JP2021021020A - Diallylamine-based/diallyl ether-based copolymer, manufacturing method and applications thereof - Google Patents

Abstract

To provide a novel copolymer excellent in adhesion to a metallic or resin substrate, and also in a balance to various performances such as heat resistance, etc.SOLUTION: A polymeric compound includes a structural unit derived from a diallylamine derivative (for instance, diallyldimethyl ammonium chloride, diallyl methylamine sulfamate, diallylamine sulfamate, methyldiallylamine hydrochloride, diallylamine hydrochloride, etc.) and a structure derived from an α-position aryl ether-substituted acrylic acid derivative (for instance, 2-(allyloxymethyl) methyl acrylate, etc.). A manufacturing method and applications thereof are also provided.SELECTED DRAWING: None

Description

The present invention relates to a novel copolymer, and more specifically, it has an excellent balance between adhesion to a substrate such as a metal or resin and various performances such as heat resistance, and imparts cationic property or the like as necessary. The present invention relates to a diallylamine-based / diallyl ether-based copolymer, which can be suitably used for a specific application.

So-called diallylamine-based (co) polymers, which have a structural unit derived from diallylamines, are widely manufactured industrially because they can be easily synthesized in an aqueous solution, and are used for various substrates such as glass, fiber, paper, metal, and resin. It has been used for purposes such as surface modification (see, for example, Patent Document 1).
However, the adhesion to a base material such as metal or resin may not always be sufficient in relation to the application, and further improvement of the adhesion to these base materials is required. In addition, higher performance has been required for other performances such as heat resistance.

On the other hand, it has been reported that (co) polymers derived from diallyl ether compounds such as 2- (allyloxymethyl) methyl acrylate are also excellent in heat resistance and adhesion to a substrate (for example, Patent Documents). See 2.).
However, even with these (co) polymers, the adhesion to metal substrates such as aluminum and stainless steel and some resin substrates is not always sufficient, and the adhesion to these substrates can be improved. I was asked. Further, in relation to some uses, it has been desired to improve the degree of freedom in design so as to impart cationicity and the like.

Japanese Unexamined Patent Publication No. 2004-115675 Japanese Unexamined Patent Publication No. 2014-040585

In view of the above background technology, it is an object of the present invention to provide a novel copolymer having an excellent balance between adhesion to a substrate such as a metal or resin and various performances such as heat resistance.
As a result of diligent studies, the present inventors have obtained a combination of a diallylamine-based structural unit having a specific structure and a diallyl ether-based structural unit having a specific structure to obtain adhesion to various substrates such as metals and resins. We have found that it is possible to realize a copolymer having various performances such as heat resistance at a high level, and have completed the present invention.

That is, the first invention of the present application is
[1]
At least one structural unit (I) having a structure represented by the following structural formula (Ia) or (Ib), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formulas (Ia) and (Ib), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. ), And at least one structural unit (II) having a structure represented by the following structural formula (IIa).

(However, in the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
It is a polymer compound, which has.

Hereinafter, [2] and [3] are preferred embodiments or embodiments of the first invention of the present application, respectively.
[2]
The polymer compound according to [1], wherein the proportion of the structural unit (I) is 0.1 to 50 mol%, and the proportion of the structural unit (II) is 99.9 to 50 mol%.
[3]
The polymer compound according to [1] or [2], wherein the structural unit (I) is an addition salt having a structure represented by the following structural formula (Ia') or (Ib').


(However, in the above formula (Ia '), and (Ib'), ^{R 1} is the same as defined in formula (Ia) and (Ib), ^{R 1} 'is a hydrogen atom, a hydroxyl group Yes from carbon atoms 1 even though 10 alkyl group, or an aralkyl group having 7 to 10 carbon atoms, R ¹ and R ^{1 ',} or different and are identical, X ^- is a counter Ion.),

The second invention of the present application is
[4]
A structural unit (i) at least one derived from a monomer (1) having a structure represented by the following structural formula (III), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.)
At least one structural unit (ii) derived from the monomer (2) having the structure represented by the following structural formula (IV).

(However, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
It is a polymer compound, which has.

Hereinafter, [5] is a preferred embodiment or embodiment of the second invention of the present application, and [6] is a preferred embodiment or embodiment of the first and second inventions of the present application.
[5]
The polymer compound according to [4], wherein the proportion of the structural unit (i) is 0.1 to 50 mol%, and the proportion of the structural unit (ii) is 99.9 to 50 mol%.
[6]
The polymer compound according to any one of [1] to [5], which has a weight average molecular weight of 10,000 or more.

The third invention of the present application is
[7]
At least one monomer (1) having a structure represented by the following structural formula (III), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.)
At least one monomer (2) having a structure represented by the following structural formula (IV),


(However, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
Is a method for producing a polymer compound, which comprises a step of copolymerizing.

Hereinafter, [8] to [10] are preferred embodiments or embodiments of the third invention of the present application, respectively, and [11] are preferred embodiments or embodiments of the first and second inventions of the present application.
[8]
The polymer compound according to [7], wherein the molar ratio of the monomer (1) to the monomer (2) used in the above step is in the range of 0.1: 99.9 to 90:10. Manufacturing method.
[9]
The method for producing a polymer compound according to [7] or [8], wherein the above step is carried out in at least one solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene.
[10]
The height according to any one of [7] to [9], wherein the above step is carried out by dropping the monomer (2) into an organic solvent in which the monomer (1) is dissolved in advance. Method for producing a molecular compound.
[11]
Coating material, adhesive, adhesive, surface modifier, resist, dye fixing agent, ink fixing agent, pigment dispersant containing the polymer compound according to any one of [1] to [6]. , Coagulant, antibacterial agent, bactericidal agent, paper strength enhancer, corrosion inhibitor, plating brightener or optical material.

According to the present invention, a novel diallylamine-based / diallyl ether-based copolymer in which adhesion to various substrates such as metals and resins and various performances such as heat resistance are compatible at a high level is realized.
Further, according to the production method of the present invention, there is provided a production method capable of producing a novel diallylamine-based / diallyl ether-based copolymer with high efficiency and high quality.
Further, according to one aspect of the present invention, various uses utilizing the excellent properties of such a novel diallylamine-based / diallyl ether-based copolymer are provided.

The first invention of the present application The copolymer of the first invention of the present application is a structural unit having a structure represented by the following structural formula (Ia) or (Ib), or an addition salt thereof, or a structure which is a quaternary ammonium salt. (I) A polymer compound having at least one type and at least one type of structural unit (II) having a structure represented by the following structural formula (IIa).


In the above formulas (Ia) and (Ib), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.

In the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.

Structural unit (I)
The structural unit (I) (hereinafter, also referred to as “diallylamine-based structural unit (I)”) constituting a part of the polymer compound of the first invention of the present application is the structural formula (Ia) or (Ib) of the above formula. It has a structure represented by, or an addition salt thereof, or a structure which is a quaternary ammonium salt.
By having the structural unit (I), the polymer compound of the first invention of the present application may have excellent adhesion to various substrates, and may have a cationic or silica scale suppressing effect as necessary or desired. It's easy.

