JPH09169817A - Silicon-containing water-soluble polymer compound, production method and use thereof - Google Patents

Abstract

(57) Abstract: A novel water-soluble compound which can be used as an additive for papermaking in place of a conventionally known water-soluble polymer compound having a cationic group and thereby exhibits further improved properties. A polymer compound is provided. A water-soluble polymer compound having an amino group or an ammonium group, wherein the silicon-containing compound (S) having an epoxy group is bonded to the silicon-containing water-soluble polymer compound. This polymer compound can be produced, for example, by reacting a water-soluble polymer compound (A) having a primary, secondary, or tertiary amino group with a silicon-containing compound (S) having an epoxy group. This polymer compound is particularly useful as an additive for papermaking. [Effect] This polymer compound exerts an excellent effect in enhancing the paper strength and improving the fixing rate of the filler in the papermaking process in the pulp system containing the filler, and particularly when white carbon is used as the filler. It is remarkable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silicon-containing water-soluble polymer compound, a method for producing the same, and its use as an additive for papermaking. More specifically, it relates to a water-soluble polymer compound having an amino group or an ammonium group and showing improved properties, a method for producing the same, and use thereof.

[0002]

2. Description of the Related Art Water-soluble polymer compounds having an amino group or an ammonium group as a cationic group are widely used in paper processing agents, fiber processing agents, coagulants, adhesives, paint additives, petroleum recovery aids, etc. Is used in the field of. For example,
BACKGROUND OF THE INVENTION (Meth) acrylamide polymers having a cationic group are widely used in the paper industry as a paper strength enhancer, a drainage improver or a filler retention improver.

In the paper manufacturing industry in recent years, water is becoming closed due to regulation of waste water and the percentage of used pulp is increasing from the viewpoint of protecting the global environment. Since many inorganic and organic impurities are present in such a papermaking system, in order to avoid these effects, a paper strengthening agent,
The use of drainage improvers or filler retention improvers has become popular. However, the conventionally known agents are not always sufficiently effective when used in a papermaking system in which a lot of recent impurities are present, and development of further improved agents has been desired.

JP-A-7-102496 describes acrylamides, vinyl monomers having anionic groups, vinyl monomers having cationic groups, and copolymers obtained by polymerizing vinyl monomers having a silicon atom in the molecule. Has been proposed as an additive for papermaking.

[0005]

The object of the present invention is to replace the conventionally known water-soluble polymer compound having a cationic group with a water-soluble polymer compound, which can be used as an additive for papermaking and the like, thereby further improving the properties. Is to produce and provide a novel water-soluble polymer compound.

[0006]

Means for Solving the Problems As a result of intensive studies aimed at achieving such an object, the inventors have found a water-soluble polymer compound to which a specific silicon-containing compound is bound, and
It was found that excellent results were obtained when it was used as an additive for papermaking, and the present invention was completed.

That is, the present invention provides a water-soluble polymer compound having an amino group or an ammonium group, the silicon-containing water-soluble polymer compound having a silicon-containing compound (S) having an epoxy group bonded thereto. Is. Further, the present invention comprises reacting a water-soluble polymer compound (A) having a primary, secondary or tertiary amino group with a silicon-containing compound (S) having an epoxy group to give the silicon-containing water-soluble polymer. The present invention also provides a method for producing a compound, and further provides a papermaking additive containing the silicon-containing water-soluble polymer compound as an active ingredient.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the silicon-containing compound (S) used for introducing a silicon atom may have at least one silicon atom and at least one epoxy group in the molecule. . Specific examples thereof include compounds having at least one group represented by the following formulas (I) and (II) in the molecule.

[0009]

Wherein R ¹ represents alkyl or alkenyl, R ² and R ³ independently of one another represent alkyl, alkenyl, alkoxy or alkenyloxy,
R ⁴ represents hydrogen or alkyl.

In a more concrete form, the following formula (III)
The compound shown by these is mentioned.

[0012]

In the formula, R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings, R ⁵ represents hydrogen or alkyl, and X represents an aliphatic linking group. R ⁵ may combine to form a saturated carbocycle.

Among them, the preferred silicon-containing compound (S) is a compound represented by the following formula (IV).

[0015]

Where R ¹ , R ² , R ³ , R ⁴ and R ⁵
Represents the above-mentioned meaning, n represents an integer of 1 to 3, Y represents a direct bond, an oxygen atom or CHR ⁶ , wherein R ⁶ represents hydrogen or alkyl, but R ⁵ and R ⁶ are bonded to each other. To form an alkylene having 1 to 4 carbon atoms.

In the definitions of the above formulas (I) to (IV), alkyl and alkoxy each preferably have about 1 to 4 carbon atoms, and alkenyl and alkenyloxy preferably each have about 2 to 4 carbon atoms. . Further, as the aliphatic linking group represented by X in the formula (III), alkylene having 1 to 6 carbon atoms, alkylene having 1 to 6 carbon atoms having a terminal oxygen atom bonded to a silicon atom, oxygen atom And alkylene having a total of 2 to 6 carbon atoms interrupted by, and the carbon atom in the alkylene is R in any case.
^May combine with ⁵ to form a ring. The alkyls, alkenyls, alkoxys, alkenyloxys and alkylenes described so far can each be straight-chain or branched if they have a corresponding number of carbon atoms.

Specific examples of such a silicon-containing compound (S) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
(3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) methyldiisopropenyloxysilane, 4-trimethoxysilylbutane-
1,2-epoxide, 4-triethoxysilylbutane-
1,2-epoxide, 1- (2-trimethoxysilylethyl) cyclohexane-3,4-epoxide, 1- (1
Examples include -methyl-2-triethoxysilylethyl) -4-methylcyclohexane-3,4-epoxide and 1- (2-triethoxysilylethyl) cyclohexane-3,4-epoxide. These silicon-containing compounds (S) may be used alone or in combination of two or more.

