JPS58120897A - Sizing of paper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for sizing paper using substituted succinic anhydride as a sizing agent component, and is capable of obtaining sized paper that is easy to operate industrially and has excellent sizing effects. This paper provides a paper sizing method that allows for

Although a paper sizing method using an aqueous dispersion of substituted succinic anhydride as a sizing agent is known, it is difficult to obtain an aqueous dispersion of substituted succinic anhydride, and the aqueous dispersion is difficult to obtain. Paper sizing methods using substituted co-phosphoric acid anhydride as a sizing agent component have not been realized on an industrial scale because the sizing effect rapidly decreases over time after the dispersion is prepared. is the current situation.

The present invention provides a paper sizing method that is easy to operate on an industrial scale and can obtain sized paper with excellent sizing effects. It is something.

The structure of the paper sizing method of the present invention will be explained below.

The water-soluble synthetic polymer having a cationic group used in the present invention has the effect of dispersing substituted cono-phosphoric acid anhydride, which is a sizing agent component, in water, and has a cationic group known as a papermaking additive. A water-soluble synthetic polymer having, for example,
Cationic or amphoteric acrylamide polymers, polyethyleneimine, polyamide polyamine-epichlorohydrin resins, dialkylaminoalkyl (meth)acrylate polymers or copolymers or their guarized products, allylamine or diallylamine polymers or copolymers, or their 7th compound, cation-modified polyvinyl alcohol, etc. can be used. As mentioned above, this water-soluble synthetic polymer having a cationic group not only has excellent dispersion performance for dispersing the substituted succinic anhydride used as a sizing agent component in water in the present invention, but also It also has excellent fixing properties to fibers, and among the water-soluble synthetic polymers having cationic groups, amphoteric acrylamide polymers having both cationic groups and anionic groups, polyethyleneimine, or their The modified product has a dispersion performance for dispersing the substituted succinic anhydride in water, and as an acrylamide-based polymer with pulp fiber properties, it has a cationic group of about 3 to 50 moles and an anionic group of about 3 to S moles. Preferably, these water-soluble polymers are poly(meth)acrylamide or a copolymer of (meth)acrylamide and other comonomers, which are subjected to a Hoffman decomposition reaction of 1.458-120397.
(3) Alternatively, (meth)acrylamide, (meth)acrylic acid, and cations such as dimethylamine ethyl methacrylate, dimethylaminomethyl acrylamide, allylamine, vinylimidazole, or vinylpyridine, which can be easily obtained by subjecting to Mannich reaction. It can also be obtained by copolymerization with a monomer.

In the present invention, by utilizing the high dispersion performance of the substituted succinic anhydride in the water-soluble synthetic polymer having a cationic group and the excellent fixing performance to pulp fibers, sufficiently fine particles can be obtained. It is easy to continuously obtain an aqueous dispersion of a substituted co-phosphoric acid anhydride.
This aqueous solution of a water-soluble synthetic polymer having a cationic group has a viscosity of 10 to 10,000 c at the operating humidity.
ps (preferably 100 to 1000 cps), it is easy to emulsify in a mixer and can also be emulsified easily in a simple mixer with a gentle stirring rate.

The substituted succinic anhydride used as a sizing agent component in the present invention is a substituted succinic anhydride having a hydrophobic group and a cyclic acid anhydride group, that is, a substituted succinic anhydride known as a sizing agent raw material, e.g. Alkyl or alkenyl succinic anhydride having an alkyl group or alkenyl group having carbon number S or more, preferably carbon number g or more, an addition reaction product of an oligomer such as propylene or butene and maleic anhydride, or an aliphatic diene such as butadiene. An addition reaction product between an oligomer or a partially hydrogenated product thereof and maleic anhydride, an addition reaction product between an unsaturated fatty acid ester such as an alkyl oleate and maleic anhydride, etc. can be used.