In the polymer compound of the first invention of the present application, the ratio of the diallylamine-based structural unit (I) to the total structural units is preferably 0.1 to 50 mol%, preferably 0.5 to 30 mol%. More preferably, it is particularly preferably 1 to 20 mol%. When the proportion of the structural unit (I) is within the above range, it becomes easier to realize excellent adhesion to various substrates, cationicity, silica scale suppressing effect, and the like.
The proportion of the diallylamine-based structural unit (I) in the polymer compound of the first invention of the present application can be measured by elemental analysis, for example, by analyzing the combustion gas of the polymer compound by anion chromatography. Specifically, for example, it can be measured by the method described in Examples of the present specification.
Further, in the practical copolymer production process, if the production conditions are established to some extent, the composition of the constituent unit (I) can be determined from the monomer composition in the starting material without analyzing the composition of the copolymer one by one. The proportion can be estimated with considerable accuracy.

The proportion of the structural unit (I) in the polymer compound of the first invention of the present application can be appropriately increased or decreased by adjusting the monomer composition in the starting material. Further, it is possible to appropriately adjust by changing the polymerization conditions such as the order in which the monomers are brought into contact with each other.

As described above, in the structural formulas (Ia) and (Ib) representing one form of the structural unit (I), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group. Alternatively, it is an aralkyl group having 7 to 10 carbon atoms.


Here, the alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group may be linear, branched, or cyclic, and as a preferable example thereof, it may have a hydroxyl group. Alkyl groups having 1 to 4 carbon atoms, specifically methyl groups, ethyl groups, n-propyl groups, isopropyl groups, various butyl groups, 2-hydroxyethyl groups, 2-hydroxypropyl groups, 3-hydroxypropyl groups, etc. , Further, a cyclohexyl group and the like can be mentioned. Further, preferred examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group and a phenethyl group.

The additional salt or quaternary ammonium salt having the structure represented by the structural formula (Ia) or (Ib) has the structure represented by the following structural formula (Ia') or (Ib'). Is preferable.


The formula (Ia '), and (Ib'), ^{R 1} is the same as that defined above in formula (Ia) and (Ib), ^{R 1} 'has a hydrogen atom, a hydroxyl group which may be an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, R ¹ and R ^{1 ',} or different and are identical, X ^- is a counter ion Is.
The counter ion may be a monovalent anion, and the type thereof is not particularly limited, but it is preferably an anion derived from an organic acid or an inorganic acid, and particularly preferably a halogen ion (more preferably Cl ⁻ , Br ^−. , Or I ⁻ ), methyl sulfate ion, ethyl sulfate ion, or acetate ion.

Preferred addition salts include, for example, hydrochloride, hydrobromide, sulfate, nitrate, sulfite, phosphate, amide sulfate, methanesulfonate and the like, among which amide sulfate and methanesulfonate. Etc. are preferable from the viewpoint of solubility in a solvent.
Preferred quaternary ammonium salts include, for example, N, N-dimethylammonium chloride, N, N-diethylammonium chloride, N, N-dipropylammonium chloride, N, N-dibutylammonium chloride, N, N-methylbenzylammonium. Examples thereof include chlorides, N, N-ethylbenzylammonium chlorides, and bromides, iodides, and methylsulfates corresponding to these chlorides, among which N, N-dimethylammonium chlorides, N, N-diethylammonium chlorides, etc. However, it is preferable from the viewpoint of solubility in a solvent.

The polymer compound of the first invention of the present application may have only one type of diallylamine-based structural unit (I), or may have two or more types of diallylamine-based structural unit (I). When there are two or more types of structural units (I), two or more types represented by the same general formula among the general formulas (structural formulas) (Ia), (Ib), (Ia'), and (Ib'). The structural units (I) of the above may be combined, or two or more types of structural units (I) represented by different general formulas may be combined.
When it has two or more kinds of structural units (I), it may be derived from different monomers or may be derived from the same monomer. Regarding the latter, for example, from the same dial rear ether monomer (1), both the structural unit represented by the structural formula (Ia) and the structural unit represented by the structural formula (Ib) may be generated. The ratio can be appropriately adjusted depending on the polymerization conditions and the like. Further, when the addition salt is added or changed, two or more kinds of the constituent units (I) may be generated by adding or changing only a part of the constituent unit (I).

Structural unit (II)
The structural unit (II) (hereinafter, also referred to as “diallyl ether-based structural unit (II)”) constituting a part of the polymer compound of the first invention of the present application has a structure represented by the following structural formula (IIa). Have.
Since the structure represented by the following structural formula (IIa) that characterizes the diallyl ether-based structural unit (II) has a ring structure (tetrahydrofuran ring) in the main chain, it has excellent heat resistance to the polymer compound of the first invention of the present application. In addition, since it has methylene groups on both sides of the tetrahydrofuran ring, it is possible to impart excellent flexibility to the polymer compound of the first invention of the present application.

In the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. The hydrocarbon group having 1 to 4 carbon atoms may be linear, branched or cyclic, and may contain an ether bond.

Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a vinyl group, an allyl group and a metalyl group. , Crotyl group, cyclopropyl group, cyclobutyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, vinyloxyethyl group, epoxy group, oxetanyl group and the like, but are not limited thereto. ..

Examples of the substituent include a chain unsaturated hydrocarbon group such as a vinyl group, an allyl group, a metalyl group and a crotyl group; a cyclic ether group such as an epoxy group, a glycidyl group and an oxetanyl group; a methoxy group and an ethoxy group. Alkoxy groups such as methoxyethoxy group; alkylthio groups such as methylthio group and ethylthio group; acyl groups such as acetyl group and propionyl group; acyloxy groups such as acetyloxy group and propionyloxy group; alkoxy such as methoxycarbonyl group and ethoxycarbonyl group Carbonyl group; alkylthiocarbonyl group such as methylthiocarbonyl group, ethylthiocarbonyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; ureido group; amide group; cyano group; hydroxyl group; trimethylsilyl group and the like. However, it is not limited to these.

Among these R ² options, the monomer (2) that leads to the diallyl ether-based constituent unit (II) is industrially advantageously produced, and the viscosity of the monomer (2) is lowered to make it dilute. From the viewpoint of improving the above, a chain saturated hydrocarbon group having 1 to 4 carbon atoms, a chain unsaturated hydrocarbon group having 1 to 4 carbon atoms and a hydrocarbon group having an ether bond having 1 to 4 carbon atoms are used. Preferably, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an allyl group, a metalyl group, a crotyl group, a methoxyethyl group, an ethoxyethyl group and a glycidyl group. And vinyloxyethyl group is more preferable, and chain saturated carbide having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Hydrogen groups are even more preferred, methyl groups, ethyl groups, n-propyl groups, isopropyl groups and tert-butyl groups are even more preferred, and methyl and ethyl groups are particularly preferred.

