JP2007204597A - Diallylamine-based copolymer, method for producing the same, and treating agent for rigid surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new diallylamine-based copolymer useful as a component of a treating agent for a rigid surface; to provide a method for producing the copolymer; and to provide the treating agent for the rigid surface containing the copolymer. <P>SOLUTION: The diallylamine-based copolymer has a constituent unit derived from diallylamines, a constituent unit derived from an ethylenically unsaturated sulfonic acid compound and/or an ethylenically unsaturated carboxylic acid compound, and a constituent unit derived from sulfur dioxide. The method for producing the diallylamine-based copolymer involves copolymerizing monomers constituting each of the above constituent units in a polar solvent in the presence of a radical initiator. The treating agent for the rigid surface contains the diallylamine-based copolymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a diallylamine copolymer, a production method thereof, and a hard surface treating agent. More specifically, the present invention relates to a novel diallylamine-based copolymer, an industrially advantageous production method for producing the same in a high yield by a simple operation, and a hard surface treating agent containing the copolymer. Is.

  Conventionally, water-soluble or water-dispersible polymer compounds using allylamines as raw materials have been mainly used in the papermaking field as papermaking agents. For such applications, amphoteric polymer compounds obtained by copolymerizing, for example, monoallylamine compounds and diallylamine compounds with unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid are known ( For example, see Patent Document 1).

In addition, the paper used in the ink jet printer is generally surface-treated with a paper treatment agent, and polyallylamine is used as one of the paper treatment agents, which is useful as a paper treatment agent having excellent light resistance. An allylamine-acrylamide-allylsulfonic acid copolymer (for example, see Patent Document 2) and a diallylamine-allylsulfonic acid-sulfur dioxide-based copolymer (for example, see Patent Document 3) have been developed.
As described above, water-soluble or water-dispersible polymer compounds using allylamines as raw materials have been widely used in the papermaking field.

  On the other hand, as a hard surface treating agent used for the purpose of imparting effects such as drying acceleration and finishing improvement to the hard surface of a watering facility, a copolymer of diallyldimethylammonium chloride and acrylic acid, maleic acid, etc. ( For example, as in Patent Document 4), a polymer compound containing a cationic group is known.

Japanese Patent Laid-Open No. 6-212597 JP 2004-27162 A JP 2004-115675 A Special table 2003-505535 gazette

  However, the conventionally known hard surface treatment agents described above have little effect or little effect on hydrophobic substrates such as plastics. Therefore, there has been a demand for a compound that can be adsorbed and retained on a target surface efficiently even in a small amount even on a hydrophobic substrate, and can be hydrophilized.

  That is, the object of the present invention is to provide a novel diallylamine-based copolymer useful as a hard surface treating agent for a hydrophobic substrate, and an industrially advantageous production method for producing this in a high yield by a simple operation. It is to be.

As a result of intensive studies to achieve the above object, the present inventors have found that a structural unit derived from a diallylamine compound, a structural unit derived from an ethylenically unsaturated sulfonic acid compound or an ethylenically unsaturated carboxylic acid compound, and carbon dioxide. A novel diallylamine-based copolymer having a sulfur-derived structural unit is obtained by using a radical initiator in a polar solvent, diallylamines and quaternary diallylammonium salts, ethylenically unsaturated sulfonic acid compounds and ethylenically unsaturated carboxylic acids. It was found that a high yield was obtained by copolymerizing an acid compound and sulfur dioxide, and that this was useful as a component for a hard surface treatment agent, and the present invention was completed based on this finding. It came to do.

That is, the present invention
(1) (A) General formula (Ia) and general formula (Ib)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group having 7 to 10 carbon atoms having 1 to 10 carbon atoms which may have a hydroxyl group.)
And the acid addition salts thereof, and the general formulas (Ic) and (Id)

(In the formula, R ² may have a hydroxyl group and may be an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ³ may be an alkyl group having 1 to 4 carbon atoms or a carbon number 7 to 10). aralkyl group, D ^- is - indicates the valency of the anion).
At least one selected from quaternary ammonium salt structural units represented by the formula (B) (B-1) general formula (II)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, Q ¹ represents a hydrocarbon group having 2 to 10 carbon atoms which may contain an amide group and / or a carbonyloxy group, and X ¹ represents a hydrogen atom, an alkali metal or an ammonium group. Show.)
And / or (B-2) the general formula (III)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, Q ² represents a hydrocarbon group having 1 to 10 carbon atoms, and X ² represents a hydrogen atom, an alkali metal or an ammonium group.)
A structural unit represented by formula (IV):

A diallylamine copolymer characterized by having a structural unit represented by:
(2) The content of (B) structural unit is 0.1 to 60 mol%, the content of (C) structural unit is 0.1 to 60 mol%, and the balance is (A) the structural unit. The diallylamine copolymer according to item (1),
(3) In a polar solvent, in the presence of a radical initiator, (a) General formula (Va)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group having 7 to 10 carbon atoms having 1 to 10 carbon atoms which may have a hydroxyl group.)
And acid addition salts of diallylamines represented by general formula (Vb)

(In the formula, R ² may have a hydroxyl group and may be an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ³ may be an alkyl group having 1 to 4 carbon atoms or a carbon number 7 to 10). aralkyl group, D ^- is - indicates the valency of the anion).
At least one selected from quaternary ammonium salts represented by the formula: (b) (b-1) general formula (VI)

