JPH0123599B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an internal 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 paper stock, paper sizing treatment can be performed appropriately. The internal sizing agent for paper making that can be made is related to this. 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 processes that use calcium carbonate as a filler in aqueous emulsions. It is added to paper stock in the form of This aqueous emulsion is made by using water-soluble polymers (cationized starch, oxidized starch, carboxymethyl cellulose, polyvinyl alcohol, etc.), surfactants (polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol laurate, polyoxyethylene alkylaryl ether, This is done by forcibly emulsifying in water using an emulsifier such as oxyethylene alkyl ether (oxyethylene alkyl ether, etc.) and an emulsifying device such as a high-speed mixer, high-pressure homogenizer, or aspirator. However, if these emulsifiers and acid anhydrides are mixed together, they cannot be stored for even 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 arrived at the present invention as a result of extensive research into paper sizing agents that do not have the above-mentioned drawbacks.
That is, the present invention has the general formula and/or (In the formula, R ₁ and R ₂ are alkyl groups having 6 or more carbon atoms,
alkenyl group, aralkyl group or aralkenyl group, R ₃ is an alkyl group, alkenyl group, aralkyl group or aralkenyl group, n is an integer of 2 to 3; ) to the acid anhydride (a) represented by the general formula R ₆ −[(A ₁ O) _o1 −X ₁ ] _n1 (3) (wherein, R ₆ is an active hydrogen-containing compound residue) as an emulsifier.
A ₁ is an alkylene group having 2 to 4 carbon atoms, n ₁ is an integer of 1 or more, X ₁ is R ₅ —, R ₅ CO—, R ₅ NHCO— or —CO—Q ₁ —COOM ₁ , and R ₅ has 1 or more carbon atoms
6 alkyl group or allyl group. Q ₁ is a residue of a saturated or unsaturated aliphatic or aromatic dicarboxylic acid having 4 to 8 carbon atoms, and M ₁ is a cation.
m ₁ is an integer from 1 to 8. ) Compound (b)
This is a stable internal sizing agent for paper manufacturing. In the general formula (1) representing the acid anhydride (a), R ₁ is preferably a C _12-25 linear or branched alkyl group or alkenyl group. Particularly preferred is a _C12-25 alkenyl group. n is preferably 2. Specific examples of acid anhydrides include the following. (1) Alkenylsuccinic anhydride Branched alkenylsuccinic anhydride [monoalkenylsuccinic anhydride (1-methyl-2-pentadecenylsuccinic anhydride, 1-ethyl-2-tetradecenylsuccinic anhydride] substance, 1-propyl-
2-tridecenylsuccinic anhydride, 1-propyl-2-pentadecenylsuccinic anhydride, etc.), polyalkenylsuccinic anhydride (poly(4-10) propylenylsuccinic anhydride, poly(3-3) ~8) Butenylsuccinic anhydride, poly(3
~6) Isobutenyl succinic anhydride, etc.)], linear alkenyl succinic anhydride [n-octadecenyl succinic anhydride, isooctadecenyl succinic anhydride, n-hexadecenyl succinic anhydride] Acid anhydrides, n-hexadecenylsuccinic anhydride, eicosenylsuccinic anhydride, etc.) These acid anhydrides are linear or branched olefins and maleic anhydrides that have double bonds at their ends or internally. It can be easily produced by reaction with an acid. (2) Alkyl succinic anhydride Dodecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. (3) Alkyl glutaric anhydride Dodecyl glutaric anhydride, n-hexadecyl glutaric anhydride, etc. Preferred among these From the viewpoint of handling properties such as viscosity and fluidity, and size performance, alkenylsuccinic anhydrides are preferred, and branched alkenylsuccinic anhydrides and mixtures of two or more thereof are particularly preferred. In general formula (2), R ₂ is R ₁ of general formula (1)
A similar group can be mentioned. Examples of R ₃ include 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, specifically those listed for R ₁ and an alkyl group having _{1 to 5} carbon atoms. and alkenyl groups. Examples of the compound represented by the general formula (2) include distearic anhydride, dipalmitic anhydride, acetic stearic anhydride, and the like. In the compound represented by the general formula (4), the active hydrogen-containing compound residue of R ₆ refers to a group obtained by removing active hydrogen from the active hydrogen-containing compound. Examples of the active hydrogen-containing compound include alkylphenols or alkylnaphthols having at least one alkyl group usually having 8 to 12 carbon atoms; styrenated phenols, specifically monocyclic phenols (usually having 8 to 12 carbon atoms);
