JP3453505B2 - Bulking agent for paper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bulking agent for paper, which can improve the bulkiness of a sheet obtained by making a pulp raw material into paper without impairing the paper strength.

[0002]

2. Description of the Related Art In recent years, there has been a demand for paper of high quality, for example, excellent in printability and volume. The printability and the volume feeling are closely related to the bulkiness of the paper, and various methods for improving the bulkiness have been tried so far. For example, cross-linked pulp may be used (Japanese Unexamined Patent Publication No. 4-185792, etc.), or a method of mixing with synthetic fibers (Japanese Unexamined Patent Publication No. 3-269199, etc.). In addition, a filler such as an inorganic substance may be filled between the pulp fibers (Japanese Patent Laid-Open No. 3-1248).
No. 95, etc.), a method of introducing voids (Japanese Patent Laid-Open No. 5-23
No. 0798) is also available. On the other hand, as a mechanical improvement, there has been reported a method (Japanese Patent Laid-Open No. 4-370298) in which the calender processing is improved, such as softening the calender processing.

However, the use of crosslinked pulp or synthetic fiber makes recycling of pulp impossible, and it is necessary to simply fill the space between the pulp fibers as described above.
Providing voids significantly impairs paper strength. In addition, there is a limit in mechanical processing, and it is the current situation that a satisfactory one has not been obtained yet.

Further, a method for adding bulkiness to a paper by adding a bulking agent at the time of paper making is also known, and as such bulking agent, fatty acid polyamide polyamine type compounds are commercially available. A decrease in strength was observed and satisfactory performance was not obtained.

[0005]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above problems, as a result, a specific fatty acid and a polyoxyalkylene adduct of a fatty acid ester are blended with a pulp raw material, for example, a pulp slurry, in a papermaking process. As a result, they have found that the bulkiness can be improved without impairing the paper strength of the sheet obtained by papermaking, and have completed the present invention.

That is, the present invention provides a bulking agent for paper containing a compound represented by the following general formula (1). R ₁ COO (EO) _m (PO) _n R ₂ (1) (In the formula, R ₁ has a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms or an alkyl group having 4 to 20 carbon atoms. It represents an alkylaryl group, E is an ethylene group, P is a propylene group, m and n are average addition mole numbers, 0 ≦ m ≦ 20, and 0 ≦ n ≦ 50. , (EO) _m (PO) _n may be either block or random, and either EO or PO may come first, R ₂ is H or an alkyl group having 1 to 4 carbon atoms, and m = n = 0 In the case of, R ₂ is an alkyl group having 1 to 4 carbon atoms.) Here, the bulking agent for paper is the same amount of pulp raw material when paper is obtained to obtain a sheet, even if the basis weight is the same. An agent that can increase the paper thickness (making the sheet bulkier).

Further, in the present invention, in any of the paper making steps, the above-mentioned bulking agent for paper is added, and the tightness is 5% or more lower than that of the product without the bulking agent for paper, and JIS P 8116 is used. The present invention provides a method for producing a highly bulky and high-quality pulp sheet, which has a tear strength measured by 90% or more of that of an additive-free product.

Further, the present invention is produced by adding the above-mentioned bulking agent for paper in any of the paper making steps, and has a tenacity of 5% or more lower than that of the product without adding the bulking agent for paper, Further, it provides a high bulky pulp sheet having a tear strength measured according to JIS P 8116 of 90% or more of that of an additive-free product.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the above general formula (1) can be obtained by adding ethylene oxide (E
O), propylene oxide (PO), and other alkylene oxides are added. In the present invention, the average addition mole number m of ethylene oxide is 0 ≦ m ≦ 20, preferably 0 ≦ m ≦ 10, and more preferably Is used in the range of 0≤m≤5. When m exceeds 20, the effect of imparting bulkiness to paper decreases. Also, propylene oxide (PO)
Has an average added mole number n of 0 ≦ n ≦ 50, preferably 0 ≦ n ≦
The range of 20, more preferably 0 ≦ n ≦ 10 is used. Even if n exceeds 50, there is little deterioration in performance, but it is economically disadvantageous.

R ₁ in the general formula (1) has a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms or an alkyl group having 4 to 20 carbon atoms in order to obtain an excellent bulking effect. The alkylaryl group is preferably a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms. R ₂ is H or an alkyl group having 1 to 4 carbon atoms, preferably H or a methyl group, and particularly preferably
H. When m = n = 0, R ₂ is an alkyl group having 1 to 4 carbon atoms.