(Wherein R ⁴ is a hydrogen atom or a methyl group, Q ¹ is a hydrocarbon group having 2 to 10 carbon atoms which may contain an amide group and / or a carbonyloxy group, X ¹ is a hydrogen atom, an alkali metal or an ammonium group. Show.)
And / or (b-2) the general formula (VII)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, Q ² represents a hydrocarbon group having 1 to 10 carbon atoms, and X ² represents a hydrogen atom, an alkali metal or an ammonium group.)
A method for producing a diallylamine-based copolymer as described in (1) or (2) above, wherein (c) sulfur dioxide is copolymerized with an ethylenically unsaturated carboxylic acid compound represented by
(4) The polar solvent is water, an inorganic acid, an aqueous solution of an inorganic acid, an aqueous solution of a metal salt of an inorganic acid, an organic acid, an aqueous solution of an organic acid, a polar organic solvent, or a mixed solvent thereof. the method of,
(5) A hard surface treating agent comprising the diallylamine-based copolymer according to (1) or (2) above,
Is to provide.

  According to the present invention, a novel diallylamine-based copolymer useful as a treatment agent that efficiently adsorbs and remains on a hard surface, particularly a hydrophobic hard surface, and modifies the properties of the surface, and this is a simple operation Thus, it is possible to provide an industrially advantageous production method for producing at a high yield and a hard surface treating agent containing the copolymer. In addition, since the copolymer of this invention has moderate hydrophobicity unlike the polymer used for the conventional processing agent for hard surfaces, it is excellent in the effect on a hydrophobic surface.

  The diallylamine-based copolymer of the present invention is a novel compound, and includes (A) general formula (1-a) and general formula (1-b) as structural units.

Units, acid addition salts thereof, and general formulas (1-c) and (1-d)

At least one selected from quaternary ammonium salt structural units represented by the formula (B) (B-1) general formula (II)

And / or (B-2) general formula (III)

And a unit represented by (C) formula (IV)

It has a unit represented by these. This copolymer may be either random or block.

In the structural unit (A), R ¹ in the general formulas (Ia) and (Ib) is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, or 7 to 10 carbon atoms. Represents an aralkyl group. Here, the alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group may be linear, branched or cyclic, and as such, it may have a hydroxyl group. Good alkyl group having 1 to 4 carbon atoms, specifically methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, etc. Furthermore, a cyclohexyl group can be mentioned preferably. Moreover, as an example of a C7-10 aralkyl group, a benzyl group, a phenethyl group, etc. can be mentioned preferably. Among these, a hydrogen atom, a methyl group, an ethyl group, and a benzyl group are particularly preferable.

  Examples of the acid addition salt of the structural unit represented by the general formulas (Ia) and (Ib) include hydrochloride, hydrobromide, acetate, sulfate, nitrate, sulfite, and phosphoric acid. Salts, amide sulfates, methanesulfonates and the like. Among these, hydrochloride, hydrobromide, and acetate are particularly preferable.

Furthermore, in the quaternary ammonium salt structural unit, R ² in the general formulas (Ic) and (Id) is an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group or 7 to 7 carbon atoms. 10 aralkyl groups are shown. These are as described for R ¹ above.

R ³ represents an alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and D ⁻ represents a -valent anion.

The alkyl group having 1 to 4 carbon atoms in R ³ may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and various butyl groups. Examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group. D ^- In The monovalent anion represented may include, for example, halogen ions, such as methyl sulfate ion.

As a specific example of the partial structure of the quaternary ammonium salt structural unit (partial structure represented by> N ⁺ R ² R ³ · D ⁻ in the general formula (Ic) and the general formula (Id)), N, N-dimethylammonium chloride, N, N-diethylammonium chloride, N, N-dipropylammonium chloride, N, N-dibutylammonium chloride, N-methyl-N-benzylammonium chloride, N-ethyl-N-benzyl Ammonium chloride and bromides, iodides, methyl sulfates, and the like corresponding to these chlorides can be mentioned. Of these, N, N-dimethylammonium chloride and N-methyl-N-benzylammonium chloride are preferable.

In the structural unit (B), R ⁴ in the general formula (II) of the structural unit (B-1) is a hydrogen atom or a methyl group, and Q ¹ may contain an amide group and / or a carbonyloxy group. Ten hydrocarbon groups, X ¹ represents a hydrogen atom, an alkali metal or an ammonium group.

Examples of the hydrocarbon group having 2 to 10 carbon atoms in Q ¹ include a linear or branched alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an aralkylene group having 7 to 10 carbon atoms. A linear or branched alkylene group having 4 to 9 carbon atoms which may contain an amide group and / or a carbonyloxy group, an arylene group having 6 to 9 carbon atoms, and an aralkylene having 7 to 9 carbon atoms. It is preferably a group.

Examples of the alkali metal in X ¹ include lithium, sodium, and potassium.

  The structural unit (B-1) is a structural unit derived from an ethylenically unsaturated sulfonic acid compound. For example, styrene sulfonic acid, α-methylstyrene sulfonic acid, vinyl toluene sulfonic acid, vinyl naphthalene sulfonic acid, vinyl benzyl Derived from 2-acrylamido-2-methylpropanesulfonic acid as a compound having an amide group in the main chain and acryloyloxyethylsulfonic acid or methacryloyloxypropylsulfonic acid as a compound having a carbonyloxy group in the main chain A structural unit can be illustrated.

