JP2001026695A - Hydrophilic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide hydrophilic polymer compositions which excel in adhesion to a base material such as polymers and metals, and also excel in any of antistatic properties, heat resistance, hydrophilicity, and water resistance and can be used as the antistatic agent of the coating type for PET films and the like and, in addition, are applicable to various other uses. SOLUTION: Hydrophilic polymer compositions comprise, as the major components, (A) a block copolymer having a block chain having a hydrophilic group and a block chain having a hydrophobic group with a ratio of the number of the hydrophilic group-introduced constituting unit to that of the constituting monomer unit of the block chain having a hydrophilic group of not less than 50% and (B) a (co)polymer mainly having an olefinic monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrophilic polymer composition containing a block copolymer having a hydrophilic group, and more particularly, to a binder, a coating material,
The present invention relates to a hydrophilic polymer composition effective as an antistatic agent.

[0002]

2. Description of the Related Art Hitherto, polymers having a polar group such as a sulfonic acid group, a carboxylic acid group and a phosphoric acid group have been known, and have been used in various applications such as surfactants, emulsifiers and dispersants. It is used. On the other hand, in recent years, such properties as the dispersibility of the polar group, hydrophilicity, ion-capturing property, ionic conductivity, and adhesion to the base material are utilized to make the binder resin, the coating material, the antistatic agent, the surface treatment agent, Application to battery materials is being studied. In particular, the sulfonic acid group-containing polymer easily exhibits the above characteristics due to the strong ionicity of the sulfonic acid group, and its application has attracted attention.

However, a polymer containing a polar group such as a sulfonic acid group has poor hydrophilicity when the polar group content is higher than a certain level due to the hydrophilicity (water solubility) of the polar group. When used as a material, there is a problem that the material expands violently in the presence of water, or easily peels off from the surface of the base material, thereby lowering durability. For this reason, the content of the polar group is limited to a certain extent, and the characteristics such as hydrophilicity, ion trapping property, ionic conductivity, and dispersibility have not been sufficiently exhibited.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to increase the polar group content while maintaining sufficient water resistance, and to improve functions such as hydrophilicity, ion trapping property, ionic conductivity and dispersibility. It is to provide a hydrophilic polymer composition.

[0005]

The present invention provides (A) a block copolymer having a block chain having a hydrophilic group and a block chain having a hydrophobic group, wherein the number of monomer units constituting the block chain having a hydrophilic group is A block copolymer having a ratio of the number of constituent monomer units into which a hydrophilic group is introduced to 50% or more, and (B) a hydrophilic polymer mainly composed of a (co) polymer mainly composed of an olefin monomer. It provides a composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention is a block copolymer having a block chain having a hydrophilic group and a block chain having a hydrophobic group. The block chain having such a hydrophobic group is a polymer or copolymer unit containing a hydrocarbon monomer as a main component. Examples of the polymer or copolymer unit containing a hydrocarbon monomer as a main component include a (co) polymer mainly containing a diene monomer and an olefin monomer such as an aromatic vinyl compound or an olefin. (Co) polymers mainly composed of monomers or (co) polymers obtained by hydrogenating these. Examples of the block chain having a hydrophilic group include those in which the above-mentioned hydrophobic polymer unit contains a hydrophilic group. Such hydrophilic groups include a sulfonic acid group,
Examples include a carboxylic acid group (carboxylic acid group), a phosphoric acid group, an amine group, an amide group, and a hydroxyl group. Among these, a sulfonic acid group and a carboxylic acid group (carboxyl group) are preferable, and a sulfonic acid group is more preferable. For example, a (co) polymer mainly composed of a diene monomer, a (co) polymer mainly composed of an olefin monomer such as an aromatic vinyl compound or an olefin, or a (co) polymer obtained by hydrogenating the above. And a unit of a (co) polymer having a hydrocarbon-based monomer as a main component such as a unit containing a hydrophilic group such as a sulfonic acid group. Examples of a method for containing a sulfonic acid group in a (co) polymer unit containing a hydrocarbon monomer as a main component include a method of adding a hydrophilic group such as sulfonation of these (co) polymer unit, Examples include a method of copolymerizing a monomer containing a hydrophilic group such as an acid group. Preferred is a block copolymer containing a (co) polymer unit mainly composed of a diene monomer and a (co) polymer unit mainly composed of an olefin monomer such as an aromatic vinyl compound or an olefin. (Hereinafter referred to as a base polymer) or a method of adding a hydrophilic group to a block copolymer obtained by hydrogenating them.

The diene monomers used in the (co) polymer unit mainly composed of the diene monomers include:
A diene-based compound having 4 to 12 carbon atoms is preferred, and a diene-based compound having 4 to 8 carbon atoms, particularly preferably 4 to 6 carbon atoms, is more preferred. Specific examples of these diene compounds include, for example, 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene,
2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-
Heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene,
In addition to 3,4-heptadiene, 3,5-heptadiene, cyclopentadiene, dicyclopentadiene, ethylidene norbornene, etc., various aliphatic or alicyclic dienes having 4 to 7 carbon atoms which are branched may be mentioned. These can be used alone or in combination of two or more.
Of these, particularly preferred are 1,3-butadiene,
Isoprene.

The (co) polymer unit mainly composed of an olefin monomer is a (co) polymer unit mainly composed of an olefin monomer such as an aromatic vinyl compound or an olefin. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene and the like. Examples of the olefin include ethylene and propylene. These monomers may be used alone or in combination of two or more. Of these, aromatic vinyl compounds are preferred, and styrene is particularly preferred.

Further, a (co) polymer mainly composed of the diene monomer, a (co) polymer mainly composed of an olefin monomer such as an aromatic vinyl compound or an olefin, or a hydrogenated product thereof ( In the unit of the (co) polymer, other monomers can be used in combination with the above monomers.
Other monomers include, for example, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid, crotonic acid, and maleic acid. Acid, fumaric acid,
Mono- or dicarboxylic acid or anhydride of dicarboxylic acid such as itaconic acid, vinyl cyanide compound such as (meth) acrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl acetate, (meth) acrylamide, glycidyl (meth) acrylate And unsaturated compounds. These other monomers can be used alone or in combination of two or more.

