JPH09301926A - Amphipatic compound and its copolymer and paper production additive containing the copolymer as active component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having excellent solubilities not only in organic solvents but also in water in response to the conditions of pH and temperature, etc., and useful as a copolymerization component for acrylamide polymers used for paper production additives. SOLUTION: An amphipathic compound of formula I or II (R1 is a 6-48C saturated hydrocarbon, an unsaturated hydrocarbon containing one to twelve unsaturated double bonds, etc.; R<2> is a 2-6C saturated hydrocarbon; R3 is H, methyl; M is H, an alkali metal, etc.). The compound is obtained by reacting a hydroxyalkyl acrylate or methacrylate with the reaction product of maleic anhydride with an olefin oligomer in a solvent-free system or organic solvent system.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel amphiphilic vinyl compound having a succinic acid half ester structure,
Further, a copolymer of these novel vinyl compounds and a copolymerizable vinyl compound, and a water-soluble or dispersible copolymer of these novel vinyl compounds and (meth) acrylamide and the copolymer are effective. The present invention relates to a papermaking additive contained as a component (hereinafter abbreviated as PAM-based sizing agent). The compounds according to the present invention and the copolymers of these compounds are novel compounds which have never been reported.

[0002]

2. Description of the Related Art Most conventional sizing agents have reduced paper strength due to their use, and some surface sizing agents are known to have the ability to improve the strength. Wasn't enough.

[0003]

The object of the present invention is to provide an amphiphilic acrylic acid ester compound having a novel succinic acid half ester structure (hereinafter referred to as ASA-HA) or methacrylic acid having a succinic acid half ester structure. The object is to provide an ester compound (hereinafter abbreviated as ASA-HM) and a copolymer of the compound. Furthermore, A
Addition for water-soluble or dispersible papermaking, which has the ability to significantly improve paper strength and size performance, produced by copolymerizing SA-HA or ASA-HM with (meth) acrylamide Regarding agents.

[0004]

That is, the present invention provides an amphipathic compound represented by the formula (1) or (2)

[0005]

Embedded image (In the formula, R ₁ is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or 1 or more and 12 unsaturated double bonds.
It represents a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms contained below. R ₂ represents a linear or branched saturated hydrocarbon chain having 2 to 6 carbon atoms, and R ₃ represents a hydrogen atom or a methyl group. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base. ) A mixture comprising an amphipathic compound represented by the formula (1) or (2), a compound represented by the formula (1) or (2) or a mixture thereof in an amount of 0.1 to 90.0% by weight, A polymer compound obtained by copolymerizing 10.0 to 99.9% by weight of a polymerizable vinyl compound, 0.1 to 90.0% by weight of a compound represented by the formula (1) or (2) described above, or a mixture thereof. A water-soluble or dispersible copolymer compound obtained by copolymerizing with (meth) acrylamide 10.0 to 99.9% by weight, and containing the water-soluble or dispersible copolymer compound described as an active ingredient The present invention relates to a papermaking additive.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The novel vinyl compound having a succinic acid half-ester structure of the present invention is a hydrophobic compound soluble in organic solvents. However, since it has a carboxyl group in the molecule, pH, temperature conditions, etc. It is an amphipathic compound that is water-soluble or water-dispersible. Further, since the compound has a double bond in the molecule, it can be polymerized with various vinyl compounds in a solventless system, an aqueous system or an organic solvent system, and is a compound useful as a synthetic resin raw material.

Specific applications of the amphipathic compound and its copolymer of the present invention include plasticizers, heat resistant resins, lubricants, antistatic agents, paints, adhesives, dispersants, and polymerizable surfactants. Its use as an admixture for cement is exemplified. Among them, the copolymer of the amphipathic compound of the present invention and (meth) acrylamide is soluble or dispersible in water,
It has been found that it has a high utility value as a new sizing agent (papermaking additive) capable of significantly improving paper strength performance.

ASA-HA or ASA-H of the present invention
M is a compound (hereinafter abbreviated as ASA) obtained by the reaction of an oligomer of an olefin produced from ethylene, propylene, isobutene, butadiene and the like with maleic anhydride, and is a solvent-free or organic solvent-based hydroxy compound. It can be produced by reacting with alkyl acrylate (HA) or hydroxyalkyl methacrylate (HM).

