JPS5930993A - Stable papermaking size agent - 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 sizing agent for paper manufacturing.

More specifically, even if an acid anhydride and an emulsifier coexist for a long period of time, an excellent emulsion is produced during use, and by adding this to the paper stock, paper sizing treatment can be performed appropriately. The sizing agent is related.

Acid anhydrides (alkenylsuccinic anhydrides, dialkyl anhydrides, etc.) that covalently bond to the hydroxyl groups of cellulose fibers are usually used as internal sizing agents in neutral papermaking methods that use calcium carbonate as a filler. It is added to the stock in the form of an aqueous emulsion. This aqueous emulsion produces water-soluble polymers (cationized starch, oxidized starch).

Carboxymethyl cellulose, polyvinyl alcohol 6
), emulsifiers such as surfactants (polyethylene ethylene norbitane trioleate, polyoxyethylene sorbitol laurate, polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, etc.), and a high-speed mixer 2 high-pressure homogenizer. .

This is done by forcibly emulsifying in water using an emulsifying device such as an aspirator.

However, when these emulsifiers and acid anhydrides are mixed:
! 1 cannot be stored for more than several hours and the size effect is also reduced. Therefore, after mixing the acid anhydride and emulsifier, it must be used within a short time.

The inventors of the present invention have conducted extensive studies on paper-making sizing agents that do not have the above-mentioned drawbacks, and as a result have arrived at the present invention, which has the general formula % (2) (wherein R, and R2 are alkyl groups having 6 or more carbon atoms.

Alkenyl Aoi, aralkyl Aoi, or aralkenyl group, R
3 is an alkyl group, an alkenyl group, an aralkyl group, or an aralkenyl group, and n is an integer of 2 to 3. ) as an emulsifier to the acid anhydride (a) represented by the general formula % formula % (3) (wherein R4 is a residue of a polyoxine alkylene nonionic activator. Xl is R5-, R5C0-.

R5NHCO-, i: CO-Ql-COOMl], R5 is an alkyl group having 1 to 6 carbon atoms or an allyl group, Ql is a dicarboxylic acid residue, and M1 is a cation.

In the general formula (1) representing the acid anhydride (a), R1 is preferably a C12-25 linear or branched alkyl group or alkenyl group. Particularly good J is C1
2 to 25 alkenyl groups. n is preferably 2.

Specifically, the acid anhydrides include the following.

(1) Alkenylsuccinic anhydride Branched alkenylsuccinic anhydride [monoalkenylsuccinic anhydride (1-methyl-2-pentadecenylsuccinic anhydride, 1-ethyl-2-tetradecenylsuccinic anhydride) 1-propyl-2-F--lysocenylsuccinic anhydride.

1-propyl-2-pentadecenyl succinic anhydride, etc.), polyalkenyl succinic anhydride (poly(4-10)
Propylenylsuccinic anhydride, poly(3-8)butenylsuccinic anhydride.

poly(3-6) isobutenylsuccinic anhydride, etc.)],
Linear alkenylsuccinic anhydride (n-octadecenylsuccinic anhydride, inoctadecenylsuccinic anhydride, n
-hexadecenyl succinic anhydride, eicosenyl succinic anhydride, etc.] These acid anhydrides are produced by the reaction of linear or branched olefins having terminal or internal double bonds with maleic anhydride. It can be easily manufactured by

(2) Alkyl succinic anhydride, dodecyl succinic anhydride, n-hegisadenlucuccinic anhydride, etc. (3) Alkyl glutaric anhydride, dodecyl glutaric anhydride, n-hexadecyl glutaric anhydride, etc. Among these, alkenylsuccinic anhydrides are preferred from the viewpoint of handling properties such as viscosity and fluidity, and sizing performance, and particularly preferred are branched alkenylsuccinic anhydrides and mixtures of two or more thereof.

In general formula (2), R2 is general formula (1)
A similar group such as R1 can be opened. Further, R3 includes an alkyl group having 1 to 25 carbon atoms, an alkenyl group having 1 to 25 carbon atoms, an aralkyl group, or an aralkenyl group,
Specific examples include argyl groups and alkenyl groups of c1-5 as listed for R1.

Examples of the compound represented by the general formula (2) include distearic anhydride, cybalmitic anhydride, acetic stearic anhydride, and the like.