The silicon-containing water-soluble polymer compound according to the present invention has an amino group or an ammonium group, and the silicon-containing compound (S) having an epoxy group described above is bonded to the structure of the polymer compound. There is. Generally, the epoxy group in the silicon-containing compound (S) is ring-opened to form a structure in which it is bonded to the nitrogen atom of the amino group or ammonium group. Here, a silicon-containing compound (S) having an epoxy group
The reaction between the amino group and the amino group may be carried out before forming the polymer compound or after forming the polymer compound. That is, by reacting the water-soluble polymer compound (A) having a primary, secondary or tertiary amino group with the silicon-containing compound (S) having an epoxy group, the water-soluble polymer compound (A) A silicon atom can be introduced into the compound, and an amino compound having a primary, secondary, or tertiary amino group is reacted with a silicon-containing compound (S) having an epoxy group, followed by polymerization or polycondensation reaction. Also by carrying out, a water-soluble polymer compound having a silicon atom introduced therein can be obtained. The water-soluble polymer compound (A) or amino compound with which the silicon-containing compound (S) reacts preferably has a primary or secondary amino group.

Examples of the water-soluble polymer compound (A) having a primary, secondary or tertiary amino group, which is a base resin for the silicon-containing water-soluble polymer compound, include the following.

(A1) a cationic group-containing polymer obtained by polymerization of a cationic monomer (a) having a primary, secondary or tertiary amino group as at least one constituent, (A2) having an amide group Modified cationic group-containing polymer obtained by modification reaction of precursor polymer, (A3) polyethyleneimine, (A4) amine and cation obtained by addition or condensation reaction of compound having at least two reactive groups Additions or condensates containing functional groups.

The above cationic group-containing polymer (A1) is 1
In addition to the homo- or copolymer of the cationic monomer (a) having a secondary, secondary or tertiary amino group, in addition to the cationic monomer (a), other monomers within a range not impairing water solubility, for example, The nonionic monomer (b), the anionic monomer (c), the cationic monomer having a quaternary ammonium group (d), and the like may be copolymerized in one kind or in two or more kinds.

Specific examples of the cationic monomer (a) having a primary, secondary or tertiary amino group used in the synthesis of the cationic group-containing polymer (A1) include allylamine,
Primary amines such as methallylamine, secondary amines such as methylallylamine, ethylallylamine, diallylamine and dimethallylamine, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl ( (Meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide,
Tertiary amines such as diallylmethylamine, diallylethylamine, triallylamine may be mentioned, and these may be in the form of free amines, but also hydrochloric acid, sulfuric acid, phosphoric acid,
It may be in the form of a salt of an inorganic or organic acid such as formic acid or acetic acid. These cationic monomers (a) may be used alone or in combination of two or more.

Further, these cationic monomers (a)
Among the other monomers that may be copolymerized with, specific examples of the nonionic monomer (b) include (meth) acrylamide, N-methyl (meth) acrylamide, N-
(Meth) acrylamides such as ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide,
N-vinyl amides such as N-vinyl acetamide,
Methyl (meth) acrylate, hydroxyethyl (meth)
Examples thereof include acrylates, (meth) acrylic acid esters such as ethylene glycol di (meth) acrylate, and other (meth) acrylonitrile, N-vinylpyrrolidone, styrene, vinyl acetate and the like.

Specific examples of the anionic monomer (c) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and styrene sulfone. Examples thereof include acids, unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, and alkali metal salts and ammonium salts such as sodium salts and potassium salts thereof.

Specific examples of the cationic monomer (d) having a quaternary ammonium group include the cationic monomer (a) described above and a quaternizing agent such as alkyl halides such as methyl chloride and methyl bromide. , Benzyl chloride, aralkyl halides such as benzyl bromide, compounds obtained by reacting with dimethylsulfate, diethylsulfate, epichlorohydrin and the like.

In polymerizing the cationic monomer (a) or in addition to the cationic monomer (a), other monomers such as a nonionic monomer (b), an anionic monomer (c) and a quaternary ammonium group are included. When copolymerizing one or more cationic monomers (d) with each other, a usual polymerization initiator can be used. For example, persulfates such as ammonium persulfate and potassium persulfate, 2,2'-azobis (2-amidinopropane) dihydrochloride, azo compounds such as azobisisobutyronitrile, di-t-butylperoxide. Oxide, t-
Examples thereof include butyl hydroperoxide, cumene hydroperoxide, lauryl peroxide, benzoyl peroxide and peroxides such as hydrogen peroxide. Further, a known redox-based initiator, for example, a combination of potassium persulfate and sodium sulfite or a tertiary amine can be used. The polymerization initiator is preferably used in the range of 0.01 to 5% by weight based on the total amount of the monomers,
Further, it is more preferable to use it in the range of 0.05 to 2 wt%. It is also possible to use a so-called chelating agent such as ethylenediaminetetraacetic acid or its alkali metal salt as a scavenger of the transition metal existing or mixed in the polymerization system.

The polymerization is usually carried out at a temperature of 10 to 100 ° C., preferably 40 to 90 ° C. for about 1 to 15 hours. This polymerization reaction may be carried out in the air, but generally it is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.
In the polymerization, the charging method of the monomers is not particularly limited, and for example, it is possible to polymerize after charging all the constituent monomers, or to carry out the polymerization while continuously supplying a part or all of the constituent monomers. it can.

The cationic group-containing polymer (A
When the silicon-containing compound (S) having an epoxy group is bonded to 1), the introduction reaction of the silicon-containing compound (S) is
A cationic monomer (a) having a primary, secondary or tertiary amino group, or optionally, a nonionic monomer (b), an anionic monomer (c) or a cationic monomer (d) having a quaternary ammonium group. It may be carried out after polymerizing one or more of
You may perform it with respect to the cationic monomer (a) which has a secondary or tertiary amino group. In the latter case, the polymerization reaction is carried out using the cationic monomer (a) into which the silicon-containing compound (S) has been introduced. In either case, since the silicon-containing compound (S) having an epoxy group reacts with an amino group, when it reacts with a primary amino group, the amino group becomes secondary and when it reacts with a secondary amino group. Has an amino group that becomes tertiary, and when reacted with a tertiary amino group, that amino group becomes a quaternary ammonium group.
In addition, not all amino groups are consumed in the reaction, so that amino groups to which the silicon-containing compound (S) is not bonded may of course remain.

Next, as an example of the modified cationic group-containing polymer (A2), a Huffman-decomposed poly (meta) in which a part of the amide group is converted into an amino group by Hoffmann decomposition of poly (meth) acrylamides is given. ) Mannich-modified poly (meth) acrylamides obtained by converting a part of amide groups into aminoalkylamide groups by the Mannich reaction of acrylamides and poly (meth) acrylamides, N-
Examples include poly (vinylamine) s in which a part or all of the amide group is converted to an amino group by hydrolyzing poly (N-vinylamide), which is a polymer of vinylamides.

