JPS59137599A - Internal additive for papermaking - 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 an internal additive for papermaking for addition to a pulp dispersion comprising a cationized polyvinyl alcohol containing a specific cationic structural unit.

A is the conventional paper making method. A method has been used in which a rosin-based sizing agent, filler, paper strength enhancer, etc. are added to the Luno dispersion, and then aluminum sulfate is added to fix the above-mentioned additions and processing to the pulp. However, since aluminum sulfate is acidic in this method, the resulting paper has disadvantages such as a decrease in strength, discoloration, decrease in printability, and corrosion of the equipment over time.

In contrast, cationic correction has been developed in which paper is made in a neutral or alkaline environment, and in this case, there is no need to use aluminum sulfate, and starch or polyacrylamide into which cationic groups have been introduced can be used industrially. being produced.

Neutral paper making performed in this manner has the following advantages over acid paper making.

(1) There is no need for surface treatment after paper making, which has a large economic effect.

(2) Since the yield of fine fibers, fillers, etc. is good, there is less pollution of white water and wastewater treatment is improved.

(3) Since there is no need to use aluminum sulfate, this cost reduction and disadvantages such as discoloration of paper, decrease in strength, corrosion of equipment, etc. that occur over time when using aluminum sulfate are eliminated.

(4) Since the cationic internal additive itself has excellent fixing properties to the pulp, the dry paper strength of the paper improves.

However, these cationic internal additives are still not said to be sufficient in terms of paper strength, size, and cost.

Polyvinyl alcohol (hereinafter abbreviated as PVA) has traditionally been used for paper surface sizing, warp sizing, and its film-forming properties.
Strength has been used effectively. Therefore, if it is possible to introduce cationic groups into PVA, it will be possible to increase paper strength, improve sizing properties, improve filler retention, improve F water resistance, reduce waste water, etc. by adding internally during paper making, etc. Despite expectations for this, the current situation is that it has not yet been put into practical use.

The following are disclosed as internal additives for papermaking using cationized PVA.

JP-A-56-14504 and JP-A-56-88413
In this issue, it is proposed to use cationized PVA obtained by saponifying a copolymer of a cationic monomer of (meth)acrylamide tyzo and vinyl acetate as a paper strength agent.

In JP-A-56-118997, quaternized PVA,
A paper manufacturing method is disclosed in which cationized PVA of acrylamide or other cationized PVA resin with a special structure is added to a pulp dispersion.

However, cationized PVA having an amide group or an ester group in its molecule may undergo hydrolysis during the saponification process, resulting in a decrease or disappearance of the cationic group. Therefore, it is expected that it will not be sufficiently effective as an internal polishing tool. Furthermore, quaternized PVA and cationized PVA with a special structure have significant drawbacks in reactivity and copolymerizability, and their effectiveness in industrial production and as internal additives remains questionable.

As a result of repeated research to compensate for these drawbacks, the present inventors have developed an internal additive for papermaking whose main component is a cationic copolymer having a stable ether bond in its cationic structural unit.
By adding it to the Gurzo dispersion, it improves the strength, size, and F.
It was discovered that paper with excellent aqueous properties and filler retention could be obtained, and the present invention was completed.

That is, the present invention is obtained by saponifying a copolymer of a polymerizable cation group-containing monomer corresponding to the general formula % and vinyl acetate. X is cte, B.
θ, ■e, etc... Dan anion, CH30SO3, C
kbC6H4SOse etc. (7) Yes'fM 7 = ,
t is selected from 7, but α○ is preferable in terms of safety and economy.

Examples of monomers having a cationic group include N-(3-
Allyloxy-2-hydroxypropyl)trimethylammonium chloride, N-(3-allyloxy-2-hydroxypropyl)triethylammonium chloride,
N-(3-allyloxy-2-hydroxy-2-methylglobyl)trimethylammonium chloride, N-(3
-allyloxy-2-hydroxy-2-methylglobil) triethylammonium chloride, N-(4-allyloxy-3-hydroxybutyl) trimethylammonium chloride, N=(4-allyloxy-3-hydroxybutyl) triethylammonium chloride, etc. .