Further, a diene monomer is mainly used (co)
The polymer unit may be copolymerized with the aromatic vinyl compound or olefin as a lower monomer in an inferior amount. In the (co) polymer unit mainly composed of an aromatic vinyl compound, the diene monomer or the olefin may be copolymerized in an inferior amount. Further, in the (co) polymer unit mainly composed of olefin, the diene-based monomer or the aromatic vinyl compound may be copolymerized in an inferior amount as another monomer. When these other monomers are used in combination, the amount of the monomers used in each (co) polymer unit is usually 60% or less, preferably 50% by weight or less, more preferably 30% by weight or less.
% By weight or less, particularly preferably 20% by weight or less.

Examples of the monomer having a sulfonic acid group include those obtained by adding a sulfonic acid group to the diene monomer or the olefin monomer. Specific examples thereof include sulfonic acid group-containing butadiene, sulfonic acid group-containing isoprene, sulfonic acid group-containing styrene, sulfonic acid group-containing ethylene, and sulfonic acid group-containing propylene. Of these, sulfonic acid group-containing isoprene and sulfonic acid group-containing styrene are preferred. Also,
As a method for adding a hydrophilic group other than sulfonation, known methods such as carboxylation, phosphorylation, amination, amidation, and hydroxylation can be used.

Production of a base polymer, that is, a (co) polymer unit mainly composed of a diene monomer and a (co) polymer unit mainly composed of an olefin monomer such as an aromatic vinyl compound or an olefin. The contained block copolymer can be produced by (co) polymerizing each monomer using an initiator and, if necessary, a solvent. Examples of such an initiator include a radical polymerization initiator such as hydrogen peroxide, benzoyl peroxide, and azobisisobutyronitrile, and an anionic polymerization initiator such as n-butyllithium, sodium naphthalene, and metallic sodium. Further, the polymerization temperature is usually -100 to 150C, preferably 0 to 130C. As the polymerization method, anionic polymerization is particularly preferably used from the viewpoint of obtaining a block copolymer.

The above block copolymer may be used by hydrogenating (hydrogenating) a part or all of the remaining double bond based on the diene monomer. In this case, a known hydrogenation catalyst can be used.
Examples of the catalyst and the method are described in JP-A-222115. After hydrogenation of the above-mentioned block copolymer as a base polymer, a hydrophilic group can be introduced by a method described later, but after introducing a hydrophilic group into the copolymer, hydrogenation may be carried out.

The base polymer used in the present invention is preferably a polymer unit A containing a diene monomer.
And a block copolymer containing a polymer unit B containing an olefin-based monomer. The preferred structure of the block copolymer is AB type or A (BA)
n-type or B (AB) n-type or (AB) n-type (where n is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and particularly preferably 1). Further, a diene-based block copolymer having the following structure can also be used. Bm- (AB) x-An, Am-B- (AB) x-An,
Bm- (AB) x-A-Bn (where m and n are 2 to 5, preferably 2 to 3, more preferably 2, and x is 0 to 3, preferably 0 to 0)
2, more preferably 1. )

Of these, AB type and A type are preferred.
BA-type and BAB-type block copolymers. Specific preferred base polymers include, for example, isoprene-styrene block copolymer, styrene-isoprene-styrene triblock copolymer, isoprene-styrene-isoprene triblock copolymer, butadiene-styrene block copolymer , Styrene-butadiene-
Examples include a styrene triblock copolymer, a butadiene-styrenebutadiene triblock copolymer, and hydrogenated products of these block copolymers. Further, in the block chain of the diene monomer unit, the aromatic monomer or another monomer may be partially copolymerized,
The diene monomer or another monomer may be partially copolymerized in the block chain of the aromatic monomer unit.

The weight average molecular weight (hereinafter referred to as "Mw") of these base polymers or hydrogenated products thereof in terms of polystyrene is preferably from 4,000 to 1,000,000.
0, more preferably 7,000 to 500,000, particularly preferably 10,000 to 200,000. M
When w is less than 4,000, water resistance and the like when a hydrophilic group is introduced are not sufficient, while when w exceeds 1,000,000, problems such as gelation may occur.

In the block copolymer, the ratio A / B of the polymer unit A containing the diene monomer and the polymer unit B containing the olefin monomer is the same as that of the unhydrogenated block copolymer. Is preferably 5 to
80/95 to 20, more preferably 10 to 70
/ 90-30, particularly preferably 20-50 / 80-50
It is. In the case of a hydrogenated block copolymer, it is preferably from 20 to 95/80 to 5, more preferably from 30 to 90/70 to 10, and particularly preferably from 50 to 90/70 to 10.
８０80/50２０20.

The degree of polymerization of each of the polymer units A and B is preferably not less than 10 and not less than 20 and more preferably not less than 50 and more preferably not less than 10 in the case of a block copolymer not hydrogenated. Is 100 or more, and particularly preferably A is 100 or more, and B is 200 or more. Also,
In the case of a hydrogenated block copolymer, preferably A
Is 20 or more, B is 10 or more, and more preferably A
Is 100 or more and B is 50 or more, and particularly preferably A
Is 200 or more and B is 100 or more.

The block copolymer having a hydrophilic group of the present invention can be produced by introducing a hydrophilic group into a base polymer comprising the above block copolymer by a method such as addition. As such a method, a known method can be used. When a sulfone group is introduced, for example, edited by the Japan Society of Science, New Experimental Course (Vol. 14, III, p. 1773) or
It can be produced by sulfonation according to a method described in JP-A-2-227403.

That is, when the hydrophilic group-containing block copolymer of the present invention is produced by sulfonating the block copolymer, the base polymer is replaced with a double bond moiety based on a diene monomer in the polymer. Alternatively, it can be produced by preferentially sulfonating either one of the aromatic moieties with a sulfonating agent. In addition,
(1) When a base polymer which is not hydrogenated or a base polymer in which a diene unit is partially hydrogenated is used, it is preferable to preferentially sulfonate the diene unit, while (2) the diene unit is preferably used. In the base polymer in which is hydrogenated, it is preferable to preferentially sulfonate the aromatic unit. When the diene unit is preferentially sulfonated as in (1), the sulfonating agent may be a complex of sulfuric anhydride and an electron donating compound or a bisulfite (Na salt, K salt, Li salt).
It is preferable to use salts and the like. Also, (2)
In order to preferentially sulfonate the aromatic unit as described above, it is preferable to use, as the sulfonating agent, sulfuric anhydride, chlorosulfonic acid, fuming sulfuric acid and the like in addition to the above complex.