Further, E and P in the general formula (1) each represent a linear or branched alkylene group having 2 or 3 carbon atoms,
Specific examples include ethylene and propylene. When the (EO) _m (PO) _n group in the general formula (1) is a mixed form of polyoxyethylene and polyoxypropylene, the addition form of the C ₂ H ₄ O group and the C ₃ H ₆ O group may be a block even if it is random. But it's okay. In that case, it is preferable that the content of the polyoxypropylene group (C ₃ H ₆ O group) is 50 mol% or more, and particularly preferably 70 mol% or more in the total average number of added moles. The order of adding EO and PO does not matter, and either may be added first.

Among the compounds represented by the general formula (1), a fatty acid PO adduct is preferable from the viewpoint of the tenacity of the pulp sheet, and a fatty acid lower ester or its EO.PO adduct is preferable from the viewpoint of tear strength.

The bulking agent for paper of the present invention preferably further contains a polyhydric alcohol type nonionic surfactant. The effect of the present invention can be enhanced by using the compound of the formula (1) in combination with the polyhydric alcohol type nonionic surfactant, and in particular, the compound represented by the formula (1) alone can be dissolved in water. When it is difficult to dissolve and it is difficult to mix it uniformly with pulp raw materials, such as pulp and pulp slurry, for example, when the number of moles m of EO added is 2 or less, and even when it is 0, it is possible to disperse by mechanical force. It is more effective to use the compound of formula (1) in an emulsified state with a polyhydric alcohol type nonionic surfactant.

Examples of polyhydric alcohol type nonionic surfactants are AO adducts of sugar alcohols or fatty acid esters thereof, fatty acid esters of sugar alcohols, A0 adducts of sugars or fatty acid esters thereof, AO additions of sugar fatty acid esters and fats and oils. One or more selected from the above are preferable, and further, a fatty acid ester of an AO adduct of sugar alcohol and an AO adduct of a fat and oil are particularly preferable to use a combination of both.

(1) Sugar Alcohol Nonionic Surfactant Examples of sugar alcohol nonionic surfactants include sugar alcohol AO adducts, sugar alcohol AO adduct fatty acid esters, and sugar alcohol fatty acid esters. . Here, the sugar alcohol constituting the polyhydric alcohol type nonionic surfactant is an alcohol obtained by reducing an aldehyde group or a ketone group of a monosaccharide having 3 to 6 carbon atoms,
Specifically, glycerin, erythritol, arabite,
Examples include sorbit and mannite. The fatty acid constituting the fatty acid ester of the AO adduct of sugar alcohol may be either a saturated fatty acid having 1 to 24 carbon atoms, preferably 12 to 18 carbon atoms, or an unsaturated fatty acid, and further preferably oleic acid. Further, the ester substitution degree of the sugar alcohol may be any from 0 to that in which all -OH is substituted,
1-3 are preferable. AO is ethylene oxide (EO) and / or propylene oxide (PO), and when both EO and PO are used, either random addition or block addition may be used. It is preferably an EO adduct. The average number of moles of EO added is 0 to 100, preferably 10
~ 50 moles. The average number of moles of PO added is also 0 to 100,
It is preferably 10 to 50 mol. Examples of the sugar alcohol-based nonionic surfactant used in the present invention include sugar alcohol
Fatty acid esters of EO adducts are preferred, with polyoxyethylene sorbitan fatty acid esters being most preferred.

(2) Sugar-based nonionic surfactant Examples of sugar-based nonionic surfactants include sugar AO adducts, sugar AO adduct fatty acid esters, and sugar fatty acid esters. As the sugar, in addition to the monosaccharides described in the above sugar alcohol, polysaccharides such as sucrose can be used,
The type of AO and the number of moles added are the same as in (1). AO
When the average number of added moles is 0, a sugar fatty acid ester is obtained.
Examples of the sugar fatty acid ester include sucrose fatty acid ester, and as the fatty acid constituting the ester, those described above can be used.

(3) AO adducts of fats and oils Examples of fats and oils as raw materials for AO adducts of fats and oils include vegetable oils such as castor oil, coconut oil and palm oil, animal oils such as lard and beef tallow, and fish oils. Examples include hardened oil and semi-hardened oil, and recovered oil obtained in the step of refining these fats and oils. Among these fats and oils, hydrogenated castor oil is most preferable. Also, AO
The type and the number of moles added are the same as in (1).

When the polyhydric alcohol type nonionic surfactant as described above is used in combination, the ratio is [compound of formula (1)] / [polyhydric alcohol type nonionic surfactant] = 5 /
It is 5 to 10/0, preferably 7/3 to 10/0 (weight ratio). When a polyhydric alcohol type nonionic surfactant is used in combination, the mixture of the compound of formula (1) and the polyhydric alcohol type nonionic surfactant is added to water with stirring to give a concentration of 10 to 10
An emulsion of about 0% may be used.