The oil-in-water surfactant used as the g-th compound of the second invention, like the water-soluble synthetic polymer having a cationic group, is a substituted succinic anhydride in water. The oil-in-water surfactant that effectively acts on dispersion includes anionic and cationic surfactants that are compatible with the above-mentioned substituted succinic anhydride and form a uniform liquid mixture. , nonion type.

or amphoteric oil-in-water surfactants, particularly preferably
For example, polyoxyethylene alkyl ether sulfate or a salt thereof, polyoxyethylene alkylaryl ether sulfate or a salt thereof, or a mixture thereof can be used.

The mixing ratio of the substituted succinic anhydride and the oil-in-water surfactant in the liquid anhydrous mixture of the substituted succinic anhydride and the oil-in-water surfactant can be changed arbitrarily; Depending on the type of synthetic polymer in the aqueous solution of a water-soluble synthetic polymer having a cationic group to be mixed in the seed mixer, the viscosity of the aqueous solution, and the type and performance of the mixer used, It is advisable to conduct a preliminary test and determine the amount.Generally, 0.5 to 30 parts by weight of oil-in-water surfactant, preferably 1 to 700 parts by weight of substituted co-phosphoric acid anhydride.
In other words, it is preferable to use about 70 parts by weight.

The liquid anhydrous mixture of the liquid substituted cono-phosphate anhydride and the oil-in-water surfactant used in the gth invention, which is the second invention, does not contain water, so it can be used for a long period of time. Due to the good stability over time, the various effects of the mixture do not deteriorate during storage.

In the second invention, which uses a liquid anhydrous mixture of a liquid substituted co-phosphate anhydride and an oil-in-water surfactant,
Since the action of dispersing substituted succinic anhydride in water is performed by a water-soluble synthetic polymer having a cationic group and the oil-in-water type surfactant, dispersion of substituted succinic anhydride in water is effective. Since the properties are further significantly improved, a stable fine particle aqueous dispersion of substituted succinic anhydride can be obtained very easily using a simple mixer with gentle stirring.

In the present invention, (a) an aqueous solution of a water-soluble synthetic polymer having a cationic group, (t) a liquid substituted succinic anhydride, or (d) a liquid substituted co-phosphoric anhydride and an oil in water. The liquid anhydrous mixture with type surfactant is sent to the mixer 1
The (c) water introduced is not necessarily required, but if the aqueous solution of the water-soluble synthetic polymer having (a) a cationic group has a high viscosity, this (c) water By feeding the emulsion into the mixer, the viscosity of the emulsion produced in the mixer can be adjusted, so the emulsification operation can be easily performed and the concentration of the emulsion produced can be adjusted. .

In the present invention, the ratio of (a) an aqueous solution of a water-soluble polymer having a cationic group and (b) liquid substituted co-phosphate anhydride fed into the mixer, or (a) having a cationic group The ratio of the aqueous solution of a water-soluble polymer to (d) a liquid anhydrous mixture of a liquid substituted cono-phosphate anhydride and an oil-in-water surfactant is determined by the ratio of (a) a water-soluble synthetic polymer having a cationic group. The type and viscosity of the aqueous solution, and (b) the liquid substituted co-phosphate anhydride, or (d) the type of liquid anhydrous mixture of the liquid substituted co-phosphate anhydride and the oil-in-water surfactant. The particle size of the aqueous dispersion produced in the mixer should be set so that it is Sμ or less, preferably /μ or less, although it can be changed as appropriate depending on the As an aqueous solution of a water-soluble synthetic polymer having a group, a commercially available amphoteric acrylamide polymer aqueous solution (concentration 10 Wt
It is preferable to use about 5 to 100 parts by weight of the liquid substituted acid anhydride (b) per 100 parts by weight of the viscosity 3θ0.