ASA used in the present invention is (1) 1-
Hexene, 1-octene, 1-decene, 1-dodecene,
Addition products of maleic anhydride with α-olefins having 6 to 48 carbon atoms such as 1-tetradecene, 1-hexadecene, 1-octadecene, 1-dococene, and (2) having 6-carbon atoms A reaction product of an internal olefin isomerized with 48 α-olefins or a mixture thereof in the presence of a catalyst and maleic anhydride, (3)
A reaction product of an internal olefin and maleic anhydride obtained by dehydrogenating a linear paraffin having 6 to 48 carbon atoms or a mixture thereof, (4) propylene,
Oligomers such as isobutene and butadiene with 6 to 6 carbon atoms
Those obtained by known techniques such as the reaction product of 48 with maleic anhydride, which may be a mixture of those having different carbon numbers and double bond positions of internal olefins. When the number of carbon atoms of the olefin oligomer is less than 6 or more than 48, the amphipathic properties of ASA-HA and ASA-HM are not remarkable, which is not suitable for the purpose of the present invention and is not preferable.

As HA or HM used in the present invention, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3
-Hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-
Hydroxybutyl methacrylate, 1-methyl-2-hydroxypropyl acrylate, 1-methyl-2-hydroxypropyl methacrylate, 2-methyl-2-hydroxypropyl acrylate, 2-methyl-2-hydroxypropyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 1,2-dimethyl-2-hydroxypropyl acrylate, 1,2-dimethyl-2-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate,
6-hydroxyhexyl methacrylate, 1-methyl-
4-hydroxypentyl acrylate, 1-methyl-4
-Hydroxypentyl methacrylate, 1,3-dimethyl-3-hydroxybutyl acrylate, 1,3-dimethyl-3-hydroxybutyl methacrylate, 1,1,
Examples thereof include 2-trimethyl-2-hydroxypropyl acrylate, 1,1,2-trimethyl-2-hydroxypropyl methacrylate, 3-methyl-5-hydroxypentyl acrylate and 3-methyl-5-hydroxypentyl methacrylate.

The reaction between ASA and HA or HM is usually carried out by stirring HA in an organic solvent solution while stirring HA.
Alternatively, HM is dropped. As an example of the organic solvent that can be used as the reaction solvent, any solvent capable of dissolving both ASA and HA may be used, and acetone, 2-butanone, benzene, toluene, xylene, pentane, hexane, cyclohexane, DMF, DMSO, THF, Examples include diethyl ether, dioxane, dichloromethane, dichloroethane, chloroform and the like. Alcohol solvents such as methanol, ethanol, isopropanol, methyl cellosolve, ethyl cellosolve, 2-ethylhexanol, and cyclohexanol are not preferable because they cause an esterification reaction with succinic anhydride.

[0012] ASA having a short carbon number such as ASA, which is liquid at room temperature, can be reacted in a solventless system. When it is necessary to remove the reaction solvent, such as when using ASA-HA or ASA-HM in an aqueous system, it is preferable to carry out the reaction in a solventless system.

Although the reaction proceeds without a catalyst, it is preferable to use a catalyst in order to accelerate the reaction. The catalyst used in this reaction is not particularly limited, and the catalyst used in this type of reaction can be used. Specifically, mineral acids such as sulfuric acid, hydrochloric acid and phosphoric acid, or those supporting these on an inorganic carrier such as silica, organic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, acidic ion exchange resins Examples thereof include solid acids such as Zinc, zinc chloride, sodium acetate, pyridine, and the like, and one or more of these can be used. The amount used varies depending on the catalyst used, so it cannot be specified unconditionally, but it is usually 0.001% by weight to 300% by weight with respect to the raw material ASA.
%, Preferably 0.01% to 30% by weight.