Hoffman-decomposed poly (meth) acrylamides are described, for example, in Tanaka et al., Polymers, 33 (6), 309-31.
6 (1976), using (meth) acrylamide as an essential constituent monomer, polymerization was performed by the usual method as shown above, and then the reaction with hypochlorous acid and hydrolysis with alkali were carried out. It is obtained by performing decomposition. On the other hand, Mannich-modified poly (meth) acrylamides are prepared by the conventional method as described above, using (meth) acrylamides as essential constituent monomers, as disclosed in, for example, JP-A-60-151400. It is obtained by reacting a dialkylamine such as dimethylamine or diethylamine with formaldehyde after the polymerization. Constituting poly (meth) acrylamides for Hoffmann degradation and Mannich modification (meth)
The acrylamides are the (meth) acrylamides exemplified above in the nonionic monomer (b), that is, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-.
It can be isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide and the like. Of these, acrylamide or methacrylamide, especially acrylamide, is commonly used.

Poly (vinyl amine) s are polymerized by the usual method as described above, using N-vinyl amides as an essential constituent monomer, as disclosed in, for example, JP-A-63-165412. After that, it is obtained by performing acid hydrolysis. The N-vinyl amides used here can be the N-vinyl amides exemplified above for the nonionic monomer (b), that is, N-vinyl formamide, N-vinyl acetamide and the like.

When such a modified cationic group-containing polymer (A2) is used as the base resin, the introduction reaction of the silicon-containing compound (S) having an epoxy group is generally carried out after the base resin is produced. When a cationic monomer (a) having a primary, secondary or tertiary amino group is used as a part of the constituent monomers, after reacting the cationic monomer (a) with the silicon-containing compound (S), It is also possible to carry out a polymerization reaction. In the latter case, the modification reaction is carried out after the polymerization reaction, and then the introduction reaction of the silicon-containing compound (S) can be carried out again.

The polyethyleneimines (A3) which can be another base resin in the present invention are, for example, CR Dick.
et al., J. Macromol. Sci.-Chem., A4 (6), 1301-1
314 (1970) et al., By a method of polymerizing ethyleneimine, or by T. Saegusa et al., Ma.
Cromolecules, 5 , 108 (1972) and the like, it can be obtained by a method of hydrolyzing poly (N-acylethyleneimine) with an acid or an alkali. In either case, the introduction reaction of the silicon-containing compound (S) having an epoxy group is generally performed on this base resin, but if the reaction can be controlled, this introduction reaction is performed on ethyleneimine. It can also be carried out and then polymerized.

Further, examples of the cationic group-containing addition or condensate (A4) which can be another base resin in the present invention include amines and epihalohydrins or α,
Polyamine epihalohydrin resins obtained by reaction with γ-dihalo-β-hydrins, polyamide resins obtained by reaction of polyamines with polycarboxylic acids, epihalohydrins or α, γ-dihalo-β added to the polyamide resins Examples thereof include polyamide-epoxy resins obtained by reacting hydrins, polyamines or polyalkylene polyureas obtained by reacting polyamide resins with ureas.

The polyamine epihalohydrin resins are prepared by reacting amines with epihalohydrins, α, γ-dihalo-β-hydrins or polyepoxy compounds, as disclosed in, for example, Japanese Patent Publication No. 53-44567. can get. Specific examples of amines used here include methylamine, ethylamine, propylamine, isopropylamine, butylamine, t-butylamine,
Like pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-ethylhexylamine, benzylamine, dimethylamine, diethylamine, diisopropylamine, dibutylamine, dicyclohexylamine, N-methylcyclohexylamine, N-methylbenzylamine. Monoamines,
Ethylenediamine, 1,2-propanediamine, 1,3
-Propanediamine, hexamethylenediamine, 1,3
-Or 1,4-diaminocyclohexane, 4,4'-
Diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethylbicyclohexyl, xylylenediamine, isophoronediamine,
Menthanediamine, 1,3-, 1,2- or 1,4-
Bis (aminomethyl) cyclohexane, N-aminopropylcyclohexylamine, 1,5- or 2,6-bis (aminomethyl) octahydro-4,7-methanoindene, 2,2-bis (4-aminocyclohexyl) propane, bis (4-aminocyclohexyl) methane, 4,
4'-oxybis (cyclohexylamine), 4,4 '
-Sulfone bis (cyclohexylamine), N-ethylethylenediamine, N-ethylhexamethylenediamine, N, N-diethylethylenediamine, N, N-dimethylpropanediamine, N-methyl-1,3-diaminocyclohexane, N, N-dimethyl -1,3-diaminocyclohexane, 3-N-methylamino-3,5,5-
Diamines such as trimethylcyclohexylamine, N, N-dimethylbis (4-aminocyclohexyl) methane and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, 3-azahexane-1, 6-diamine, 4,7-diazadecane-1,1
Mention may be made of tri- or higher amines such as 0-diamine, 1,3,5-triaminocyclohexane and N-methyliminobispropylamine. These amines may be used alone or in combination of two or more.

Specific examples of epihalohydrins used in the production of polyamine epihalohydrin resins include epichlorohydrin, epibromohydrin, and the like. Specific examples of α, γ-dihalo-β-hydrins are the same. , 1,3-dichloro-2-propanol and the like. These epihalohydrins and α, γ-
The dihalo-β-hydrins may be used alone or in combination of two or more. Further, specific examples of the polyepoxy compound used in the production of another polyamine epihalohydrin resin include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, glycerol triglycidyl ether, and diglycidyl adipate. In addition to such diglycidyl compounds, 3,4-epoxycyclohexylmethyl
Examples include 3,4-epoxycyclohexanecarboxylate.

Further, the polyamine epihalohydrin resin is a cationic monomer having a quaternary ammonium group in addition to the amines and epihalohydrins, α, γ-dihalo-β-hydrins or polyepoxy compounds described above. The quaternizing agent described in (d) may be reacted to such an extent that the primary, secondary or tertiary amino group does not disappear.