alkylphenol or naphthol having at least one alkyl group) and/or polycyclic phenol (phenol having two or more aromatic rings, such as 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; Esters of polyhydric alcohols or their intramolecular anhydrides with fatty acids usually having 10 to 20 carbon atoms; Polyphenols; polyamines; polycarboxylic acids; oxycarboxylic acids; alkylamines usually having 10 to 20 carbon atoms; alkyl mercaptans usually having 10 to 20 carbon atoms; alkylolamides. R ₅ is usually an alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.) or an allyl group. When R ₅ is an alkyl group having more than 6 carbon atoms, the emulsifying property decreases. Q ₁ is a residue of a saturated or unsaturated aliphatic or aromatic dicarboxylic acid having 4 to 8 carbon atoms, and examples of this dicarboxylic acid include maleic acid,
Examples include itaconic acid and succinic acid. Examples of the cation of M ₁ include H or alkali metals (Na, K, etc.). n ₁ 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 1~
It is an integer of 8. Polyoxyalkylene nonionic surfactant R ₆ [-(A ₁ O))- _o1 constituting the residue R ₄ of compound (b)
H] Examples of _n1 include the following. (1) Polyoxyalkylene alkylaryl ether AO adduct of alkylphenol or alkylnaphthol having at least one alkyl group having usually 8 to 12 carbon atoms (the number of moles of AO added is usually 2 to 50, preferably 5 to 20; For example, nonylphenol EO (8), nonylphenol EO (10),
Octylphenol EO (10), dodecylphenol EO (10) [In the above and below, AO has 2 carbon atoms.
~4 alkylene oxide, EO represents ethylene oxide, and PO represents propylene oxide. The number in parentheses indicates the number of moles of AO added. ] (2) Polyoxyalkylene styrenated aryl ether Monocyclic phenol (such as a phenol having at least one alkyl group, usually having 8 to 12 carbon atoms) or polycyclic phenol (such as a phenol having two or more aromatic rings, such as phenylphenol) , cumylphenol, alkylnaphthol, etc.) and 1 to 20 moles of styrene (referred to as styrenated phenols); For example, styrenated phenol PO
(10)EO(25)PO(3), styrenated phenol EO
(10), etc. [the above styrenated phenol PO (10)]
EO(25)PO(3) indicates a compound having a structure in which 10 moles of PO, 25 moles of EO, and 3 moles of PO are sequentially added to styrenated phenol obtained by reacting phenol and styrene at a molar ratio of 1:2. Same below. ] (3) Polyoxyalkylene alkyl ether AO adduct (AO
The number of moles added is usually 2 to 50, preferably 5 to 50.
20); For example, C _6-20 Ziegler alcohol EO
(8), octyl alcohol EO (10), coconut oil reduced alcohol EO (10) (4) Polyoxyalkylene fatty acid ester AO adduct of fatty acid (usually 10 to 20 carbon atoms) (the number of moles of AO added is usually 2 to 20) 50, preferably 5 to 20); for example, stearic acid EO (15), lauric acid EO (10), oleic acid EO (15), etc. (5) Polyoxyalkylene polyhydric alcohol fatty acid ester Polyhydric alcohol or its intramolecular anhydride AO adducts of esters of substances (ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, sucrose, etc.) and fatty acids (usually 10 to 20 carbon atoms) (number of moles of AO added) is usually 2 to 50, preferably 5 to 40); for example,
Sorbitol laurate EO (10), castor oil (30) (6) Polyoxyalkylene polyols The above polyhydric alcohols, polyhydric phenols (bisphenols, etc.), polyamines (alkylene diamines, polyalkylene polyamines, arylene diamines, etc.), polycarbonate AO adducts such as acids (maleic acid, succinic acid, etc.), oxycarboxylic acids (ricinolenic acid, etc.) (the number of moles of AO added is usually 2 to 50), preferably 5 to 40, but adducts of two or more types of AO case, usually 10-500,
For example, polyethylene glycol (average molecular weight () 200-2000), polypropylene glycol (hereinafter referred to as PPG).
