O-R ⁴ - means ")..

  It has been found that when the component (A) and the aliphatic alcohol (component (B)) are used in combination, the flexibility effect of the component (A) is further increased.

  Further active ingredients include softeners, various vitamins such as vitamin C and vitamin E, amino acids such as glycine, aspartic acid, arginine, alanine, cystine, cystine, aloe extract, amacha extract, ashitaba extract, karin extract, cucumber extract Plant extract extracts such as extract, horsetail extract, tomato extract, wild rose extract, loofah extract, lily extract, and spinach extract, chitosan, urea, honey, royal jelly and the like can be used. Components such as various vitamins and plant extracts are preferably contained in the active ingredient in an amount of 0.000001 to 0.001% by weight.

  Further, sublimation components such as menthol, camphor, and cyclohexanol can be added to the active component at a ratio of 3% or less.

On the other hand, the thin paper of the present invention is not limited by the manufacturing method, but in the case of a product form to be folded and stacked, for example, in case of a box-type tissue paper , a chemical solution is applied to the produced base paper and then a folding device such as an interfolder. Rather than folding in the folding device, the chemical solution is applied in the process of transporting the base paper for folding in the folding device, so that it can be manufactured efficiently and the chemical solution and moisture are less evaporated so that a product with stable quality can be manufactured. Therefore, it is preferable. An example of the latter method is Japanese Patent Application No. 2004-251874 filed by the present applicant.

  In any case, the above-mentioned components can be contained in the base paper by a method such as internal addition, external addition or transfer.

(Examples 1-16 and Comparative Examples 1-6)
Various two-ply tissue papers (Examples 1 to 16 and Comparative Examples 1 to 6) shown in Tables 1 to 3 were manufactured, and various physical properties were measured and calculated, and sensory evaluation was performed.
The chemical stock solution used was composed of 92% by weight of the active ingredient excluding the powder and 8% of the moisture. In addition to the moisturizer and softener described in the table, the active ingredient contained 1% by weight of the antioxidant and the emulsified ingredient 1 It contained 0.0% by weight.
In Examples 1 to 10 and Comparative Examples 1 to 6, titanium oxide having an average particle diameter of 7 μm was used.
The base paper used was 19 g / m ² in weight per square meter (1 ply), 50% NBKP content, 650 ml of pulp freeness, 15 kg / t of internal paper strength agent (vs. pulp slurry), longitudinally dried The paper strength was 298 cN / 25 mm, the horizontal dry paper strength was 70 cN / 25 mm, the vertical wet paper strength was 169 cN / 25 mm, and the horizontal wet paper strength was 50 cN / 25 mm.
The physical properties were measured under the conditions defined in JIS P 8111 except for the moisture content.

(Evaluation method of softness)
For sensory evaluation of the feeling of softness, a maximum of 4 points (4 points: soft, 3 points: slightly soft, 2 points: slightly hard, 1 point) by 30 test subjects when touching the surface of the paper with the hand : Is hard), and an average score is calculated. When the average score is 3.5 points or more, “soft (◎)”, when 3 points or more and less than 3.5 points, “slightly soft (○ ) ”, The case of 2 points or more and less than 3 points was evaluated as“ slightly hard (Δ) ”, and the case of less than 2 points was evaluated as“ hard (×) ”.

(Sensory evaluation of touch feeling)
For sensory evaluation (smooth feeling) of the feel of touch, a total of 4 points (4 points: feel smoothness, 3 points: feel slightly smoothness) when 30 subjects touch the surface of the paper with their hands (2 points: slightly rough, 1 point: rough) and calculating the average score, and when the average score is 3.5 or more, "feel smoothness (◎) "Slightly smooth (○)" when 3 points or more and less than 3.5 points, "Slightly rough (△)" when 2 points or more and less than 3 points, and less than 2 points Each of them was evaluated as “Rough (×)”.

(Deodorization test method)
Evaluation of deodorization was carried out by leaving the samples of Examples and Comparative Examples in an airtight container for 60 minutes together with an odor sample (using food “Kusaya”, which is generally said to have a strong odor), and thereafter Samples and odor samples of Examples and Comparative Examples were taken out, and 30 subjects evaluated the odor in the container (sensory evaluation). The case where it felt that there was no smell was set as “◯”, and the case where it felt that there was a smell was evaluated as “x”.

(Antimicrobial test method)
Based on JIS L 1902 antibacterial test, bacteriostatic activity value was measured using Staphylococcus aureus. ○ indicates “antibacterial (bacteriostatic activity value of 2.2 or more)” and x indicates “no antibacterial activity (less than bacteriostatic activity value of 2.2)”.

(Test method for improving wet paper strength)
The tensile strength value [N / 25 mm] of the tissue (longitudinal direction) and lateral (short direction) of the tissue paper in a wet state with a brush was measured according to a method according to JIS P8113.

  As can be seen from Tables 1 to 3, Examples 1 to 16 according to the present invention are different from Comparative Examples 1 to 6 in that they exhibit not only excellent softness, paper strength, deodorant properties and antibacterial properties. As a result, an excellent hand feeling (so-called “smooth feeling”) was also obtained. In particular, in Examples 11 to 13, the touch feeling (smooth feeling) was more excellent.

(Examples 28 to 32)
Test papers were produced in the same manner as in Example 1, except that the amount of additive used in Example 1 was changed, and the softness and feel of the paper were evaluated in the same manner as in Example 1. The results are shown in Table 3. In Table 3, the results of Example 1 are also shown for reference.

(Example 17)
An additive [pH (25 ° C.) 5] having the following composition was produced in substantially the same manner as in Example 13.
(weight%)
Behenyltrimethylammonium chloride 6.3
Cetyltrimethylammonium chloride 13.3
Cetostearyl alcohol 7.7
Alkyl ketene dimer (AKD) 0.03
Polyoxyethylene sorbitan monolaurate 2.0
Sodium benzoate 0.5
Citric acid (50%) Suitable amount Water Remaining ―――――――――――――――――――――――――――――――――――
Total 100.0

(Example 18)
A softening agent [pH (25 ° C.) 5] having the following composition was produced in substantially the same manner as in Example 13.
(weight%)
Behenyltrimethylammonium chloride 6.3
Cetyltrimethylammonium chloride 13.3
Cetostearyl alcohol 7.7
Alkyl ketene dimer (AKD) 0.03
Polyoxyethylene sorbitan monolaurate 2.0
Glycerin 25.0
Sodium benzoate 0.5
Citric acid (50%) Suitable amount Water Remaining ―――――――――――――――――――――――――――――――――――
Total 100.0

  The paper treated in the same manner as in Example 5 using the softener produced in Examples 17 and 18 with respect to 100% hardwood bleached kraft pulp used in Example 13, has excellent paper strength, Not only deodorant and antibacterial properties, but also softness and touch (smooth feeling) were even better.

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

Claims (3)

A two-ply tissue paper,
The basis weight per ply is 10 to 35 g / m ² , the thickness at 2 plies is 100 to 300 μm,
The base paper is provided with a chemical agent containing titanium oxide having an average particle size (D50) of 0.05 to 30 μm, a softener for paper, and a moisturizing component, based on a laser diffraction scattering particle size distribution,
Sanitary paper, wherein the titanium oxide is contained in an amount of 10 to 30% by weight based on the base paper.   The sanitary paper according to claim 1, further comprising a paper strength agent.   The sanitary paper according to claim 2, wherein the paper strength agent is selected from the group consisting of saponified rosin, natural reinforced rosin, alkyl ketene dimer, alkenyl succinic anhydride and stearic anhydride.