These sulfonic acids can be used free state (X ¹ is a hydrogen atom) also can be used alkali metal salts, as ammonium salt. Examples of alkali metal salts include lithium salts, sodium salts, and potassium salts.
Among these, structural units derived from styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and metal salts thereof are particularly preferable.

  One type of structural unit derived from these ethylenically unsaturated sulfonic acid compounds may be introduced, or two or more types of structural units may be introduced.

On the other hand, R ⁵ in the general formula (III) of the structural unit (B-2) is a hydrogen atom or a methyl group, Q ² is a hydrocarbon group having 1 to 10 carbon atoms, and X ² is a hydrogen atom, an alkali metal or an ammonium group. Indicates.

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by Q ² include a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an aralkylene having 7 to 10 carbon atoms. Although a group can be mentioned, a C3-C9 linear or branched alkylene group is preferable.

  The structural unit (B-2) is a structural unit derived from an ethylenically unsaturated carboxylic acid compound. For example, an ethylenically unsaturated carboxylic acid (ω-alkenylcarboxylic acid), specifically 4-pentenoic acid, Examples include structural units derived from 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, and 11-dodecenoic acid.

These carboxylic acids include, but free state (X ² is a hydrogen atom) also can be used, it is possible to use alkali metal salts, as ammonium salt. Examples of alkali metal salts include lithium salts, sodium salts, and potassium salts.
Among these, structural units derived from 10-undecenoic acid and metal salts thereof are particularly preferable.

  One type of structural unit derived from these ethylenically unsaturated carboxylic acid compounds may be introduced, or two or more types of structural units may be introduced.

  In the diallylamine-based copolymer of the present invention, the (B) constituent unit may have only the (B-1) constituent unit, or (B-2) only the constituent unit. Moreover, you may have both (B-1) structural unit and (B-2) structural unit.

  In the diallylamine-based copolymer of the present invention, the content of the (B) structural unit is preferably 0.1 to 60 mol%, more preferably 1 to 50 mol%, and the content of the (C) structural unit. However, it is preferably 0.1 to 60 mol%, more preferably 1 to 50 mol%, and the remainder being (A) structural unit.

  Moreover, molecular weight is the weight average molecular weight of polyethyleneglycol conversion by a gel permeation chromatography (GPC) method, and is 500-200,000 normally, Preferably it is the range of 800-100,000.

Next, the diallylamine-based copolymer of the present invention can be efficiently produced in high yield by the method of the present invention described below.
In the method of the present invention, (a) the general formula (Va) in the presence of a radical initiator in a polar solvent.

(In the formula, R ¹ is the same as described above.)
And acid addition salts of diallylamines represented by general formula (Vb)

(Wherein R ² , R ³ and D ⁻ are the same as described above.)
At least one selected from quaternary ammonium salts represented by the formula: (b) (b-1) general formula (VI)

(In the formula, R ⁴ , Q ¹ and X ¹ are the same as above.)
And / or (b-2) the general formula (VII)

(Wherein R ⁵ , Q ² and X ² are the same as described above.)
The ethylenically unsaturated carboxylic acid compound represented by the formula (c) and sulfur dioxide are copolymerized.

  Examples of the polar solvent include water, inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, etc.) or aqueous solutions thereof, aqueous solutions of inorganic acid metal salts (zinc chloride, calcium chloride, magnesium chloride, etc.), and organic acids (formic acid). , Acetic acid, propionic acid, lactic acid, etc.) or an aqueous solution thereof, or a polar organic solvent (alcohol, dimethyl sulfoxide, dimethylformamide, etc.), and a mixture thereof may be used. Of these, aqueous solvents are preferred.

  As the radical initiator, for example, a water-soluble radical initiator having an azo group in the molecule (hereinafter sometimes referred to as a water-soluble azo initiator) or a persulfate radical initiator is preferably used. it can. In the present invention, a persulfate radical initiator is particularly preferable as the radical initiator.

As the water-soluble radical initiator having an azo group in the molecule, a radical polymerization initiator having an azo group and a group having a cationic nitrogen in the molecule is preferable. As such a radical polymerization initiator, It can be arbitrarily selected from known compounds, and among them, general formula (VIII)
R ⁶ —N═N—R ⁷ (VIII)
[In the formula, at least one of R ⁶ and R ⁷ is a group containing a cationizable nitrogen atom selected from an aminohydrocarbyl group, an amidinylhydrocarbyl group and a cyanoaminohydrocarbyl group, and the remainder is a hydrocarbyl group or a cyanohydrocarbyl group. And R ⁶ and R ⁷ together are represented by the general formula (IX)

(R is an alkylene group, Y is a group containing a cationizable nitrogen atom, and the covalent bonds (a) and (b) are each bonded to the nitrogen atom of the azo group to form a ring containing the azo group. )
A single alkylene group represented by may be formed. ]
An inorganic acid salt or an organic acid salt of an azo compound represented by the formula is put to practical use in terms of ease of synthesis.

In R ⁶ and R ⁷ in the general formula (VIII), examples of the aminohydrocarbyl group include an aminoalkyl group, an aminoaryl group, an aminoalkaryl group, an aminoaralkyl group, and the like, and examples of the amidinylhydrocarbyl group include Is, for example, an amidinylalkyl group, an amidinylaryl group, an amidinylalkaryl group, an amidinylaralkyl group, etc., and examples of the cyanoaminohydrocarbyl group include a cyanoaminoalkyl group, a cyanoaminoaryl group, A cyanoaminoalkaryl group, a cyanoaminoaralkyl group and the like can be mentioned. Examples of the hydrocarbyl group include an alkyl group, an aryl group, an alkaryl group, and an aralkyl group. Examples of the cyanohydrocarbyl group include a cyanoalkyl group, a cyanoaryl group, a cyanoalkaryl group, and a cyanoaralkyl group. Can be mentioned.