Since HAs have high polymerizability, it is preferable to use a polymerization inhibitor in the reaction. The polymerization inhibitor is not particularly limited as long as it can be used as a polymerization inhibitor for HAs. Specifically, phenols such as hydroquinone, hydroquinone monomethyl ether and p-tert-butylcatechol; nitro compounds such as nitrobenzene and nitropropane; amines such as p-phenylenediamine, N-diphenyl-p-phenylenediamine and diphenylamine Stable radicals such as diphenylpicrylhydrazyl, galvinoxyl, ferdazyl, tri-p-nitrophenylmethyl, di-p-fluorophenylamine; nitrite compounds such as sodium nitrite, ethyl nitrite, isopropyl nitrite; Other examples include sulfur, copper salts, and thiourea compounds, and one or more of these can be used. The amount used depends on the polymerization inhibitor used, but is usually 1 ppm to HA of the raw material.
It is in the range of 300% by weight, preferably 50 ppm to 5% by weight.

The amount of HA or HM used is such that an equimolar amount is reacted with the succinic anhydride group of ASA (that is, in this case, 1 mol of the hydroxy group per 1 mol of the acid anhydride). If it is less than equimolar, unreacted ASA remains. If the amount exceeds the equimolar range, HAs remain, and in the presence of a catalyst, H
The hydroxy group of A is ASA-HA or ASA-H
It is not preferable because it may react with the carboxyl group of M to form a diester compound.

The reaction is carried out at 0 ° C. to 15 ° C. under normal pressure or under pressure.
0 ° C, preferably 5 ° C to 130 ° C, more preferably 1
The desired ASA-HA or ASA-HM is obtained by reacting for 30 minutes to 20 hours in a temperature range of 0 ° C to 100 ° C.
Is obtained in high yield. It is not necessary to keep the temperature constant during the reaction, and the reaction temperature may be changed for the purpose of controlling the reaction rate or adjusting the viscosity of the reaction solution.

The amphipathic compound of the present invention can also be produced by an esterification reaction of a succinic acid derivative which is a hydrolyzate of ASA with HA and HM. To more preferred.

Since ASA is an asymmetric compound, HA,
In the reaction product with HM, there are Formula (1) in which an ester is bonded to the carbon side to which a substituent is bonded and Formula (2) in which an ester is bonded to the opposite side, and the reaction conditions are the same as those under normal reaction conditions. Then it becomes a mixture of them. ¹ existence of regioisomer of ester
This can be proved by the detection of two corresponding carboxylic acid ester groups by using 1 H-NMR and ¹³ C-NMR analysis methods. HA and HM have a high rate of forming an ester bond on the carbon to which no substituent is bonded, and this tendency is remarkably observed in the substituent having a large number of carbon atoms. The abundance ratio of these is considered to be determined by the reaction conditions such as the chain length of the substituent of ASA, the reaction solvent, the reaction temperature, and the reaction concentration, but for normal use, the two may be used without separation. No problem.

Examples of vinyl compounds copolymerizable with ASA-HA and ASA-HM are aromatic vinyl compounds, vinyl cyanide compounds, diene compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid compounds, It is one or more compounds selected from the group consisting of unsaturated carboxylic acid amide compounds, alkyl vinyl ether compounds, and other vinyl compounds.

As the aromatic vinyl compound, styrene,
α-methylstyrene, α-chlorostyrene, p-ter
Examples thereof include t-butylstyrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, divinylbenzene and the like.

The vinyl cyanide compound may, for example, be acrylonitrile or methacrylonitrile. Examples of the diene compound include diolefin compounds such as allene, butadiene and isoprene, and chloroprene.

Examples of unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate and lauryl. Methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3
-Hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
Ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, dimethacrylic acid Ethylene glycol, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate,
Examples include ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, isopropoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, and divinyl compounds such as epoxy acrylates and urethane acrylates. .

As the unsaturated carboxylic acid compound, acrylic acid, methacrylic acid, crotonic acid, angelic acid, tiglic acid, 2-pentenoic acid, β-methylcrotonic acid, β-
Methyl tiglic acid, α-methyl-2-pentenoic acid, β-
Methyl-2-pentenoic acid, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid,
Glutaconic acid, α-dihydromuconic acid, 2,3-dimethylmaleic acid, 2-methylglutaconic acid, 3-methylglutaconic acid, 2-methyl-α-dihydromuconic acid, 2,
Examples thereof include acids such as 3-dimethyl-α-dihydromuconic acid and their alkali metal salts, ammonium salts, organic amine salts and the like.