In the polymer compound of the first invention of the present application, the ratio of the diallyl ether-based structural unit (II) to the total structural units is preferably 99.9 to 50 mol%, preferably 99.5 to 70 mol%. Is more preferable, and 99 to 80 mol% is particularly preferable. When the proportion of the structural unit (II) is within the above range, it becomes easier to realize excellent adhesion to various substrates, high heat resistance, and the like.
The proportion of the diallyl ether-based structural unit (II) in the polymer compound of the first invention of the present application can be measured, for example, by analyzing the combustion gas of the polymer compound by anion chromatography, and is more specific. Can be measured, for example, by the method described in Examples of the present specification.
Further, in the practical copolymer production process, if the production conditions are established to some extent, the composition of the constituent unit (II) can be determined from the monomer composition in the starting material without analyzing the composition of the copolymer one by one. The proportion can be estimated with considerable accuracy.
The proportion of the structural unit (II) in the polymer compound of the first invention of the present application can be appropriately increased or decreased by adjusting the monomer composition in the starting material. Further, it is possible to appropriately adjust by changing the polymerization conditions such as the order in which the monomers are brought into contact with each other.

The polymer compound of the first invention of the present application may have only one type of diallyl ether-based structural unit (II), or may have two or more types of diallyl ether-based structural unit (II).

Other Structural Units The polymer compound of the first invention of the present application may be composed of only the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II), or the structural unit (I) and the structural unit ( It may have a structural unit other than II).
The structural unit other than the structural unit (I) and the structural unit (II) is not particularly limited. For example, a structural unit derived from a monomer conventionally used in combination with a diallylamine-based monomer, or a conventional diallyl ether. A structural unit derived from the monomer used in combination with the system monomer can be appropriately used.
Examples of the former include structural units derived from sulfur dioxide; various allyl sulfonic acids; various amides such as acrylamide; various anionic monomers such as unsaturated carboxylic acids and unsaturated dicarboxylic acids; Not limited to these.

Examples of the latter include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. Acid s-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid n-amyl, (meth) acrylic acid s-amyl, (meth) acrylic acid t-amyl, (meth) acrylic acid n-hexyl, 2-Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylate Lauryl, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) 2-Hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) 4-Hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfurfryl (meth) acrylate, glycidyl (meth) acrylate , (Meta) acrylate β-methylglycidyl, (meth) acrylate β-ethylglycidyl, (meth) acrylate (3,4-epoxycyclohexyl) methyl, (meth) acrylate N, N-dimethylaminoethyl, α (Meta) acrylates such as methyl-hydroxymethylacrylate and ethyl α-hydroxymethylacrylate; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; Meta) Unsaturated monocarboxylic acids such as acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid; unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; mono succinic acid (meth) Unsaturated monocarboxylic acids in which the chain is extended between unsaturated groups such as 2-acrylic acid (2-acryloyloxyethyl) and monosuccinate (2-methacryloyloxyethyl); unsaturated groups such as maleic anhydride and itaconic anhydride. Acrylic acids; styrene, α-methyls Aromatic vinyls such as thyrene, vinyltoluene and methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and naphthylmaleimide; polystyrene, polymethyl (meth) acrylate, poly Macromonomonics having a (meth) acryloyl group at one end of polymer molecular chains such as ethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, Vinyl ethers such as ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholin , N-vinyl compounds such as N-vinylacetamide; structural units derived from unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate, but are not limited thereto.
Of these, maleic acid, acrylic acid, and acrylamide are particularly preferably used.

As described above, in the diallylamine-based / diallyl ether-based copolymer of the present invention of the first invention of the present application, the proportion of the constituent unit (I) is 0.1 to 50 mol%, and the constituent unit (II) It is preferable that the proportion of the mixture is 99.9 to 50 mol%.
It is more preferable that the proportion of the constituent unit (I) is 0.5 to 30 mol%, the proportion of the constituent unit (II) is 99.5 to 70 mol%, and the proportion of the constituent unit (I). Is 1 to 20 mol%, and the proportion of the constituent unit (II) is particularly preferably 99 to 80 mol%.
Regarding the ratio of the diallylamine-based structural unit (I) to the diallyl ether-based structural unit (II), the molar ratio of the diallyl ether-based structural unit (II) / diallylamine-based structural unit (I) is 2.3 to 200.0. It is preferably 4.0 to 100.0, and particularly preferably 4.0 to 100.0.

Since the diallyl ether-based monomer generally exhibits higher radical polymerizable properties than the diallylamine-based monomer, even if both are conventionally attempted to be copolymerized, the polymerization proceeds only with the diallyl ether-based monomer. A homopolymer containing only the diallyl ether-based structural unit (II) was obtained. From this point of view, the diallylamine-based / diallyl ether-based copolymer of the present invention is a novel polymer, and in particular, the molar ratio of the diallyl ether-based constituent unit (II) / diallylamine-based constituent unit (I) is 2.3 to. The diallylamine-based / diallyl ether-based copolymer of the present embodiment, which is 200.0, is a copolymer that exceeds the prediction from the prior art.
In the first invention of the present application, the molar ratio of the diallyl ether-based structural unit (II) / diallylamine-based structural unit (I) is not limited to the above-mentioned preferable range, and the diallyl ether-based structural unit (II). And the diallylamine-based structural unit (I) can be contained in a desired copolymer composition.

The molecular weight of the diallylamine-based / diallyl ether-based copolymer of the first invention of the present application is not particularly limited, and a copolymer having an appropriate molecular weight may be appropriately polymerized in relation to the required physical properties and applications.
Preferably, the weight average molecular weight (Mw) of the diallylamine-based / diallyl ether-based copolymer of the first invention of the present application is 5000 or more, more preferably 5000 to 500000, and particularly preferably 1000 to 100,000.
The molecular weight of the diallylamine-based / diallyl ether-based copolymer can be measured by the GPC method when it is soluble in the eluent, and more specifically, for example, the weight average molecular weight by the method described in Examples of the present application. (Mw) can be measured.
The molecular weight of the copolymer of the first invention of the present application can be adjusted by adjusting the types and compositions of essential and arbitrary monomers, the temperature, time and pressure in the polymerization step, the type and amount of radical initiator used in the polymerization step, and the like. It can be adjusted as appropriate.

As described above, the diallylamine-based / diallyl ether-based copolymer of the first invention of the present application may have the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II), and other structural units. It may have, and it may not have other structural units.
The ratio of the diallylamine-based constituent unit (I) and the diallyl ether-based constituent unit (II) to all the constituent units of the diallylamine-based / diallyl ether-based copolymer is not particularly limited, but is 25 to 100 mol%. Is preferable, and 50 to 100 mol% is more preferable.
When the ratio of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II) is within the above range, adhesion, heat resistance, cohesiveness, dispersibility, and solubility in a solvent are based on these structural units. Such favorable characteristics can be more easily realized.
The composition of the diallylamine-based / diallyl ether-based copolymer, including the ratio of the diallylamine-based structural unit (I) and the diallyl ether-based structural unit (II), depends on the polymerization conditions, particularly the composition of the monomer supplied during the polymerization. It can be adjusted as appropriate.