In the general formula (3), R4 is a residue of a polyoxyalkylene nonionic surfactant and IJ is a group obtained by removing a hydroxyl group from the nonionic surfactant.

As the compound (b) represented by the general formula (3), the general formula % formula % (4) (In the formula, R6 is an active hydrogen-containing compound residue.

A1 is an alkylene group having 2 to 4 carbon atoms. nl is an integer greater than or equal to ], Xl is R5-, R5C0-, R5NHCO-
Also, -〇〇-Q, -COOM, R5 is an alkyl group having 1 to 6 carbon atoms or an allyl group, Q is a dicarboxylic acid residue, and M1 is a cation/. ml is an integer from 1 to 8. ), and the hydrogen-containing compound residue refers to a group obtained by removing active hydrogen from an active hydrogen-containing compound. This active hydrogen-containing compound usually has 8 to 8 carbon atoms.
Alkylnaphthol having as few as 6 or more than 12 alkyl groups (t: alkylnaphthol; styrenated phenols, specifically monocyclic phenols (usually having 8 to 1 carbon atoms)
alkylphenols or naphthols having at least one alkyl group of 12) and/or polycyclic phenols (phenols having two or more aromatic rings: for example phenylphenol).

cumylphenol, alkylnaphthol, etc.) and styrene; aliphatic alcohols usually having 6 to 20 carbon atoms; saturated or unsaturated fatty acids usually having 10 to 20 carbon atoms; polyhydric alcohols or their intramolecular anhydrides ester of a substance and a fatty acid having usually 10 to 20 carbon atoms; polyhydric phenol: polyamine; polycarboxylic acid; oxycarboxylic acid;
Examples include alkylamines, which usually have 10 to 20 carbon atoms; alkylmercaptans, which usually have 10 to 20 carbon atoms; and alkylolamides.

R5 is an alkyl group usually having 1 to 6 carbon atoms (methyl group,
(ethyl group, propyl group, isopropyl group, butyl group, pentyl group, etc.) or allyl group. If R5 is an alkyl group with a carbon number larger than 6, it is rumored that e, tf mainly y/
, Buddha T■j.

The dicarboxylic acid residue of Ql refers to a group obtained by removing two carboxyl groups from a dicarboxylic acid. Examples of the dicarboxylic acid include saturated or unsaturated aliphatic or aromatic dicarboxylic acids having from +8 carbon atoms, such as maleic acid, itaconic acid, and succinic acid.

The cation of Ml is H or alkali metals (Na,
etc.).

nl is an integer of 1 or more, preferably an integer of 2 to 50.

Particularly preferably, it is an integer of 5 to 40. m is an integer from 1 to 8. .

Polyoxyalkylene nonionic surfactant Rsfi A10 constituting residue R4 of compound (b) H,1
As for ml, the following can be mentioned.

(1) Polyoxyalkylene alkylaryl ether A of an alkylphenol or alkylnaphthol having at least one alkyl group usually having 8 to 12 carbon atoms.
O adduct (the number of moles of AO added is usually 2 to 50, preferably 5 to 20; for example, nonylphenol E OA81
, nonylphenol E□ (101, octylphenol EO (II, dodecylphenol E 000) The number indicates the number of moles of AO added.] (2) Polyoxyalkylene styrenated arylether monocyclic phenol (usually having at least one alkyl group having 8 to 12 carbon atoms), nor, etc.) or polycyclic phenol A reaction product of (a phenol having two or more aromatic rings, such as phenylphenol, cumylphenol, alkylnaphthol, etc.) and 1 to 20 moles of styrene (
E
0(25) P O(3) , styrenated phenol EO00), etc. [the above styrenated phenol P OfIO) E O(25) P O(3) is a mixture of phenol and styrene in a molar ratio of 1 : 2010 mol of styrenated phenol obtained by reacting with 2, E O
Compounds having a structure in which 25 moles/P03 moles are added in order are shown. The same applies below] (3) Polyoxyalkylene algyl ether aliphatic alcohol (usually has 6 carbon atoms)
~20° AO adduct (A,
The number of moles of O added is usually 2 to 50. Preferably 5-20
); t: For example, c6-2o Ziegler alcohol E O
f81, octyl alcohol PiO(IQ).