The reaction for producing the polyamine epihalohydrin resins is usually carried out in an aqueous solution at a temperature of 10 to 100 ° C., preferably 40 to 90 ° C. for about 1 to 15 hours.

Polyamide resins which are another example of the cationic group-containing addition or condensate (A4) have been described in the above-mentioned polyamine epihalohydrin resins as disclosed in, for example, Japanese Patent Publication No. 35547/35. It is obtained by reacting polyamines selected from diamines and tris or more amines among amines with polycarboxylic acids. Specific examples of the polycarboxylic acids used here include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid, and aromatic compounds such as phthalic acid, isophthalic acid and terephthalic acid. Dicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,3-
Or -1,4-dicarboxylic acid, cyclopentanedicarboxylic acid, 3- or 4-methyltetrahydrophthalic acid,
Examples thereof include alicyclic dicarboxylic acids such as 3- or 4-methylhexahydrophthalic acid and endomethylenetetrahydrophthalic acid. In addition to these free acids, the polycarboxylic acids may be esters thereof, acid anhydrides and the like. Specific examples of the esters include mono- or diesters with lower alcohols and polyesters with glycols. Specific examples of the acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3- or 4-methyltetrahydrophthalic anhydride, 3- or 4-methylhexahydrophthalic anhydride, Endomethylene tetrahydrophthalic anhydride etc. are mentioned. These polycarboxylic acids may be used alone or in combination of two or more.

In producing polyamide resins by reacting polyamines with polycarboxylic acids, the polycarboxylic acids are usually used in an amount of 0.3 with respect to 1 mol of the polyamines.
It is used in the range of 2 to 2 mol, preferably in the range of 0.5 to 1.2 mol. This reaction is usually carried out at a temperature of 100 to 250 ° C. while removing generated water and alcohol out of the system. In this case, an inorganic or organic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid or paratoluenesulfonic acid can be used as a catalyst. At this time, monoamines, monocarboxylic acids, aminocarboxylic acids and the like can be used in combination for the purpose of adjusting the molecular weight. Specific examples of the monoamines used here include those similar to the monoamines among the amines described above for the polyamine epihalohydrin resins. Specific examples of the monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, stearic acid, benzoic acid and the like. Specific examples of aminocarboxylic acids include glycine and the like. These monocarboxylic acids and aminocarboxylic acids may be in the form of their esters, like the above-mentioned polycarboxylic acids, and the aminocarboxylic acids can also be used in the form of lactams. Specific examples of lactams include caprolactam and lauryllactam.

Addition or Condensation Product Containing Cationic Group (A4)
Another example of the polyamide epoxy resin is a polyamide epoxy resin obtained by reacting the above polyamide resin with an epihalohydrin or an α, γ-dihalo-β-hydrin, as shown in JP-B-35-3547. Obtained by
This reaction can be carried out according to the method described above for the polyamine epihalohydrin resins.

Further, another example of the addition or condensation product (A4) containing a cationic group is a polyalkylene polyurea,
For example, as shown in Japanese Examined Patent Publication No. 44-11667, polyamines selected from the diamines and tri or higher amines described in the polyamine epihalohydrin resins and the polyamide resins, or the polyamide resins. It can be obtained by reacting urea with. Specific examples of ureas used here include urea, thiourea, guanylurea, methylurea and dimethylurea. These may be used alone or in combination of two or more, and urea is preferably used from the industrial viewpoint. Urea is usually 0.3 to 1 mol, preferably 0.5 to 1 mol of amino groups in polyamines or polyamide resins.
It is used in the range of 1 mol.

The reaction between the polyamines and the ureas is usually 100 to 20 while removing the generated ammonia out of the system.
It can be performed at a temperature of 0 ° C. The same can be done when using polyamide resins instead of polyamines, but in this case, the order of the reactions is arbitrary. For example, urea may be reacted after synthesizing the polyamide resins. It is also possible to first react the polyamines with the ureas and then the polycarboxylic acids.

In the synthesis of polyalkylene polyureas, epihalohydrins, for the purpose of adjusting the molecular weight,
One or more α, γ-dihalo-β-hydrins or aldehydes can be additionally reacted. Specific examples of the epihalohydrins or α, γ-dihalo-β-hydrins used here are the same as those described above for the polyamine epihalohydrin resin. Specific examples of aldehydes include monovalent aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, glyoxylic acid and glycol aldehyde, and polyvalent aldehydes such as glyoxal and glutaraldehyde. The aldehydes referred to here may be those which react as aldehydes in the reaction system, and in addition to the above free aldehydes, for example, multimers such as paraformaldehyde, trioxane and triacetin, dimethyl acetal, diethyl acetal, 1 It may also be in the form of acetals such as 3,3-dioxolane. The epihalohydrins, α, γ-dihalo-β-hydrins or aldehydes are usually used in an amount of 2 mol or less, preferably 1 mol or less, based on 1 mol of the urea used in the synthesis of the polyalkylene polyureas. Can be used. When reacting epihalohydrins, α, γ-dihalo-β-hydrins or aldehydes, they are usually added in an aqueous solution at 20 to 20%.
It can be carried out at a temperature of 100 ° C.

When the cationic group-containing addition or condensation product (A4) as described above is used as the base resin, the introduction reaction of the silicon-containing compound (S) having an epoxy group is carried out after the base resin is synthesized. Alternatively, it may be carried out with respect to the starting amines. In addition, for example, in the case where the reaction has multiple steps such as polyamide epoxy resins and polyalkylene polyureas, the reaction of the silicon-containing compound (S) with It is also possible to carry out an introduction reaction.

Whatever the base resin is, the amount of the silicon-containing compound (S) to be introduced into the water-soluble polymer compound (A) is generally in the range of silicon atom with respect to the silicon-containing water-soluble polymer compound. It is preferably in the range of 0.1 to 10% by weight. When the water-soluble polymer compound (A) is obtained by addition polymerization from a vinyl monomer, based on the total molar amount of the constituent monomers of the water-soluble polymer compound (A) excluding the silicon-containing compound (S). , The amount of silicon is 0.2-10
It is preferable to react in the range of mol%.