The second invention of the present application The copolymer of the second invention of the present application is composed of a monomer (1) having a structure represented by the following structural formula (III), an addition salt thereof, or a structure which is a quaternary ammonium salt. Derived structural unit (i) At least one type, and
It is a polymer compound having at least one structural unit (ii) derived from the monomer (2) having the structure represented by the following structural formula (IV).

In the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.

In the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.

The diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is a monomer (1) having a structure represented by the above structural formula (III), an addition salt thereof, or a structure which is a quaternary ammonium salt. ) (I) (hereinafter, also referred to as “diallylamine-based structural unit (i)”), and a monomer (2) having a structure represented by the following structural formula (IV). It is a polymer compound having at least one structural unit (ii) derived from (hereinafter, also referred to as “diallyl ether-based structural unit (ii)”). That is, the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application may have a diallylamine-based structural unit (i) and a diallyl ether-based structural unit (ii), and has other structural units. It may be used, and it may not have any other structural units.

In the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application, the proportion of the constituent unit (i) is 0.1 to 50 mol%, and the proportion of the constituent unit (ii) is 99.9. It is preferably ~ 50 mol%. It is more preferable that the proportion of the constituent unit (i) is 0.5 to 30 mol%, the proportion of the constituent unit (ii) is 99.5 to 70 mol%, and the proportion of the constituent unit (i). Is 1 to 20 mol%, and the proportion of the constituent unit (ii) is particularly preferably 99 to 80 mol%.
Regarding the ratio of the diallylamine-based structural unit (i) to the diallyl ether-based structural unit (ii), the molar ratio of the diallyl ether-based structural unit (ii) / diallylamine-based structural unit (i) is 2.3 to 200.0. It is preferably 4.0 to 100.0, and particularly preferably 4.0 to 100.0.

Since the diallyl ether-based monomer generally exhibits higher radical polymerizable properties than the diallylamine-based monomer, the polymerization proceeds conventionally only with the diallyl ether-based monomer, and the diallyl ether-based constituent unit (ii) Only a homopolymer was obtained. From this point of view, the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is also a novel polymer, and in particular, the molar ratio of the diallyl ether-based structural unit (ii) / diallylamine-based structural unit (i) is 2. The diallylamine-based / diallyl ether-based copolymer of the present embodiment, which is 3 to 200.0, is a copolymer that exceeds the prediction from the prior art.
In the second invention of the present application, the molar ratio of the diallyl ether-based structural unit (ii) / diallylamine-based structural unit (i) is not limited to the above-mentioned preferable range, and the diallyl ether-based structural unit (ii) is not limited to the above-mentioned preferable range. And the diallylamine-based structural unit (i) can be contained in a desired copolymer composition.

The ratio of the diallylamine-based constituent unit (i) and the diallyl ether-based constituent unit (ii) to all the constituent units of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is determined by elemental analysis, for example, of the copolymer. It can be measured by analyzing the combustion gas by anion chromatography, and more specifically, it can be measured by, for example, the method described in Examples of the present specification.

The molecular weight of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is not particularly limited, and a copolymer having an appropriately suitable molecular weight may be polymerized in relation to required physical properties and applications.
Preferably, the weight average molecular weight (Mw) of the diallylamine-based / diallyl ether-based copolymer of the present invention is 5000 or more, more preferably 5000 to 500000, and particularly preferably 1000 to 100,000.
The molecular weight of the diallylamine-based / diallyl ether-based copolymer can be measured by the GPC method when it is soluble in the eluent, and more specifically, for example, the weight average molecular weight by the method described in Examples of the present application. (Mw) can be measured.

The diallylamine-based / diallyl ether-based copolymer of the second invention of the present application may have a diallylamine-based structural unit (i) and a diallyl ether-based structural unit (ii), and has other structural units. It may also have no other structural units.
The ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) to the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application is not particularly limited, but is 25 to 100 mol%. It is preferably 50 to 100 mol%, and more preferably 50 to 100 mol%.
When the ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) is within the above range, the adhesion, heat resistance, cohesiveness, dispersibility, and solubility in a solvent are based on these structural units. Such favorable characteristics can be more easily realized.
The composition of the diallylamine-based / diallyl ether-based copolymer, including the ratio of the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii), depends on the polymerization conditions, particularly the composition of the monomer supplied during the polymerization. It can be adjusted as appropriate.

Dialylamine-based structural unit (i) and diallylamine-based monomer (1)
The diallylamine-based structural unit (i), which is an essential structural unit of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application, has a structure represented by the following structural formula (III), an addition salt thereof, or a quaternary salt. It is derived from a monomer (1) having a structure that is an ammonium salt (hereinafter, also referred to as “diallylamine-based monomer”).

In the above formula (III), R ¹ is the same as that in the structural formulas (Ia) and (Ib) described above, and more specifically, the number of carbon atoms 1 which may have a hydrogen atom and a hydroxyl group. To 10 alkyl groups, or 7 to 10 aralkyl groups. Among these, the preferred group as R ^{1 is the same} as that described for R ¹ in the above-mentioned structural formulas (Ia) and (Ib). Further, those preferable as the additive salt having the structure represented by the structural formula (III) or the quaternary ammonium salt are also preferable with respect to the additive salt having the structure represented by the structural formulas (Ia) and (Ib) and the quaternary ammonium salt. Similar to the one described.

In deriving the diallylamine-based structural unit (i), only one type of diallylamine-based monomer (1) may be used alone, or two or more types may be used in combination. It is often advantageous in terms of cost and ease of control of the polymerization process to use only one type of diallylamine-based monomer (1), and using two or more types in combination is a copolymer. Is often advantageous in imparting the desired properties to the polymer.

Dialyl ether-based structural unit (ii) and diallyl ether-based monomer (2)
The diallyl ether-based structural unit (ii), which is an essential structural unit of the diallylamine-based / diallyl ether-based copolymer of the second invention of the present application, is a monomer (2) having a structure represented by the following structural formula (IV). Hereinafter, it is also referred to as "diallyl ether-based monomer").

In the above formula (IV), R ² is the same as that in the above-mentioned structural formula (IIa), and more specifically, it may have a hydrogen atom or a substituent, and has 1 to 4 carbon atoms. It is a hydrocarbon group of. Among them, the group preferable as R ^{2 is the same} as that described for R ² in the above-mentioned structural formula (IIa).

In deriving the diallyl ether-based structural unit (ii), only one type of diallyl ether-based monomer (2) may be used alone, or two or more types may be used in combination. It is often advantageous in terms of cost and ease of control of the polymerization process to use only one type of diallyl ether-based monomer (2), and it is common weight to use two or more types in combination. It is often advantageous in imparting the desired properties to the coalescence.