EO adduct (EO usually accounts for 10 to 80% by weight, preferably 40 to 80% by weight in the molecule) with an average molecular weight () of 900 to 2900; for example, PPG
(1200) EO40 wt% adduct, PPG (
50 wt% adduct of EO (1750), glycerin EO,
PO (weight ratio 1:1) random adduct (molecular weight
2800), EO adduct of polyoxypropylene alkylene diamine [Tetronik 304, 704, 707
(Manufactured by Wyandot) Bisphenol AEO (8)
etc. (7) Polyoxyalkylene alkylamine AO adduct of an alkylamine 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 EO (10) (8 ) Polyoxyalkylene alkyl mercaptan An alkyl mercaptan with usually 10 to 20 carbon atoms.
AO adduct (the number of moles of AO added is usually 2 to 50,
Preferably 5 to 20); for example, cetyl mercaptan EO(10) (9) Alkylolamide nonionic surfactant general formula (In the formula, R' is a hydrocarbon group residue having 5 to 24 carbon atoms, and R'' is (A ₁ O)n'H or a hydrocarbon group having 1 to 18 carbon atoms. _{A 1} is a hydrocarbon group having 2 to 18 carbon atoms. (4) alkylene group, m' is an integer of 1 or more, n' is an integer of 0 or 1 or more, m'+n' = 1 to 100.) Specifically, the compound usually has 6 to 6 carbon atoms. Reaction products of 25 fatty acids and alkanolamines and their AO adducts; for example, lauric acid diethanolamide EO (4) Among these, in consideration of emulsifying properties and size effects, (1) polyoxyalkylene is preferable. Alkylaryl ether, (2) polyoxyalkylene styrenated aryl ether, (3) polyoxyalkylene alkyl ether, and (4)
It is a polyoxyalkylene fatty acid ester. 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. Can be done. 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.]
etc. can be mentioned. Examples of the alkyl or allyl carbamoylating agent include alkyl monoisocyanates (methyl isocyanate, ethyl isocyanate, etc.), allyl monoisocyanate, and the like. In addition, the compound represented by the general formula (3) is an AO adduct of monohydric alcohol [R ₅ OH], a fatty acid having 10 to 20 carbon atoms, and a compound having 4 carbon atoms as mentioned above in the section of the acylating agent.
It can also be produced by reacting dicarboxylic acids or anhydrides thereof, or diisocyanates (tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.). Specific examples of the compound (b) represented by the general formula (3) are as follows. (1) R ₆ - [(A ₁ O) _o1 ] Alkoxylated product of _n1 Nonylphenol EO(10) methoxylated product, nonylphenol EO(10) ethoxylated product, nonylphenol EO(10) propyloxylated product, styrene (2)
phenol PO(10)EO(25) methoxylated product, etc. (2) R ₆ ― [(A ₁ O) _o1 ] _n1 acyloxylated product Nonylphenol EO(10) acetylated product, cetyl alcohol EO(10) acetylated product, styrene (2)
phenol EO(7)PO(2) acetylated product, stearic acid EO(15) acetylated product, styrenated phenol EO(20)PO(3) acetylated product, sorbitan monooleate EO(10) acetylated product, Sorbitan monooleate EO (35) acetylated product,