  On the other hand, examples of the alkylene group represented by R in the general formula (IX) include a linear alkylene group, an alkylalkylene group, and an arylalkylene group.

  Examples of the radical polymerization initiator represented by the general formula (IX) include 2,2′-diamidinyl-2,2′-azopropane hydrochloride [2,2′-azobis (2-amidinopropane) hydrochloride 2,2'-diamidinyl-2,2'-azobutane hydrochloride, 2,2'-diamidinyl-2,2'-azopentane hydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N, N-dimethylamidinii) ) -2,2'-azopropane · hydrochloride, 2,2'-bis (N, N-dimethylamidinyl) -2,2'-azobutane · hydrochloride, 2,2'-bis (N, N -Diethylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bi (N, N-diethylamidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N-din-butylamidinyl) -2,2'-azopropane hydrochloride, 2,2 ' -Bis (N-di-n-butylamidinyl) -2,2'-azobutane hydrochloride, 3,3'-bis (N, N-din-butylamidinyl) -3,3'-azopentane hydrochloride, azo- Bis-N, N'-dimethyleneisobutylamidine hydrochloride; 2,2'-azo-bis (2-methyl-4-diethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl) -4-dimethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl-4-diethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl-4-) Diethylamino) -butyronitrile Or quaternary ammonium salt form azonitrile obtained by quaternization of 2,2'-azo-bis (2-methyl-4-dimethylamino) -butyronitrile with dimethylsulfuric acid or methyl p-toluenesulfonate; 5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3-methyl-3,4-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3-ethyl-3,5-diamidinyl- 1,2-diazo-1-cyclopentene hydrochloride, 3,5-dimethyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,6-diamidinyl-1,2-diazo- 1-cyclohexene hydrochloride, 3-phenyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,5-diphenyl-3,5-dia Jiniru 1,2-diazo-1-cyclopentene hydrochloride and the like. In the case of hydrochloride, it may be dihydrochloride.

  Further, as the water-soluble azo initiator, the general formula (X)

[Wherein R ^{8 to} R ¹¹ are each independently a lower alkyl group, and R ¹² and R ¹³ are each independently a group of the general formula (XI)

(However, Z is an alkylene group having 1 to 12 carbon atoms)
A hydroxyalkylamide group or a hydroxyalkylester group represented by The compound represented by this can also be used.

In the general formula (X), examples of the lower alkyl group represented by R ^{8 to} R ¹¹ include a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, and the alkyl group is linear, branched, It may be any of cyclic and one or more carbon atoms may be substituted by O, S or N. For example, R ^{8 to} R ¹¹ may be an alkoxyalkyl group having 2 to 9 carbon atoms.

Among the compounds represented by the general formula (X), R ^{8 to} R ¹¹ are all methyl groups, and as R ¹² and R ¹³ , Z in the general formula (XI) is an ethylene group 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is particularly preferable.

  Further, as water-soluble azo initiators, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azobis (2-methylbutanamidoxime) hydrochloride and the like are also included. It can be preferably used.

  As these water-soluble azo initiators, one kind may be used alone, or two or more kinds may be used in combination.

  On the other hand, examples of the persulfate-based radical initiator include ammonium persulfate, sodium persulfate, and potassium persulfate. These may be used alone or in combination of two or more.

  Further, as other radical initiators, catalysts usually used for radical polymerization, for example, organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and ascaridol Organic azo compounds such as azobisisobutyronitrile and azobisisobutyric acid amide, and various redox catalysts can also be used.

  In the method of the present invention, as a raw material monomer, (a) an acid addition salt of a diallylamine represented by the general formula (Va) and a quaternary ammonium salt represented by the general formula (Vb) At least one selected from the group consisting of (b) (b-1) an ethylenically unsaturated sulfonic acid compound represented by the general formula (VI) and / or (b-2) the general formula (VII) The ethylenically unsaturated sulfonic acid compound represented and (c) sulfur dioxide are used.

Here, as the acid addition salt of diallylamines represented by the general formula (Va) as the component monomer (a), diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N- Hydrochloride, hydrobromide, sulfate, nitrate, sulfite, phosphate, amide of butyl diallylamine, N-2-hydroxyethyl diallylamine, N-2-hydroxypropyl diallylamine, N-3-hydroxypropyl diallylamine, etc. Examples of quaternary ammonium salts of diallylamines represented by the general formula (Vb) such as sulfate and methanesulfonate include diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, Diallyldimethylammonium methylsulfate, Diallyl diethyl ammonium bromide, diallyl diethyl ammonium bromide, diallyl diethyl ammonium iodide, diallyl diethyl ammonium methyl sulfate, diallyl methyl benzyl ammonium chloride, diallyl methyl benzyl ammonium bromide, diallyl methyl benzyl ammonium iodide, diallyl methyl benzyl ammonium methyl sulfate, Examples include diallylethylbenzylammonium chloride, diallylethylbenzylammonium bromide, diallylethylbenzylammonium iodide, diallylethylbenzylammonium methylsulfate, and the like. Among these, diallylamine, diallyldimethylammonium chloride, diallyldimethylammonium sulfate, diallyldiethylammonium chloride, and diallylmethylbenzylammonium chloride are preferable.