Coconut oil reduced alcohol E O10+ (4) AO adduct of polyoquine alkylene fatty acid ester fatty acid (carbon number usually 10 to 20) (number of moles of AO added is usually 2 to 50, preferably 5"-20); t: and For example, stearic acid EO (151゜lauric acid EO (
10+, oleic acid E O1151, etc. (5) Polyoquine alkylene polyhydric alcohol fatty acid ester polyhydric alcohol or its intramolecular anhydride (ethylene glycol, propylene glycol, glycerin, trimethylolpropane.

AO adducts of esters of pentaerythritol, sorbitan, sorbitol, sima sugar, etc.) and fatty acids (usually 10 to 20 carbon atoms) (the number of moles of AO added is usually 2 to 5)
0. Preferably 5-40); For example, sorbitol laurate EO (10), human oil EO (30)
(6) Polyoxyalkylene polyol The above-mentioned polyhydric alcohols, polyhydric phenols (bisphenols, etc.), polyamines (alkylene diamines, polyalkylene polyamines, arylene diamines, etc.), polycarboxylic acids (maleic acid, succinic acid, etc.), oxocarboxylic acids ( lysirucic acid, etc.) (the number of moles of AO added is usually (~~) preferably E~+Ot: 1 usually 10~500 in the case of an adduct of AO on 1st stock). 10-400); t: For example, EO adducts (EO is 9 in the molecule usually 10-80% by weight.

Preferably it accounts for 40 to 80% by weight. ); For example, P
8040 wt% adduct of PG (MW1200.),
PPG (MW 1750) no EO50 weight adduct, glycerin EO1PO (weight ratio 1:1) random adduct (molecular weight 2800).

BO adduct of polyoxypropylene alkylene diamine [Tetronic 304,704°707 (manufactured by Wyandotte)], bisphenol A EO+8], etc. (7) Polyoxyalkylene alkylamine AO adduct of alkyl amine having 10 to 20 carbon atoms (The number of moles of AO added is usually 2 to 50, preferably 5 to 40); for example, stearylamine E OtlO) (8) Polyoquine alkylene alkyl mercaptan A of an alkyl mercaptan having usually 10 to 20 carbon atoms,
O adduct (the number of moles of AO added is usually 2 to 50, preferably 5 to 2); for example, cetyl mercaptan B O00
) (9) Alkylolamide nonionic surfactant general formula (in the formula, nl is a hydrocarbon group residue having 5 to 24 carbon atoms).

R'' is (A, 10) n'Hj or carbon number 1-18
is a hydrocarbon group. A1 is an alkylene group having 2-4 carbon atoms; m' is an integer of 1 or more; nL is O; i7: is an integer of 1 or more; m'+n'-1 to 100; ), specifically reaction products of fatty acids usually having 6 to 25 carbon atoms and alkanolamines, and their O adducts; for example, lauric acid jetanolamide EOt41 polyoxyalkylene nonionic surfactants Among them, polyoxyalkylene alkylene aryl ether, polyoxine alkylene styrenated aryl ether, polyoxine alkylene alkyl ether and polyoxyalkylene fatty acid ester are preferred in view of emulsifying properties and size effects.

Compound (b) represented by general formula (3) can be produced by reacting a polyoxyalkylene nonionic surfactant with an alkyl or allylating agent, an acylating agent, or an alkyl or allyl carbamoylating agent. I can do it. Examples of the alkyl or allylating agent include alkyl halides (methyl chloride, ethyl chloride, etc.), dialkyl sulfates (dimethyl sulfate, diethyl sulfate, etc.), allyl halides (allyl chloride, allyl bromide, etc.), and the like. As the acylating agent, monocarboxylic acids having 2 to 7 carbon atoms, dicarboxylic acids having 4 to 8 carbon atoms, anhydrides thereof, and halides thereof [
(anhydrous) acetic acid, (anhydrous) propionic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (anhydrous) succinic acid, acetyl chloride, propionyl chloride, etc.).

As the alkyl or allyl carbamoylating agent, alkyl monoisoneanate (methylisonanate, ethylynoneanate, etc.), allyl monoisocyanate-1
・And so on.

The compound represented by the general formula (3) is an AO adduct of a monohydric alcohol [R50H], a fatty acid having 10 to 20 carbon atoms, and a dicarboxylic acid having + to 8 carbon atoms listed in the section of the acylating agent above. or its anhydrous form.

Alternatively, it can also be produced by reacting with a carbonate ester (tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisonanate, etc.).