As the unsaturated carboxylic acid amide compound,
Acrylamide, methacrylamide, diacetone acrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl acrylamide, N,
N-dimethylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide,
N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorpholine, N, N-di-n-propylacrylamide, Nn-butylacrylamide, Nn-hexylacrylamide, Nn-hexyl Methacrylamide,
N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide,
N-dodecyl acrylamide, Nn-dodecyl methacrylamide, N, N-diglycidyl acrylamide,
N, N-diglycidylmethacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6 -Glycidoxyhexyl) acrylamide, methylenebisacrylamide, N, N'-ethylenebisacrylamide, N,
Examples thereof include N'-hexamethylene bisacrylamide and N-methylol acrylamide.

As the alkyl vinyl ether compound,
Examples thereof include vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether, vinyl isobutyl ether, vinyl-2-ethylhexyl ether and vinyl-n-octadecyl ether.

Other vinyl compounds include vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, isoprene, N-vinyl-2-pyrrolidone, N-vinylformamide, N-vinylacetamide, divinyl adipate, sebacine. Divinyl esters such as acid divinyl, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-
Phenylpropanesulfonic acid, 2-acrylamide-2
Examples thereof include sulfonic acids such as methylpropanesulfonic acid and their alkali metal salts, ammonium salts, organic amine salts and the like.

In addition to the above vinyl compounds, allylamines such as allylamine, N-methylallylamine, 2-methylallylamine, diallylamine and dimethyldiallylammonium chloride and salts thereof, allylsulphonic acid, methallylsulfonic acid and allyls. It is also possible to copolymerize sulfonic acids and their salts, allyl compounds such as allyl alcohol, methallyl alcohol, diallyl isophthalate, diallyl terephthalate, diethylene glycol diallyl carbonate and triallyl cyanurate.

ASA-HA or ASA-HM of the present invention
The copolymerization ratio of the above-mentioned copolymerizable vinyl compound is in the range of 0.1 to 90.0% by weight of ASA-HA or ASA-HM and 10.0 to 99.9% by weight of the copolymerizable vinyl compound. The copolymerization ratio with the copolymerizable allyl compound is similar to that of the vinyl compound, and the vinyl compound and the allyl compound may be used in combination.

ASA-HA or ASA-HM of the present invention
There is no particular limitation on the copolymerization method of the above-mentioned vinyl compound, and the copolymerization can be carried out by a known method. Usually, polymerization is carried out by maintaining a predetermined temperature in the presence of a radical polymerization initiator. It is not necessary to maintain the same temperature during the polymerization, and the temperature may be changed appropriately as the polymerization progresses. The heating is performed or the heat is removed as necessary. The polymerization temperature varies depending on the type of monomer used and the type of polymerization initiator, and is generally in the range of 30 to 200 ° C. in the case of a single initiator, lower in the case of a redox type polymerization initiator, and collectively. The temperature is generally -5 to 50 ° C when polymerization is performed, and is generally 30 to 90 ° C when sequentially added. The atmosphere in the polymerization vessel is not particularly limited, but it is preferable to replace with an inert gas such as nitrogen gas in order to carry out the polymerization rapidly. The polymerization time is not particularly limited, but is generally 1 to 40 hours.

As the polymerization solvent, the above vinyl compound and A
As long as SA-HA or ASA-HM can be uniformly dissolved, examples of the organic solvent include hexane, cyclohexane, decalin, tetralin, dioxane, carbon tetrachloride, toluene, xylene, cumene, ethylbenzene,
Carbon disulfide, chloroform, ethyl acetate, acetic acid, morpholine, benzene, tetrahydrofuran, pyridine, methyl ethyl ketone, acetone, methanol, ethanol,
Examples include alcohols such as propanol, butanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and ethylene glycol, formamide, dimethylformamide, dimethyl sulfoxide, and the like.

