JP3482336B2 - 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 Patent Laid-Open No. 4-185792, etc.), or a method of mixing with synthetic fibers (Japanese Patent Laid-Open No. 3-269199, etc.). There is also a method of filling a filler such as an inorganic substance between pulp fibers (Japanese Patent Laid-Open No. 124948/1993) or providing voids (Japanese Laid-Open Patent Publication No. 5-230798). 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-mentioned problems, as a result of blending a specific nonionic surfactant with a pulp raw material, for example, a pulp slurry in a papermaking step, papermaking The inventors have found that the bulkiness can be improved without impairing the paper strength of the obtained sheet, and have completed the present invention.

That is, the present invention provides a bulking agent for paper containing at least one of the following nonionic surfactants. (1) Fat-based nonionic surfactant (2) Sugar alcohol-based nonionic surfactant (3) Sugar-based nonionic surfactant Nonionic surfactants (1) to (3) are oxyethylene groups and Those having a polyoxyalkylene structure composed of an oxypropylene group can be used.

Further, the present invention adds the above-mentioned bulking agent in any of the paper making steps, and has a tightness of 5% or more lower than that of a non-added product of the bulking agent for paper, and according to JIS P 8116. Provided is a method for producing a highly bulky pulp sheet having a measured tear strength of 90% or more of an additive-free product.
In the present invention, it is preferable that a bulking agent, water and a pulp raw material are mixed to obtain a uniform slurry, and then papermaking is performed.

Further, the present invention comprises the above bulking agent and pulp paper, and has a tenacity of 5% or more lower than that of a bulking agent-free manufactured product and a tear strength measured according to JIS P 8116 without any manufacturing process. We also provide high bulky pulp sheets that are more than 90% of the product.

Here, the bulking agent for paper is capable of increasing the paper thickness even if the basis weight is the same when the same amount of pulp raw material is used to make a sheet (making the sheet bulkier). Refers to the agent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant used in the present invention will be described below.

(1) Oil / fat nonionic surfactant As the oil / fat nonionic surfactant (1), for example, an oil / fat as described in JP-A-4-352891 or the oil / fat is reacted with glycerin in advance. Product and monovalent
The thing which added the alkylene oxide (AO) to the mixture with a 14-valent alcohol is mentioned. AO is preferably added to a mixture of fats and oils and polyhydric alcohols. Here, as AO, ethylene oxide (E
O) and / or propylene oxide (PO),
When both EO and PO are used, either random addition or block addition may be used. The average addition mole number of each EO is preferably 0 to 200 moles, more preferably 10 to 100 moles. PO is preferably 0 to 150 mol, 2 to 100
Molar is more preferred.

Examples of fats and oils used for this type of nonionic surfactant include land animal oils, marine animal oils, hydrogenated oils thereof, semi-hardened oils, and recovered oils obtained in the refining process of these oils and fats. . Preference is given to palm oil, beef tallow, fish oil, linseed oil, rapeseed oil, castor oil.
In addition, the ratio in the case where these oils and fats and glycerin are reacted in advance is preferably oil / fat / glycerin = 1 / 0.05 to 1/1.

Among the monohydric alcohols used in the nonionic surfactants of this type, the monohydric alcohols include linear or branched saturated or unsaturated alcohols having 1 to 24 carbon atoms and cyclic alcohols. Examples thereof include alcohols, and linear or branched saturated alcohols having 4 to 12 carbon atoms are preferable. Two
Examples of the polyhydric alcohol include α, ω-glycol having 2 to 32 carbon atoms, 1,2-diol, symmetrical α-glycol and cyclic 1,2-diol, and α, ω-having 2 to 6 carbon atoms.
Glycol is preferred. Examples of trihydric or higher alcohols include alcohols having any of 3 to 24 carbon atoms such as glycerin, diglycerin, sorbitol, and stachyose. As the alcohol, a divalent to hexavalent alcohol having 2 to 6 carbon atoms is particularly preferable.

(2) Sugar alcohol-based nonionic surfactant The sugar alcohol-based nonionic surfactant (2) includes sugar alcohol AO adducts, sugar alcohol AO adduct fatty acid esters, and sugar alcohol fatty acid esters. Can be mentioned. 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, and specifically, Examples thereof include glycerin, erythritol, arabite, sorbite, and mannitol. Particularly, those having 6 carbon atoms are preferable. The fatty acid which constitutes the fatty acid ester of the AO adduct of sugar alcohol has 1 to 24 carbon atoms,
It may be either a saturated fatty acid having 12 to 18 carbon atoms or an unsaturated fatty acid, and oleic acid is more preferable. Further, the degree of ester substitution of sugar alcohol is 0 to all -O.
Any of those in which H is substituted may be used, but 1 to 3 is preferable. The type of AO and the average number of moles added are the same as in (1).

(3) Sugar-based nonionic surfactant Examples of the sugar-based nonionic surfactant (3) 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, and glucose and sucrose are preferable. AO
And the average number of added moles are the same as in (1). As the sugar-based nonionic surfactant (3), an AO adduct of sugar is particularly preferable, and among them, PO is added to glucose on average from 1 to 10
Those with a mole added are preferred.