Nonylphenol EO (10) propionyl oxide, etc. (3) R ₆ - [(A ₁ O) _o1 ] _n1 alkyl carbamoylate Nonylphenol EO (10) methyl carbamoylate, stearic acid EO (15) methyl carbamoylate, octyl Phenol EO (15) methyl carbamoylate, etc. (b) can be used as necessary with other nonionic surfactants (c) and/or anionic surfactants (d) that do not have active hydrogen {provided that X ₁ is -CO-Q ₁ --excluding the compound (b) represented by general formula (3) which is COOM ₁ } can be used. (c) is an ester type nonionic surfactant having active hydrogen [polyhydric alcohol fatty acid ester, such as polyhydric alcohol or its intramolecular anhydride (glycerin, pentaerythritol, sorbitol, sorbitan, etc.) and carbon number usually 10 to 20 partial esters with fatty acids; for example, lauric acid monoglyceride, sorbitan stearic acid (mono- or sesqui)ester, sucrose stearic acid mono- or di)ester], in which the active hydrogen is replaced by X ₁ [for example, this active agent and [obtained by reacting the above alkyl or allylating agent, acylating agent, alkyl or allyl carbamoylating agent]; and ester nonionic surfactants that do not have active hydrogen (sorbitan stearate triester, sorbitan olein); acid triesters, etc.). Examples of the anionic surfactant include sulfonate type, sulfate ester salt type, and carboxylate type anionic surfactants. Sulfonate type anionic surfactants include alkali (earth) metal salts of alkylbenzenesulfonic acids such as Ca dodecylbenzenesulfonate, alkali (earth) metal salts of α-olefin sulfonates, and 2-ethylhexylsulfosuccinates. Sulfosuccinate alkali (earth) metal salts such as Ca salts, (alkyl)naphthalenesulfonic acid alkali (earth) metal salts such as diisopropylnaphthalenesulfonic acid Ca salts, (alkyl)naphthalenesulfonic acid alkali (earth) metal salts formalin condensates, alkanesulfonic acid alkali (earth) metal salts such as Ca tetradecylsulfonate, ligninsulfonic acid alkali (earth) metal salts, fatty acid amidosulfonic acid alkali (earth) metal salts, and petroleum sulfonic acids. Examples include alkali (earth) metal salts. Sulfate ester salt type anionic surfactants include alkyl sulfate ester alkali (earth) metal salts such as lauryl alcohol sulfate ester Ca salt, and polyoxyalkylene sulfate ester alkali (earth) metal salts such as cetyl alcohol EO(8) sulfate ester Ca salt. Polyoxyalkylene aryl ether sulfate ester alkali (earth) metal salts such as nonylphenol EO(2) sulfate ester Ca salt, coconut oil fatty acid monoglyceride sulfate ester
Sulfate ester alkali (earth) metal salts of higher fatty acid esters such as Ca salts, higher fatty acid alkylolamide sulfate esters alkali (earth) metal salts such as coconut oil fatty acid monoethanolamide sulfate ester Ca salts, sulfated oils, high Examples include sulfated oils, sulfated fatty acid esters, alkali (earth) metal salts of sulfated fatty acids, and alkali (earth) metal salts of sulfated olefins such as sulfated Ca salts of α-olefins having 12 to 18 carbon atoms. . As a carboxylate type anionic surfactant,
Examples include alkali metal salts of saturated or unsaturated fatty acids having usually 6 to 20 carbon atoms (preferably 12 to 18 carbon atoms). The addition ratio of the emulsifier [(b) and optionally (C), (d)] 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, if it exceeds 30% by weight, emulsification is good, but the size performance is significantly reduced. Also, the addition ratio of (b) as an emulsifier to acid anhydride (a) can be varied depending on the type of (a), the type and size performance of the emulsifier used,
Usually 0.05-20% by weight, preferably 1-15%
Weight%. If the addition rate is less than 0.05% by weight, it is difficult to obtain a good emulsion, and if it exceeds 20% by weight, the emulsification is good but the size performance deteriorates. Also, the weight ratio of (b) and (c) is usually from 100:0.