In the present invention, the above-mentioned (a) aqueous solution of a water-soluble synthetic polymer having a cationic group, Q)) liquid substituted succinic anhydride, or (d) liquid substituted succinic anhydride and oil-in-water type The liquid anhydrous mixture with the surfactant and (0) water as needed are quantitatively and continuously added to a preset composition ratio through a flow meter or metering pump that can adjust the flow rate. The aqueous dispersion produced in the mixer is continuously and quantitatively added to pulp slurry, which is a separate raw material for papermaking, and the paper is cysonged. Of course, other papermaking additives may be used in combination as appropriate. As a mixer for continuously and quantitatively feeding the above-mentioned various components into the pulp slurry, which is a raw material for papermaking, a line mixer, a Rusup mixer, etc. are suitable, but ordinary propeller-type stirrers, various homogenizers, etc. can also be used.

The paper sizing method of the present invention, which is constructed as follows, can be widely applied to general acidic papermaking using sulfuric acid band, neutral or alkaline papermaking using alno-based filler, etc. It is something.

The paper sizing method of the present invention, which consists of the following two configurations, uses the dispersibility in water of substituted co-phosphoric anhydride of a water-soluble synthetic polymer having a cationic group, or The dispersibility of substituted succinic anhydride in water, which the water-soluble synthetic polymer and oil-in-water surfactant have, allows the substituted succinic anhydride to be instantly dispersed into uniform fine particles in a mixer, and the substituted succinic anhydride is Uniform filtration of phosphoric acid anhydride
This method easily generates an aqueous dispersion and then immediately adds the aqueous dispersion to a separate papermaking raw material taro pulp slurry to achieve paper sizing, which requires a special powerful emulsifying machine. Therefore, it is possible to achieve extremely good sizing of filter paper on a commercial scale, very economically, and without reducing the sizing effect inherent to the aqueous dispersion at all.

In addition, in the method of the present invention, the fine particles of substituted succinic anhydride added to the pulp slurry, which is a raw material for papermaking, are added to the cellulose pulp by the action of the cationic group of the water-soluble synthetic polymer added at the same time. Due to intimate contact, the substituted succinic anhydride bonds with the hydroxyl groups of cellulose, resulting in an excellent size effect.

In addition, in the method of the present invention, the aqueous dispersion produced in the mixer is immediately added to the pulp slurry, which is the raw material for papermaking, and consumed, so when the paper machine is stopped or when the type of paper material is changed. Disadvantages of using conventional, pre-prepared aqueous dispersions of substituted succinic anhydride: no excess aqueous dispersion remains in the mixer even when
That is, the remaining aqueous dispersion loses its size effect over time and must be disposed of.
Not only is it uneconomical, but the expense required for disposal operations is
Disadvantages such as a large burden on labor etc. are eliminated.

Furthermore, in the paper sizing method of the present invention, as a dispersant for substituted succinic anhydride, its dispersibility in water is better than that of cationically modified starch, which has been conventionally used as a dispersant for substituted succinic anhydride. Since it uses a water-soluble synthetic polymer with a cationic group that has far superior properties, a uniform aqueous dispersion of fine particles of substituted co-phosphoric acid anhydride can be easily and quickly obtained, and the size effect can be improved. However, there are drawbacks to using cationically modified starch as a dispersant, namely, an aqueous solution of cationically modified starch is susceptible to deterioration such as rotting. Not only is it inconvenient to store, but the viscosity changes greatly over time, making it difficult to feed quantitatively to the mixer.Also, it increases the burden of wastewater treatment.Furthermore, neutral All the disadvantages, including the disadvantage of promoting the generation of slime, which is the biggest technical problem in paper making, are eliminated.

Hereinafter, the specific structure of the paper sizing method of the present invention will be explained using examples.

Examples/(a) An aqueous solution of a water-soluble synthetic polymer having a cationic group is an aqueous solution of an amphoteric acrylamide polymer, which is a Hofmann decomposition reaction product of an acrylamide polymer [trade name Nystargum A, D-x, Seiko Kagaku] Industry■
Product, concentration/Qvrt, person in charge.