  These (a) component monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) Component monomer (b-1) As the ethylenically unsaturated sulfonic acid compound represented by the general formula (VI), styrene sulfonic acid, α-methyl styrene sulfonic acid, vinyl toluene sulfonic acid, Examples thereof include vinyl naphthalene sulfonic acid, vinyl benzyl sulfonic acid, and the like. Furthermore, as ethylenically unsaturated sulfonic acid containing amide group, 2-acrylamido-2-methylpropane sulfonic acid, etc., and ethylenically unsaturated containing carbonyloxy group Examples of the sulfonic acid include acryloyloxyethyl sulfonic acid and methacryloyloxypropyl sulfonic acid. These sulfonic acids can be used free state (X ¹ is a hydrogen atom) also can be used alkali metal salts, as ammonium salt. Examples of alkali metal salts include lithium salts, sodium salts, and potassium salts. Among these, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and sodium salts thereof are preferable.

  These sulfonic acid compounds may be used alone or in combination of two or more.

  On the other hand, (b-2) the ethylenically unsaturated carboxylic acid compound represented by the general formula (VII) includes 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid and 8-nonene. Examples thereof include acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid and the like. Among these, 10-undecenoic acid is preferable.

These carboxylic acids include, but free state (X ² is a hydrogen atom) also can be used, it is possible to use alkali metal salts, as ammonium salt. Examples of alkali metal salts include lithium salts, sodium salts, and potassium salts.

  These carboxylic acid compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the present invention, as the component (b), only the component (b-1) may be used, or only the component (b-2) may be used, and the component (b-1) and the component (b- 2) Components may be used in combination.

As a polymerization method in the present invention, for example, a predetermined proportion of the (a) component monomer, (b) component monomer, and (c) component monomer are added to the polar solvent, and the radical initiator is added to the total amount of monomers. On the other hand, it is preferably added at a ratio of 0.1 to 10 mol%, more preferably 0.5 to 7 mol%, and the polymerization reaction is carried out at a temperature of about 0 to 100 ° C, preferably 25 to 75 ° C. The reaction time depends on the type of monomer, the type of radical initiator, the reaction temperature, and the like, and cannot be generally defined, but is usually within 200 hours. In addition, the sulfur dioxide of (c) component monomer is normally added in gaseous form.

  The polymerization reaction is carried out in the above-mentioned polar solvent according to a conventional method. Usually, the produced copolymer is precipitated as the polymerization proceeds. However, when the polymerization is performed in an aqueous solvent, the copolymer may not be precipitated until the end depending on the type and concentration of the monomer.

  The produced polymer is filtered off as it is, or precipitated with a suitable solvent and filtered off. However, when polymerized in an aqueous solvent, it may be put to practical use as it is.

  The diallylamine-based copolymer thus obtained is useful as a component of a hard surface treating agent, for example. When treated with a hard surface treating agent containing this copolymer, the moderate hydrophobicity of the copolymer is effective on the surface of hard substrates, especially hydrophobic hard substrates such as plastics and resins. It is adsorbed and retained well, and the cationic groups and anionic groups in the copolymer change the properties of the hard substrate surface, such as hydrophilicity / hydrophobicity. That is, the hard surface treating agent capable of modifying the wettability of the hydrophobic substrate surface is obtained by the copolymer of the present invention. Furthermore, by optimizing the types and ratios of the constituent units of the copolymer, it becomes possible to make the substrate surface hydrophilic and impart water drainage. The term “water break” as used herein refers to a phenomenon in which, when a treated substrate surface is washed with water, for example, after a water film is formed once, it is cleanly cut without remaining water droplets or water film fragments. . If the substrate is dried with water droplets or water film fragments remaining, so-called water spots are formed due to, for example, impurities contained in tap water, which is unfavorably aesthetically pleasing. The provision of water drainage is useful as a method for solving this problem, and at the same time leads to accelerated drying, and is also expected to have an effect of preventing the occurrence of mold.

  The hard surface treating agent of the present invention contains one or more of the aforementioned diallylamine-based copolymers of the present invention. The hard surface treating agent of the present invention may consist of a copolymer alone, or may be dissolved or dispersed in water or a solvent. Further, the hard surface treating agent of the present invention includes various surfactants; silicones; oils excluding silicones such as squalene, squalane, paraffin, vegetable oil, animal oil, higher alcohol, polyhydric alcohol, fatty acid, fatty acid ester; Preservatives; chelating agents; moisturizers; colorants such as dyes and pigments; viscosity modifiers such as hydroxyethylcellulose, methylcellulose, polyethylene glycol and clay minerals; pH adjusters such as citric acid and potassium hydroxide; plant extracts; A fragrance | flavor; Ultraviolet absorber; Antioxidant etc. can also be included.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The polymerization average molecular weight of the copolymer was measured according to the following method.

<Measurement of weight average molecular weight of copolymer>
The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC) using a Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS- 620HQ (exclusion limit molecular weight 2 million) and a double connection were used. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. A 0.4 mol / L sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. Molecular weight 106, 194 as standard sample
A calibration curve was determined using polyethylene glycol such as 440, 600, 1470, 4100, 7100, 10300, 12600, 23000, and the weight average molecular weight (Mw) of the copolymer was determined based on the calibration curve.