For a vinyl compound which is compatible with ASA-HA or ASA-HM and requires desolvation, copolymerization in a solventless system may be preferable for the purpose of simplifying the process. ASA-HA or ASA
-HM becomes soluble in water when the carboxyl group in the molecule is neutralized with alkali. Although the pH at which water becomes soluble varies depending on the chain length of the substituent, for example, when the carbon number of the substituent is 16, uniform polymerization using water as a solvent is possible under conditions of pH 8 or higher. It is also possible to carry out emulsion polymerization in the presence of a surfactant even under pH conditions insoluble in water.

A general polymerization initiator can be used as the polymerization initiator. In the peroxide system, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 1,1,3,3,
-Tetramethylbutyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, tert-butylperbenzoate, te
rt-butyl peracetate, tert-butyl perphenylacetate, tert-butyl peroxylaurate, cumyl perbivalate Further, as the azo compound, azobisisobutyronitrile, 2,2'-azobis (4-methoxy- 2,4
-Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2 -Phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2 ' -Azobis (2-methylpropionate) can be used. Furthermore, the above-mentioned polymerization initiator 2
More than one species can be used in combination.

The polymerization initiator in the case of using water as the solvent is not particularly limited as long as it is water-soluble. Specifically, examples of the peroxide type include ammonium persulfate, potassium persulfate, hydrogen peroxide, and tert-butyl peroxide. In this case, although it can be used alone, it can also be used as a redox polymerization initiator in combination with a reducing agent. Examples of the reducing agent include sulfite, bisulfite,
Iron, copper, cobalt, etc., low ionic salts, hypophosphorous acid,
Examples thereof include organic amines such as hypophosphite and N, N, N ′, N′-tetramethylethylenediamine, and reducing sugars such as aldose and ketose. Further, as the azo compound, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2-amidinopropane hydrochloride,
2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleic acid and salts thereof can be used. Further, two or more of the above-mentioned polymerization initiators may be used in combination.

The addition amount of the polymerization initiator is 0.00 with respect to the monomer.
The range is 01 to 10% by weight, preferably 0.01 to 8% by weight
It is. In the case of a redox system, the amount of the reducing agent added to the polymerization initiator is 0.1 to 100%, preferably 0.2 to 80% on a molar basis. If necessary, a chain transfer agent such as isopropyl alcohol, α-thioglycerol, mercaptosuccinic acid, thioglycolic acid, triethylamine and sodium hypophosphite can be used appropriately. For the purpose of adjusting the polymerization rate, sodium ethylenediamine tetraacetate (EDTA-Na), citric acid, tartaric acid, urea, thiourea, L-ascorbic acid,
Compounds such as ethylene trithiocarbonate, phenothiazine, nicotinamide may be used. The amount of the chain transfer agent, the regulator of the polymerization rate, or the like used varies depending on the purpose of use of the copolymer, but is generally 0.01% with respect to the total amount of the monomers.
It is in the range of ppm to 5.0%.

The monomers, the polymerization initiator, the solvent, the chain transfer agent and the like to be used for the polymerization may be charged into the reaction vessel at once at the time of starting the polymerization, but one or more components may be added depending on the progress of the polymerization. , May be added individually or as a mixture with a solvent.

The polymer compound of the present invention thus obtained is a plasticizer, a heat resistant resin, an antistatic agent, a lubricant, a paint,
It is used as an adhesive, dispersant, surfactant, cement admixture, etc. Among them, the copolymer of the amphipathic compound of the present invention and (meth) acrylamide is soluble or dispersible in water, and is used as a novel PAM-based sizing agent capable of significantly improving paper strength performance. High value.
Although its action is not always clear,
The amide group of the copolymer forms a hydrogen bond with the cellulose fiber in the drying process after coating, so that the strength of paper strength is significantly improved, and at the same time, the substituent groups are aggregated and oriented on the surface side of the paper. It is considered that the size performance is expressed by.

