JP2009052152A - Water-disintegrable paper, method for producing the same, and water-disintegrable cleaning article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide water-disintegrable paper having water disintegrability so as to be flushed away with water after use and excellent productivity, to provide a method for producing the paper, and to provide a water-disintegrable cleaning article using the paper. <P>SOLUTION: The water-disintegrable paper is obtained by using an anionic adhesive and a cationic oligomer represented by general formula (1) or general formula (2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a water-degrading paper, a method for producing the same, and a water-degradable cleaning article using the same.

  2. Description of the Related Art Conventionally, as a product for cleaning around a toilet or wiping away a buttocks, a water-decomposing paper or a cleaning product carrying a drug on it has been used so that it can be flowed to a toilet after use.

  These water-disintegrating papers are produced by spraying and impregnating an adhesive to a web of water-dispersible pulp fibers, or by adding an adhesive to a water-dispersible pulp fiber slurry and making paper. When an anionic material such as carboxymethyl cellulose is used as the adhesive, the yield of the fiber surface is poor because the fiber is negatively charged. Especially in the latter method, it was economically disadvantageous to use an anionic adhesive.

  In the case of ordinary paper that does not cause water decomposability, a sulfuric acid band or a water-soluble cationic polymer is added to improve the yield of the anionic adhesive. For example, in Patent Document 1, after adding an anionic paper strength enhancer to a pulp slurry, a water-soluble cationic polymer is added to fix the anionic paper strength enhancer, and then a rosin adhesive is added and stirred. A paper making method for fixing an adhesive by adding a band, in Patent Document 2, after adding and mixing a water-soluble polycationic polymer substance to a pulp slurry, adding an anionic adhesive and stirring and then adding a sulfuric acid band In the paper making method for fixing an adhesive, Patent Document 3, a resin emulsion having cationic particle charge is added to a pulp slurry, and then a water-soluble anionic polymer is added. The pH of the pulp slurry is adjusted to 4 to 9. The paper making method of the processed paper which is adjusted is described. As described above, various types of cationic polymers are used in the manufacture of paper that does not require water disintegration in order to improve the yield of the anionic adhesive.

JP-A-53-103003 JP 54-68405 A Japanese Patent Laid-Open No. 55-12824

Hydrolytic paper is required to have a practically sufficient strength that can withstand wiping work, etc., and an adhesive is required to ensure such strength. In the production of hydrolytic paper, the yield of this adhesive is poor. Has become a problem, and improvement in the productivity of hydrolytic paper has been demanded. In order to improve the yield of the adhesive in the production of water-disintegrating paper, when the yield improving technology relating to the manufacture of paper that does not require the water-disintegrating property described in Patent Documents 1 to 3 is adopted, that is, the yield of the anionic adhesive is improved. When a conventionally known cationic polymer is used as the agent, the yield of the anionic adhesive is improved, but at the same time, there is a problem that water disintegration is impaired.
There has not yet been provided a technology that can improve the yield of the adhesive in the production of hydrolyzed paper and ensure the water disintegration property that can be poured into water after use.

  Accordingly, an object of the present invention is to provide a water decomposing paper having water decomposability and excellent productivity, a manufacturing method thereof, and a water degradable cleaning article using the same.

  As a result of intensive studies on a yield improving agent that improves the yield of an anionic adhesive and does not impair the water decomposability in hydrolytic paper, the present inventors have found that a specific cationic oligomer is effective.

［式中、Ｒ₁は、炭素数２〜２４の直鎖若しくは分岐のアルキレン基、脂環式アルキレン基、アラルキレン基又は（Ｒ₄−Ｏ）ｐ−（Ｒ₄）ｑ〔但し、Ｒ₄は炭素数２〜５の直鎖又は分岐のアルキレン基を示し、ｐは平均で０〜３０の数、ｑは平均で１〜３０の数〕を示し、Ｒ₂は、炭素数１〜２４の直鎖若しくは分岐のアルキル基又はアラルキル基を示し、Ｙは、ＯＨ又はＮ（Ｒ₂）₂を示し、Ｒ₃は、炭素数１〜２４の直鎖若しくは分岐のアルキル基又はアラルキル基を示し、Ｘは、ハロゲン原子又はアルキル硫酸エステルを示す。Ｓは１以上の整数、Ｔは０以上の整数をそれぞれ示す。ｎは、ＳとＴの合計値であり、平均で１〜５０である。式（１）及び（２）それぞれにおいて、複数のＲ₁、複数のＲ₂、複数のＲ₃、複数のＹは、それぞれ、同一でもよく或いは異なっていてもよい。］ The present invention has been made on the basis of the above findings, and provides the hydrolytic paper using an anionic adhesive and a cationic oligomer represented by the following general formula (1) or (2). Is achieved.