Depending on the polymerization conditions, the structural unit (ii) derived from the diallyl ether-based monomer (2) is not only the structural unit (II) having the structure represented by the structural formula (IIa) described above, but also the following. It may contain a structural unit having a structure represented by the structural formula (IIb) of.

In the above formula (IV), R ² is the same as that in the above-mentioned structural formula (IIa), and more specifically, it may have a hydrogen atom or a substituent, and has 1 to 4 carbon atoms. It is a hydrocarbon group of. Among them, the group preferable as R ^{2 is the same} as that described for R ² in the above-mentioned structural formula (IIa).

In this case, the ratio of the structural unit (II) having the structure represented by the structural formula (IIa) to the total structural unit (ii) derived from the diallyl ether-based monomer (2) is 70 mol% or more. It is preferably 90 mol% to 100 mol%. When the proportion of the structural unit (II) having the structure represented by the structural formula (IIa) is 70 mol% or more, it becomes easy to realize excellent heat resistance due to the tetrahydrofuran ring, and the composition formula (IIa). Cross-linking and gelation due to the branched structure caused by the structure shown in IIb) can be effectively suppressed.
The proportion of the structural unit (II) having the structure represented by the structural formula (IIa) in the entire diallyl ether-based structural unit (ii) should be appropriately adjusted by using polymerization conditions, particularly a specific chain transfer agent. Can be done.

Other Structural Units The structural units other than the diallylamine-based structural unit (i) and the diallyl ether-based structural unit (ii) that can form the copolymer of the second invention of the present application are the same as those described for the first invention of the present application. The preferred examples thereof are the same as those described for the first invention of the present application.

Method for producing diallylamine-based / diallyl ether-based copolymer The method for producing the diallylamine-based / diallyl ether-based copolymer of the present invention (first invention and second invention of the present application) is not particularly limited, but the third invention of the present application. It is preferably produced by a production method, and more specifically, a monomer (1) having a structure represented by the following structural formula (III), an addition salt thereof, or a quaternary ammonium salt. (Hereinafter, also referred to as "diallylamine-based monomer (1)") At least one kind,


(However, in the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.)
At least one monomer (2) having a structure represented by the following structural formula (IV) (hereinafter, also referred to as "diallyl ether-based monomer (2)").

(However, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.) A production method comprising a step of copolymerizing. It is preferably manufactured by.

In the above production method, the ratio of the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) supplied to the copolymerization step is not particularly limited, and the target diallylamine-based / diallyl ether-based monomer is used. The ratio can be appropriately set in consideration of the composition of the copolymer and the ease of polymerization of the monomer (1) and the monomer (2). For example, after taking measures to reduce the amount of unreacted monomers, the monomers (1) and the monomers (2) have almost the same composition as the target diallylamine-based / diallyl ether-based copolymer. And specifically, for example, the molar ratio of the monomer (1) and the monomer (2) is in the range of 0.1: 99.9 to 50:50. The monomer (1) and the monomer (2) can be supplied. The molar ratio is preferably 0.5: 99.5 to 30:70, more preferably 1: 99 to 20:80.
Further, in general, the diallylamine-based monomer (2) tends to promote the polymerization reaction more easily than the diallylamine-based monomer (1), and therefore, the composition of the target diallylamine-based / diallyl-ether-based copolymer Alternatively, the ratio of the diallyl ether-based monomer (2) may be set lower and the ratio of the diallylamine-based monomer (1) may be set higher than that of the supply. In this case, the molar ratio of the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is preferably in the range of 70:30 to 90:10, preferably 80:20 to 90:10. It is more preferable that it is within the range.

From the viewpoint of reaction uniformity and the like, the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is preferably carried out in a solvent.
The solvent used in the copolymerization step of the above embodiment is not particularly limited and may be a polar solvent or a non-polar solvent, but a polar solvent is preferable.
Examples of the polar solvent include water, an aqueous solution of an inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, etc.) or an aqueous solution thereof, an aqueous solution of a metal salt of an inorganic acid (zinc chloride, calcium chloride, magnesium chloride, etc.), and an organic acid (giric acid, Acetic acid, propionic acid, lactic acid, etc.) or an aqueous solution thereof, or a polar organic solvent (alcohol, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, toluene, etc.) and the like can be mentioned, and among these, the polar organic solvent is preferable. Particularly preferably, at least one polar organic solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene can be used.
It is particularly preferable to use dimethylformamide because it has high solubility in the diallyl ether-based monomer (2) and also dissolves the obtained diallylamine-based / diallyl ether-based copolymer well.
One of these solvents may be used alone, or two or more of these solvents may be used in combination (mixed).

As a measure to reduce the number of unreacted monomers, the diallyl ether-based monomer (2) is added dropwise to an organic solvent in which the diallylamine-based monomer (1) is dissolved in advance. The step of copolymerizing (1) and (2) can be carried out. By adopting such a copolymerization step, the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) having different polymerizable properties can be obtained in good yield and unreacted monomer. It can be copolymerized while being reduced. This makes it even easier to produce a diallylamine-based / diallyl ether-based copolymer having the desired composition and degree of polymerization with practical efficiency and cost.
The diallyl ether-based monomer (2) may also be dissolved in a solvent in advance for dropping.

The mechanism by which the above-mentioned advantageous effect can be obtained by having the step of dropping the diallyl ether-based monomer (2) into the organic solvent in which the diallylamine-based monomer (1) is dissolved in advance is not always clear. By sequentially dropping the more polymerizable diallyl ether-based monomer (2) into the solution of the less polymerizable diallylamine-based monomer (1), the less polymerizable diallylamine-based monomer (1) is added. It is presumed that there is some relation to the fact that the polymerization can be carried out while maintaining the condition that 1) is always excessive.

The temperature at which the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is carried out is not particularly limited, but is carried out within a temperature range of 50 to 120 ° C. Is preferable, and it is particularly preferable to carry out the process within a temperature range of 70 to 90 ° C. The pressure at that time is not particularly limited, but it is preferable to carry out the pressure at or near atmospheric pressure in consideration of cost and the like.

In the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2), it is preferable to use a polymerization initiator in order to promote the copolymerization reaction. The type of the polymerization initiator is not particularly limited, and for example, a generally used radical polymerization initiator can be used. The radical polymerization initiator is a substance that generates radicals by heat or a reducing substance to cause addition polymerization of a polymerizable monomer, and is a water-soluble, water-dispersible or oil-soluble persulfate, peroxide, etc. There are azobis compounds and the like. Of these, water-soluble or water-dispersible azobis compounds are preferable, and 2,2'-azobis (2-methylpropylene amidine) dihydrochloride, 2,2'-azobis (2-methylpropionic acid) dimethyl, and the like are preferably used. be able to.
The time for carrying out the step of copolymerizing the diallylamine-based monomer (1) and the diallyl ether-based monomer (2) is not particularly limited, but from the viewpoint of productivity and the like, it should be 24 hours or less. It is preferable to set the conditions, and it is particularly preferable that the time is 8 to 12 hours. Further, when the diallyl ether-based monomer (2) is added dropwise to the organic solvent in which the diallylamine-based monomer (1) is dissolved in advance, a large excess of the diallylamine-based monomer (1) is maintained. From the viewpoint of stable polymerization reaction and the like, the dropping is preferably carried out over 1 to 4 hours, and particularly preferably over 2 to 3 hours.

