JP3929588B2 - Carboxymethylcellulose salts and binder for hydrolytic paper - Google Patents

Description

【００３２】
応用例１
実施例１で得たＣＭＣを水解紙用粘結剤として用い、下記の方法によりシート状のトイレ清掃用品を製造した。
まず、パルプ（ティッシュロール,クリンペットＷ−８０,５層構造，８６．５ｇ／ｍ²）１００部を３層と２層に分け、３層（６０部）上に、ＣＭＣ２％水溶液１０部、塩化カルシウム２％水溶液[１／１（mol／CMC）]及び水からなる溶液（全量で６００部）を滴下して均一に塗布した。この溶液には不溶物の析出は見られず、濁度は８％であった。次に、パルプの残り２層を３層の上に重ね、軽く押圧したのち、約７０℃で約１５０分間乾燥し、水解紙基材を得た。
その後、水７０部、エタノール２０部、プロピレングリコール１０部及びラウリル硫酸ナトリウム０．１部からなる溶液（水解紙基材重量の１．６倍量）に対して、ＺｎＳＯ₄・７Ｈ₂Ｏを４／１（mol／CMC）添加して溶解し、清浄剤液とした。次に、この清浄剤液を水解紙基材に含浸させたのち、ポリエチレン製の袋に入れて密封した状態で室温で一夜放置して、水解紙を得た。なお、比較例１〜３のＣＭＣ水溶液を用い、同様にしてシート状のトイレ清掃用品の製造を試みた。しかし、比較例１、２のＣＭＣ水溶液は不溶物が生成したため、水解紙基材への塗布操作を円滑になすことができず、比較例３のＣＭＣ水溶液も高粘度であるため、やはり塗布作業を円滑になすことができず、いずれも目的とする製品を得ることができなかった。
このようにして得られた水解紙を用い、温度２４℃、相対湿度６０％の恒温恒湿雰囲気中において、下記の方法により、湿潤引張強度崩壊性を測定した。
【００３３】
（湿潤強度試験）
シート状のトイレ清掃用品を、幅２５mm、長さ１００mmの短冊状に裁断し、可変速引張試験機（(株)東洋精機製作所製；Ａ−121506602）を用いて、試験片つかみ間隔５０mm、引張速度３００mm／minの条件で、縦方向への破断時の強度を測定した。なお、試験は、温度２４℃、相対湿度６０％の恒温恒湿雰囲気で行った。その結果、引張強度は平均１２５０ｇであった。
同様にして、計１００枚の水解紙を製造し、それらを１枚ずつ水洗トイレに流したところ、いずれも容易に崩壊して排水とともに流されていき、詰まったりすることはなかった。
【００３４】
【発明の効果】
本発明のカルボキシメチルセルロース塩類は、２価金属塩化合物と水の存在下で接触した場合においても不溶物が析出することがなく、しかも高濃度でかつ低粘度溶液にすることができる。従って、各種用途の粘結剤成分として使用することができ、例えば、水解紙基材となるパルプ繊維に、容易にかつ均一に水解紙用粘結剤を付着させることができるため、作業性が向上し、高品質の水解紙を安定して供給することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to carboxymethylcellulose salts suitable as various binder components. The present invention also relates to a binder for hydrolytic paper for binding pulp fibers to be a base for hydrolytic paper in the production of hydrolytic paper that has the property of being finely disintegrated in water and drained with water as it is.
[0002]
[Prior art and problems to be solved by the invention]
Water disintegrating paper is widely used as a base material for disposable items such as toilet cleaning that can be reused after being used once because it breaks up finely in water and can be drained together with water.
[0003]
A toilet cleaning product using such water-degrading paper, for example, sprays a water-degradable sheet obtained from pulp fiber with a mixed liquid containing an aqueous solution of a carboxymethyl cellulose salt aqueous solution as a binder and a compound that generates divalent metal ions. It is manufactured through a first step of coating and drying, and a second step of impregnating with an organic solvent, a wetting agent, a surfactant, water and the like. In this production method, a carboxymethyl cellulose salt aqueous solution is spray-coated in the first step, and a compound aqueous solution, an organic solvent, a wetting agent, a surfactant, water and the like that generate divalent metal ions are impregnated in the second step. You can also. The product obtained by this production method has wet durability during use due to the action of a compound that generates divalent metal ions and an organic solvent, and rapid disintegration when thrown into water after use. It is also very good as a toilet cleaning product.