The pulp raw material to which the bulking agent of the present invention can be applied is widely applicable to general pulp from virgin pulp such as mechanical pulp and chemical pulp to various used paper pulp. Further, the place to add the bulking agent of the present invention is not particularly limited as long as it is a papermaking process, for example, in a factory, a refiner, a machine chest,
A place where it can be uniformly blended with the pulp raw material, such as addition with a headbox, is desirable. The bulking agent of the present invention, after being added to the pulp raw material, is directly made into paper and remains on the paper.
The addition amount of the bulking agent for paper of the present invention is 0.01 to pulp.
It is 10% by weight, preferably 0.1-5% by weight.

The pulp sheet obtained by using the bulking agent for paper of the present invention has a tightness (measurement method according to a method described in Examples described later) of 5% or more, preferably 7 as compared with a non-additive product.
% Or more, and the tear strength measured according to JIS P 8116 is 90% or more, preferably 95% or more, of the additive-free product.

[0021]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Parts and% in the examples are based on weight unless otherwise specified.

Examples 1 to 10 and Comparative Examples 1 to 6 [Pulp Raw Material] As pulp raw materials, used paper pulp and virgin pulp shown below were used. <Waste Paper Pulp> Waste paper pulp is made from recycled waste paper (newspaper / flyer = 70/30%) collected in the city with warm water and sodium hydroxide (against raw material) 1%, sodium silicate (against raw material) 3% and 30%.
Add 3% hydrogen peroxide solution (against raw material) and 0.3% beef tallow / glycerin (1: 1) EO 70 moles PO 10 mole block adduct (average number of moles added) as deinking agent (against raw material), and flotation after disaggregation A 1% deinked pulp (DIP) slurry that had been treated, washed with water and adjusted in concentration was used. The DIP freeness at this time was 220 ml. <Virgin pulp> For virgin pulp, LBKP (hardwood bleached pulp) was disintegrated and beaten in a beating machine at room temperature to 1
% LBKP slurry was used. L at this time
The freeness of BKP was 420 ml.

[Papermaking method] The above pulp was weighed out so that the weight of the sheet after papermaking with 1% pulp slurry was 60 g / m ² , and the pH was adjusted to 4.5 with a sulfuric acid band. Next, various bulkiness improvers were added to the pulp in an amount of 3%, and the sheets were obtained by making paper with an 80 mesh wire using a square tapping paper machine. The sheet after paper making was pressed by a press at 3.5 kg / cm ² for 2 minutes and dried at 105 ° C. for 1 minute using a mirror surface dryer. The dried sheet was conditioned at 20 ° C. and a humidity of 65% for 1 day, and then the bulkiness of the paper and the strength of the paper and the tear strength as the paper strength performance were measured. The measured value is an average value of 10 times.

<Evaluation Items / Methods> Bulkiness (Tightness) The weighed (g / m ² ) and thickness (mm) of the humidity-controlled sheet are measured, and the tightness (g / cm ³ ) is calculated from the calculated values. I asked. Calculation formula: bulkiness (tightness) = (weighing) / (thickness) x 0.001 The smaller the absolute value of the tightness, the higher the bulk, and the 0.02 difference in the tightness is sufficiently recognized as a significant difference. . -Paper strength (tearing strength) The humidity-conditioned sheet was measured according to JIS P 8116 (Tear strength test method for paper and paperboard). Tear strength = A / S x 16 Tear strength; (gf) A; Scale reading S; Number of tears The stronger the absolute value of the tear strength, the stronger the paper strength, and the difference in tear strength of 20gf is significant. It is well recognized.

[0025]

[Table 1]