The concentration of the diallylamine-based monomer (1) and the concentration of the diallyl ether-based monomer (2) in the solvent in the copolymerization step are not particularly limited, but from the viewpoint of stable and uniform copolymerization. Therefore, the concentration is preferably a certain value or less, and from the viewpoint of polymerization efficiency and the like, the concentration is preferably a certain value or more. More specifically, the concentration of the diallylamine-based monomer (1) is 1.0 × 10 ^-4 to. It is preferably 5.0 × 10 ⁻³ mol / g, and particularly preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻³ mol / g. The concentration of the diallyl ether-based monomer (2) in the dropping solution is preferably 5.0 × 10 ^{-5 to} 5.0 × 10 ^-3 mol / g, preferably 1.0 × 10 ^-3 to 2. It is particularly preferably 0.0 × 10 ^-3 mol / g.
The amount of the polymerization initiator used is not particularly limited, but when a water-soluble or water-dispersible azobis compound is used as the polymerization initiator, the diallylamine-based monomer (1) and the diallyl ether-based monomer (1) and the diallyl ether-based monomer ( It is preferable to use 0.01 to 10 mol% with respect to the total of 2), and it is particularly preferable to use 0.5 to 2.0 mol%.

The diallylamine-based / diallyl ether-based copolymer obtained by the production method of the third invention of the present application preferably corresponds to the first invention or the second invention of the present application, but is not limited thereto. The preferred form of the copolymer in the case corresponding to the first invention or the second invention of the present application is the same as that described for the diallylamine-based / diallyl ether-based copolymer of the first invention or the second invention of the present application. Therefore, the proportion of the diallylamine-based constituent unit (I) in the diallylamine-based / diallyl ether-based copolymer obtained by the production method of the third invention of the present application is preferably 5 to 50 mol%, and the diallyl ether-based constituent unit. The proportion of (II) is preferably 95 to 50 mol%. The preferred molecular weight, intrinsic viscosity, and the like are the same as those described above for the diallylamine-based / diallyl ether-based copolymers of the first and second inventions of the present application.

Applications, etc. The copolymers of the first and second inventions of the present application have a high level of balance between the excellent properties of the diallylamine-based polymer and the excellent properties of the diallyl ether-based polymer, or are appropriately selected. Since it can be expressed, it can be suitably used in applications in which a diallylamine-based (co) polymer or a diallyl ether-based (co) polymer has been conventionally used.
Specifically, coating materials, adhesives, adhesives, surface modifiers, paper treatment agents, dyeing aids, dye fixing agents, optical materials and other information recording materials, optical fiber materials, color filter resists, solder resists, plating Resists, insulators, sealants, inkjet inks, printing inks, paints, casting materials, decorative plates, WPCs, coating agents, photosensitive resin plates, dry films, lining agents, civil engineering and building materials, putties, repair materials, floors Examples include, but are not limited to, materials, paving materials, gel coats, overcoats, hand lay-ups / spray-ups, drawing moldings / filament windings / SMCs / BMCs and other molding materials, polymer solid electrolytes and the like.
As described above, the copolymers of the first and second inventions of the present application are particularly preferable because they can achieve both adhesion to various substrates such as metals and resins and various performances such as heat resistance at a high level. Applications include coating materials, adhesives, adhesives, surface modifiers, resists, and optical materials.
Further, since the copolymers of the first and second inventions of the present application can be imparted with cationic properties and silica scale suppressing performance as desired, a dye fixing agent, an ink fixing agent, a silica scale suppressing agent, and a pigment It can also be used particularly preferably in applications such as dispersants and flocculants.
Further, it can be suitably used for applications such as antibacterial agents, bactericidal agents, plating solutions, plating brighteners, corrosion inhibitors, and paper strength enhancers.

When the copolymers of the first and second inventions of the present application are used in the above-mentioned various uses, the solvent used in the production of the copolymer may be removed before use, depending on the use. It may be used with a solvent.
Further, one or more of various additives may be appropriately added as long as they do not contradict the object of the present invention and the object of use. Examples of such additives include other resins, antioxidants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, plasticizers, fillers, tackifiers, colorants, pigments, dyes, Examples include, but are not limited to, conductive materials, antibacterial agents, bactericidal agents, plating solutions, corrosion inhibitors, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. The technical scope of the present invention is not limited to these examples in any sense.

In the following examples / comparative examples, the following abbreviations may be used for convenience.
DADMAC: Dialyldimethylammonium chloride MeAMA: 2- (allyloxymethyl) methyl acrylate DAMA-SA: diallylmethylamine sulfamate DAA-SA: diallylamine sulfamate DMF: dimethylformamide DAMA-HCl: methyldiallylamine hydrochloride DAA- HCl: diallylamine hydrochloride