[0004]
Therefore, when applying the above manufacturing method to obtain toilet cleaning products, etc., the carboxymethyl cellulose salt generates divalent metal ions in order to improve the workability during manufacturing and to stably supply high-quality products. It is desirable that the aqueous solution be stable (for example, not insolubilized) when contacted with the aqueous compound solution, and that the aqueous carboxymethyl cellulose salt solution has a high concentration and a low viscosity. When insolubilization or the like occurs during production, the carboxymethyl cellulose salt cannot be uniformly attached to the pulp fiber, and the desired wet strength during use cannot be imparted. Also, when diluted to reduce the viscosity (reduced concentration) to facilitate the work of attaching to the pulp fibers, a large amount of aqueous solution is required to attach the required amount of carboxymethylcellulose salt. It takes too long.
[0005]
Then, this invention can solve the said problem, and it aims at providing the carboxymethylcellulose salt suitable as various binder components.
[0006]
In addition, the present invention improves the stability of the carboxymethyl cellulose salt when the aqueous solution of the carboxymethyl cellulose salt and the aqueous solution of the compound that generates divalent metal ions are in contact, and maintains the carboxymethyl cellulose salt aqueous solution at a high concentration and low viscosity. It is another object of the present invention to provide a binder for hydrolytic paper that can improve the workability and can stably supply a product using hydrolytic paper such as toilet cleaning supplies with high quality.
[0007]
[Means for Solving the Problems]
The present invention provides carboxymethylcellulose salts characterized by having one or more of the following requirements (a), (b) and (c).
(A): Measured by using an integrating sphere method (JIS K0101) turbidimeter using a halogen lamp as a light source in an aqueous solution mixture of carboxymethylcellulose salts and a divalent metal salt compound:
Turbidity (%) = (scattered light intensity / total transmitted light intensity) × 100
The turbidity calculated in step 20 is 20% or less;
(B): The viscosity ratio of a 5 wt% aqueous solution of carboxymethylcellulose salts to a 1 wt% aqueous solution at 25 ° C (5 wt% aqueous solution viscosity / 1 wt% aqueous solution viscosity) is in the range of 80 to 160;
(C): The number of unsubstituted glucose units per 1000 anhydroglucose units in the carboxymethylcellulose salt molecule is 65 or less.
[0008]
Moreover, this invention provides the binder for hydrolytic paper characterized by containing the said carboxymethylcellulose salt.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the carboxymethylcellulose salts of the present invention include carboxymethylhydroxyethylcellulose salts as well as carboxymethylcellulose salts. Examples of the salt form of carboxymethyl cellulose salts include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used.
[0010]
The carboxymethyl cellulose salt of the present invention has one or more of the requirements (a), (b) and (c). Therefore, the carboxymethyl cellulose salt of the present invention includes the following embodiments (1) to (7) depending on the requirements of the carboxymethyl cellulose salt.
[0011]
(1) Carboxymethylcellulose salts having only the requirements of (a);
(2) Carboxymethylcellulose salts having only the requirements of (b);
(3) Carboxymethylcellulose salts having only the requirements of (c);
(4) Carboxymethylcellulose salts having the requirements of (a) and (b);
(5) Carboxymethylcellulose salts having the requirements of (a) and (c);
(6) Carboxymethylcellulose salts having the requirements of (b) and (c);
(7) Carboxymethylcellulose salts having the requirements of (a), (b) and (c).
[0012]
In the requirement of (a), the following formula is measured using an integrating sphere method (JIS K0101) turbidimeter using a halogen lamp as the light source of the aqueous mixture of carboxymethylcellulose salts and divalent metal salt compounds:
Turbidity (%) = (scattered light intensity / total transmitted light intensity) × 100
The turbidity determined by is 20% or less, preferably 10% or less. In this turbidity measurement, the compounding ratio of the carboxymethyl cellulose salt and the divalent metal salt compound is set so that the ion equivalent ratio of the carboxymethyl cellulose salt and the divalent metal salt compound is 1.0.
In addition, the detail of the measuring method using the turbidimeter (Tokyo Denshoku Co., Ltd. Model T-2600D) by an integrating sphere system (JIS K0101) is as follows.
(Optical system)
Light source: Halogen lamp (12V, 20W, 2.000H)
Measurement diameter: 10mm
Optical path length: 50mm
Detection element: Silicon photocell (measurement unit)
Display method Digital display 0-100.0
(Operating voltage)
AC-100v, 50 / 60Hz, about 100VA.
[0013]
By setting the turbidity to 20% or less in this manner, it is possible to prevent the carboxymethyl cellulose salts from becoming insoluble even when the carboxymethyl cellulose salts and the divalent metal salt compound are contacted in the presence of water. “Contacting carboxymethylcellulose salt and divalent metal salt compound in the presence of water” means that when carboxymethylcellulose salt aqueous solution and divalent metal salt compound aqueous solution are contacted, carboxymethylcellulose salt and divalent metal salt compound When contacting with aqueous solution, it means the case where carboxymethylcellulose salt aqueous solution and a divalent metal salt compound are contacted.