Specifically, ASA-HA and ASA-
The copolymer of HM and (meth) acrylamide is 5 to 30.
The viscosity at 25 [deg.] C. in the concentration by weight is 0.01 to 50.
It is in the range of 0 poise. The PAM-based sizing agent (additive for papermaking) of the present invention, unlike ASA which is a starting material, has water dispersibility by itself, so that it is not necessary to emulsify using a surfactant, and it is used as it is. it can. When the PAM-based sizing agent is applied (externally added) to the surface of the paper, the sizing property is imparted to the paper and the strength of the paper strength is significantly improved. The concentration of the coating liquid when coated on paper is 0.01 to 10.0%, preferably 0.
It is in the range of 10 to 8.0%. The coating amount is 0.001-5.0g / m
² , preferably in the range of 0.005 to 1.0 g / m ² .

For coating the paper, general methods such as impregnation, size press, gate roll coater, calender, blade coater and spray are used. The drying temperature after coating may be a temperature at which water evaporates, and preferably 100
It is in the range of ℃ to 180 ℃. Furthermore, the PAM-based sizing agent of the present invention is further improved in surface strength and internal strength by combining with conventionally known chemicals for surface coating such as starch-based, carboxymethylcellulose-based, PVA-based, PAM-based and the like. You can also let it.

Incidentally, ASA-HA or ASA-HM
Is an anionic hydrophobic monomer having a carboxyl group and therefore imparts an anionic property to the acrylamide polymer (PAM). Therefore, PAM-based sizing agents are widely used as fixing agents for improving the yield of sizing agents, such as aluminum sulfate, aluminum chloride, sodium aluminate, polyethyleneimine, Mannich modified products of polyacrylamide and Hoffmann modified products, and polyalkylenepolyamines. , Can be fixed to pulp by interaction with water-soluble polymers having cationic groups such as cationized starch, and can be used as an internal sizing agent for acidic papermaking. In this case, among the above-mentioned copolymerizable vinyl compounds, unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc. It is also possible to enhance the same effect by copolymerizing the unsaturated sulfonic acid compound.

Further, N, N-dimethylaminoethyl acrylate (DA), N, N-dimethylaminoethyl methacrylate (DM), N, N-dimethylaminopropyl acrylamide (DMAPAA), N, N-dimethylaminopropyl methacrylamide. By using a vinyl compound and an allyl compound which show a cationic property under acidic to weakly acidic conditions such as (DMAPMA), allylamine and diallylamine as copolymerization components, the fixability to pulp can be further improved.

Further, DA, DM, DMAPAA, DM
APMA, etc., with dimethylsulfate, halogenated alkyls such as methyl chloride and methyl bromide, allyl chloride, halogenated benzyls such as benzyl chloride and benzyl bromide, epihalohydrins such as epiclohydrin and epibromohydrin, propylene oxide and styrene oxide, etc. When a vinyl compound quaternized with the epoxy compounds and an allyl compound such as dimethyldiallylammonium chloride are used as copolymerization components, they can be fixed on the pulp even under neutral to weakly alkaline conditions. It can also be used as an agent.

At this time, a fixing agent for a sizing agent such as aluminum sulfate as exemplified above may be used in combination. When the PAM-based sizing agent is used as an internally added sizing agent, it is added in an amount of 0.01 to 4.0% by weight, preferably 0.05 to 2.0% by weight, based on the weight of the pulp, and it is an ordinary internally added sizing agent such as a seed box or a machine chest. It may be added at the same place as.

The PAM type sizing agent of the present invention may be mixed with an antifoaming agent, an antiseptic agent, an anticorrosive agent, an antislip agent, etc., if necessary.
Or you may use together at the time of use.

[0044]

The present invention will be described in detail below with reference to Examples.
The present invention is not limited to these examples. In the following,% is based on weight and viscosity is B at 25 ° C.
It is a value measured by a viscometer. The molecular weight was determined by GPC analysis, the column was ShodexOH-pak SB-80M + SB-804 (Showa Denko KK), and the eluent was Na ₂ HPO ₄ -KH ₂ PO ₄ (50 mM) -NaNO.
_The measurements were performed using ₃ (0.1M) (pH 6.5). For NMR analysis, a sample is uniformly dissolved in deuterated chloroform to a concentration of about 20% w / v, put into a sample tube for measuring an NMR spectrum having an outer diameter of 5 mmφ, and a 500 MHz NMR spectrum measuring apparatus A500 (JEOL Ltd.) is used. Ltd.) using ¹ H
-And ¹³ C-NMR spectra were measured. For IR analysis, a KRS-5 window plate or KBr tablet method was used, and for an infrared analyzer, FT / IR-8300 (manufactured by JASCO Corporation) was used. CHN analyzer Model 2400 (Perk
in- Elmer) was used.