Example 1 Copolymer of diallyldimethylammonium chloride, 2-acrylamido-2-methylpropanesulfonic acid and sulfur dioxide (2: 1: 1)
In a 1 liter four-necked separable flask equipped with a stirrer, Dimroth reflux, and thermometer, 52.87 g (0.25 mol) of 2-acrylamido-2-methylpropanesulfonic acid, 102 g of distilled water, diallyldimethyl 80.84 g (0.5 mol) of ammonium chloride was charged. To the mixture was added 16.02 g (0.25 mol) of sulfur dioxide. To the resulting mixture, 4.56 g (0.02 mol) of ammonium persulfate was added, and polymerization was carried out at 45 ° C. for 24 hours. When a part of the obtained copolymer solution was taken and water was added to bring the polymer concentration to 10% by mass, the solution became cloudy. However, it was dissolved when salt was added to it. This behavior was the same for other copolymers (copolymers of Examples 2 to 3). When a part of the copolymer solution was reprecipitated with an acetone solvent, a copolymer of diallyldimethylammonium chloride, 2-acrylamido-2-methylpropanesulfonic acid and sulfur dioxide with a reprecipitation yield of 74% (2: 1: 1) was obtained. The IR spectrum is shown in FIG. 1, and the chromatogram obtained by GPC measurement is shown in FIG. The weight average molecular weight of the copolymer by GPC was 6100.
The IR spectrum, 1540 cm ^-1 in -CONH- (amide) derived, from 1,120 cm ^-1 to SO ₂ (sulfur dioxide), there are absorption from sulfonic acid 1200 cm ^-1, and supports the structure.

Example 2 Copolymer of diallylmethylamine hydrochloride, 2-acrylamido-2-methylpropanesulfonic acid and sulfur dioxide (2: 1: 1)
The same treatment as in Example 1 was carried out using 73.83 g (0.5 mol) of diallylmethylamine hydrochloride instead of diallyldimethylammonium chloride, and diallylmethylamine hydrochloride and 2-acrylamide- were obtained in a reprecipitation yield of 80%. A copolymer of 2-methylpropanesulfonic acid and sulfur dioxide (2: 1: 1) was obtained.
The weight average molecular weight of this copolymer by GPC was 4500.

Example 3 Copolymer of diallylamine hydrochloride, 2-acrylamido-2-methylpropanesulfonic acid and sulfur dioxide (2: 1: 1)
The same treatment as in Example 1 was carried out using 66.81 g (0.5 mol) of diallylamine hydrochloride instead of diallyldimethylammonium chloride, and diallylamine hydrochloride and 2-acrylamido-2-methylpropane were obtained in a reprecipitation yield of 71%. A copolymer of sulfonic acid and sulfur dioxide (2: 1: 1) was obtained.
The weight average molecular weight of this copolymer by GPC was 5000.

Example 4 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (4: 1: 5)
In a four-necked separable flask equipped with a stirrer, a Dimroth reflux condenser, and a thermometer, 19.33 g (0.075 mol) of a sodium styrenesulfonate aqueous solution having a concentration of 80% by mass, 102 g of distilled water, and a concentration of 65% by mass 74.62 g (0.30 mol) of diallyldimethylammonium chloride was charged. To the mixture was added 24.02 g (0.375 mol) of sulfur dioxide. To the resulting mixture, 1.711 g (0.0075 mol) of ammonium persulfate was added, and polymerization was performed at 45 ° C. for 24 hours.
A part of the copolymer solution was reprecipitated with an acetone solvent to obtain a copolymer (4: 1: 5) of diallyldimethylammonium chloride, sodium styrenesulfonate, and sulfur dioxide. The polymerization yield was quantitative. The results of elemental analysis are C = 40.51, H = 6.43, N =
4.80 and S = 15.28, which were close to the theoretical values (C = 40.95, H = 6.10, N = 4.78, S = 16.40).
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 5 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (9: 1: 10)
In Example 4, the amount of sodium styrenesulfonate having a concentration of 80% by mass was 12.89 g (0.05 mol), the amount of distilled water was 73 g, and the amount of diallyldimethylammonium chloride having a concentration of 65% by mass was 111.93 g ( 0.45 mol), treated in the same manner as in Example 4 except that 32.03 g (0.5 mol) of sulfur dioxide and 2.28 g (0.01 mol) of ammonium persulfate were used. A copolymer (9: 1: 10) of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide was obtained.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 6 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (24: 1: 25)
In Example 4, the amount of sodium styrenesulfonate having a concentration of 80% by mass was 5.15 g (0.02 mol), the amount of distilled water was 71 g, and the amount of diallyldimethylammonium chloride having a concentration of 65% by mass was 119.39 g ( 0.48 mol), treated in the same manner as in Example 4 except that 32.03 g (0.5 mol) of sulfur dioxide and 2.28 g (0.01 mol) of ammonium persulfate were used. A copolymer (24: 1: 25) of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide was obtained.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 7 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (2: 1: 1)
In Example 4, the amount of sodium styrenesulfonate having a concentration of 80% by mass was 38.66 g (0.15 mol), the amount of distilled water was 132 g, and the amount of diallyldimethylammonium chloride having a concentration of 65% by mass was 119.39 g ( 0.30 mol), 9.61 g (0.15 mol) of sulfur dioxide and 1.37 g (0.006 mol) of ammonium persulfate were used in the same manner as in Example 4 to obtain a polymerization yield. A copolymer (2: 1: 1) of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide was obtained at a rate of 90%.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 8 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (1: 4: 5)
In Example 4, the amount of sodium styrenesulfonate having a concentration of 80% by mass was 12.81 g (0.16 mol), the amount of distilled water was 197 g, and the amount of diallyldimethylammonium chloride having a concentration of 65% by mass was 9.75 g ( 0.04 mol), treated in the same manner as in Example 4 except that 12.81 g (0.2 mol) of sulfur dioxide and 0.91 g (0.004 mol) of ammonium persulfate were used. A copolymer (1: 4: 5) of diallyldimethylammonium chloride, sodium styrenesulfonate, and sulfur dioxide was obtained.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 9 Copolymer of diallyldimethylammonium chloride, sodium styrenesulfonate and sulfur dioxide (1: 4: 5)
In Example 4, the amount of sodium styrenesulfonate having a concentration of 80% by mass was 12.81 g (0.15 mol), the amount of distilled water was 1332 g, and the amount of diallyldimethylammonium chloride having a concentration of 65% by mass was 18.65 g ( 0.60 mol), processed in the same manner as in Example 1 except that 48.05 g (0.75 mol) of sulfur dioxide and 3.42 g (0.015 mol) of ammonium persulfate were used. A copolymer (1: 4: 5) of diallyldimethylammonium chloride, sodium styrenesulfonate, and sulfur dioxide was obtained.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 10 Copolymer of diallylamine hydrochloride, sodium styrenesulfonate and sulfur dioxide (1: 4: 5)
In Example 4, instead of diallyldimethylammonium chloride, 100.79 g (0.2 mol) of diallylamine hydrochloride having a concentration of 66.29% by mass, and 128.87 g (0. 8 mol), 375 g of distilled water, 64.06 g (1 mol) of sulfur dioxide, and 4.56 g (0.02 mol) of ammonium persulfate were used in the same manner as in Example 1. Quantitatively, a copolymer (1: 4: 5) of diallylamine hydrochloride, sodium styrenesulfonate and sulfur dioxide was obtained.
The weight average molecular weight of this copolymer was 82,000.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 11 Copolymer of diallylmethylamine hydrochloride, sodium styrenesulfonate and sulfur dioxide (1: 4: 5)
In Example 4, instead of diallyldimethylammonium chloride, 105.60 g (0.2 mol) of diallylmethylamine hydrochloride having a concentration of 69.91% by mass, and 128.87 g of sodium styrenesulfonate having a concentration of 80% by mass ( 0.8 mol), 390 g of distilled water, 64.06 g (1 mol) of sulfur dioxide, and 4.56 g (0.02 mol) of ammonium persulfate were used in the same manner as in Example 1. After the treatment, a copolymer (1: 4: 5) of diallylmethylamine hydrochloride, sodium styrenesulfonate and sulfur dioxide was quantitatively obtained.
The weight average molecular weight of this copolymer was 72,000.
The copolymer became cloudy when water was added to bring the polymer concentration to 10% by mass.