Here, as the electron donating compound, N,
Ethers such as N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, diethyl ether; pyridine, piperazine, trimethylamine,
Amines such as triethylamine and tributylamine;
Sulfides such as dimethyl sulfide and diethyl sulfide; nitrile compounds such as acetonitrile, ethyl nitrile and propyl nitrile; and the like, of which N, N-dimethylformamide and dioxane are preferable.

When a non-hydrogenated or partially hydrogenated base polymer is used, the amount of the sulfonating agent is 0.5 mol per mol of diene units in the base polymer. It is at least 1.2 mol and preferably at least 0.8 mol and at most 1.1 mol. If it is less than 0.5 mol, sufficient hydrophilicity may not be obtained. It is not preferable because the reaction sulfonating agent remains as an impurity. When a hydrogenated base polymer is used, the amount of the sulfonating agent is usually from 0.5 mol to 1.2 mol, preferably from 1 mol to 1 mol of the aromatic unit in the base polymer. If it is 0.8 mol or more and 1.1 mol or less, if it is less than 0.5 mol, sufficient hydrophilicity may not be obtained, and if it exceeds 1.2, the unreacted sulfonating agent remains as an impurity.

In the sulfonation, a solvent inert to a sulfonating agent such as sulfuric anhydride or sulfuric acid may be used. Examples of the solvent include halogens such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene and dichloromethane. Nitro compounds such as nitromethane and nitrobenzene; aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane; ether solvents such as dioxane and tetrahydrofuran; and water. These solvents may be used as a mixture of two or more. The reaction temperature of this sulfonation is usually-
70 to 200 ° C, preferably -30 to 50 ° C,
If the temperature is lower than 70 ° C., the sulfonation reaction is slow, which is not economical.

The sulfonated diene block copolymer used in the hydrophilic polymer composition of the present invention is preferably obtained by reacting water or a basic compound with the sulfonated product. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium-t-butoxide, potassium-t-butoxide and the like. Alkali metal alkoxides; carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate; methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium bromide, and propyl magnesium Iodide, diethylmagnesium,
Organometallic compounds such as diethylzinc, triethylaluminum and triisobutylaluminum; aqueous ammonia;
Examples include amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, aniline, and piperazine; and metal compounds such as sodium, lithium, potassium, calcium, and zinc. These basic compounds can be used alone or in combination of two or more. Among these basic compounds, alkali metal hydroxides and aqueous ammonia are preferable, and sodium hydroxide, lithium hydroxide and potassium hydroxide are particularly preferable.

The amount of the basic compound used is preferably 1.5 mol or less, more preferably 1.2 mol or less, based on 1 mol of the sulfonating agent used. And the purity of the product decreases. In this reaction, the basic compound can be used in the form of an aqueous solution, or can be used by dissolving it in an organic solvent inert to the basic compound. Examples of the organic solvent include the above-mentioned various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; and alcohols such as methanol, ethanol, propanol, isopropanol, and ethylene glycol. These solvents may be used as a mixture of two or more.

When the basic compound is used as an aqueous solution or an organic solvent solution, the basic compound concentration is usually
It is about 1 to 70% by weight, preferably about 10 to 50% by weight. The reaction temperature is usually -30 to 150 ° C,
Preferably it is 0-120 degreeC, More preferably, it is + 50-1.
It is carried out at 00 ° C. and can be carried out under normal pressure, reduced pressure or increased pressure. Further, the reaction time is generally 0.1 to 24 hours, preferably 0.5 to 5 hours. When a hydrophilic group other than a sulfonic acid group is introduced, it can be produced, for example, by copolymerizing (meth) acrylic acid, (meth) acrylic phosphate, amino (meth) acrylate, hydroxyalkyl (meth) acrylate, and the like. it can.

The content of the polar group in the block copolymer into which the hydrophilic group is introduced as described above is usually preferably 50 mol% or more, more preferably 70 mol%, of the constituent monomer unit in the block containing the hydrophilic group. % Or more. When the content is 50 mol% or more, sufficient hydrophilicity can be obtained. Further, a block copolymer in which the ratio of the number of hydrophilic constituent monomer units (units) to the number of constituent monomer units (units) of the block chain having a hydrophilic group is 50% or more, more preferably 70% or more, It is particularly preferably at least 80%.

The content of the sulfonic acid (salt) group in the component (A) is preferably 0.5 to 5.5 mmol / g, more preferably 1.0 to 5.0 mmol / g, and particularly preferably 2. 0 to 4.5 mmol / g. 0.5mmo
If it is less than 1 / g, functions such as hydrophilicity are hardly exhibited, and if it is too large, water resistance may become a problem.

The component (A) of the present invention may be emulsified and dispersed in water to be used as an emulsion (hereinafter, this emulsification step is also referred to as "re-emulsification") or may be dissolved in a non-aqueous solvent. It is also possible to use those obtained by dissolving in a non-aqueous solvent and emulsifying and dispersing in water to form an emulsion.

When the component (A) is used as an emulsified product, the emulsifying step is as follows: the polymer of the component (A) or a solution of the polymer in an organic solvent is stirred and mixed with water, emulsified, and then water is added. The removal can be carried out by removing the organic solvent while leaving. Examples of the organic solvent used for preparing the component (A) into an organic solvent solution in the emulsification step include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and heptane, and acetone. , Ketone solvents such as methyl ethyl ketone, ether solvents such as tetrahydrofuran and dioxane, ester solvents such as ethyl acetate and butyl acetate, methanol,
Alcohol solvents such as ethanol and isopropyl alcohol, and amide solvents such as dimethylformamide are used. These solvents may be used alone or in combination of two or more. This emulsification step can be carried out by a general method, a method in which water is added to the organic solvent solution of the component (A) while stirring, or a method in which the organic solvent solution of the component (A) is added to water while stirring. And a method in which water and an organic solvent solution of the component (A) polymer are simultaneously added and stirred, and the like are not particularly limited.

The amount of the organic solvent used in the emulsification step is preferably 20 to 5,000 parts by weight, more preferably 50 to 2,000 parts by weight, based on 100 parts by weight of the component (A) polymer. It is. If the amount is less than 20 parts by weight, it is difficult to obtain a stable emulsion, while if it exceeds 5,000 parts by weight, economic efficiency is degraded. Further, the amount of water used in the emulsification step depends on the amount of the component (A) polymer 10
It is preferably 50 to 10,000 parts by weight, more preferably 100 to 5,000 parts by weight, based on 0 parts by weight.