(b) As the liquid substituted succinic anhydride, an addition reaction product of a propylene oligomer containing propylene pentamer as a main component and maleic anhydride is used.

The aqueous solution of the water-soluble synthetic polymer having a cationic group and (b) the liquid substituted succinic anhydride are passed through a metering pump from each storage tank to a mixer [Product name: T
(a) an aqueous solution of a water-soluble synthetic polymer having a cationic group at a rate of 30 p/hour, and (b) liquid substitution. Succinic anhydride was fed continuously at a rate of Aky/hour.

Aqueous dispersion discharged from the mixer [average particle size approximately/μ
, maximum particle diameter of about 3μ, substituted succinic anhydride content of about 1/2, weight of Otsu] was diluted 70 times with water through a continuous diluter, and immediately mixed into pulp slurry (57m = g/62B).
It was continuously added (equivalent to a weight factor of 0.3 in terms of substituted succinic anhydride to pulp dry weight) to a seed box of a Fourdrinier paper machine using KP, C3F 110cc), and sizing was performed.

The obtained paper had a basis weight of 59/m2 and a Steckigt size of 33 seconds.

Example (a) As an aqueous solution of a water-soluble synthetic polymer having a cationic group, an aqueous solution of an amphoteric acrylamide-based polymer, which is a Mannich reaction product of an acrylamide-based polymer [
Product name Nippearl Flock FR-X, manufactured by Seiko Kagaku Kogyo ■, concentration 5wt, %, viscosity 3000cps/, 230C)
use.

(b) As a liquid substituted succinic anhydride, Examples/
Use the same liquid substituted co-phosphoric acid anhydride used in .

Using the above-mentioned (a) aqueous solution of a water-soluble synthetic polymer having a cationic group and (b) liquid substituted succinic anhydride, the same mixing operation and paper sizing operation as in Example 2 will be carried out. Each operation was performed and the paper was sized.

The aqueous dispersion discharged from the mixer in this example is
It has an average particle size of about /μ, a maximum particle size of about 3μ, and contains substituted succinic anhydride of about /2 wt.%.

The obtained paper had a basis weight of 5 g/nX and a Steckigt sizing degree of 3.2 seconds.

Example 3 ((Transfer) As an aqueous solution of a water-soluble synthetic polymer having a cationic group, an aqueous solution of a terpolymer consisting of acrylamide gb mole, methacrylic acid 7 mole, and dimethylamine ethyl methacrylate S mole (concentration 10 wt, %
, viscosity 7300 cps/, 25°C).

(1) As the liquid substituted succinic anhydride, the one in Example is used.

Using the aqueous solution of the water-soluble synthetic polymer having a cationic group (a) and the canned liquid of (bl) liquid substituted succinic anhydride, the same mixing operations and paper sizing operations as in Example 1 will be carried out. The operation was performed and the paper was sized.

The aqueous dispersion discharged from the mixer in this example is
It has an average particle size of about /μ, a maximum particle size of about 3μ, and contains substituted succinic anhydride of about /O and Otsu weight.

The obtained paper had a basis weight of A 3 ')/m'' and a Steckigt size of 32 seconds.

Example G (a) As an aqueous solution of a water-soluble synthetic polymer having a cationic group, a commercially available aqueous polyethyleneimine derivative solution [
Product name: Polymin SK, manufactured by Badish ■, concentration, 2.
twt, %, viscosity ocps/23 (→ liquid 1
As the succinic anhydride, the same liquid substituted phosphoric anhydride used in Examples is used.

(a) an aqueous solution of a water-soluble synthetic polymer having a cationic group; and (b) a liquid can of a liquid substituted cono-phosphate anhydride;
From each storage tank through the metering pump, mixer
, T, Homomic Life 0-F00 type, manufactured by Tokushu Kika Kogyo ■], (a) an aqueous solution of a water-soluble synthetic polymer having a cationic group was added at a rate of 41g13/hour, and (1 )
) Liquid substituted cono-phosphoric anhydride was continuously fed at a rate of 1 kti/hour.