In the following Examples / Comparative Examples, evaluation and measurement of physical properties and characteristics were carried out by the following methods.
(Weight average molecular weight)
The weight average molecular weight (MW) was measured by gel permeation chromatography (GPC) using a Hitachi L-2130 high performance liquid chromatograph.
The eluent flow path pump used was Hitachi L-2130, the detector used was a Hitachi L-2490 differential refractive index detector, and the column used was a shodex GPS K-805L (exclusion limit molecular weight 4 million) connected in series. .. Samples were prepared with eluent to a concentration of 0.5 g / 100 mL and 20 μL was used for measurement. A dimethylformamide (DMF) solution was used as the eluent.
Measurements were performed at a column temperature of 40 ° C. and a flow rate of 1.0 mL / min. A calibration curve was obtained using polystyrene having a molecular weight of 10200, 18100, 37900, 96400, 427000 or the like as a standard substance, and the weight average molecular weight (MW) of the copolymer was determined based on the calibration curve.
(Polymerization yield)
It was determined by the peak area ratio obtained by the GPC method.
(Copolymer composition)
The copolymer solution obtained in each Example / Comparative Example was diluted to 5 wt% using DMF, and anion analysis was performed by anion chromatography with a combustion device, Dionex ICS-1000 (manufactured by Thermo Fisher), and the results were obtained. The molar ratio of diallylamines to MeAMA was calculated from the above.
(Heat-resistant)
The (co) polymer solutions obtained in each Example / Comparative Example were vacuum dried for 24 hours to obtain solids of each (co) polymer. The obtained solid matter was measured for weight loss and endothermic heat in a nitrogen atmosphere at a heating rate of 5 ° C./min using a differential thermal balance Thermo plus 8120 (manufactured by Rigaku Co., Ltd.). In the obtained measurement data, the temperature at which the first observed endothermic peak reached the peak was defined as the thermal decomposition temperature, which is an index of heat resistance.
(Adhesion)
The (co) polymer solution obtained in each Example / Comparative Example was diluted with tetrahydrofuran (THF) so that the (co) polymer concentration was 5 wt%, and an aluminum test plate [manufactured by TP Giken Co., Ltd., Table] A coating film was obtained by applying the symbol: AL in 3 with a bar coder (No. 8) and then drying at 70 ° C. for 30 minutes. Next, the adhesion of the coating film obtained above to the aluminum test plate was examined in accordance with JIS K5600-5-6 (cross-cut method). When examining the adhesion, the squares are 10 squares in length and 10 squares in width, for a total of 100 squares, and the coating film is based on the number of squares remaining without peeling or breakage in the 100 squares. Adhesion to the above aluminum test plate was evaluated.
Further, instead of the aluminum test plate, a stainless steel test plate [manufactured by TP Giken Co., Ltd., symbol in Table 3: SUS], an ABS resin test plate [manufactured by Standard Test Piece Co., Ltd., symbol in Table 3: ABS], Polycarbonate test plate [manufactured by Standard Test Piece Co., Ltd., symbol in Table 3: PC], silicon wafer [manufactured by AS ONE Co., Ltd., symbol in Table 3: SI], and ethylene vinyl acetate polymer test plate [Standard Co., Ltd. The adhesion to each test plate was evaluated in the same manner by using each of the test pieces manufactured by the symbol: EVA in Table 3.
(Cationic)
The (co) polymer solution obtained in each Example / Comparative Example was diluted with THF so that the (co) polymer concentration was 5 wt%, and was placed on a slide glass [manufactured by Matsunami Glass Industry Co., Ltd.] with a bar coder ( After coating in No. 8), a coating film was obtained by drying at 70 ° C. for 30 minutes. The substrate with a coating film was immersed in an anionic dye solution (Coomassie Brilliant Blue R-250: 0.2 g, acetic acid: 20 g, methanol: 180 g) under room temperature conditions for 30 minutes, washed with methanol, and dried. The degree of dyeing on the surface of the coating film after drying was visually observed and evaluated according to the following criteria.
◯: The entire coated surface is dyed with a dye.
Δ: Part of the coated surface is dyed with a dye.
X: The coated surface is hardly dyed with dye.
(Silica scale suppression effect)
Anhydrous sodium metasilicate is added to pure water so as to have a silica concentration of 400 ppm, and the (co) polymer synthesized in Examples / Comparative Examples as a scale inhibitor after fractionation thereof has a solid content concentration of 50 ppm. The test water was used as the test water. After adjusting the pH to 7.4 to 7.6 by adding hydrochloric acid or sodium hydroxide to each test water, the test water 24 hours later was collected and filtered through a filter having a pore size of 0.45 μm. The concentration of ionic silica in the filtrate was measured, and the ionic silica retention rate was calculated by the following formula. The ionic silica concentration was measured by the silicolybdic acid method using a spectrophotometer UH5300 (manufactured by Hitachi High-Tech Science Corporation).

Example 1 (DADMAC: MeAMA = 1: 8, drop polymerization)
6.06 g of DMF and 0.038 mol of diallyldimethylammonium chloride (DADMAC) were placed in a 300 mL separable flask equipped with a stirrer, a thermometer and a cooling tube. Also, in a 200 mL pear-shaped flask, 0.300 mol of methyl 2- (allyloxymethyl) acrylate (MeAMA), 117.13 g of DMF and the initiator V-601 (2,2'-azobis (2-methylpropionic acid)). 1.55 g (equivalent to 2 mol% of the monomer) of dimethyl) was mixed under ice-cooling. The internal temperature in the separable flask was heated to 70 ° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was completed, and the GPC yield was 100%. W. A copolymer in the form of a cloudy viscous solution of 13337 was obtained.
Tables 1 to 5 show the results of evaluating the copolymerization composition, heat resistance, adhesion, cationicity, and silica scale suppressing effect of the obtained copolymer.

Example 2 (DAMA-SA: MeAMA = 1: 8, drop polymerization)
A 300 mL separable flask equipped with a stirrer, a thermometer and a cooling tube was charged with 6.06 g of DMF and 0.038 mol of diallylmethylamine sulfamate (DAMA-SA). Further, in a 200 mL pear-shaped flask, 0.300 mol of MeAMA, 117.13 g of DMF and 1.55 g of the initiator V-601 (corresponding to 2 mol% of the monomer) were mixed under ice cooling. The internal temperature in the separable flask was heated to 70 ° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was completed, and the GPC yield was 100%. W. A reddish-brown solution copolymer of 14481 was obtained.
Tables 1 to 4 show the results of evaluating the copolymerization composition, heat resistance, adhesion, and cationic property of the obtained copolymer.

Example 3 (DAA-SA: MeAMA = 1: 8, drop polymerization)
A 300 mL separable flask equipped with a stirrer, a thermometer and a cooling tube was charged with 6.06 g of DMF and 0.038 mol of diallylamine sulfamate (DAA-SA). Further, in a 200 mL pear-shaped flask, 0.300 mol of MeAMA, 117.13 g of DMF and 1.55 g of the initiator V-601 (corresponding to 2 mol% of the monomer) were mixed under ice cooling. The internal temperature in the separable flask was heated to 70 ° C., and the solution in the pear-shaped flask was added dropwise to initiate polymerization. The solution in the pear-shaped flask was added dropwise over 2 hours and 30 minutes. After 24 hours, the polymerization reaction was completed, and the GPC yield was 100%. W. A reddish brown solution copolymer of 15463 was obtained.
Tables 1 to 4 show the results of evaluating the copolymerization composition, heat resistance, adhesion, and cationic property of the obtained copolymer.

Example 4 (DADMAC: MeAMA = 1: 8, batch polymerization)
12.69 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DADMAC were charged into a 20 mL test tube. The internal temperature in the test tube was heated to 50 ° C., and 0.04 g of the initiator V-601 (corresponding to 2 mol% of the monomer) was added. After 24 hours, the polymerization reaction was terminated, and the GPC yield was 95.78%, M.I. W. A copolymer in the form of a colorless transparent solution of 27952 was obtained.
The results of evaluating the copolymerization composition, heat resistance, and adhesion of the obtained copolymer are shown in Tables 1 to 3, respectively.

Example 5 (DAMA-SA: MeAMA = 1: 8, batch polymerization)
A 20 mL test tube was charged with 13.02 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DAMA-SA. The internal temperature in the test tube was heated to 50 ° C., and 0.04 g of the initiator V-601 (corresponding to 2 mol% of the monomer) was added. After 24 hours, the polymerization reaction was terminated and M.I. W. : A copolymer in the form of a yellow solution of 48621 was obtained.
Since the polymer peak and the DAMA-SA monomer peak overlapped, the GPC yield could not be calculated.