Specific examples of the compound (b) represented by the general formula (3) are as follows.

) Alcokynes of polyoquine alkylene nonionic surfactants, nonylphenol EO (river) methoxylates, nonylphenol EOa ethoxylates, nonylphenol Fi
O(In) propylene oxide.

Styrenated phenol PO (kawa) E O (25
) Methoxylated products, etc. (2) Acyloxylated polyoxyalkylene nonionic surfactants Nonylphenol B Ot+01 acetylated product, cetyl alcohol EOαO) Acetylated product, styrenated phenol B O(7) P O(2) Acetylated product .

Stearic acid E O (151 acetylated product, styrene (
2) acetylated phenol E O(20) P O(3).

Sorbitan monooleate B O(]σ acetylation (3
) Alkylcarbamoylate of polyoxyalkylene nonionic surfactant Nonylphenol B Oflo) Methylcarbamoylate, stearic acid EOi+51 methylcarbamoylate, octylphenol EOf151 methylcarbamoylate, etc. Ionic surfactant (c) and/or anionic surfactant (
d) can be used in combination. As for (c), ester type nonionic surfactants having active hydrogen [polyhydric alcohol fatty acid esters, such as polyhydric alcohols or their intramolecular anhydrides (glycerin, pentaerythritol, sorbitol).

t: For example, lauric acid monoglyceride, sorbitan stearic acid (mono.

Replace the active hydrogen of the compound [for example, with this activator and the above-mentioned argyl or allylic compound, acylating agent, alkyl or allyl carbamoylate] and ester nonionic surfactants (such as sorbitan stearate triester and sorbitan oleate triester 6) that do not have active hydrogen. 1t: Sulfonate type anionic surfactant.

Sulfate salt type or carboxylate type anionic surfactants are preferred. Examples of the anionic surfactant include alkaline earth metal salts of sulfonic acids or sulfuric esters and/or their alkali metal salts (Na salts, salts, etc.) described in Japanese Patent Application No. 57-100974, Examples include alkali metal salts of 6 to 20 (preferably 12 to 18) saturated or unsaturated fatty acids.

Emulsifier [(b) and optionally (C), (d)
The addition ratio of () to the acid anhydride (a) is usually 1 to 30% by weight, preferably 5 to 20% by weight. If the addition rate is less than 1% by weight, it is difficult to obtain a good emulsion. Moreover, when it exceeds 30% by weight, emulsification is good.

Scythe performance is drastically reduced.

The addition ratio of (1) as an emulsifier to the acid anhydride (a) can be varied depending on the type of (a), the type and size performance of the emulsifying device used, but it is usually 0.05 to 20. % by weight, preferably from 1 to 15 weights. If the addition rate is less than 0.055% by weight, it is difficult to obtain a good emulsion, and if it exceeds 20% by weight, the emulsification is good but the sizing performance deteriorates.

The weight ratio of (b) and (c) is usually 100:D and O:tO (l, preferably Ioo:o
Furthermore, the tonnage weight ratio of [(b) and optionally (C)] and (d) is usually 1.1110.
:::O from uo:$On, preferably 100:
FiOgara s'o: to. In the former and latter, if the ratio is outside the above range, it is difficult to obtain a good emulsion.

(a) and (b) [as necessary (C), (d)
) Methods for obtaining emulsions include (a), (b)
The simplest method is to homogeneously mix (C) and (d)) if necessary and disperse the mixture in water to obtain an emulsion. This is preferable because a small size can be obtained and the size effect for one sheet of paper is also high. Also (a) and (b) or (C),
(d) was mixed uniformly and dispersed in water.9 Next, (C),
An emulsion can also be obtained by adding (d) or (b). mixture.

Emulsification can be performed using an emulsifying device such as a homomixer, high-pressure homogenizer, ultrasonic homogenizer, or turbine mixer.

Emulsification Level 1 In addition to the size reduction of the present invention, polyoxyalkylene nonionic surfactants and ester nonionic surfactants can also be used in combination.

The sizing agent of the present invention is used for paper manufacturing.

The papers used herein include sheet products and molded articles made from fibrous cellulosic materials derived from natural and synthetic sources.

Specifically, general paper such as printing, writing paper, and packaging paper;
Special paper; paperboard, etc. Also, wall materials.

It also includes building materials such as ceiling materials. Also cellulosic substances and synthetic products (t: e.g. polyamides).