Aqueous dispersion discharged from the mixer [average particle size approximately/μ
, maximum particle size of about 3μ, substituted co-phosphoric anhydride content of about 3μ,
20 wt.
Continuously added to the seed box of a Fourdrinier paper machine using KP, C8F 'I 00CC) (equivalent to pulp O1 weight),
Performed paper sizing. The obtained paper had a basis weight of 39/nX and a Steckigt size of 34 seconds.

Example 5 (a) As the aqueous solution of a water-soluble synthetic polymer having a cationic group, the same aqueous solution of a water-soluble polymer having a cationic group used in Example 1 is used.

(a) 100 parts by weight of an addition reaction product of a propylene oligomer containing propylene pentamer as a main component and maleic anhydride as a liquid anhydrous mixture of a liquid substituted co-phosphoric acid anhydride and an oil-in-water surfactant; , polyoxyethylene alkyl ether sulfate ester salt [trade name: )・itenol/g, manufactured by Daiichi Kogyo Seiyaku ■] Parts by weight of S are used as a homogeneous liquid mixture.

The (a) aqueous solution of a water-soluble synthetic polymer having a cationic group and (d) the canned liquid of the liquid substituted succinic anhydride are passed through a metering pump from each storage tank to a mixer (Rusap mixer); (a) An aqueous solution of a water-soluble synthetic polymer having a cationic group was continuously fed into A, 3 at a rate of 301/hour, and (d) a homogeneous liquid anhydrous mixture was fed into A, 3 at a rate of 9/hour.

Aqueous dispersion discharged from the mixer [average particle size 0.3
~/μ, maximum particle size of approximately λμ, substituted phosphoric anhydride content of approximately 100 g/μ] was immediately added to the pulp (L/N=g/μ).
) BKP, C8F 3 left θCC] was continuously added to the seed box of a Fourdrinier paper machine (corresponding to a weight ratio of 0.3 in terms of substituted co-phosphoric anhydride to pulp dry weight), and the sizing operation was carried out. went.

The obtained paper had a basis weight of 39/m" and a Steckigt size of 39 seconds.

Example 2 *1-h Hijiri・7 Inquiry Women Adults European Gentlemen 7 As a small aqueous solution, the same aqueous solution of the amphoteric acrylamide polymer used in Example 2 is used.

(d) The same homogeneous liquid anhydrous mixture used in Example S is used as the liquid anhydrous mixture of the liquid substituted succinic anhydride and the oil-in-water surfactant.

(a) using an aqueous solution of a water-soluble synthetic polymer having a cationic group and (d) a can of a homogeneous liquid anhydrous mixture;
Thereafter, the same mixing operation and paper sizing operation in Example S were performed to size the paper.

The aqueous dispersion discharged from the mixer in this example is
It has an average particle size of about /μ, a maximum particle size of about 3μ, and contains about 4gwt% of substituted succinic anhydride.

The obtained paper has a basis weight of 39/m'', and is used as the aqueous solution of the polyethyleneimine derivative used in Example D as the aqueous solution of the water-soluble synthetic polymer having a cationic group.

(d) The same homogeneous liquid anhydrous mixture used in Example S is used as the liquid anhydrous mixture of the liquid substituted succinic anhydride and the oil-in-water surfactant.

The above-mentioned (a) aqueous solution of a water-soluble synthetic polymer having a cationic group and (d) a homogeneous liquid anhydrous mixture are passed through a metering pump from each storage tank to a mixer (Ruzap mixer) K, (a) cationic. The aqueous solution of the water-soluble synthetic polymer having groups is ', 'gA/hour, and (d)
A homogeneous liquid anhydrous mixture is/2. At the rate of Aky/hour,
At the same time, (c) high pressure water at a rate of 2013/min,
Continuously sent.