[Wherein, R ₁ is a linear or branched alkylene group having 2 to 24 carbon atoms, an alicyclic alkylene group, an aralkylene group, or (R ₄ —O) p- (R ₄ ) q [wherein R ₄ is R represents a straight chain or branched alkylene group having 2 to 5 carbon atoms, p represents an average number of 0 to 30, q represents an average number of 1 to 30, and R ₂ represents a straight chain of 1 to 24 carbon atoms. A chain or branched alkyl group or an aralkyl group; Y represents OH or N (R ₂ ) ₂ ; R ₃ represents a linear or branched alkyl group or aralkyl group having 1 to 24 carbon atoms; Represents a halogen atom or an alkyl sulfate. S represents an integer of 1 or more, and T represents an integer of 0 or more. n is a total value of S and T, and is 1 to 50 on average. In each of the formulas (1) and (2), the plurality of R ₁ , the plurality of R ₂ , the plurality of R ₃ , and the plurality of Y may be the same or different. ]

  Moreover, this invention achieves the said objective by providing the manufacturing method of the hydrolytic paper which adds and mixes the said cationic oligomer to a pulp slurry, and then adds anionic adhesive and makes paper.

  Further, the present invention provides a hydrolytic solution obtained by impregnating the hydrolytic paper with an aqueous cleaning agent containing a metal ion selected from the group consisting of potassium, alkaline earth metal, manganese, zinc, cobalt and nickel, and a water-soluble solvent. The above-mentioned object is achieved by providing a cleaning property article.

  ADVANTAGE OF THE INVENTION According to this invention, the water disintegrating paper and the water disintegrating cleaning article which have the water disintegrating property which can be poured into water after use, the yield of an anionic adhesive agent was excellent, and were excellent in productivity can be provided.

Hereinafter, first, the hydrolytic paper of the present invention and the production method thereof will be described.
The hydrolytic paper of the present invention comprises an anionic adhesive and a cationic oligomer represented by the general formula (1) (hereinafter also referred to as a cationic oligomer 1) or the general formula (2) as a yield improver of the adhesive. ) And a fiber such as wood pulp as a main component and water degradability. The water disintegration is a performance that allows water disintegration to flow without clogging the flush toilet when the disintegration paper flows into a normal flush toilet.

By using the cationic oligomers 1 and 2 together with an anionic adhesive, an anionic property that could not be realized with a conventionally known yield improver (cationic polymer) used for paper that does not require water degradability. It becomes possible to realize both improvement in the yield of the adhesive (improvement in productivity of hydrolyzed paper) and water disintegration.
Further, the cationic oligomers 1 and 2 (yield improver) have high performance stability with respect to the liquidity (pH) of the pulp slurry to which the yield improver is added. Thus, it can be used as it is without adjusting the pH. Therefore, the use of the cationic oligomers 1 and 2 makes it possible to omit the pH adjustment step, and the productivity of hydrolytic paper is also improved in this respect.
Furthermore, in the conventional water disintegrating paper, the reaction initiator derived from the cationic polymer as a yield improving agent, unreacted materials, incomplete reaction materials, etc. are mixed, resulting in inconvenience such as bad odor. In some cases, there is a problem that the quality is lowered. Cationic oligomers 1 and 2 can be produced without using a reaction initiator, and unreacted substances and reaction incomplete substances are almost completely removed in the production process. Therefore, by using the cationic oligomers 1 and 2 as a yield improver, high quality hydrolytic paper can be obtained.