Also included are sheet products and molded products made from combinations of polystyrene, polyester, polyacrylic resin fibers and mineral fibers derived from asbestos, glass, etc.

It also includes sheet products and molded products made solely from the above synthetic products.

When producing paper using the sizing agent of the present invention, various cationic fixing agents are used to fix the sizing agent to the bulb fibers. Substances that can be used as cationic fixatives include:

Inorganic compounds of polyvalent metal type such as alum, aluminum chloride, sodium altriphosphate and various cationized starches, polyamine polyamide-ebichlorohydrin resins,
Examples include cationic polymers such as cyclized polymers of diallylammonium halides, polyvinylpyridine, and various cationized polyacrylamides.

1. How much of the glue agent of the present invention should be used in papermaking?

The amount usually ranges from 0.05 to 5.0% of the dry weight of the pulp in the final pulp or web, depending to a large extent on the type of pulp used, the operating conditions and the end use of the paper. If necessary, other internal sizing agents may be added, such as rosin and petroleum resin.

Even when used in combination with alkyl ketene dimer, paraffin wax, etc.)

This sizing agent is suitable for pulp, headboard, waste, beater,
Can be added to the pulp while in the hydropulper or stock chest.

Any cationic adhesion promoter can be added to the raw material, ie, pulp slurry, at the same time, before, or after the addition of the size agent. However, for optimum distribution it is best added after the sizing agent.

The wet paper after paper-making with the lathe cutter of the present invention added is 70~
It is dried at a normal temperature range of 150°C.

It should be noted that the paper sized with the sizing agent of the present invention can contain all kinds of pigments and fillers. The analogy is ゛, Carbonic Power Runum.

Examples include talc, clay, titanium white, and white clay 2 gypsum.

The paper sizing agent of the present invention has good long-term storage stability,
It also has the effect of making a stable emulsion during use. In other words, the present invention, in which the emulsifier (b) is uniformly mixed with the acid anhydride (a), produces a uniform and stable aqueous solution without losing its emulsifying function when used for a long period of time, even if left unused for 6717 months. Generate emulsion. As a result, a mixture of acid anhydride (a) and emulsifier (b) can be stored in a stock tank, and the conventional disadvantage of having to use it up within a short period of time has been overcome, making it easier to handle industrially. be.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 10 and Comparative Examples 1 to 3 In the present invention shown in Table 1, alkenylsuccinic anhydride derived from a straight-chain internal olefin having 14 to 20 carbon atoms and maleic anhydride was used. Emulsifier (Example 1~
10) and conventional emulsifiers (Comparative Examples 1 to 3) were uniformly blended at 5% by weight, and then left at a temperature of 30°C for 5 hours. % and emulsify with a high-speed experimental mixer.Note (2)
Note (3) Paper making t: The Steckcht-Zeiss degree test results of neutral paper are also shown in Table-1.

Conventional sizing agents containing emulsifiers hardly emulsify and have almost no size effect; however, the sizing agent of the present invention exhibits a good emulsification state with a particle diameter of 5 to 8μ, and has a good size effect. showed that.

Displays particle diameters distributed over 90 meters.

Note (2) Paper making conditions Valve LBKP 100% 430c, s, f.

Basis weight 70g/777' Ash content 20 Filler Heavy calcium carbonate fixer Cationized starch paper machine Tarapi square paper machine Drying 105℃, 2 portions (3) Measurement method JTS P-81, 22 Note (4) )
The addition rate (weight %) of the sizing agent to the pulp is shown.

Patent applicant: Sanyo Chemical Industries, Ltd.

Claims (1)

[Claims] 1. General formula) % formula % (2) (In the formula, R1 and R2 are an alkyl group, an alkenyl group, an aralkyl group, or an aralkenyl group having 6 or more carbon atoms, R3
is an alkyl group/alkenyl group, an aralkyl group or an aralkenyl group. n is an integer of 2 to 3. ) Acid anhydride (a)
General formula % formula % (31 (wherein, R4 is a residue of a polyoxyalkylene nonionic surfactant, Xl is R5-2R5CC1-,
R5NHCO-, or -CO-Q. -C00M, R5 is an alkyl group or allyl group having 1 to 6 carbon atoms, and Ql is a dicarboxylic acid residue 1M1
is a cation. m] is an integer from 1 to 8