When the amino compound, which is the raw material of the water-soluble polymer compound (A), is reacted with the silicon-containing compound (S) having an epoxy group, this reaction is carried out without a solvent or in the presence of a solvent. It can be carried out. When a solvent is used, any solvent can be used as long as it can dissolve both reaction materials, and the type thereof is not particularly limited. This reaction is generally carried out at a temperature of 70 ° C or lower, preferably about 0 to 50 ° C, and generally 1
It is performed for about 0 minutes to 10 hours, preferably for about 30 minutes to 5 hours.

When the water-soluble polymer compound (A) having a primary, secondary or tertiary amino group is reacted with the silicon-containing compound (S) having an epoxy group, the reaction is generally carried out in water or alcohol. Is done. The alcohol can be a lower alcohol such as methanol, ethanol, isopropanol, butanol. It is particularly preferable to carry out this reaction in an aqueous solution. This reaction is generally performed at a temperature of 70 ° C or lower, preferably about 0 to 50 ° C,
In addition, generally 10 minutes to 10 hours, preferably 30 minutes to
It is performed for about 5 hours.

The silicon-containing water-soluble polymer compound of the present invention is generally used for applications in which a water-soluble polymer compound having a cationic group is used, for example, paper processing agents such as papermaking additives, fiber treatment agents, It can be used for applications such as flocculants, adhesives, paint additives, petroleum recovery aids and the like.

Above all, it is useful as an additive for papermaking,
In this case, the silicon-containing water-soluble polymer compound is preferably a (meth) acrylamide polymer having a cationic group. The (meth) acrylamides that are the constituent monomers of the (meth) acrylamide polymer can be those exemplified above for the nonionic monomer (b). The (meth) acrylamide polymer may be a cationic polymer having a cationic group, or an amphoteric copolymer having a cationic group as well as an anionic group. Specifically, a reaction product of a (meth) acrylamide polymer having a cationic group and optionally an anionic group with a silicon-containing compound (S) having an epoxy group, or a primary After reacting the cationic monomer (a) having a secondary or tertiary amino group with the silicon-containing compound (S) having an epoxy group, (meth) acrylamides, or optionally further described above ( A polymer obtained by copolymerizing a copolymerizable nonionic monomer (b) other than (meth) acrylamides, an anionic monomer (c) and / or a cationic monomer (d) having a quaternary ammonium group, It is preferably used as an additive for papermaking. More preferably, it is a reaction product of the former (meth) acrylamide polymer having a cationic group and a silicon-containing compound (S) having an epoxy group. Particularly, the (meth) acrylamide polymer preferably has a primary or secondary amino group.

Preferred (meth) acrylamide-based polymers as papermaking additives are (meth) acrylamide components,
Essentially contains a cation component and a silicon-containing compound component,
Optionally, further components such as anionic and / or nonionic components can be included, and the amount of the silicon-containing compound component is as described above, but the quantitative proportion of the other component is the silicon-containing compound. It is preferable that the (meth) acrylamide unit is in the range of 50 to 99 mol% and the unit having a cationic group is 1 mol% or more based on the total molar amount of the polymer constitutional units excluding the compound unit, and the anion When a unit having a functional group is introduced, the range is preferably 20 mol% or less. More specifically, (meta)
The acrylamide unit, the unit having a cationic group and the unit having an anionic group have respective molar ratios of 50
It is preferably in the range of 99/30 to 1/20 to 0.

The weight average molecular weight of the (meth) acrylamide polymer introduced with a silicon-containing compound when used as an additive for papermaking is preferably in the range of 10,000 to 10,000,000, and more preferably in the range of 50,000 to 5,000,000. Is more preferable. In terms of the viscosity of the aqueous solution serving as an index of the molecular weight, it is preferable that the Brookfield viscosity of the 15 wt% aqueous solution at 25 ° C. is in the range of 5 poise to 200 poise. The molecular weight or product viscosity affects the properties as a paper strength enhancer and as a retention aid for fillers, and when the molecular weight or product viscosity becomes low, the paper strength effect and the retention effect of fillers decrease, and When the molecular weight or the viscosity is high, the texture of the paper tends to be broken, so that the molecular weight or the viscosity is preferably within the above range.

When the silicon-containing water-soluble polymer compound of the present invention is used as an additive for papermaking, it is used by adding it to an aqueous pulp slurry at the time of papermaking, and usually 0.01-2 based on the dry pulp weight. It is added in an amount of about wt. This additive may be added so that it can be mixed well with pulp, and there is no particular limitation on the timing of addition or the method of addition. The papermaking itself is performed according to a conventional method, and the papermaking additive containing the silicon-containing water-soluble polymer compound of the present invention may be added to the aqueous pulp slurry and mixed well before papermaking. On this occasion,
A filler is generally added, and for example, talc, white carbon, titanium oxide, calcium carbonate or the like can be used as the filler. The amount of the filler added is preferably about 0.1 to 10% by weight based on the dry weight of pulp. Further, other chemicals used in ordinary papermaking, such as aluminum sulfate (so-called sulfuric acid band), sizing agents, size fixing agents, and other paper strength agents and retention agents can be blended.

The paper-making additive containing the silicon-containing water-soluble polymer compound of the present invention has an excellent effect in enhancing the paper strength of the obtained paper and improving the fixing rate of the filler in the papermaking process in the pulp system containing the filler. Exert. The effect is particularly remarkable when white carbon is used as a filler.

[0056]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples,% indicating the content or the used amount is
Unless otherwise stated, it is% by weight, and pH and viscosity were measured at 25 ° C.

Further, elemental analysis of the obtained silicon-containing polymer compound was carried out by adding acetone to an aqueous solution of this compound to cause precipitation, taking out this polymer compound and drying it, and then simultaneously analyzing the C, H, and N analyzers. And ICP (inductively coupled plasma) emission spectroscopy analyzer.

Example 1 A four-necked flask equipped with a thermometer, a stir bar, a dropping funnel and a reflux condenser was charged with 50 g (0.5 mol) of 98% sulfuric acid and 106 g of ion-exchanged water, and the temperature was lowered to 20 ° C. or lower. With cooling, 111.2 g (1 mol) of diallylmethylamine was charged. After adjusting the pH to 3.0 with sulfuric acid and replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. After adding 1.6 g of ammonium persulfate, the temperature was kept for 5 hours while keeping the internal temperature at 60 to 80 ° C. The product obtained is an aqueous solution of 60% polymer component,
The pH was 3.1 and the viscosity was 53 poise.