Example 6 (DAA-SA: MeAMA = 1: 8, batch polymerization)
12.90 g of DMF, 0.008 mol of MeAMA and 0.001 mol of DAA-SA were charged into a 20 mL test tube. The internal temperature in the test tube was heated to 50 ° C., and 0.04 g of the initiator V-601 (corresponding to 2 mol% of the monomer) was added. After 24 hours, the polymerization reaction was terminated and M.I. W. : A copolymer in the form of a pale yellow solution of 29710 was obtained.
Since the polymer peak and the DAA-SA monomer peak overlapped, the GPC yield could not be calculated.

Comparative Example 1 (MeAMA, homopolymer)
7.27 g of DMF and 0.02 mol of MeAMA were placed in a 20 mL test tube. The internal temperature in the test tube was heated to 50 ° C., and 0.06 g of the initiator V-601 (corresponding to 2 wt% of the monomer) was added. After 24 hours, the polymerization reaction was completed, and the GPC yield was 100%. W. A copolymer in the form of a colorless transparent solution of 37521 was obtained.
The results of evaluating the heat resistance, adhesion, cationicity, and silica scale suppressing effect of the obtained polymer are shown in Tables 2 to 5, respectively.

Reference Examples 1 to 3 (diallylamine-based homopolymer)
As Reference Examples 1 to 3, diallylamine-based homopolymers PAS-H-5L (DADMAC homopolymer), PAS-M-1 (DAMA-HCl homopolymer), and PAS-, which are commercially available from Nittobo Medical Co., Ltd. The results of evaluating the heat resistance of 21Cl (DAA-HCl homopolymer) are shown in Table 2.
For Reference Example 1 (DADMAC homopolymer), the silica scale suppressing effect was also evaluated. The results are shown in Table 5.

The copolymer composition in Example 1 in which MeAMA was added dropwise to DMF in which DADMAC was dissolved in advance was closer to the supplied DADMAC: MeAMA composition and more uniform composition as compared with Example 4 in which batch polymerization was performed. It is shown that the copolymer of the above was obtained. Similarly, the copolymer compositions of Examples 2 and 3 subjected to the dropping polymerization were also obtained as the copolymers having a more uniform composition as compared with the copolymers of Examples 5 and 6 which were subjected to the batch polymerization.

The copolymers obtained in each example have a significantly higher decomposition temperature than the diallylamine-based homopolymers of each reference example, and are heat resistant to almost the same level as the MeAMA homopolymer of Comparative Example 1. The sex was greatly improved.

The coating film using the copolymer obtained in each example showed high adhesion to various metal and resin substrates. In particular, as shown in Comparative Example 1, high adhesion is surely realized even for an aluminum base material or a stainless steel base material, which cannot always realize sufficient adhesion with the conventional MeAMA homopolymer. Was made.

The coating films using the copolymers of Examples 1 and 2 each had dyeability that could be dyed with an anionic dye and had high cationic properties. That is, the copolymers of the embodiments corresponding to Examples 1 and 2 can exhibit high cationic properties, and for example, stainability and heat resistance can be achieved at a high level that could not be realized by the prior art. It can be compatible.

The scale inhibitor using the copolymer of Example 1 showed the same silica scale inhibitory effect as the scale inhibitor using the DADMAC monopolymer of Reference Example 1, and the scale using the copolymer of Comparative Example 1 was used. It had a silica scale inhibitory effect that was significantly superior to that of the inhibitor. That is, the copolymer of the embodiment corresponding to Example 1 can achieve, for example, a silica scale suppressing effect and heat resistance at a high level that could not be realized by the prior art.

The diallylamine-based / diallyl ether-based copolymer of the present invention has both adhesion to various substrates such as resins and various performances such as heat resistance at a high level, and is also according to the production method of the present invention. For example, since a diallylamine-based / diallyl ether-based copolymer having excellent properties can be produced with high efficiency and high quality, the present invention provides a coating material, an adhesive, an adhesive, a surface modifier, a resist, etc. It is suitably used in various applications of the above, and has high utility value and availability in each field of industries such as information technology industry, automobile industry, and manufacturing of daily necessities.

Claims (11)

At least one structural unit (I) having a structure represented by the following structural formula (Ia) or (Ib), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formulas (Ia) and (Ib), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms. ), And at least one structural unit (II) having a structure represented by the following structural formula (IIa).

(However, in the above formula (IIa), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
A polymer compound having. The polymer compound according to claim 1, wherein the proportion of the constituent unit (I) is 0.1 to 50 mol%, and the proportion of the constituent unit (II) is 99.9 to 50 mol%. The polymer compound according to claim 1 or 2, wherein the structural unit (I) is an addition salt having a structure represented by the following structural formula (Ia') or (Ib').


(However, in the above formula (Ia '), and (Ib'), ^{R 1} is the same as defined in formula (Ia) and (Ib), ^{R 1} 'is a hydrogen atom, a hydroxyl group Yes from carbon atoms 1 even though 10 alkyl group, or an aralkyl group having 7 to 10 carbon atoms, R ¹ and R ^{1 ',} or different and are identical, X ^- is a counter Ion.), A structural unit (i) at least one derived from a monomer (1) having a structure represented by the following structural formula (III), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.)
At least one structural unit (ii) derived from the monomer (2) having the structure represented by the following structural formula (IV).

(However, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
A polymer compound having. The polymer compound according to claim 4, wherein the proportion of the constituent unit (i) is 0.1 to 50 mol%, and the proportion of the constituent unit (ii) is 99.9 to 50 mol%. The polymer compound according to any one of claims 1 to 5, wherein the weight average molecular weight is 10,000 or more. At least one monomer (1) having a structure represented by the following structural formula (III), or an addition salt thereof, or a structure which is a quaternary ammonium salt.


(However, in the above formula (III), R ¹ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom and a hydroxyl group, or an aralkyl group having 7 to 10 carbon atoms.)
At least one monomer (2) having a structure represented by the following structural formula (IV),

(However, in the above formula (IV), R ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.),
A method for producing a polymer compound, which comprises a step of copolymerizing. The polymer compound according to claim 7, wherein the molar ratio of the monomer (1) to the monomer (2) used in the above step is in the range of 0.1: 99.9 to 90:10. Manufacturing method. The method for producing a polymer compound according to claim 7 or 8, wherein the above step is carried out in at least one solvent selected from the group consisting of dimethylformamide, tetrahydrofuran and toluene. The polymer compound according to any one of claims 7 to 9, wherein the above step is carried out by dropping the monomer (2) into an organic solvent in which the monomer (1) is dissolved in advance. Manufacturing method. A coating material, an adhesive, an adhesive, a surface modifier, a resist, a dye fixing agent, an ink fixing agent, a pigment dispersant, and an agglomerate containing the polymer compound according to any one of claims 1 to 6. Agents, antibacterial agents, bactericides, paper strength enhancers, corrosion inhibitors, plating brighteners or optical materials.