In the general formulas (1) and (2), R ₁ is preferably a linear or branched alkylene group having 2 to 18 carbon atoms, an alicyclic alkylene group, an aralkylene group, or (R ₄ —O) p—. (R ₄ ) q (however, in a preferred embodiment, p is an average number of 0 to 15 and q is an average number of 1 to 15). Particularly preferred as R ₁ is a linear or branched alkylene group having 2 to 12 carbon atoms.

In the general formula (1), R ₂ is preferably a linear or branched alkyl group having 1 to 24 carbon atoms. Particularly preferred as R ₂ is a linear alkyl group having 1 to 18 carbon atoms.

  In the general formulas (1) and (2), Y is preferably OH (hydroxyl group).

In the general formulas (1) and (2), R ₃ is preferably a linear alkyl group or aralkyl group having 1 to 24 carbon atoms. Particularly preferred as R ₃ is a linear alkyl group having 1 to 22 carbon atoms from the viewpoint of industrial production efficiency.

  In the general formula (1), specific examples of X include Cl, Br, I, methyl sulfate ester, and ethyl sulfate ester.

  Each of the total of S and T in the general formula (1) and n (the total value of S and T) in the general formula (2) is an average, preferably 2 to 50, more preferably 4 to 30. is there. When n exceeds 50 on average, a considerable time is required for production (polymerization reaction), which is not preferable in terms of productivity.

［式中、Ｒ₁、Ｙ、Ｒ₂、Ｒ₃及びＸは、一般式（１）及び（２）と同じ定義であり、ｎは、平均で１〜５０の整数を示す。］ The cationic oligomer 1 represented by the general formula (1) is a quaternizing agent represented by the following general formula (B) in a tertiary amine having a repeating unit represented by the following general formula (1A). Can be produced by reacting (quaternization reaction). Further, the cationic oligomer 2 represented by the general formula (2) is a quaternary represented by the following general formula (B) in a tertiary amine having a repeating unit represented by the following general formula (2A). It can be produced by reacting an agent.

[Wherein, R ₁ , Y, R ₂ , R ₃ and X have the same definition as in general formulas (1) and (2), and n represents an integer of 1 to 50 on average. ]

  The tertiary amine having the repeating unit represented by the general formula (1A) and the tertiary amine having the repeating unit represented by the general formula (2A) are related to the earlier application of the present applicant, It can be produced according to the methods described in JP-A-3-83955, JP-A-4-346965 and JP-A-5-140051.

  Examples of the quaternizing agent represented by the general formula (B) include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, octyl chloride, decyl chloride, dodecyl chloride, octadecyl chloride, methyl bromide, ethyl bromide. Alkyl halides such as propyl bromide, butyl bromide, octyl bromide, decyl bromide, dodecyl bromide and methyl iodide; aralkyl halides such as benzyl chloride; and dialkyl sulfates such as dimethyl sulfate and diethyl sulfate. .

  The amount of the quaternizing agent represented by the general formula (B) (the amount added to the reaction system) is based on the amino group of the tertiary amine represented by the general formula (1A) or (2A). In addition, 0.01 to 10 times mol is preferable, and 0.02 to 3 times mol is more preferable.

  In the quaternization reaction of the tertiary amine with the quaternizing agent, water alone may be used as a solvent, or an organic solvent such as methanol, ethanol, isopropyl alcohol, or the like may be used. In order to increase the reaction rate, an alkali such as sodium carbonate or sodium hydroxide may be added to the reaction system. The reaction temperature of the quaternization reaction is usually 30 to 150 ° C.

The degree of quaternization of the cationic oligomers (cationic oligomer 1, cationic oligomer 2) according to the present invention is preferably 5% to 100% from the viewpoint of enhancing the effect as a yield improver of an anionic adhesive. Preferably, it is 20% to 100%. The degree of quaternization of the cationic oligomer is calculated based on the ratio between the amine value of the tertiary amine before the quaternization reaction and the amine value of the compound after the quaternization reaction. That is, it is calculated by the following equation.
(Degree of quaternization of cationic oligomer) = 1- (amine value of compound after quaternization reaction) / (amine value of tertiary amine before quaternization reaction)
The amine value here is a value obtained by converting the amount of hydrochloric acid necessary for neutralizing 1 g of amine into mg of potassium hydroxide (according to ASTM D 2074).