In the emulsification step, a surfactant may be used in combination. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxysorbitan ester, and polyoxyethylene alkylamine ether, oleate, laurate, rosinate, dodecylbenzene sulfonate. ,
Examples include anionic surfactants such as polyoxyethylene alkyl ether sulfate, and cationic surfactants such as octyltrimethylammonium bromide, dioctyldimethylammonium chloride, and dodecylpyridinium chloride. These surfactants can be used alone or in combination of two or more. The surfactant,
The (A) component polymer may be dissolved or dispersed in an organic solvent solution, or may be dissolved or dispersed in water for use. The amount of the surfactant used is
The amount is usually 10 parts by weight or less, preferably 6 parts by weight or less, more preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the component (A) polymer.

Further, in order to adjust the pH in the system, an alkali compound such as sodium hydroxide or lithium hydroxide;
Inorganic acids such as hydrochloric acid and sulfuric acid can also be added. If the amount is small, an organic solvent other than water can be used in combination. Further, an antifoaming agent or the like can be added. The particle size of the emulsion obtained by emulsifying the component (A) polymer thus obtained is usually preferably from 10 to 1,000 nm, more preferably from 20 to 500 nm.
The solid content concentration of the obtained emulsion of the component (A) polymer is usually from 5 to 50% by weight, preferably from 10 to 40% by weight, depending on the use conditions and storage conditions.
It can be selected as appropriate.

The component (A) polymer of the present invention can be used by dissolving it in a non-aqueous solvent. Examples of the non-aqueous solvent include aliphatic hydrocarbons such as hexane and heptane, and benzene. , Toluene, xylene and other aromatic hydrocarbons, tetrahydrofuran, ether solvents such as 1,4-dioxane, ketone solvents such as methyl ethyl ketone and methyl isopropyl ketone, ester solvents such as ethyl acetate, dimethylformamide, dimethyl sulfone Examples include polar solvents such as phonates, and alcohols such as methanol, ethanol, and isopropanol.
These can be used as a mixture of two or more kinds. The mixing ratio of the obtained component (A) polymer and the non-aqueous solvent is usually 3 to 5 in terms of the solid content concentration of the blend composition.
The content is 0% by weight, preferably 5 to 30% by weight, which can be appropriately selected depending on use conditions, storage conditions and the like.

As the (co) polymer mainly composed of the olefin monomer which is the component (B) used in the present invention, olefins such as ethylene and propylene may be used. A (co) polymer consisting of at least one of a monomer, an aromatic monomer, another monomer, and a sulfonic acid (salt) group-containing monomer such as styrene sulfonic acid (salt) and isoprene sulfonic acid (salt); And a hydrogenated product thereof.

Among these, a copolymer of ethylene and a carboxylic acid group-containing monomer such as (meth) acrylic acid is preferred, and a copolymer of ethylene and (meth) acrylic acid is particularly preferred.

The proportion of (meth) acrylic acid in the copolymer of ethylene and (meth) acrylic acid is preferably 50% by weight or less, more preferably 0.5 to 20% by weight, particularly preferably 1 to 20% by weight. -10% by weight. If the proportion of (meth) acrylic acid in the copolymer exceeds 50%, water resistance may become a problem.

The component (B) of the present invention can be used as an emulsion or dissolved in a non-aqueous solvent. As a method for obtaining an emulsion of the component (B),
There are a method of obtaining the same emulsification step as that of the component (A) and a method of obtaining the same by emulsion polymerization, and any method may be used.

The weight average molecular weight (hereinafter referred to as “Mw”) of the component (B) of the present invention in terms of polystyrene is preferably 5,000 to 1,000,000, and more preferably 10,000 to 500,000. Particularly preferably 5
It is between 000 and 300,000. Mw is 5,000
If it is less than 1, adhesion and the like are inferior.
When it exceeds 00, the viscosity of the emulsion becomes large.

As a method for obtaining an emulsion of the hydrophilic polymer composition of the present invention in which the components (A) and (B) coexist or a solution in a non-aqueous solvent, the emulsion of the component (A) is used. And an emulsion of the hydrophilic polymer composition is obtained by a simple mixing method of the emulsion of the component (B). A solution of the hydrophilic polymer composition in the non-aqueous solvent is obtained by a simple mixing method of the solution of the component (A) in the non-aqueous solvent and the solution of the component (B) in the non-aqueous solvent. An emulsion of the hydrophilic polymer composition is obtained by a simultaneous emulsification method of the component (A) and the component (B). The components (A) and (B) are simultaneously dissolved in a non-aqueous solvent to obtain a solution of the hydrophilic polymer composition in the non-aqueous solvent. An emulsion of the hydrophilic polymer composition is obtained by an emulsion polymerization method of the component (B) in the presence of the component (A). By emulsifying the above or a solution in a non-aqueous solvent, an emulsion of the hydrophilic polymer composition is obtained. Etc., but any method may be used.
Among these methods, there is a method of mixing the components (A) and (B) and then obtaining an emulsion by the same method as that for obtaining the emulsion of the component (A). Is a method in which water, an initiator, a monomer, and in some cases, an emulsifier are mixed in the presence of the component (A) to carry out emulsion polymerization to obtain an emulsion. In the case of (1), the non-aqueous solvent dissolving the component (A) and the non-aqueous solvent dissolving the component (B) are desirably the same solvent or a combination of solvents that can be easily and uniformly mixed.

(A) in the hydrophilic polymer composition of the present invention
The blend ratio of the component and the component (B) is preferably 5 to 90.
/ 95-10, more preferably 10-80 / 90-2
0, particularly preferably 20 to 50/80 to 50% by weight. If the amount is less than 5% by weight, functions such as hydrophilicity and ion trapping ability are hardly exhibited, and if the amount is more than 90% by weight, resistance to water is reduced.

The structures of the component (A) and the component (B) of the present invention can be confirmed from the absorption of the sulfone group by an infrared absorption spectrum, and their composition ratio can be known by elemental analysis or the like. The structure can be confirmed by a nuclear magnetic resonance spectrum.

The hydrophilic polymer composition of the present invention can be used by mixing additives such as a surfactant and a stabilizer, if necessary.

The hydrophilic polymer composition of the present invention can be used in combination with a crosslinking agent comprising one or more compounds selected from a radical generator, a vulcanizing agent and a vulcanization accelerator, and then cross-linked. Examples of the radical generator include known organic peroxides, inorganic peroxides, and azo compounds. For example, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t- Butyl peroxide,
t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, t-butylperoxyisopropyl carbonate, t-butylhydroperoiside, hydrogen peroxide, azobis Isobutyronitrile, 2,2'-azobis (4-methoxy-2--4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2- (carbamoylazo) isobutyro Examples thereof include nitrile and hydrochloride of 2,2'-azobis-2-amidopropane.