Aqueous dispersion discharged from the mixer [average particle size approximately/μ
, maximum particle size of about 3μ, substituted succinic anhydride content of about 0.
95 weight] was immediately converted into pulp (L/N=g/2
BKP, C3F 33 Qcc ) was continuously added to the seed box of a Fourdrinier paper machine (corresponding to a weight ratio of 0.6 in terms of substituted succinic anhydride to pulp dry weight), and a sizing operation was performed.

The obtained paper had a basis weight of 4 shi/m2 and a Steckigt size of 4'5 seconds.

patent applicant Seiko Chemical Industry Co., Ltd. Hokuetsu Paper Co., Ltd. agent City River Riyoshi (7 other people)

Claims (1)

[Scope of Claims] (1) (a) an aqueous solution of a water-soluble synthetic polymer having a cationic group, (b) a liquid substituted succinic anhydride, and optionally further (C) water. Paper sizing characterized by continuously and quantitatively feeding the pulp slurry to a mixer, and immediately adding the aqueous dispersion produced in the mixer continuously and quantitatively to pulp slurry, which is a raw material for papermaking. Method. (2) A water-soluble synthetic polymer having a cationic group is
The method for sizing paper according to claim 1, wherein the paper sizing method is an amphoteric acrylamide-based polymer. (31) The paper sizing method according to claim 2, wherein the amphoteric acrylamide polymer is a Hofmann decomposition reaction product of an acrylamide polymer. A method for sizing paper according to claim Ω, which is a product. (5) The amphoteric acrylamide-based polymer is a ternary compound of (meth)acrylamide, (meth)acrylic acid, and dialkylaminoalkyl (meth)acrylate. A method for sizing paper according to Claim 2, which is a copolymer. (6) Claim 2, wherein the water-soluble polymer having a cationic group is polyethyleneimine, a derivative thereof, or a mixture of the two. The paper sizing method according to claim 1. (7) The paper sizing method according to claim 1, wherein the substituted succinic anhydride is a substituted succinic anhydride having an alkenyl group or an alkyl group having a carbon number of g or more. Method. fQll-IJ, Knee,!-11.ht-U-Imo~
an aqueous solution of d-y-1-'/''+5-p-8-11-h, and (
d) Continuously and quantitatively feeding a liquid anhydrous mixture of a liquid substituted succinic anhydride and an oil-in-water surfactant, and (C) water as necessary, to a mixer, and mixing. A paper sizing method characterized in that an aqueous dispersion produced in a machine is immediately, continuously and quantitatively added to pulp slurry, which is a papermaking raw material. (9) A water-soluble synthetic polymer having a cationic group is
The method for sizing paper according to claim 7, wherein the paper is an amphoteric acrylamide polymer. 00) The paper sizing method according to claim 9, wherein the amphoteric acrylamide polymer is a Hofmann decomposition reaction product of an acrylamide polymer. (11) The paper sizing method according to claim 9, wherein the amphoteric acrylamide polymer is a Mannich reaction product of an acrylamide polymer. 10. The paper sizing method according to claim 9, wherein the paper sizing method is a terpolymer of acrylamide, (meth)acrylic acid, and dialkylaminoalkyl (meth)acrylate. 03) The paper sizing method according to claim g, wherein the water-soluble polymer having a cationic group is polyethyleneimine, a derivative thereof, or a mixture of both. (1) The paper sizing method according to claim g, wherein the substituted succinic anhydride is a substituted cono-phosphoric anhydride having an alkenyl group or an alkyl group having a carbon number of g or more. 05) Oil-in-water type The surfactant is polyoxyethylene alkyl ether sulfate or its salt. Or a simple substance or Ω selected from polyoxyethylene alkylaryl ether sulfate or its salt.
The method for sizing paper according to claim g, which is a mixture of more than one species.