To 134 g of this aqueous solution were further added 362 g of ion-exchanged water and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane, and the temperature was 25 to 30 ° C.
The temperature was kept for 2 hours to obtain an aqueous solution of a silicon-containing polymer compound. This had a polymer content of 20%, a pH of 3.1 and a viscosity of 18 centipoise. The elemental analysis values of this polymer were as follows.

C 51.4%; H 8.5%; N 7.7
%; Si 0.9%.

Example 2 In the same container used in Example 1, 50 g of 98% sulfuric acid was added.
(0.5 mol) and 145 g of ion-exchanged water were charged, and while cooling to 20 ° C. or lower, diallylamine 97.2
g (1 mol) was charged. Adjust the pH to 3.0 with sulfuric acid,
After replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 50 ° C. Ammonium persulfate 2
After adding g, 3 while keeping the internal temperature at 50-60 ° C.
It was kept warm for 0 hours. Further, 292 g of ion-exchanged water was added to obtain an aqueous solution having a polymer content of 25%, a pH of 3.1 and a viscosity of 130 centipoise.

234 g of this aqueous solution is mixed with ion-exchanged water 23
5 g and 13.9 g (0.05 mol) of 3-glycidoxypropyltriethoxysilane were added, and the mixture was kept warm at 25 to 30 ° C. for 2 hours to obtain an aqueous solution of a silicon-containing polymer compound.
This product contains 15% polymer, pH 3.1 and viscosity 67.
It was centipoise. The elemental analysis values of this polymer were as follows.

C 47.3%; H 7.6%; N 7.6
%; Si 1.6%.

Example 3 In addition to 234 g of the 25% aqueous solution of the cationic polymer obtained in the first half of Example 2, 423 g of ion-exchanged water and 4-glycidoxypropyltrimethoxysilane 4 were further added.
7.2 g (0.2 mol) was added and the mixture was kept at 25 to 30 ° C. for 2 hours to obtain an aqueous solution of a silicon-containing polymer compound. This had a polymer content of 15%, had a pH of 3.1 and a viscosity of 64 centipoise. The elemental analysis values of this polymer were as follows.

C 47.4%; H 7.9%; N 5.4
%; Si 4.4%.

Example 4 In the same container used in Example 1, 50 g of 36% concentrated hydrochloric acid was added.
(0.5 mol), 134.7 g (0.5 mol) of 60% diallyldimethylammonium chloride aqueous solution and 12 g of ion-exchanged water were charged, and while further cooling to 20 ° C. or lower, diallylamine 48.5 g (0.5 mol) Was charged.
After adjusting the pH to 3.0 with hydrochloric acid and replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. After adding 1.6 g of ammonium persulfate, the temperature was kept for 5 hours while keeping the internal temperature at 60 to 80 ° C. The obtained product was an aqueous solution containing 60% of a polymer component and had a pH of 3.2 and a viscosity of 73 poises.

To 124 g of this aqueous solution, 295 g of ion-exchanged water and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the temperature was adjusted to 25-30 ° C.
The temperature was kept for 2 hours to obtain an aqueous solution of a silicon-containing polymer compound. This had a polymer content of 20%, a pH of 3.1 and a viscosity of 16 centipoise. The elemental analysis values of this polymer were as follows.

C 55.2%; H 9.1%; N 8.3
%; Si 1.2%.

Example 5 To the same container as used in Example 1, 23.4 g of polyallylamine hydrochloride (manufactured by Nitto Boseki Co., Ltd., 10S type) and 266 g of ion-exchanged water were added, and the pH was adjusted to 3.0 with hydrochloric acid. After adjustment, 3-glycidoxypropyltrimethoxysilane 2
3.6 g (0.1 mol) was added, and the mixture was kept at 25 to 30 ° C for 2 hours to obtain an aqueous solution of a silicon-containing polymer compound. This had a polymer content of 20%, a pH of 3.1 and a viscosity of 17 centipoise. The elemental analysis values of this polymer were as follows.

C 47.4%; H 8.8%; N 7.5
%; Si 5.1%.

Example 6 In the same container used in Example 1, diallylamine 35 was added.
g (0.36 mol), 17.1 g (0.24 mol) of acrylamide and 346 g of deionized water were charged, and further 20
While cooling below ℃, 36% concentrated hydrochloric acid 36.5g (0.36g)
Mol). After adjusting the pH to 3.0 with hydrochloric acid and replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 70 ° C. After adding 0.4 g of ammonium persulfate, the temperature was kept for 10 hours while keeping the internal temperature at 65 to 75 ° C. The obtained product was an aqueous solution containing 15% of a polymer component, and had a pH of 3.0 and a viscosity of 4.4 poise.

To 242 g of this aqueous solution, 133 g of ion-exchanged water and 23.6 g (0.1 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was kept warm at 25 to 30 ° C. for 2 hours to give a silicon-containing polymer. An aqueous solution of the compound was obtained. This had a polymer content of 15%, had a pH of 3.0 and a viscosity of 4.3 poise. The elemental analysis values of this polymer were as follows.

C 50.0%; H 7.0%; N 8.1
%; Si 4.1%.

Example 7 In the same container as used in Example 1, 59.1 g (0.2 mol) of 50% diallylmethylamine hydrochloride aqueous solution and 343 g of ion-exchanged water were charged, and the pH was adjusted to 3.0 with hydrochloric acid. Adjusted to. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. After adding 0.6 g of ammonium persulfate, 113.7 g (0.8 mol) of 50% acrylamide aqueous solution and 60 g of 1% sodium hypophosphite aqueous solution were added over about 3 hours while maintaining the internal temperature at 55 to 65 ° C. Dropped. After dropping, the internal temperature is 55-65 ° C.
It was kept warm for 5 hours. The obtained product is a polymer component 15
% Aqueous solution, the pH was 3.0 and the viscosity was 74 poise.

To 288 g of this aqueous solution, 14 g of ion-exchanged water and 2.4 g (0.01 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was added at 25-30 ° C. for 2 hours.
After keeping the temperature for a while, an aqueous solution of a silicon-containing polymer compound was obtained. This had a polymer content of 15%, a pH of 3.0 and a viscosity of 68 poise. The elemental analysis values of this polymer were as follows.