Further, as the vulcanizing agent and the vulcanization accelerator,
For example, those described in “Rubber Industry Handbook, P219 to P263” (Japan Rubber Association, published in 1973) can be used. Among them, as the vulcanizing agent, sulfur, sulfur chloride, selenium, inorganic vulcanizing agents such as tellurium,
p-benzoquinone dioxime, p, p-dibenzoylquinone dioxime, 4,4'-dithiobisdimorpholine, poly-p-dinitrosobenzene, tetrachlorobenzoquinone, alkylphenol-formaldehyde,
Organic vulcanizing agents such as ammonium benzoate and N, N'-m-phenylenedimaleimide are exemplified.

Examples of the vulcanization accelerator include ammonia such as hexamethylenetetramine, guanidine such as diphenylguanidine, thiourea such as N, N'-dimethylthiourea and dibutylthiourea, and thiazole such as mercaptobenzothiazole; Examples thereof include dithiocarbamates such as dimethyldithiocarbamate, and thiurams such as tetramethylthiuram disulfide and tetraethylthiuram disulfide.

The total amount of the crosslinking agent used is usually 0.1 to 15% by weight based on the hydrophilic polymer composition of the present invention.
Preferably it is 0.5 to 10% by weight. The use of 0.1% by weight or more is preferable in terms of the solvent resistance and mechanical strength of the crosslinked product, but if too much is used, various physical properties may be deteriorated.

The hydrophilic polymer composition of the present invention can be used in combination with an organic filler or an inorganic filler dispersed therein. Organic fillers and inorganic fillers that provide mechanical properties such as stiffness, tensile strength, impact resistance, toughness, and slidability, and that provide thermal properties such as heat resistance, thermal expansion, and heat radiation Objects, those that impart electrical or magnetic properties such as conductivity, insulation, piezoelectricity, pyroelectricity, dielectricity, semiconductor properties, magnetism, electromagnetic wave absorption, electromagnetic wave reflection, light transmission, light shielding, light What imparts optical properties such as scattering, light absorption, photochromic properties, ultraviolet absorption, infrared absorption, light resistance, antibacterial properties,
Those that impart vibration damping properties, sound insulation properties, moisture absorption properties, gas absorption properties, oil absorption properties, radiation absorption properties, and the like can be used.

Specific examples of the organic or inorganic filler include carbon black, Ketjen black, graphite, charcoal powder, carbon fiber, iron, silver, copper, lead, nickel, silicon carbide, tin oxide, iron oxide, and oxide. Titanium,
Magnesium oxide, zinc oxide, cerium oxide, calcium oxide, zirconium oxide, antimony oxide, ferrite, alumina, aluminum hydroxide, magnesium hydroxide, potassium titanate, barium titanate, titanic acid,
Lead zirconate, zinc borate, zinc carbonate, mica, barium sulfate, calcium carbonate, molybdenum sulfide, polytetrafluoroethylene (teflon) powder, talc, asbestos, silica beads, glass powder, hydrotalcite, iron phthalocyanine, silica gel, Examples include zeolite, sepiolite, zonotolite, activated clay, and polymer beads. The amount of the organic / inorganic filler used is usually 500% by weight or less based on the hydrophilic polymer composition.

The hydrophilic polymer composition of the present invention can be applied to various uses such as an antistatic agent, a coating material, and a binder resin. In addition, when applied to various uses, other polymers can be used in combination to improve the properties of the polymer. Examples of other polymers include known polymers such as urethane resins, acrylic resins, polyester resins, polyamide resins, polyethers, polystyrenes, polyesteramides, polycarbonates, polyvinyl chlorides, and diene polymers such as SBR polymers. These other polymers are preferably used in an emulsified state when the hydrophilic polymer composition is used as an emulsion.

The hydrophilic polymer composition of the present invention usually comprises
It is used alone or as a coating on a substrate as the compound. The coating method is not particularly limited, and brush coating, spray, roll coater, flow coater, bar coater, dipping treatment, or the like can be used. The thickness of the applied film varies depending on the application, but is generally 0.01 to 1,000 μm, preferably 0.05 to 500 μm as a dry film thickness.

When the hydrophilic polymer composition of the present invention is applied in the form of an emulsion, an aromatic solvent such as toluene and xylene, an aliphatic solvent such as hexane and heptane, a ketone solvent such as acetone and methyl ethyl ketone, and tetrahydrofuran are applied at the time of coating. It is also possible to use ether solvents such as dioxane, ester solvents such as ethyl acetate and butyl acetate, and alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol. Co-use of these organic solvents may improve coating performance and the like.

The substrate used is not particularly limited. For example, polycarbonate resin, acrylic resin, A
Polymer materials such as BS resin, polyethylene terephthalate, polyethylene, polypropylene, and nylon; non-ferrous metals such as aluminum, copper, and duralumin; steel plates such as stainless steel and iron; glass; wood; paper; gypsum; alumina; Can be The shape of the substrate is not particularly limited, and it can be used for a flat type or a porous material.

Here, examples of the porous material include a nonwoven fabric, a woven fabric, a knitted fabric, and the like, and the material may be a natural fiber, an artificial fiber, a synthetic fiber, or a mixture thereof. The components include olefin homopolymers such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1;
Known olefin or block copolymers such as cotton, wool, rayon, acetate, polyamide, polyester and acrylic fiber can be used. Further, rock wool, ceramic wool, glass fiber and the like can be used. The amount of coating on these porous materials depends on the material of the porous material, the pore size, and the intended use, and cannot be unconditionally defined.
0.5 to 30 g / m2. If the amount is less than 0.5 g / m 2, the desired performance such as hydrophilicity and ion-trapping property is hardly exhibited.