[0014]
Examples of the divalent metal salt compound in the turbidity measurement include calcium compounds such as calcium hydroxide, chloride, sulfate, nitrate, carbonate, formate, and acetate. However, as long as the above turbidity can be satisfied, there is no particular limitation as long as it generates divalent metal ions in an aqueous solution other than calcium compounds, and alkaline earths such as magnesium, strontium and barium Metals, hydroxides such as manganese, zinc, cobalt, nickel, chlorides, sulfates, nitrates, carbonates, formates, acetates, and the like can also be used.
[0015]
Further, in the requirement (b), the ratio of the viscosity (mPa · s) of a 5% by weight aqueous solution of carboxymethylcellulose salts to the viscosity (mPa · s) of a 1% by weight aqueous solution at 25 ° C. (5% by weight aqueous solution viscosity / 1% by weight) The aqueous solution viscosity) is in the range of 80 to 160, preferably in the range of 80 to 130.
[0016]
Thus, by setting the viscosity ratio within the above range, it is possible to achieve a high concentration and a low viscosity, so that workability can be improved.
[0017]
Further, in the requirement (c), the substituent distribution in the carboxymethylcellulose salt molecule, that is, the number of unsubstituted glucose units per 1000 anhydroglucose units in the carboxymethylcellulose salt molecule is 65 or less, preferably 40 or less. Yes, particularly preferably 30 or less.
[0018]
Thus, by making the substituent distribution 65 or less, it is possible to prevent the carboxymethyl cellulose salts from being insolubilized even when the carboxymethyl cellulose salts and the divalent metal salt compound are contacted in the presence of water, and at a high concentration. And low viscosity.
[0019]
Further, in order to achieve the object of the present invention, the carboxymethylcellulose salts used in the present invention have a substituent distribution of 65 or less and a degree of etherification of 0.9 to 1.4 as described above. Those having a ratio of 1.0 to 1.3 are particularly preferable.
[0020]
The binder for hydrolytic paper of the present invention contains the carboxymethyl cellulose salt of any one of the above (1) to (7) , and preferably comprises only the carboxymethyl cellulose salt, but does not impair the object of the present invention. Within the range, a part of the carboxymethylcellulose salts may be substituted with other adhesive components.
[0021]
Other adhesive components used in combination with carboxymethylcellulose salts include polysaccharide derivatives other than carboxymethylcellulose salts, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, and fumaric acid. Synthetic polymer having at least one selected from acids, olefins such as unsaturated carboxylic acid esters, vinyl acetate and ethylene, acrylamide and vinyl ether, sodium alginate, glue, casein, carrageenan, guar gum, xanthan gum, gellan gum, pectin And natural polymers such as
[0022]
The binder for hydrolytic paper of the present invention is a binder for pulp fibers that has the property of splitting and disintegrating in water like various pulp fibers such as wood pulp fibers, non-wood pulp fibers, and rayon fibers. Can be used.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In the following, “%” indicating the blending amount means “% by weight” and “part” means “part by weight”.
[0024]
Example 1
In a reactor having a biaxial stirring blade, a solution obtained by dissolving 933 parts of isopropyl alcohol and 117 parts of sodium hydroxide in 148 parts of water was added, and 200 parts of pulverized pulp was added thereto. Stir and mix for 120 minutes. Next, a solution in which 130 parts of monochloroacetic acid was dissolved in 105 parts of isopropyl alcohol was added and mixed, and then heated to 70 ° C. and reacted for 1 hour. After completion of the reaction, the cotton wool taken out from the reactor and drained with a centrifuge was washed with about 80% aqueous methyl alcohol solution, drained and dried. The CMC thus obtained was measured for turbidity, viscosity ratio and substituent distribution. The results are shown in Table 1.
[0025]
(1) Turbidity A 2% aqueous solution of CMC was prepared, and calcium acetate monohydrate was added and dissolved therein to obtain a sample solution. The amount of calcium acetate monohydrate added was such that the ion equivalent ratio of CMC to calcium acetate monohydrate was 1.0. The ion equivalent and the ion equivalent ratio were determined as follows.