C 52.2%; H 7.6%; N 1
5.5%; Si 0.4%.

Example 8 In the same container as used in Example 1, 26.3 g (0.09 mol) of 50% diallylamine sulfate aqueous solution and 232 g of ion-exchanged water were charged, and the pH was adjusted to 3.0 with sulfuric acid. Next, after replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. Ammonium persulfate 0.4
After adding g, while maintaining the internal temperature at 55 to 65 ° C,
68.2 g (0.48 mol) of 50% acrylamide aqueous solution,
A mixture of 2.7 g (0.03 mol) of 80% acrylic acid aqueous solution and 0.04 g of sodium hypophosphite was added dropwise over about 3 hours. After the dropping was completed, the temperature was kept at 55 to 65 ° C for 5 hours. The obtained product was an aqueous solution containing 15% of a polymer component, and had a pH of 3.0 and a viscosity of 81 poise.

To 275 g of this aqueous solution, 14 g of ion-exchanged water and 2.4 g (0.01 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was heated at 25-30 ° C. for 2 hours.
After keeping the temperature for a while, an aqueous solution of a silicon-containing polymer compound was obtained. It had a polymer content of 15%, a pH of 3.0 and a viscosity of 74 poises. The elemental analysis values of this polymer were as follows.

C 49.8%; H 7.2%; N 1
6.1%; Si 0.5%.

Example 9 244 g of deionized water was placed in the same container as used in Example 1.
Was charged, the pH was adjusted to 3.0 with sulfuric acid, and then the air inside the apparatus was replaced with nitrogen gas to make it oxygen-free, and then the internal temperature was adjusted to
The temperature was raised to 0 ° C. After adding 0.8 g of ammonium persulfate, 27.4 g of 50% diethylaminoethyl acrylate sulfate aqueous solution while maintaining the internal temperature at 55 to 65 ° C.
(0.06 mol), 50% acrylamide aqueous solution 72.5 g
(0.51 mol) and 80% acrylic acid aqueous solution 2.7 g
A mixed solution of (0.03 mol) was added dropwise over about 3 hours. After the dropping was completed, the temperature was kept at 55 to 65 ° C for 5 hours. The product obtained was an aqueous solution containing 15% of a polymer component and had a pH of 3.0,
The viscosity was 43 poise.

To 290 g of this aqueous solution, 14 g of ion-exchanged water and 2.4 g (0.01 mol) of 3-glycidoxypropyltrimethoxysilane were further added, and the mixture was heated at 25-30 ° C. for 2 hours.
After keeping the temperature for a while, an aqueous solution of a silicon-containing polymer compound was obtained. This had a polymer content of 15%, a pH of 3.0, and a viscosity of 38 poise. The elemental analysis values of this polymer were as follows.

C 50.4%; H 7.1%; N 1
4.6%; Si 0.4%.

Example 10 Acrylamide 7 was placed in the same container used in Example 1.
After charging 1.1 g (1 mol) and 403 g of ion-exchanged water and replacing the air in the apparatus with nitrogen gas to make it oxygen-free, the internal temperature was raised to 60 ° C. and ammonium persulfate 0.7
g and 0.36 g of sodium bisulfite were added. The internal temperature reached 95 ° C. due to heat generation, and the temperature was kept at 85 to 95 ° C. for 5 hours. After cooling the inner temperature to 20 ° C., 33 g of 48% aqueous sodium hydroxide solution and 30 g of sodium hypochlorite were added, and the mixture was kept at about 25 ° C. for 30 minutes. After further adding 50 g of sodium sulfite, hydrochloric acid and water were added to adjust the pH to 3.0 and the polymer component concentration to 1
Adjusted to 2.5%, a product with a viscosity of 29 poise was obtained.

To 288 g of this aqueous solution, 17 g of ion-exchanged water and 2.4 g (0.01 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was added at 25-30 ° C. for 2 hours.
After keeping the temperature for a while, an aqueous solution of a silicon-containing polymer compound was obtained. It has a polymer content of 12.5% and a pH of 3.1.
The viscosity was 27 poise. The elemental analysis values of this polymer were as follows.

C 48.0%; H 6.9%; N 1
8.4%; Si 0.5%.

Example 11 In the same container used in Example 1, 64 g (0.9 mol) of N-vinylformamide and 5.3 g of acrylonitrile were used.
(0.1 mol) and 608 g of ion-exchanged water were charged, and after replacing the air in the apparatus with nitrogen gas to make it oxygen-free,
The internal temperature was raised to 60 ° C., and 0.2 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added. Internal temperature 6
While maintaining the temperature at 0 to 70 ° C., the temperature was kept for 5 hours to obtain a suspension.
Further, 67 ml of 36% concentrated hydrochloric acid was added, and the mixture was kept at 70 to 80 ° C. for 8 hours and then adjusted to pH 3.0 with hydrochloric acid to obtain an aqueous solution having a viscosity of 1.9 poise and a polymer component concentration of 10%.

To 308 g of this aqueous solution, 212 g of ion-exchanged water and 23.6 g (0.1 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was kept warm at 25 to 30 ° C. for 2 hours to give a silicon-containing polymer. An aqueous solution of the compound was obtained. This product had a polymer content of 10%, a pH of 3.1 and a viscosity of 1.4 poise. The elemental analysis values of this polymer were as follows.

C 38.1%; H 7.5%; N 1
0.5%; Si 4.7%.

Example 12 Polyethyleneimine [manufactured by Nippon Shokubai Co., Ltd., "Epomin P-1000"] 25.8 g, in the same container as used in Example 1,
30% of 98% concentrated sulfuric acid (0.3 mol) and ion-exchanged water 4
After charging 46 g and adjusting the pH to 3.0 with sulfuric acid, 3-
Glycidoxypropyltrimethoxysilane 23.6g
(0.1 mol) was added and kept warm at 25-30 ° C for 2 hours.
An aqueous solution of a silicon-containing polymer compound was obtained. This one is
The polymer component was 15% and had a pH of 3.1 and a viscosity of 18 centipoise. The elemental analysis values of this polymer were as follows.

C 31.8%; H 6.8%; N 1
0.8%; Si 2.9%.