  The amount of the cationic oligomer according to the present invention is preferably 0.01 to 10% by weight, more preferably 1 to 6% by weight, based on the total weight of fibers such as wood pulp used for the production of hydrolytic paper. is there. When the amount of the cationic oligomer used is less than 0.01% by weight, the effect of the anionic adhesive as a yield improver is not sufficient, and when it exceeds 10% by weight, the effect corresponding to the amount added is increased. It is not seen and is not industrially preferable.

  Examples of the anionic adhesive used in the present invention include sodium carboxymethylcellulose, carrageenan, sodium polyuronic acid, sodium polyacrylate, polysodium methacrylate, sodium acrylate, sodium methacrylate, acrylic acid ester, and methacrylic acid ester. Examples thereof include a copolymer of styrene and a styrene derivative. The sodium carboxymethylcellulose has water solubility or water swellability. Examples of the sodium polyuronate include sodium hyaluronate and sodium alginate. Examples of the styrene derivative include styrene sulfonic acid. Among these, carboxymethyl cellulose sodium is preferably used in the present invention as an anionic adhesive.

  The amount of the anionic adhesive according to the present invention is preferably 0.01 to 10% by weight, more preferably 0.1 to 8%, based on the total weight of fibers such as wood pulp used for the production of hydrolytic paper. % By weight, more preferably 1 to 8% by weight. If the amount of the anionic adhesive used is less than 0.01% by weight, the strength of the hydrolytic paper may be insufficient, and even if the amount exceeds 10% by weight, no further improvement in strength is observed.

  The hydrolytic paper of the present invention contains fibers as a main component as described above. Examples of the fibers used in the present invention include wood pulp, non-wood pulp, and waste paper pulp. Moreover, other fibers other than the pulp, for example, natural fibers such as cotton; rayon; mercerized pulp; and chemical fibers such as polyvinyl alcohol fibers may be used in combination with the pulp as a main component. When the hydrolytic paper of the present invention contains fibers other than pulp, the content of these other fibers is preferably 10 to 50% by weight with respect to the total weight of the fibers constituting the hydrolytic paper.

  The hydrolytic paper of the present invention can be produced by adding and mixing a cationic oligomer to pulp slurry (fiber dispersion) and then adding an anionic adhesive to make paper. Papermaking can be performed according to a conventional method. The addition of the anionic adhesive to the pulp slurry is preferably performed after the cationic oligomer is added to the pulp slurry and stirred so as to be sufficiently uniform.

  The hydrolyzed paper of the present invention thus obtained is used as it is as toilet paper, paper wiper, etc. due to the action of the above-mentioned cationic oligomer (yield improver), which has high dry strength and good water degradability. it can. Moreover, the hydrolytic paper of this invention can also be used as a cleaning article with a high cleaning effect by impregnating the non-aqueous cleaning chemical | medical agent which hardly contains water.

Next, the water-disintegrable cleaning article of the present invention will be described.
The water-decomposable cleaning article of the present invention is obtained by impregnating the above-described water-degradable paper of the present invention with a cleaning agent containing metal ions and a water-soluble solvent. That is, the water-decomposable cleaning article of the present invention includes a metal ion in addition to the above-described fiber, anionic adhesive, and the cationic oligomer (yield improver) represented by the general formula (1) or (2). And an aqueous cleaning agent containing a water-soluble solvent.

  In general, water-degrading paper using a water-soluble adhesive does not have sufficient strength to withstand cleaning operations even when impregnated with an aqueous cleaning chemical containing water, and it can withstand practical use as a cleaning article. Absent. On the other hand, the water-degradable cleaning article of the present invention is constituted by impregnating the above-described water-decomposing paper of the present invention with an aqueous cleaning agent containing metal ions and a water-soluble solvent as essential components. And has good water disintegration property. Since the water-decomposable cleaning article of the present invention having such a configuration can be impregnated with a large amount of water, the cleaning effect on water-soluble dirt can be enhanced.

  Examples of the metal ion used in the present invention include potassium, alkaline earth metals (magnesium, calcium, strontium, barium), manganese, zinc, cobalt, and nickel ions. Potassium ions are particularly useful when carrageenan is used as the anionic adhesive.