Ion equivalent of CMC = [CMC weight (g) / (162.1 + DS × 80] × DS
(In the formula, DS indicates the degree of etherification of CMC)
Ion equivalent of calcium acetate monohydrate
= [Calcium acetate monohydrate weight (g) /176.18] × 2
Ion equivalence ratio = Calcium acetate / monohydrate ion equivalent / CMC ion equivalent turbidity is measured by placing a sample solution in a glass cell of 20 × 50 × 40 mm, and a turbidimeter using an integrating sphere method (JIS K0101). The total transmitted light intensity and the scattered light intensity were measured by the above-described measurement method using and turbidity was obtained from the following equation.
Turbidity (%) = (scattered light intensity / total transmitted light intensity) × 100
(2) Viscosity Ratio The viscosity at 25 ° C. of a 1 wt% or 5 wt% aqueous solution of CMC was measured by the following method, and the viscosity ratio was determined from the following formula.
CMC precisely weighed into a predetermined amount of water was added while stirring, and after the CMC expanded to some extent, water was added to obtain 1 wt% or 5 wt% to obtain an aqueous solution. Then, after leaving for a fixed time in a 25 degreeC thermostat, the viscosity (mPa * s) was measured using the BL type viscometer by Tokyo Keiki Co., Ltd.
Viscosity ratio = 5 wt% aqueous solution viscosity / 1 wt% aqueous solution viscosity.
[0026]
(3) Substituent distribution A 1% by weight CMC aqueous solution was prepared with an acetic acid / sodium acetate buffer (pH 4.4). Next, cellulase was added to CMC at a rate of 5 mg / g (CMC), and after hydrolysis at a constant temperature of 25 ° C. for about 300 hours, the decomposition product glucose was measured by the glucose oxidase method. Cellulase is known to degrade CMC when three or more unsubstituted glucose units are continuous. Therefore, by measuring the amount of degraded glucose, an unsubstituted glucose unit is obtained, and in the CMC molecule, Expressed as the number of unsubstituted glucose units per 1000 anhydroglucose units.
[0027]
Example 2
In a reactor having a biaxial stirring blade, a solution prepared by dissolving 912 parts of isopropyl alcohol and 129 parts of sodium hydroxide in 192 parts of water was added, and 200 parts of pulverized pulp was added thereto. Stir and mix for 120 minutes. Next, a solution in which 148 parts of monochloroacetic acid was dissolved in 120 parts of isopropyl alcohol was added and mixed, and then the temperature was raised to 70 ° C. and reacted for 1 hour. After completion of the reaction, the cotton wool taken out from the reactor and drained with a centrifuge was washed with about 80% aqueous methyl alcohol solution, drained and dried. The CMC thus obtained was measured for turbidity, viscosity ratio and substituent distribution in the same manner as in Example 1. The results are shown in Table 1.
[0028]
Comparative Example 1
In a reactor having a biaxial stirring blade, a solution obtained by dissolving 906 parts of isopropyl alcohol and 112 parts of sodium hydroxide in 190 parts of water was added, and 200 parts of pulverized pulp was added thereto. The mixture was stirred for 60 minutes. Next, a solution prepared by dissolving 111 parts of monochloroacetic acid in 90 parts of isopropyl alcohol was added and mixed, and then the temperature was raised to 70 ° C. and the reaction was performed for 1 hour. After completion of the reaction, the cotton wool taken out from the reactor and drained with a centrifuge was washed with about 80% aqueous methyl alcohol solution, drained and dried. The CMC thus obtained was measured for turbidity, viscosity ratio and substituent distribution in the same manner as in Example 1. The results are shown in Table 1.
[0029]
Comparative Example 2
In a reactor having a biaxial stirring blade, a solution prepared by dissolving 717 parts of isopropyl alcohol and 150 parts of sodium hydroxide in 192 parts of water was added. The mixture was stirred for 60 minutes. Next, a solution prepared by dissolving 140 parts of monochloroacetic acid in 113 parts of isopropyl alcohol was added and mixed, and then heated to 70 ° C. and reacted for 1 hour. After completion of the reaction, the cotton wool taken out from the reactor and drained with a centrifuge was washed with about 80% aqueous methyl alcohol solution, drained and dried. The CMC thus obtained was measured for turbidity, viscosity ratio and substituent distribution in the same manner as in Example 1. The results are shown in Table 1.
[0030]
Comparative Example 3
In a reactor having a biaxial stirring blade, a solution prepared by dissolving 885 parts of isopropyl alcohol and 143 parts of sodium hydroxide in 192 parts of water was added, and 200 parts of pulverized pulp was added thereto. Stir and mix for 120 minutes. Next, a solution obtained by dissolving 152 parts of monochloroacetic acid in 123 parts of isopropyl alcohol was added and mixed, and then the temperature was raised to 70 ° C. and the reaction was performed for 1 hour. After completion of the reaction, the cotton wool taken out from the reactor and drained with a centrifuge was washed with about 80% aqueous methyl alcohol solution, drained and dried. The CMC thus obtained was measured for turbidity, viscosity ratio and substituent distribution in the same manner as in Example 1. The results are shown in Table 1.