Example 13 In the same container used in Example 1, 146 g of adipic acid was added.
(1 mol) and 103 g (1 mol) of diethylenetriamine were charged, and the temperature was raised while draining water to 155 to 160
Reaction was performed at 16 ° C. for 16 hours. Then, deionized water 210
Gradually added, viscosity 6.1 poise, polymer concentration 50
% Aqueous solution was obtained.

168 g of this aqueous solution was added to ion-exchanged water 33
1 g and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was kept at 20 to 25 ° C for 1 hour. Next, after adding 46.3 g (0.5 mol) of epichlorohydrin and keeping the temperature at 30 to 50 ° C. for 4 hours, 390 g of ion-exchanged water was added, and the pH was adjusted to 3.0 with hydrochloric acid to carry out the reaction. Stopped. The obtained aqueous solution of the silicon-containing polymer compound had a polymer content of 15% and a viscosity of 37 centipoise. The elemental analysis values of this polymer were as follows.

C 49.6%; H 7.5%; N 1
1.9%; Si 0.7%.

Example 14 In the same container as used in Example 1, 51.5 g (0.5 mol) of diethylenetriamine and 182 g of ion-exchanged water were added.
Then, 46.3 g (0.5 mol) of epichlorohydrin was added while maintaining the internal temperature at 20 to 30 ° C. Then, after keeping the temperature at 55 to 60 ° C. for 5 hours, the pH was adjusted to 3.0 and the concentration was 25% using hydrochloric acid and ion-exchanged water to obtain an aqueous solution having a viscosity of 5.4 poise.

To 215 g of this aqueous solution, 277 g of ion-exchanged water and 23.6 g (0.1 mol) of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was kept warm at 25 to 30 ° C. for 2 hours to give a silicon-containing polymer. An aqueous solution of the compound was obtained. This had a polymer content of 15%, had a pH of 3.2 and a viscosity of 49 centipoise. The elemental analysis values of this polymer were as follows.

C 33.7%; H 7.3%; N 1
3.0%; Si 1.9%.

Reference Example 1 248 g of ion-exchanged water was placed in the same container as used in Example 1.
Was charged, the pH was adjusted to 3.0 with hydrochloric acid, the air in the device was replaced with nitrogen gas to make it oxygen-free, and then the internal temperature was 60 ° C.
The temperature rose. After adding 0.8 g of ammonium persulfate, 15.6 g (0.06 mol) of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution and 72.5 g (0% of 50% acrylamide aqueous solution) while maintaining the internal temperature at 55 to 60 ° C. 0.51 mol) and an aqueous 80% acrylic acid solution (2.7 g, 0.03 mol) were added dropwise over about 3 hours. After the dropping was completed, the temperature was kept at 55 to 65 ° C for 5 hours. The obtained product was an aqueous solution containing 15% of a polymer component, and had a pH of 3.0 and a viscosity of 52 poises.

Application example Canadian Standard Freeness 410cc N
A pulp slurry having a concentration of 0.75% was prepared using / L (1/1) bleached kraft pulp (BKP). To this, aluminum sulfate to pulp dry weight ratio of 2.5
%, And the aqueous solution of each of the silicon-containing polymer compounds obtained in Examples 7 to 9 or the aqueous solution of the polymer compound obtained in Reference Example 1 was 0.2% in terms of solid content to pulp dry weight ratio. , And various fillers shown in Table 1 were added and mixed in a dry weight ratio of 5% to pulp. After stirring for 1 minute, tapp
I Papermaking with a standard type handmade machine, dehydration at 4 kg / cm ² for 7 minutes, drying at 110 ° C for 4 minutes, conditioning at 20 ° C and 65% relative humidity for 15 hours, and rice basis weight of 60 ± 1g / m ²
A handmade paper was obtained.

For each of the obtained samples, the paper quality was evaluated by the following method, and the results are shown in Table 1. Ash content (%): Measured according to JIS P 8128. Breaking length (km): Measured according to JIS P 8113.

[0100]

[Table 1] ^* WC: White carbon ["Tokushiru GU-N" manufactured by Tokuyama Corporation] Ti: Titanium oxide ["R-850" manufactured by Ishihara Sangyo Co., Ltd.] TA: Talc [manufactured by Nippon Talc Co.] Ca: Heavy Calcium carbonate ["Whiten P-30" manufactured by Shiraishi Industry Co., Ltd.]

[0101]

INDUSTRIAL APPLICABILITY The silicon-containing water-soluble polymer compound of the present invention is useful for papermaking additives and other applications where a water-soluble polymer compound having a cationic group is generally used. Among them, when used as an additive for papermaking, it exerts an excellent effect in strengthening the paper strength of the obtained paper and improving the fixing rate of the filler in the papermaking in the pulp system containing the filler. The effect is particularly remarkable when white carbon is used as a filler.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Toshige Hamaguchi 3-98 Kasugadeka, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (9)

[Claims] 1. A water-soluble polymer compound having an amino group or an ammonium group, which is bonded to a silicon-containing compound (S) having an epoxy group. 2. The method according to claim 1, which is obtained by reacting a water-soluble polymer compound (A) having a primary, secondary or tertiary amino group with a silicon-containing compound (S) having an epoxy group. Molecular compound. 3. The polymer compound according to claim 2, wherein the water-soluble polymer compound (A) has a primary or secondary amino group. 4. The polymer compound according to claim 2, wherein the water-soluble polymer compound (A) is a cationic or amphoteric (meth) acrylamide polymer having a primary, secondary or tertiary amino group. 5. The polymer compound according to claim 4, wherein the (meth) acrylamide polymer has a primary or secondary amino group. 6. A compound obtained by reacting an amino compound having a primary, secondary or tertiary amino group with a silicon-containing compound (S) having an epoxy group, and then carrying out a polymerization or polycondensation reaction. 1. The polymer compound according to 1. 7. The polymer compound according to claim 1, wherein the silicon-containing compound (S) is bonded as a silicon atom in an amount of 0.1 to 10% by weight. 8. A water-soluble polymer compound (A) having a primary, secondary or tertiary amino group and a silicon-containing compound (S) having an epoxy group are reacted in water or alcohol. A method for producing a silicon-containing water-soluble polymer compound. 9. A paper-making product comprising a water-soluble polymer compound having an amino group or an ammonium group, the silicon-containing water-soluble polymer compound having a silicon-containing compound (S) having an epoxy group bonded thereto as an active ingredient. Additive.