The hydrophilic polymer composition of the present invention is particularly effective for modifying the surface of a substrate, and is excellent in heat resistance and light resistance. In particular, by coating on hydrophobic surfaces,
It is possible to develop or maintain hydrophilicity and hygroscopicity.
Further, it is possible to prevent adhesion of dirt and dust due to static electricity and the like. Further, when coated on a porous material such as a nonwoven fabric, it exhibits a function of capturing a weak base such as ammonia or an amine existing in the air or water, or an ionic substance. In addition, by coating the surface of the battery separator, the affinity with the battery electrolyte is improved, which leads to an improvement in battery characteristics such as self-discharge characteristics. Furthermore, the emulsion of the sulfonic acid group-containing polymer of the present invention has the excellent characteristics that it has high adhesion to various substrates, prevents the coating film from peeling off from the substrate, and can maintain stable performance for a long period of time. is there.
Further, one of the characteristics is that the filler is highly dispersed, and there is also a characteristic that the properties of each filler can be sufficiently exhibited.

The hydrophilic polymer composition of the present invention can be applied to various uses. When applied to a porous material or the like, for example, a cationic dyeing aid for fibers, a water-absorbent nonwoven fabric, a nonwoven fabric for a wet tissue, a nonwoven fabric for a sealing material, an antifouling material, an ion exchange fiber, a separator for a battery separator,
Filter applications such as air and water filters for removing ammonia and ionic substances, leukocyte removal filters, pollen allergen removal materials, water vapor permeable materials, antibacterial materials, deodorant fibers, deodorant paints,
Examples include humidity control materials such as deodorant paper, antifogging materials and anti-condensation materials, antistatic materials, anticorrosion materials, oxygen absorbents, sanitary articles, and surface modification of activated carbon. It can also be applied to floor polishes, masking materials, paper sizing materials, paper strength enhancing materials, adhesives, photographic materials such as silver halide photographic materials, and the like.

Further, the hydrophilic polymer composition of the present invention comprises:
By combining various fillers, it can be applied to various uses. For example, general paints, paints for circuit boards, conductive materials, battery materials such as binders for solid electrolytes or binders for electrode materials, electromagnetic wave shielding materials, antistatic paints, sheet heating elements, electrochemical reaction electrode plates, electrical contacts Materials, friction materials, antibacterial materials, sliding materials, abrasive materials, magnetic recording media, heat-sensitive recording materials, electrochromic materials, light diffusion films, water shielding materials for communication cables, light shielding films,
Sound insulation sheet, plastic magnet, X-ray intensifying screen,
Examples include printing inks, pesticide granules, and electrophotographic toners. Also, as a coating material for surface protection, for example, metals such as stainless steel, aluminum and copper, inorganic substances such as concrete and slate, polyolefins such as polyethylene and polypropylene, polymer materials such as polyester such as polyethylene terephthalate, wood, paper, etc. Application of is also possible.

[0058]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the examples, parts and% are by weight unless otherwise specified. Various evaluations and measurements in the examples were performed by the following methods.

(1) Total Content of Sulfonic Acid Groups and Ratio of Number of Hydrophilic Groups The synthesized sulfonated product was vacuum-dried at 80 ° C. overnight. The dried product was dissolved in a toluene / isopropyl alcohol (95/5 weight ratio) solution. After dissolution, insolubles such as sulfates and hydroxides were removed with a filter, and then the solvent was removed to obtain a sulfonic acid content measurement sample. The sulfur content in the sample was determined from elemental analysis, and the amount of sulfonic acid groups in the copolymer was calculated. Using this value, the ratio of the number of hydrophilic groups to the number of monomer units constituting the block chain having a hydrophilic group was calculated.

(2) Particle size of re-emulsified product LPA-3100 LASER P manufactured by Otsuka Electronics Co., Ltd.
The average particle size of the emulsion was measured using ARTICLE ANALYZER.

(3) Weight Average Molecular Weight (Mw) The weight average molecular weight (Mw) of the base polymer was measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

(4) Measurement of Adhesion The obtained emulsion of the hydrophilic polymer composition and the solution were coated on a copper plate and PE using a 100 mil applicator.
After coating on the T film, it was dried in a thermostat at 100 ° C. for 30 minutes to obtain an evaluation sample. The adhesion to the copper plate and PET film was evaluated by a cross-cut adhesive tape (using cellophane tape) peel test. Table 2 shows the number of the grids that did not peel out of the 100 grids.

Evaluation of Antistatic Property The obtained emulsion of the hydrophilic polymer composition and the solution were adjusted to a solid concentration of 10% by weight. This solution was no. 6
It was coated on a polyethylene terephthalate film using a bar coater and dried at 105 ° C. for 3 minutes to obtain a sample for evaluation. Then, it was heated at 23 ° C and 5 ° C to 16008A (trade name) which is a concentric electrode of Yokogawa-Hewlett-Packard Company.
The sample was placed in an atmosphere of 0% RH, a voltage of 100 V was applied, and the surface specific resistivity (Ω / □) of the sample was measured using 4329A (trade name), a high resistance meter of the company.

Evaluation of heat resistance The film sample coated with the hydrophilic polymer composition obtained above was stored at 140 ° C. for 24 hours in a thermostat, and the degree of coloring of the film sample was visually observed. Was evaluated as ◎, slightly colored one was evaluated as ○, and considerably colored one was evaluated as x.

(7) Evaluation of hydrophilicity The obtained emulsion and solution of the hydrophilic polymer composition were adjusted to a solid concentration of 2% by weight. 10cm in this solution
The corner nonwoven fabric (made of polypropylene) was dipped. Then, it dried at 100 degreeC for 1 hour in the thermostat, and was set as the evaluation sample. The amount of coating was 5 g / m3 when calculated from the weight increase before and after coating due to dipping. Distilled water was poured onto the coated nonwoven fabric, and the degree of permeation into the nonwoven fabric was qualitatively observed. ◎: fairly good penetration, 比較 的: relatively good penetration, and x: poor penetration.

(8) Evaluation of Water Resistance The non-woven fabric dipped with the hydrophilic polymer composition was immersed in water at room temperature overnight, and the polymer shedding rate was measured.