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 of addition of the bulking agent of the present invention is not particularly limited as long as it is a paper making step, but for example, a place where it can be uniformly blended with a pulp raw material such as a refiner, a machine chest or a headbox in a factory 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.
It is from 01 to 10% by weight, preferably from 0.1 to 5% by weight.

The pulp sheet obtained by using the bulking agent for paper of the present invention has a tenacity (measurement method according to a method described in Examples described later) of 5% or more, preferably 7 as compared with an additive-free 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.

[0018]

By adding the bulking agent of the present invention to make a paper, a bulky sheet can be obtained without impairing the paper strength.

[0019]

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 23 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 (against raw material) and 0.3% beef tallow / glycerin (1: 1) EO 70 mol PO 10 mol block adduct (average number of moles added) as deinking agent (against raw material), then flotation after disaggregation A 1% deinked pulp (DIP) slurry that had been treated, washed with water and adjusted in concentration was used. DIP at this time
The freeness 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 basis 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. Then, various bulkiness improvers shown in Table 1 were added to pulp 3.
% Was added, and paper was obtained by making paper with an 80 mesh wire using a square tapping paper machine. The sheet after paper making is 3.5 kg / cm ²
For 2 minutes with a press machine, and dried at 105 ° C. for 1 minute using a mirror surface dryer. 20 sheets dried
The humidity was controlled for 1 day at a temperature of 65 ° C. and a humidity of 65%, and then the bulkiness of the paper was measured, and the strength of the paper was measured, and the tear strength was measured as the strength of the paper. The results are shown in Table 2. The measured value is an average value of 10 times.

<Evaluation Items / Methods> Bulkiness (Tightness) The basis weight (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) = (basis weight) / (thickness) x 0.001 The smaller the absolute value of the tightness, the higher the bulk, and the 0.02 difference in tenacity is sufficiently recognized as a significant difference. is there.

Paper strength (tear strength) The humidity-conditioned sheet was measured according to JIS P 8116 (Test method for tear strength of paper and paperboard). Calculation formula: 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 a significant difference. It is well recognized.

[0024]

[Table 1]

[0025]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor ▲ Takahashi Hiromichi 1334 Minato Minato, Wakayama, Wakayama Prefecture Kao Co., Ltd. (56) Reference JP-A-4-352891 (JP, A) JP-A-57- 136426 (JP, A) JP 7-106994 (JP, A) JP 5-156596 (JP, A) JP 1-306693 (JP, A) JP 58-149399 (JP, A) Patent 3128248 (JP, B2) Tsunetaka Sasaki, Latest application technology of antifoaming agent, Japan, CMC Co., Ltd., May 30, 1991, 1st edition, pp. 101-103, Kazuhiro Takeshita, Kenichi Sakurai, Paper Manufacturing Industry For defoaming agents, Paper and Pulp Technology Times, Japan, Timetex Co., Ltd., October 1, 1994, Volume 37 Volume 12, Volume 450, Pages 41-45 Reisaburo Oe, Paper and Pulp Papermaking And technology, Japan, (with) both inside and outside industry Committee, February 29, 1984, Vol. 2, 100 pages left column (58) investigated the field (Int.Cl. ^7, DB name) D21H 11/00 - 27 / 42

Claims (4)

(57) [Claims] 1. A bulking agent for paper, which is added in a papermaking process and contains at least one of the following nonionic surfactants, excluding those which are used in combination with the compound represented by the general formula (I). ]. (1) Oil or fat or raw material obtained by previously reacting the oil or fat with glycerin
Add a mixture of the product and monohydric to 14 hydric alcohol to
Oil / fat nonionic surfactant (2) to which xylene oxide (hereinafter referred to as AO) is added , AO adduct of sugar alcohol, sugar alcohol with AO
Fatty acid ester of additive, fatty acid ester of sugar alcohol
(3) AO adduct of sugar and fatty acid ester of AO adduct of sugar selected from
Sugar-based nonionic surfactant RO (EO) _m (PO) _n H (I) selected from sugar fatty acid ester , wherein R is a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms. Or an alkylaryl group having an alkyl group having 4 to 20 carbon atoms, E is an ethylene group, P is a propylene group, m and n are average addition mole numbers, and are numbers in the range of 0 ≦ m ≦ 20. Yes, n is 0 ≦ n ≦
It is a number in the range of 50. RO (EO) _m (PO)
_n may be either block or random, and EO
Either PO or PO may come first. ] 2. The nonionic surfactants (1) to (3) are
The bulking agent for paper according to claim 1, which has a polyoxyalkylene structure composed of an oxyethylene group and an oxypropylene group. 3. The method according to claim 1, wherein in any of the paper making steps.
The bulkiness agent described in 1) is added, and the tenacity is 5% or more lower than that of the product without addition of the bulkiness agent for paper, and the tear strength measured by JIS P 8116 is 90% or more of the additive-free product. A method for producing a high-bulk pulp sheet. 4. The bulking agent according to claim 1 and pulp paper, which has a tenacity of 5% or more lower than that of a non-added bulking agent product and has no tear strength measured according to JIS P 8116. Highly bulky pulp sheet that is 90% or more of manufactured products.