The cationic group content of the cationized PVA in the present invention is 0.01 to 20 mol, preferably 0.1 to 12 mol.
○ range is suitable. 0.01 Unfavorable. The degree of polymerization is not particularly specified, but is selected from 300 to 2000.

The amount of cationized PVA added varies depending on the type of pulp, cationic group content, etc., but is 0.1 to 1 for i4 Ruso.
It is appropriately selected and used from 0% by weight. When using cationized PVA, there is no need to particularly adjust the pulp slurry, and the entire pg can be used.

Regarding the pulp used in the present invention, L-BKP, N
- It is mainly made of wood pulp such as BKP or vegetable fiber, and can be used alone or in combination. Additionally, fillers such as clay, kaolin, bentonite, and calcium carbonate, sizing agents such as paraffin, rosin, alkyl ketene timer, alkenyl succinic anhydride, and fixing agents such as anionic polyacrylamide are used in combination. I can't help it. The timing of adding cationized PVA is not particularly specified, but it is desirable to add it to the pulp slurry before the papermaking process.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, ``chi'' is % by weight.

Examples 1 to 8, Comparative Examples 1 to 3 Canadian Standard Ton Leanes 321-LB
Calcium carbonate (Nitto Funka Kogyo NITOREX-70) 30%/pulp solids in 3% slurry dispersion of KP,
After reacting the cationic chloride shown in Table 1 with N,N-dimethyl-trimethylene diamine, the product was quaternized with methyl chloride to obtain 4.

Table 2゜PVA K-17, K-24 that does not contain cationic groups
Haha - Most of the cationic copolymers used in the present invention showed no fixing properties, and Comparative Example 3 in which cationic acrylamide was copolymerized also did not show sufficient internal addition effects, whereas none of the cationic copolymers used in the present invention showed It shows an excellent internal addition effect.

Written amendment (method) % formula % 1. Indication of the case 1982 Patent Application No. 11099 2. Name of the invention Internal additive for papermaking 3. Person making the amendment Relationship with the case Patent applicant address Chiyoda, Tokyo 1-4-1-5, Yurakucho-ku, Detailed explanation of the invention column 6 of the specification subject to amendment, Table of contents of amendment 1 Cationized PVA has the structure/unit shown in vinyl acetate and Table 1 Examples 1 to 8. Each monomer was copolymerized and then saponified.

The cationized PVA of Comparative Example 3 was composed of acrylic acid chloride and N
, N-dimethyl-trimethylene diamine was reacted and then quaternized with methyl chloride.

Table 2 PVAK-17, K-24 that does not contain monocationic groups
showed almost no fixing properties, and Comparative Example 3 in which cationic acrylamide was copolymerized also did not show sufficient internal addition effects, whereas all of the original cationic copolymers used in the present invention showed It shows an excellent internal addition effect.

Patent applicant: Denki Kagaku Kogyo Co., Ltd. Procedural Amendment May 30, 1982 1. Case description: Patent Application No. 11099 of 1982. 2. Title of the invention: Internal temperature agent for paper making. 3. Person making the amendment. Relationship to the case Patent applicant Address: 1-4, 1-4, Yurakucho, Chiyoda-ku, Tokyo, Column 5 of the detailed description of the invention in the specification subject to the amendment, Contents of the amendment, page 3, lines 3-4 1 Arakawa Chemical corrects AP-30J to ``Separan AP-304 manufactured by Dow Chemical Company.

Claims (2)

[Claims] (1) An internal additive for papermaking made of cationized polyvinyl alcohol containing a cationic structural unit represented by the general formula %. (2) The internal additive for papermaking according to claim (1), wherein the cationized polyvinyl alcohol contains 0.01 to 20 moles of cationic structural units.