Example 12 Preparation of a copolymer of diallyldimethylammonium chloride, undecenoic acid and sulfur dioxide (1: 1: 2) 92.14 g (0.5 mol), distilled water 100 g, ethyl alcohol 158 g, diallyldimethylammonium chloride 80.84 g (0.5 mol) were charged. To the mixture was added 64.07 g (1.0 mol) of sulfur dioxide. 48.04 g (0.06 mol) of 28.5 mass% aqueous ammonium persulfate solution was added to the resulting mixture, and copolymerization was carried out at 45 ° C. for 48 hours. The resulting mixture was suspended.
A part of this copolymer suspension was reprecipitated with ethyl alcohol, and the resulting solid was vacuum-dried at 50 ° C. to give a copolymer of diallyldimethylammonium chloride, undecenoic acid and sulfur dioxide (1 1: 2) was obtained. The polymerization yield was quantitative.

Example 13 Preparation of copolymer of diallyldimethylammonium chloride, undecenoic acid and sulfur dioxide (4: 1: 5) In Example 12, 36.86 g (0.2 mol) of undecenoic acid, 154 g of distilled water, ethyl alcohol 154 g, diallyldimethylammonium chloride 129.34 g (0.8 mol), sulfur dioxide 64.07 g (1.0 mol), 28.5 mass% ammonium persulfate aqueous solution 80.07 g (0.1 mol) were used. In the same manner as in Example 1, a copolymer (4: 1: 5) of diallyldimethylammonium chloride, undecenoic acid and sulfur dioxide was quantitatively obtained as a suspension.
FIG. 3 shows the IR spectrum, and FIG. 4 shows the chromatogram obtained by GPC measurement.
IR spectra from SO ₂ to 1,120 cm ^-1, there are absorption from COOH to 1720 cm ^-1, and supports the structure. The weight average molecular weight was 4800.

Example 14 Preparation of a copolymer of diallylmethylamine hydrochloride, undecenoic acid and sulfur dioxide (4: 1: 5) In Example 12, instead of diallyldimethylammonium chloride, 118.12 g of diallylmethylamine hydrochloride ( 0.8 mol) and 36.86 g (0.2 mol) of undecenoic acid, 51 g of distilled water, 95 g of ethyl alcohol, 64.07 g (1.0 mol) of sulfur dioxide, 7.82 g (0 mol of 35% by weight ammonium persulfate aqueous solution) .012 mol), except that a copolymer of diallylmethylamine hydrochloride, undecenoic acid and sulfur dioxide (4: 1: 5) was quantitatively used as a suspension. Obtained.