  Among the above metal ions, calcium, strontium, barium, zinc, cobalt, and nickel ions are preferred from the viewpoint of imparting the water-decomposable cleaning article of the present invention with excellent strength that can withstand severe cleaning work.

When a metal ion other than the above, for example, a monovalent metal ion (excluding potassium) is used, the water disintegration is satisfactory, but the strength that can withstand the cleaning operation cannot be obtained. Further, a divalent metal ion Cu ²⁺ (Cu (II) ion), Fe ²⁺ (iron (II) ion), Sn ²⁺ (stannous (II) ion), and trivalent metal ions When Fe ³⁺ (iron (III) ion) or Al ³⁺ (aluminum ion) is used, a strength that can withstand a cleaning operation is obtained, but a problem remains in terms of water decomposability.

  In order to impregnate hydrolytic paper with metal ions, water-soluble metal salts of the above metals (hydroxides, chlorides, sulfates, nitrates, carbonates, formates, acetates, etc.) are dissolved in water to form an aqueous solution. It is only necessary to immerse the hydrolytic paper in this aqueous solution. The metal ions are preferably impregnated by ¼ mol or more, more preferably ½ mol or more with respect to 1 mol of the anionic group of the anionic adhesive contained in the hydrolytic paper.

  The aqueous cleaning agent used in the present invention contains a water-soluble solvent as an essential component in order to obtain a high strength that can withstand a cleaning operation. Examples of the water-soluble solvent include monovalent lower alcohols such as ethanol, methanol, and propanol; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, and hexylene glycol; And mono- or diethers of lower alcohols such as methanol, ethanol, propanol and butanol; esters of the above glycols and lower fatty acids; polyhydric alcohols such as glycerin and sorbitol, etc., one or more of these Can be used in combination.

  The aqueous cleaning agent used in the present invention preferably contains 5% by weight or more of a water-soluble solvent, more preferably 8 to 50% by weight, still more preferably 10 to 40% by weight, and water is preferably 95% by weight or less. More preferably, it contains 92 to 50% by weight, still more preferably 90 to 60% by weight. The hydrolytic paper is preferably impregnated with 100 to 250% by weight of the aqueous cleaning agent having such a composition with respect to the weight of the hydrolytic paper.

  In addition to the water-soluble solvent and water, the aqueous cleaning agent used in the present invention, if necessary, a surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, Components such as bactericides and deodorants can be added.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these Examples.

[Examples 1-8]
The pulp oligomer obtained by dispersing softwood bleached kraft pulp (NBKP) in water so that the pulp concentration is 1% by weight, and the cationic oligomer represented by the general formula (1) as a yield improver for the adhesive After 5 wt% was added and stirred to be sufficiently uniform, sodium carboxymethyl cellulose (trade name “CMC2280”, manufactured by Daicel Chemical Industries, Ltd.) as an anionic adhesive was added and stirred for 5 wt% of pulp. did. Using the slurry thus obtained, a wet papermaking method was carried out as usual to obtain a paper having a basis weight of 25 g / m ² . Table 1 below shows the cationic oligomers used in each example.

[Comparative Examples 1-4]
In Comparative Example 1, paper was made in the same manner as in the above Example except that the cationic oligomer (adhesive yield improver) was not used, and a paper having a basis weight of 25 g / m ² was obtained.
In Comparative Example 2, paper was made in the same manner as in the above example except that cationized starch (molecular weight: 400,000, cationization degree: 1.0) was used instead of the cationic oligomer in the above example, and the basis weight was 25 g / m ² paper was obtained.
In Comparative Example 3, the same method as in the above example except that polyamine polyamide epichlorohydrin (trade name “Kaimen WS-C”, manufactured by Seiko PMC Co., Ltd.) was used instead of the cationic oligomer in the above example. Thus, paper having a basis weight of 25 g / m ² was obtained.
In Comparative Example 4, paper was made in the same manner as in the above example except that aluminum sulfate was used instead of the cationic oligomer in the above example to obtain a paper having a basis weight of 25 g / m ² .

  Various performances of the paper obtained in Examples and Comparative Examples were evaluated by the following evaluation methods. The results are shown in Table 2 below.