[0031]
[Table 1]

[0032]
Application example 1
Using CMC obtained in Example 1 as a binder for hydrolytic paper, a sheet-like toilet cleaning product was produced by the following method.
First, 100 parts of pulp (tissue roll, crimppet W-80, 5-layer structure, 86.5 g / m ² ) was divided into 3 layers and 2 layers, and 10 parts of CMC 2% aqueous solution was formed on 3 layers (60 parts). A solution (600 parts in total) consisting of a 2% calcium chloride aqueous solution [1/1 (mol / CMC)] and water was dropped and applied uniformly. In this solution, no insoluble precipitate was observed, and the turbidity was 8%. Next, the remaining two layers of the pulp were stacked on the three layers, pressed lightly, and then dried at about 70 ° C. for about 150 minutes to obtain a hydrolyzed paper base material.
Thereafter, 4 parts of ZnSO ₄ .7H ₂ O was added to a solution (1.6 times the weight of hydrolyzed paper base material) consisting of 70 parts of water, 20 parts of ethanol, 10 parts of propylene glycol and 0.1 part of sodium lauryl sulfate. / 1 (mol / CMC) was added and dissolved to obtain a detergent solution. Next, after impregnating the water-disintegrating paper base with the detergent solution, the water-disintegrating paper was obtained by placing it in a polyethylene bag and allowing it to stand overnight at room temperature. In addition, manufacture of the sheet-like toilet cleaning goods was tried similarly using the CMC aqueous solution of Comparative Examples 1-3. However, since the insoluble matter was generated in the CMC aqueous solutions of Comparative Examples 1 and 2, the application operation to the hydrolytic paper base material could not be performed smoothly, and the CMC aqueous solution of Comparative Example 3 was also highly viscous, so that the application work As a result, it was not possible to obtain a desired product.
Using the hydrolyzed paper thus obtained, wet tensile strength disintegration was measured by the following method in a constant temperature and humidity atmosphere at a temperature of 24 ° C. and a relative humidity of 60%.
[0033]
(Wet strength test)
Sheet-like toilet cleaning supplies are cut into strips with a width of 25 mm and a length of 100 mm, and using a variable-speed tensile tester (manufactured by Toyo Seiki Seisakusho; A-121506602), the distance between specimen grips is 50 mm, and the tension is The strength at break in the vertical direction was measured under the condition of a speed of 300 mm / min. The test was conducted in a constant temperature and humidity atmosphere at a temperature of 24 ° C. and a relative humidity of 60%. As a result, the average tensile strength was 1250 g.
Similarly, when 100 sheets of water-disintegrating paper were manufactured and they were poured one by one into a flush toilet, they all collapsed easily and were washed away with the drainage, and were not clogged.
[0034]
【The invention's effect】
The carboxymethyl cellulose salts of the present invention do not precipitate insolubles even when they are contacted with a divalent metal salt compound in the presence of water, and can be made into a high-concentration and low-viscosity solution. Therefore, it can be used as a binder component for various uses. For example, the binder for hydrolytic paper can be easily and uniformly attached to the pulp fiber used as the hydrolytic paper base material, so that workability is improved. It is possible to improve and stably supply high-quality hydrolytic paper.

Claims (2)

Among the requirements of (a), (b) and (c) below, the carboxymethyl cellulose salts having the requirements of (b) and (c) or the requirements of (a), (b) and (c) A binder for hydrolytic paper, comprising carboxymethyl cellulose salts.
(A): Integral sphere method (JIS K0101) using a halogen lamp as a light source in a mixed aqueous solution of carboxymethylcellulose salts and calcium hydroxide, chloride, sulfate, nitrate, carbonate, formate and acetate. The turbidity determined by the following formula: turbidity (%) = (scattered light intensity / total transmitted light intensity) × 100 measured using a turbidimeter is 20% or less;
(B): The viscosity ratio of a 5 wt% aqueous solution of carboxymethylcellulose salts to a 1 wt% aqueous solution at 25 ° C (5 wt% aqueous solution viscosity / 1 wt% aqueous solution viscosity) is in the range of 80 to 160;
(C): carboxymethylcellulose salts, the number of unsubstituted glucose units per 1000 anhydroglucose units in the molecule Ri der 65 or less, degree of etherification 0.9 to 1.4 der Rukoto.   The binder for hydrolytic paper according to claim 1, wherein the carboxymethylcellulose salt has all of the requirements (a), (b) and (c).