The ratio is 50:500, preferably 100:0 to 70:30. Furthermore, the weight ratio of [(b) and optionally (c)] and (d) is usually 100:20 to 20:800, preferably 100:50 to 50:50. In the former and latter, if the ratio is outside the above range, it is difficult to obtain a good emulsion. The method for obtaining the emulsion of (a) and (b) [(c), (d) as necessary] is to uniformly mix (a), (b) [(c), (d) as necessary], A method of obtaining an emulsion by dispersing the mixture in water is the simplest method, requires a small amount of emulsifier, produces a small particle size of the emulsion, and is preferred because it has a high size effect on paper. Also, by uniformly mixing (a) and (b) or (c) and (d),
An emulsion can also be obtained by dispersing it in water and then adding (c), (d) or (b). Mixing and emulsification can be performed using an emulsifying device such as a homomixer, high-pressure homogenizer, ultrasonic homogenizer, or turbine mixer. In addition to the sizing agent of the present invention, a polyoxyalkylene nonionic surfactant or an ester nonionic surfactant can also be used in emulsification. The sizing agent of the present invention is used for paper manufacturing. The papers used here include sheet products and molded articles made from fibrous cellulosic materials derived from natural and synthetic resources, including general papers such as printing, writing paper, and packaging paper; specialty papers; ; paperboard, etc. It also includes building materials such as wall materials and ceiling materials. Also sheet products made from a combination of cellulosic materials and synthetics (e.g. polyamide, polystyrene, polyester, polyacrylic fibers and mineral fibers derived from asbestos, glass, etc.);
and molded articles are also included. It also includes sheet products and molded products made solely from the above synthetic products. When manufacturing paper using the sizing agent of the present invention, various cationic fixing agents are used to fix the sizing agent to the pulp fibers. Substances that can be used as cationic adhesion promoters include inorganic compounds of the polyvalent metal type such as alum, aluminum chloride, sodium aluminate, and various cationized starches, polyamine polyamide-epichlorohydrin resins, cyclized diallylammonium halides, etc. Polymers, polyvinylpyridine, various cationic polyacrylamides, and other cationic polymers. In papermaking, the amount of the sizing agent of the present invention to be used depends to a large extent on the type of pulp used, the operating conditions and the intended end use of the paper, but typically ranges from 0.05 to 5.0 of the dry weight of the pulp in the final sheet or web.
The amount is in the range of %. If necessary, other internal sizing agents such as rosin, petroleum resin, alkyl ketene dimer, paraffin wax, etc. may be used in combination. The sizing agent can be added to the pulp while it is in the headbox, beater, hydropulper or stockist. 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. After internally adding the sizing agent of the present invention and making paper, the wet paper is dried at a normal temperature range of 70 to 150°C. It should be noted that the sizing agent of the present invention can contain all kinds of pigments and fillers in the paper to be sized. Examples include calcium carbonate, talc, clay, titanium white, white clay, and gypsum. The internal sizing agent for paper manufacturing of the present invention has good long-term storage stability and has the effect of being able to create a stable emulsion during use. In other words, the sizing agent of the present invention, which is a uniform mixture of acid anhydride (a) and emulsifier (b), produces a uniform and stable aqueous emulsion without losing its emulsifying function even when stored for a long period of time, for example, 6 months. generate. As a result, the 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 time is overcome, making it easy to handle industrially. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Inventions 1 to 10 and Comparative Examples 1 to 3 Emulsifiers in the invention shown in Table 1 for alkenylsuccinic anhydrides derived from (linear) internal olefins having 14 to 20 carbon atoms and maleic anhydride. (Examples 1-10) and conventional emulsifier (Comparative Example 1)
After uniformly blending 5% by weight of each of ~3), the mixture was left at a temperature of 30°C for 5 hours. Each formulation was then diluted with water to 0.5% by weight and emulsified using a high-speed laboratory mixer. Table 1 also shows the test results for the particle size of the emulsion Note (1) and the Steckigt size degree Note (3) of neutral paper Note (2) made with this emulsion added internally. Sizing agents containing conventional emulsifiers hardly emulsify and exhibit almost no sizing effect, but the sizing agent of the present invention showed a good emulsification state with a particle size of 0.5 to 8 μm and a good sizing effect.

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Claims (1)

[Claims] 1. General formula and/or (In the formula, R ₁ and R ₂ are alkyl groups having 6 or more carbon atoms,
alkenyl group, aralkyl group or aralkenyl group, R ₃ is an alkyl group, alkenyl group, aralkyl group or aralkenyl group, n is an integer of 2 to 3; ) to the acid anhydride (a) represented by the general formula R ₆ −[(A ₁ O) _o1 −X ₁ ] _n1 (3) (wherein, R ₆ is an active hydrogen-containing compound residue) as an emulsifier.
A ₁ is an alkylene group having 2 to 4 carbon atoms, n ₁ is an integer of 1 or more, X ₁ is R ₅ —, R ₅ CO—, R ₅ NHCO— or —CO—Q ₁ —COOM ₁ , and R ₅ has 1 or more carbon atoms
6 alkyl group or allyl group. Q ₁ is a residue of a saturated or unsaturated aliphatic or aromatic dicarboxylic acid having 4 to 8 carbon atoms, and M ₁ is a cation.
m ₁ is an integer from 1 to 8. ) Compound (b)
A stable internal sizing agent for paper manufacturing containing.