(Example 1) ASA (C ₁₆ type, manufactured by Seikou Kagaku Co., Coropearl Z-1) was placed in a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel.
00) 100.0 g and sulfuric acid 0.37 g are put, and 2-hydroxyethyl methacrylate (hereinafter referred to as H
A mixed solution of 40.4 g (abbreviated as EMA) and 0.2 g of hydroquinone monomethyl ether was added dropwise over 30 minutes. During the dropping, the reaction temperature was adjusted to 40 ° C with a water bath, and after the dropping was completed, stirring was continued at 40 ° C for 8 hours, 0.73 g of triethylamine was added to neutralize the sulfuric acid, and 141.7 g of an amber highly viscous liquid was obtained. Obtained. The viscosity of ASA before the reaction was 96 cp, but the reaction product (ASA-
The viscosity of HEMA) was 552 cp.

Elemental analysis value; C: 68.99%, H: 9.80%
(Calculated value: C ₂₆ H ₄₄ O ₆ ) C: 68.65%, H: 10.02% (measured value) IR analysis (Fig. 1) showed that raw material ASA was 1780 cm.
^-1 and 1860cm characteristic absorption band anhydride groups found in ^-1 (C = O stretch) disappears, behalf and carboxylic acid 1710 cm ^-1 (C = O stretching), ester 1740 cm ^-1 (C = An absorption band due to O stretching was observed.

As shown in FIGS. 2 and 3, ¹ H of ASA-HEMA is used.
-NMR spectrum and ¹³ C-NMR spectrum are shown. The magnetic field strength on the horizontal axis is shown in ppm with tetramethylsilane as a reference (0 ppm).

In the following examples, the ASA obtained above is used.
-HEMA 20.0g, 40% caustic soda aqueous solution 4.4g, distilled water
An aqueous solution (pH 10.62) in which 175.6 g was uniformly dissolved was used.

(Example 2) 15.0 g of a 10% aqueous solution of ASA-HEMA obtained in Example 1 was added to a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.
% Acrylamide aqueous solution (57.0 g), distilled water (221.4 g), sodium hydrogen sulfite (0.30 g) and sodium hypophosphite (0.30 g) were added, and the mixture was heated to 30 ° C. with stirring under a nitrogen stream. To this solution, 10% ammonium persulfate (APS) aqueous solution 6.
0 g was added. After stirring at 30 ℃ for 180 minutes, 10% AP
S aqueous solution and 10% sodium bisulfite aqueous solution
0.9 g each was added, and stirring was further continued for 120 minutes to obtain a slightly white and cloudy aqueous solution. The nonvolatile content of the obtained aqueous solution is 10.8.
%, PH was 8.43, viscosity was 176.2 cp, and weight average molecular weight was 418,600.

(Example 3) 30.0 g of a 10% aqueous solution of ASA-HEMA obtained in Example 1 was added to a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
% Acrylamide aqueous solution (54.0 g), distilled water (209.1 g), sodium hydrogen sulfite (0.3 g) and sodium hypophosphite (0.60 g) were added, and the mixture was heated to 30 ° C. with stirring under a nitrogen stream. 6.0 g of 10% APS aqueous solution was added to this solution. After continuing stirring at 30 ° C. for 180 minutes, 0.9 g each of 10% APS aqueous solution and 10% sodium bisulfite aqueous solution were added, and stirring was continued for 120 minutes to obtain a slightly turbid aqueous solution. The resulting aqueous solution has a nonvolatile content of 10.9%, a pH of 8.64, and a viscosity of 448.0 cp.
And the weight average molecular weight was 186,100.