Example 15 Hard Surface Treatment Agent A 0.5% by mass aqueous solution of the polymer obtained in Example 14 (adjusted to pH 7 with sodium hydroxide) was prepared, and water drainage was evaluated by a specialized panel. The term “water break” here means that a water film is once formed on the surface of the substrate and then cut without leaving a water droplet or a water film.
(Evaluation method) The treatment was carried out by applying 3 mL of a treatment agent to a commercially available polyvinyl chloride plate (25 cm × 8 cm) and rinsing with tap water (flow rate: about 50 mL / second) for 30 seconds. Immediately after rinsing, the water drainage time on the treated surface (the time required for the water film to recede), the number of residual water droplets after the water drainage and the state of the residual water were observed, and the determination was made according to the following criteria (rinse once). Further, after rinsing was repeated 4 times, the same observation was made (5 times rinsing).
-Number of residual water droplets A: Less than 5 per test plate B: 5 or more per test plate C: Some parts remain wet (evaluation results)
As shown in Table 1, the results of drainage time and the number of residual water droplets are shown. After forming a water film on the entire treated surface, it was drained and water droplets remained very little. There was no formation of water spots after drying, which was an aesthetically pleasing state.

Comparative Example 1
Evaluation similar to Example 15 was performed on diallyldimethylammonium chloride / acrylic acid copolymer (trade name; Marquat 280, manufactured by Ondeo Nalco).
(Evaluation results)
As shown in Table 1, the results of drainage time and the number of residual water droplets are shown. Non-uniform water breakage occurred on the treated surface, and not only a large number of water droplets remained, but there were also portions that remained wet in the form of islands. After drying, the formation of water spots was seen, which was an aesthetically unfavorable state.

Comparative Example 2
Evaluation similar to Example 15 was performed using only water containing no polymer.
(Evaluation results)
Table 1 shows the results of the number of residual water droplets. Water was repelled without forming a water film on the substrate surface. Since the water did not run out, water droplets remained throughout. After drying, the formation of water spots was seen, which was an aesthetically unfavorable state.

  The diallylamine-based copolymer of the present invention is a copolymer of diallylamines, an ethylenically unsaturated sulfonic acid compound and / or an ethylenically unsaturated carboxylic acid compound and sulfur dioxide, and is a component of a hard surface modifier. Useful as.

2 is an IR spectrum diagram of the copolymer obtained in Example 1. FIG. 2 is a chromatogram obtained by GPC measurement of the copolymer obtained in Example 1. 4 is an IR spectrum diagram of the copolymer obtained in Example 13. FIG. It is a chromatogram by GPC measurement of the copolymer obtained in Example 13.

Claims (5)

(A) General formula (Ia) and general formula (Ib)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group having 7 to 10 carbon atoms having 1 to 10 carbon atoms which may have a hydroxyl group.)
And the acid addition salts thereof, and the general formula (Ic) and the general formula (Id)

(In the formula, R ² may have a hydroxyl group and may be an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ³ may be an alkyl group having 1 to 4 carbon atoms or a carbon number 7 to 10). aralkyl group, D ^- is - indicates the valency of the anion).
At least one selected from quaternary ammonium salt structural units represented by the formula (B) (B-1) general formula (II)

(Wherein R ⁴ represents a hydrogen atom or a methyl group, Q ¹ represents a hydrocarbon group having 2 to 10 carbon atoms which may contain an amide group and / or a carbonyloxy group, and X ¹ represents a hydrogen atom, an alkali metal or an ammonium group. Show.)
And / or (B-2) the general formula (III)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, Q ² represents a hydrocarbon group having 1 to 10 carbon atoms, and X ² represents a hydrogen atom, an alkali metal or an ammonium group.)
A structural unit represented by formula (IV):

A diallylamine-based copolymer, comprising: a structural unit represented by:   The content of (B) constituent unit is 0.1 to 60 mol%, the content of (C) constituent unit is 0.1 to 60 mol%, and the balance is (A) constituent unit. The diallylamine-based copolymer described. In a polar solvent, in the presence of a radical initiator, (a) the general formula (Va)

(In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group having 7 to 10 carbon atoms having 1 to 10 carbon atoms which may have a hydroxyl group.)
And acid addition salts of diallylamines represented by general formula (Vb)

(In the formula, R ² may have a hydroxyl group and may be an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R ³ may be an alkyl group having 1 to 4 carbon atoms or a carbon number 7 to 10). aralkyl group, D ^- is - indicates the valency of the anion).
At least one selected from quaternary ammonium salts represented by the formula: (b) (b-1) general formula (VI)

(Wherein R ⁴ is a hydrogen atom or a methyl group, Q ¹ is a hydrocarbon group having 2 to 10 carbon atoms which may contain an amide group and / or a carbonyloxy group, X ¹ is a hydrogen atom, an alkali metal or an ammonium group. Show.)
And / or (b-2) the general formula (VII)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, Q ² represents a hydrocarbon group having 1 to 10 carbon atoms, and X ² represents a hydrogen atom, an alkali metal or an ammonium group.)
The method for producing a diallylamine-based copolymer according to claim 1, wherein the ethylenically unsaturated carboxylic acid compound represented by the formula (c) is copolymerized with sulfur dioxide. The method according to claim 3, wherein the polar solvent is water, an inorganic acid, an aqueous solution of an inorganic acid, an aqueous solution of a metal salt of an inorganic acid, an organic acid, an aqueous solution of an organic acid, a polar organic solvent, or a mixed solvent thereof.   The processing agent for hard surfaces containing the diallylamine-type copolymer of Claim 1 or 2.

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