<Dry tensile strength, wet tensile strength>
The paper to be evaluated is cut into a strip having a width of 25 mm and a length of 100 mm to obtain a test piece, and then immediately, using a universal compression tensile tester (RTM-25 manufactured by Orientic Co., Ltd.), a tensile speed of 300 mm. / Min. The strength at break of the test piece was measured under the condition that the distance between the test piece grips was 50 mm, and this measured value was taken as the dry tensile strength.
In measuring the wet tensile strength, an aqueous cleaning agent consisting of zinc sulfate / amphoteric surfactant / ethanol / water = 1% by weight / 1% by weight / 18% by weight / 80% by weight with respect to the paper weight was 1. The paper was impregnated so as to be 5 times the weight and used as a cleaning sheet. And about this cleaning sheet, tensile strength measurement was performed similarly to the above, and this measured value was made into wet tensile strength.

<Fuzzy state of paper dust / sheet>
Using the cleaning sheet impregnated with the aqueous cleaning agent prepared for the measurement of the wet tensile strength, the generation state of paper dust and the fluffing state of the sheet when the black tile surface (with joints) was wiped for 5 minutes were as follows: Evaluation was based on the criteria.
○: Almost no generation of paper dust is observed, and no fluffing of the sheet occurs.
Δ: Paper dust is slightly generated, but the sheet is not fluffed.
X: Generation | occurrence | production of paper dust is recognized and the fluff of a sheet | seat also arises.

<Yield yield rate>
The paper to be evaluated was stirred and dispersed in a 6% NaOH aqueous solution for 1 hour, and after filtration, carboxymethylcellulose (CMC) contained in the filtrate was added to 0.01% 2,7-dihydroxynaphthalene in sulfuric acid solution. Comparative quantification was performed using color development. From the amount of CMC in the filtrate, the yield rate (%) of the anionic adhesive (carboxymethyl cellulose sodium) was calculated.

<Water decomposability>
The water disintegrability of paper is evaluated according to JIS P4501-1993 (toilet paper). Put 500 ml of water into a beaker, stir a 600 rpm with a stirrer, put the paper to be evaluated into the beaker, visually observe the collapsed state of the paper after 40 seconds, and make the following judgment Evaluation was based on criteria.
○: Dispersibility is good.
Δ: Dispersibility is slightly poor.
X: Dispersibility is poor.

Claims (4)

Hydrolytic paper using an anionic adhesive and a cationic oligomer represented by the following general formula (1) or (2).

[Wherein, R ₁ is a linear or branched alkylene group having 2 to 24 carbon atoms, an alicyclic alkylene group, an aralkylene group, or (R ₄ —O) p- (R ₄ ) q [wherein R ₄ is R represents a straight chain or branched alkylene group having 2 to 5 carbon atoms, p represents an average number of 0 to 30, q represents an average number of 1 to 30, and R ₂ represents a straight chain of 1 to 24 carbon atoms. shows the chain or branched alkyl group or an aralkyl group, Y represents an OH or _{N (R 2) 2, R} 3 represents a linear or branched alkyl group or aralkyl group having 1 to 24 carbon atoms, X Represents a halogen atom or an alkyl sulfate. S represents an integer of 1 or more, and T represents an integer of 0 or more. n is a total value of S and T, and is 1 to 50 on average. In each of the formulas (1) and (2), the plurality of R ₁ , the plurality of R ₂ , the plurality of R ₃ , and the plurality of Y may be the same or different. ]   A method for producing hydrolytic paper, wherein the cationic oligomer according to claim 1 is added to and mixed with pulp slurry, and then an anionic adhesive is added to make paper.   The water disintegrating property obtained by impregnating the water disintegrating paper according to claim 1 with an aqueous cleaning agent containing a metal ion selected from the group consisting of potassium, alkaline earth metal, manganese, zinc, cobalt and nickel, and a water-soluble solvent. Cleaning article.   The anionic adhesive comprises sodium carboxymethylcellulose, carrageenan, sodium polyuronic acid, sodium polyacrylate, sodium polymethacrylate, sodium acrylate, sodium methacrylate, acrylic ester, methacrylic ester, styrene and styrene derivatives. The water-decomposable cleaning article according to claim 3, which is selected from the group consisting of polymers.