(Example 4) 45.0 g of a 10% aqueous solution of ASA-HEMA obtained in Example 1 was added to a 300 ml four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introducing tube.
% Acrylamide aqueous solution 51.0 g, distilled water 196.2 g, sodium hydrogen sulfite 0.3 g and sodium hypophosphite 1.50 g were added, and the mixture was heated to 30 ° C. with stirring under a nitrogen stream. 6.0 g of 10% APS aqueous solution was added to this solution. After continuing stirring at 30 ° C. for 180 minutes, 0.9 g each of 10% APS aqueous solution and 10% sodium bisulfite aqueous solution were added, and stirring was continued for 120 minutes to obtain a slightly turbid aqueous solution. The nonvolatile content of the obtained aqueous solution was 11.1%, the pH was 8.78, the viscosity was 65.9 cp, and the weight average molecular weight was 85,400.

The following coating examples were all carried out using newspaper base paper (basis weight 50 g / m ² ). Size degree is JIS P8122
The surface strength was measured by using the RI-3 type (manufactured by Akira Seisakusho Co., Ltd.) according to the Steckigt size test method of (1).
The higher the score in the 0-point method relative evaluation, the higher the surface strength),
The Z-axis strength was measured using an internal bond tester (Kumagaya Riki Kogyo Co., Ltd.).

(Coating Examples 1 to 3) The base paper to be coated was dipped in the polymer solution obtained in Examples 2 to 4 for 1 second, squeezed by two rolls, and the amount of the absorbed liquid was measured. Then, the coating amount was obtained. The concentration of the coating solution was adjusted in advance so that the coating amount was 1.0 g / m ^{2 as} the nonvolatile content of the polymer (polymer concentration: 2.5 wt
%). The pH of the coating solution was adjusted to 7.5 to 8.0. Immediately after coating, dry for 50 seconds with a drum dryer whose surface temperature is set to 120 ° C, and store in a constant temperature and constant humidity chamber (20 ° C, humidity 65 ° C).
%), The sizing degree and the paper strength were measured after conditioning for 24 hours. The results are shown in Table 1.

[0054]

[Table 1]

[0055]

The succinic acid half ester compound of the present invention is an amphipathic compound which is soluble in an organic solvent but is also highly soluble in water depending on the pH and temperature conditions.
Since this compound has a polymerizable double bond in the molecule,
It can be used for various purposes as a polymerizable surfactant. Further, when used as a copolymerization component of an acrylamide polymer, it is useful as an additive for papermaking having not only paper strength performance but also size performance as is clear from the examples.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the novel compound obtained in Example 1.

FIG. 2 ¹ H-NMR of the novel compound obtained in Example 1.
Spectral diagram

FIG. 3 ¹³ C-NMR of the novel compound obtained in Example 1.
Spectral diagram

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Yanagi Masayuki Yanagi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Kyokichi Watanabe 1-6 Takasago, Takaishi, Osaka Mitsui Toatsu Chemical Within the corporation

Claims (5)

[Claims] 1. An amphipathic compound represented by formula (1) or (2) [Chemical Formula 1]. Embedded image (In the formula, R ₁ is a linear or branched saturated hydrocarbon group having 6 to 48 carbon atoms, or 1 or more and 12 unsaturated double bonds.
It represents a linear or branched unsaturated hydrocarbon group having 6 to 48 carbon atoms contained below. R ₂ represents a linear or branched saturated hydrocarbon chain having 2 to 6 carbon atoms, and R ₃ represents a hydrogen atom or a methyl group. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic base. ) 2. A mixture comprising an amphipathic compound represented by the formula (1) or (2) according to claim 1. 3. A compound represented by the formula (1) or (2) according to claim 1 or a mixture thereof 0.1 to 90.0% by weight.
A polymer compound obtained by copolymerizing a copolymerizable vinyl compound with 10.0 to 99.9% by weight. 4. A compound represented by the formula (1) or (2) according to claim 1 or a mixture thereof 0.1 to 90.0% by weight.
And a (meth) acrylamide 10.0 to 99.9 wt% copolymerizable compound that is soluble or dispersible in water. 5. A papermaking additive containing the water-soluble or dispersible copolymer compound according to claim 4 as an active ingredient.