<Bulkiness improver used> Example 1: PO adduct of stearic acid, POp (average number of moles of PO added, the same hereinafter) = 10 moles Example 2: Beef tallow fatty acid PO adduct, POp = 5 moles -Example 3: PO adduct of oleic acid / lauric acid = 50/50 (weight ratio) mixture, POp = 2 mol-Example 4: Lauric acid EO-PO block adduct, EOp
(Average number of moles of EO added, the same below) = 3 moles, POp = 7 moles Example 5: Castor oil fatty acid EO / PO random adduct, EO
p = 2 mol, POp = 8 mol Example 6: Methyl laurate Example 7: Methyl laurate EO2 mol / PO3 mol Random adduct Example 8: Stearic acid PO10 mol adduct / Polyoxyethylene (EOp) = 20) sorbitan monooleate / polyoxyethylene (EOp = 30) 80/14/6 (weight ratio) mixture of hydrogenated castor oil Example 9: tallow fatty acid PO 5 mol adduct / polyoxyethylene (EOp = 20) sorbitan Monooleate / polyoxyethylene (EOp = 30) 82/12/6 (weight ratio) mixture of hydrogenated castor oil. Example 10: (A) Lauric acid EO 3 mol / PO 7 mol adduct, (B) Polyoxyethylene ( EOp = 20) sorbitan monooleate, and (C) polyoxyethylene (EOp = 30) (A) / (B) / (C) = 80/14/6 (weight ratio) of hydrogenated castor oil
Mixture-Comparative example 1: Blank (no bulkiness improver) -Comparative example 2: Stearic acid-Comparative example 3: Lauric acid-Comparative example 4: Stearic acid EO30 mol / PO10 mol block adduct-Comparative example 5: Lauric acid EO40 Mol / PO10 mol Random adduct-Comparative Example 6: Commercially available bulking agent "By Volume P Liquid" (fatty acid polyamide polyamine type, manufactured by Bayer)

[0027]

As shown in the examples, by adding the bulking agent of the present invention to make a paper, a bulky sheet can be obtained without impairing the paper strength.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Takahashi Hirodori 1334 Minato Minato, Wakayama City, Wakayama Prefecture Kao Corporation (56) References JP-A-8-197836 (JP, A) JP-A-2- 41451 (JP, A) JP 59-130400 (JP, A) JP 4-352891 (JP, A) JP 57-136426 (JP, A) JP 7-109694 (JP, A) JP-A-7-82662 (JP, A) JP-A-7-216786 (JP, A) JP-A-5-156596 (JP, A) International Publication 98/003730 (WO, A1) Rezaburo Oe, Paper and Pulp Papermaking Chemistry and Technology, Japan, Japan and Foreign Industry Survey Committee, February 29, 1984, Volume 2, p. 100, left column, Tsunetaka Sasaki, Latest Application Technology of Defoamer, Japan, CMC, 1991 May 30, 1st print, pages 101-103 Kazuhiro Shimo, Kenichi Sakurai, Defoaming agents in the paper industry, Pulp and Paper Technology Times, Japan, Timetex Co., Ltd., October 1, 1994, Volume 37, Volume 12, Volume 450, 41 -Page 45 (58) Fields investigated (Int.Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (6)

(57) [Claims] 1. A bulking agent for paper, which is added in a papermaking process and contains a compound represented by the following general formula (1). R ₁ COO (EO) _m (PO) _n R ₂ (1) (In the formula, R ₁ has a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms or an alkyl group having 4 to 20 carbon atoms. It represents an alkylaryl group, E is an ethylene group, P is a propylene group, m and n are average addition mole numbers, 0 ≦ m ≦ 20, and 0 ≦ n ≦ 50. , (EO) _m (PO) _n may be either block or random, and either EO or PO may come first, R ₂ is H or an alkyl group having 1 to 4 carbon atoms, and m = n = 0 In the case of, R ₂ is an alkyl group having 1 to 4 carbon atoms.) 2. The bulking agent for paper according to claim 1, further comprising one or more polyhydric alcohol type nonionic surfactants. 3. A polyhydric alcohol type nonionic surfactant is a sugar alcohol AO (alkylene oxide, the same applies hereinafter) or a fatty acid ester thereof, a sugar alcohol fatty acid ester, a sugar AO adduct or a fatty acid ester thereof, The bulking agent for paper according to claim 2, which is one or more kinds selected from sugar fatty acid esters and AO adducts of fats and oils. 4. A compound represented by the general formula (1) is
In the formula (1), m = n = 0 and R ₂ is an alkyl group having 1 to 4 carbon atoms.
And n in the general formula (1) is 0 <n ≦ 50
The paper according to any one of claims 1 to 3, which is selected from compounds.
Bulking agent. 5. The method according to claim 1, wherein in any of the paper making steps.
The bulkiness agent for paper according to any one of items 1 to 4 is added, and the tightness is 5% or more lower than that of a product without addition of the bulkiness agent for paper, and JI
The tear strength measured by SP 8116 is 90
% Or more, the method for producing a high bulky pulp sheet. 6. The method according to claim 1, wherein in any of the paper making steps.
5 is manufactured by adding the bulking agent for paper according to any one of claims 4 to 5 and has a tightness of 5% as compared with a non-added product of the bulking agent for paper.
A high bulky pulp sheet that is as low as above and has a tear strength measured according to JIS P 8116 of 90% or more of the additive-free product.