(9) Measurement of Liquid Absorption Rate The above-mentioned dipping treatment of the hydrophilic polymer composition 5
The weight increase rate after immersing the cm square nonwoven fabric in a 30% KOH aqueous solution for 10 minutes was measured. Liquid absorption rate (%) = (weight of nonwoven fabric after immersion−weight of nonwoven fabric before immersion) / weight of nonwoven fabric before immersion × 100

Reference Example Preparation of Emulsions A to C of Component (A) 500 g of dioxane was placed in a glass reaction vessel, and a specified amount of sulfuric anhydride (A; 21.4 g, B; 39.0) was added thereto.
g, C; 49.2 g) were added while maintaining the internal temperature at 25 ° C., and the mixture was stirred for 2 hours to obtain an anhydrous sulfuric acid-dioxane complex. In another glass reaction vessel, the base polymer (100 g) shown in Table 1 was dissolved in 400 g of dioxane. The whole amount of the complex obtained above was added thereto while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours. After stirring, a specified amount of sodium hydroxide (A; 11.8 g, B;
6 g, C; 27.3 g), 200 cc of a solution of water and 300 g of methanol were added, and the mixture was stirred at 80 ° C. under reflux for 1 hour. After stirring, the solvent was removed under reduced pressure to obtain the component (A) polymer. Table 1 shows the measurement results of the content of the sulfonic acid group. Next, 50 g of the component (A) polymer synthesized above was added to tetrahydrofuran / isopropyl alcohol (90/1).
(0 weight ratio) 450 g. 500 flasks of water
g, anionic / nonionic surfactant [Sanyo Chemical Co., Ltd.]
1 g of Sandet EN] was added, and the mixture was further stirred for 1 hour. Thereafter, 1000 g of water was added, and the total solvent and a part of the water were removed by azeotropic distillation to obtain a re-emulsified emulsion (re-emulsion). The solid content concentration of this emulsion is
20%. Table 1 shows the particle size of these emulsions.

Preparation of Emulsion D of Component (A) A prescribed amount of 1,2-dichloroethane (400 g) was placed in a glass reaction vessel, and 21.4 g of sulfuric anhydride was added thereto while maintaining the internal temperature at 25 ° C. To obtain a sulfuric anhydride solution. 1,2- of base polymer D (100 g) shown in Table 1
The sulfuric anhydride solution obtained above was added to a dichloroethane solution (concentration = 25%) while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours. Sodium hydroxide 1
An aqueous solution in which 1.8 g was dissolved in 100 g of water and methanol (50 g) were added, and the mixture was stirred at 80 ° C. for 1 hour.
After stirring, water and the solvent were distilled off under reduced pressure to obtain a sulfonic acid group-containing polymer. Table 1 shows the measurement results of the content of the sulfonic acid group. Next, 50 g of the component (A) polymer synthesized above was added to tetrahydrofuran / isopropyl alcohol (90/1).
(0 weight ratio) 450 g. 500 flasks of water
g, anionic / nonionic surfactant [Sanyo Chemical Co., Ltd.]
1 g of Sandet EN] was added, and the mixture was further stirred for 1 hour. Thereafter, 1000 g of water was added, and the total solvent and a part of the water were removed by azeotropic distillation to obtain a re-emulsified emulsion (re-emulsion). The solid content concentration of this emulsion is
20%. Table 1 shows the particle size of these emulsions.

[0070]

[Table 1]

Preparation of Emulsions E to H of Component (B) In a glass flask, 50 g of the component (B) polymer shown in Table 2 was dissolved in 450 g of tetrahydrofuran / isopropyl alcohol (90/10 weight ratio). 500 g of water and 1 g of an anionic / nonionic surfactant [Sandet EN, manufactured by Sanyo Chemical Co., Ltd.] were placed in the flask, and the mixture was further stirred for 1 hour. Thereafter, 1000 g of water was added, and the total solvent and a part of the water were removed by azeotropic distillation to obtain a re-emulsified emulsion (re-emulsion). The solid concentration of this emulsion was 20%. Table 2 shows the particle size of these emulsions.

[0072]

[Table 2]

Example 1 A hydrophilic polymer composition was obtained by blending Emulsion A of a sulfonic acid group-containing block polymer and Emulsion E of an olefin copolymer at a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results.

Example 2 A hydrophilic polymer composition was obtained by blending the sulfonic acid group-containing block polymer emulsion B and the olefin copolymer emulsion E at a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results.

Example 3 A hydrophilic polymer composition was obtained by blending the sulfonic acid group-containing block polymer emulsion C and the olefin copolymer emulsion E in a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results. In a mixed liquid obtained by blending the emulsion C of the sulfonic acid group-containing block polymer and the emulsion E of the olefin copolymer at a ratio of 20% by weight to 80% by weight,
A polypropylene nonwoven fabric (average fiber diameter 10 μm, basis weight 48 g / m ² , thickness 200 μm) was dipped and applied. As a result of using this as a battery separator, excellent ones such as strength, water retention and battery characteristics were obtained.

Example 4 A hydrophilic polymer composition was obtained by blending the sulfonic acid group-containing block polymer emulsion D and the olefin copolymer emulsion E at a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results.

Example-5 A hydrophilic polymer composition was obtained by blending Emulsion B of a sulfonic acid group-containing block polymer and Emulsion F of an olefinic copolymer at a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results.

Example-6 A hydrophilic polymer composition was obtained by blending the sulfonic acid group-containing block polymer emulsion B and the olefin copolymer emulsion G at a ratio of 20% by weight to 80% by weight. Table 4 shows the evaluation results.

Example -7 An emulsion B of a sulfonic acid group-containing block polymer and an emulsion H of an olefin copolymer were blended at a ratio of 20% by weight to 80% by weight to obtain a hydrophilic polymer composition. Table 4 shows the evaluation results.

Example-8 A hydrophilic polymer composition was obtained by blending Emulsion B of a sulfonic acid group-containing block polymer and Emulsion E of an olefin copolymer in a ratio of 50% by weight to 50% by weight. Table 4 shows the evaluation results.

Comparative Example 1 500 g of dioxane was placed in a glass reaction vessel, and 12.1 g of sulfuric anhydride was added thereto while maintaining the internal temperature at 25 ° C., followed by stirring for 2 hours to obtain a sulfuric anhydride-dioxane complex. . In another glass reaction vessel, base polymer I (100 g) shown in Table 3 manufactured in the same manner as in the above reference example was dissolved in 400 g of dioxane. The whole amount of the complex obtained above was added thereto while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours. After stirring, sodium hydroxide 6.
A solution in which 3 g was dissolved in 200 cc of water and 300 g of methanol were added, and the mixture was stirred at 80 ° C. under reflux for 1 hour. After stirring, the solvent was removed under reduced pressure to obtain a sulfonic acid group-containing polymer. The measurement results of the sulfonic acid group content are shown in Table 3. Next, the sulfonic acid group-containing polymer 50 synthesized above was used.
g in tetrahydrofuran / isopropyl alcohol (9
(0/10 weight ratio). 500 g of water and 1 g of an anionic / nonionic surfactant [Sandet EN, manufactured by Sanyo Chemical Co., Ltd.] were placed in the flask, and the mixture was further stirred for 1 hour. Thereafter, 1000 g of water was added, and all the solvent and a part of the water were removed by azeotropic distillation to obtain a re-emulsified product. The solid concentration of this emulsion was 20%.
Table 4 shows the evaluation results.

Comparative Example 2 The base polymer species shown in Table 3 was J, and the amount of sulfuric anhydride was 3
A re-emulsion was obtained in the same manner as in Comparative Example 1, except that 9.0 g and the amount of sodium hydroxide were changed to 21.6 g. The solid concentration of this emulsion was 20%. Table 4 shows the evaluation results.

Comparative Example 3 In a glass flask, the base polymer type K shown in Table 3 was used.
(50 g) was dissolved in 450 g of tetrahydrofuran / isopropyl alcohol (90/10 weight ratio). 500 g of water and 1 g of an anionic / nonionic surfactant [Sandet EN, manufactured by Sanyo Chemical Co., Ltd.] were placed in the flask, and the mixture was further stirred for 1 hour. Then add 1000 g of water,
By removing all the solvent and part of water by azeotropic distillation, a re-emulsified emulsion (re-emulsion) was obtained. The solid concentration of this emulsion was 20%. Table 4 shows the evaluation results.

Comparative Example 4 The base polymer species shown in Table 3 was L, and the amount of sulfuric anhydride was 1
A re-emulsified product was obtained in the same manner as in Comparative Example 1, except that 6.8 g and the amount of sodium hydroxide were changed to 8.7 g. The solid concentration of this emulsion was 20%. Next, 20 g of the re-emulsified product obtained here and 80 g of the re-emulsified product obtained in Comparative Example 1 were blended to obtain a re-emulsified product having a solid concentration of 20%. Table 4 shows the evaluation results.

Comparative Example-5 In a glass flask, the base polymer species M shown in Table 3 was used.
(50 g) was dissolved in 450 g of tetrahydrofuran / isopropyl alcohol (90/10 weight ratio). 500 g of water and 1 g of an anionic / nonionic surfactant [Sandet EN, manufactured by Sanyo Chemical Co., Ltd.] were placed in the flask, and the mixture was further stirred for 1 hour. Then add 1000 g of water,
By removing all the solvent and part of water by azeotropic distillation, a re-emulsified emulsion (re-emulsion) was obtained. The solid concentration of this emulsion was 20%. Next, 80 g of the re-emulsified product obtained here and the re-emulsified product 2 obtained in Comparative Example-2
0 g was blended to obtain a re-emulsion having a solid content of 20%. Table 4 shows the evaluation results.

[0086]

[Table 3]

[0087]

[Table 4]

As shown in Table 4, the hydrophilic polymer composition of the present invention has excellent adhesion to substrates such as polymers and metal plates, and also has excellent antistatic properties and heat resistance.
It is very effective as a coating type antistatic agent. In addition, they are excellent in both hydrophilicity and water resistance, and are excellent in liquid absorption when applied to nonwoven fabric, so that they are also effective for battery separator applications.

[0089]

Industrial Applicability The hydrophilic polymer composition of the present invention has excellent adhesion to substrates such as polymers and metal plates, and
Excellent in antistatic properties, heat resistance, hydrophilicity and water resistance. For this reason, it can be used as an antistatic agent for application to PET films, etc., as well as various applications such as binder resins, coating materials, surface treatment agents, surface modifiers, separator treatment agents for batteries, and filters for capturing ionic substances. Applicable to

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 3/03 CES C09D 123/02 3/075 CES 153/02 C08L 23/02 C09K 3/16 102J 53 / 02 108C C09D 123/02 C08J 3/03 CEQ 153/02 CES C09K 3/16 102 108 (72) Inventor Katsuhiro Ishikawa 2-11-11 Tsukiji, Chuo-ku, Tokyo F-term (reference) 4F070 AA08 AA13 AA29 AB06 AB08 AB11 AB13 AC36 AC38 AC66 AE14 AE28 CA03 CB03 CB12 4J002 BB03X BB04X BB08X BB12X BC01X BC03X BC08X BC09X BP01W FD010 FD140 FD150 HA13 HA09 HA13 HA09 HA03 HA09 HA03 HA09 HA49 HB03 HB04 HB05 HB06 HB08 HB09 HB10 HB11 HB12 HB13 HB14 HB15 HB16 HB19 HB50 HC03 HC04 HC05 HC06 HC08 HC09 HC10 HC11 HC12 HC13 HC14 HC15 HC16 HC19 HC47 HC49 HE01 HE02 HE06 4J038 CB031 CB091 CC091 CQ002 CQ012 GA03 GA06 GA08 GA13 GA14 KA06 KA09 MA08 MA10 MA13 NA03 NA14 NA20 PC02 PC04 PC08 PC10 4J100 BA17H BAH BAH HAH HB13 HB14 HB15 HB37 HB39 HB43 HB52 HB53 HC12 HC13 HC38 HC43 HC45 HC51 HC59 HC63 HC69 HC71 HC83 HC84 HC88 HE12 HE14 HG03 JA01 JA15

Claims (7)

[Claims] 1. A block copolymer having (A) a block chain having a hydrophilic group and a block chain having a hydrophobic group, wherein a hydrophilic group is introduced with respect to the number of monomer units constituting the block chain having a hydrophilic group. A block copolymer having a ratio of the number of monomer units of 50% or more, and (B) a hydrophilic polymer composition mainly composed of a (co) polymer mainly composed of an olefin monomer. 2. The hydrophilicity according to claim 1, wherein the component (A) according to claim 1 is emulsified and dispersed or dissolved in an aqueous medium, and the component (B) is emulsified and dispersed in an aqueous medium. Polymer composition. 3. The component (A) according to claim 1, wherein the hydrophilic group is at least one of sulfonic acid (salt) and carboxylic acid (salt).
The hydrophilic polymer composition according to claim 1, which is a seed. 4. The hydrophilic polymer composition according to claim 1, wherein the hydrophilic group of the component (A) is sulfonic acid (salt). 5. A block copolymer wherein the component (A) according to claim 1 comprises a diene monomer and an aromatic monomer.
2. The hydrophilic polymer composition according to claim 1, which is a hydrogenated product thereof and is a polymer obtained by sulfonating one of the monomer units. 6. A coating material comprising the hydrophilic polymer composition according to claim 1. 7. An antistatic agent comprising the hydrophilic polymer composition according to claim 1.