JPH10330545A - Crosslinkable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain composition having excellent water resistance, solvent resistance and high durability as well as having good dispersedness, hydrophilicity, ion scavenging propertins, ionic conductivity and high adhesion to substrates by compounding a sulfo- or sulfonate-containing diene (co)polymer with a compound selected from among a free radical generator, a vulcanizer and a vulcanization accelerator as the principal components. SOLUTION: A selfo- or sulfonate-containing diene (co)polymer is obtained for example by sulfonating a diene (co)polymer consisting essentially of a diene monomer. The sulfo or sulfonate content of the sulfo- or sulfonate-containing diene (co)polymer is desirably 0.1 mmol/g or above. The total amount of the compound selected from among a free radical generator, a vulcanizer and a vulcanization accelerator is usually 0.1 wt.% to below 15 wt.% based on the sulfo- sulfonate-containing polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinked composition, and more particularly to a sulfonic acid (salt) effective for a binder resin, a coating material, a surface treatment, a surface modification and the like.
The present invention relates to a group-containing hydrophilic crosslinked composition.

[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. in use. On the other hand, in recent years, by utilizing such features as dispersibility, hydrophilicity, ion-trapping property, ionic conductivity, and adhesion to a substrate of such a polar group, it has been applied to a binder resin, a coating material, a surface treatment agent, a battery material, and the like. The application of is considered. 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, these polymers having a sulfonic acid group have poor water resistance due to the hydrophilicity (water solubility) of the sulfonic acid group. For example, when used as a coating material, a binder resin, etc. There is a problem that swelling or the like is easily caused in the presence, and durability is reduced. Further, the sulfonic acid group forms an ionic association in the absence of a polar substance such as alcohol or water, and apparently forms a pseudo-crosslink. Due to this ionic cross-linking, high strength and good solvent resistance are exhibited as compared with a polymer containing no sulfonic acid group. However, for example, when used at a high temperature or when a polar substance such as water is present, such characteristics may not always be exhibited.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide water-resistance while maintaining characteristics of a sulfonic acid group such as dispersibility, hydrophilicity, ion-trapping property, ionic conductivity and high adhesion to a substrate. A hydrophilic crosslinked product containing a sulfonic acid (salt) group that is excellent in solvent resistance and has high durability under various conditions, and is useful for binder resins, coating materials, surface treatment, surface modification, etc. It is to provide a composition.

[0005]

SUMMARY OF THE INVENTION The present invention relates to (A) a diene (co) polymer containing a sulfonic acid (salt) group (hereinafter referred to as "a diene (co) polymer containing a sulfonic acid (salt) group"). Or at least one compound selected from the group consisting of (B) a radical generator, a vulcanizing agent and a vulcanization accelerator (hereinafter also referred to as a “crosslinking agent”); The present invention provides a crosslinked composition mainly composed of:

[0006]

DETAILED DESCRIPTION OF THE INVENTION The sulfonic acid (salt) group-containing diene (co) polymer used in the present invention is, for example, a diene (co) polymer containing a diene monomer as an essential component (hereinafter also referred to as "base polymer"). ) Is obtained by sulfonation. As the diene monomer used for the base polymer, 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, and the like, various aliphatic or alicyclic dienes having 4 to 7 carbon atoms may be mentioned. Alternatively, two or more kinds can be used in combination. Preferably, they are 1,3-butadiene, isoprene, and 1,3-pentadiene.

In addition to these diene monomers, other monomers can be used in combination. As other monomers,
For example, aromatic monomers such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid Alkyl (meth) acrylates such as butyl, mono- or dicarboxylic acids or anhydrides of dicarboxylic acids or dicarboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; vinyl cyanide compounds such as (meth) acrylonitrile , Vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl acetate, (meth)
Unsaturated compounds such as acrylamide and glycidyl (meth) acrylate; These other monomers are 1
These can be used alone or in combination of two or more.
When these other monomers are used in combination, the amount of the diene monomer used is preferably 0.5% by weight or more, more preferably 1% by weight or more, and particularly preferably 5% by weight or more. If it is less than 0.5% by weight, the content of sulfonic acid (salt) groups introduced into the sulfonic acid group-containing polymer obtained by sulfonation may be low, and a sufficient crosslinking reaction does not easily occur.

The base polymer comprises a diene monomer and, if necessary, other monomers, a radical polymerization initiator such as hydrogen peroxide, benzoyl peroxide, azobisisobutyronitrile, n-butyllithium, sodium naphthalene, metal In the presence of an anionic polymerization initiator such as sodium, using a known solvent if necessary,
Usually, -100 to 150 ° C, preferably 0 to 130 ° C
To obtain (co) polymerization.

On the other hand, a part of the remaining double bonds of the base polymer which is a precursor of the sulfonic acid group-containing polymer can be hydrogenated for use. In this case, a known hydrogenation catalyst can be used, and examples thereof include a catalyst and a method described in JP-A-5-222115. After hydrogenation of the base polymer, sulfonation can be performed by the method described below, but there is no problem if the (co) polymer is sulfonated and then hydrogenated.

[0010] The base polymer used in the present invention may be any of a random type or a block type copolymer such as AB type or ABA type without any particular limitation. Preferred base polymers include, for example, isoprene homopolymer, butadiene homopolymer, isoprene-styrene random copolymer, isoprene-styrene block copolymer, styrene-isoprene-styrene ternary block copolymer, butadiene-styrene random copolymer. Polymers, butadiene-styrene block copolymers, styrene-butadiene-styrene block copolymers, and hydrogenated products of these (co) polymers, ethylene-propylene-diene terpolymers, and the like, and are preferable. An aromatic monomer-conjugated diene block copolymer, more preferably a styrene-isoprene-based block copolymer.

The polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of a base polymer or a hydrogenated product thereof containing a diene monomer as an essential component is preferably 1,
000 to 1,000,000, more preferably 3,0
00 to 500,000. If Mw is less than 1,000, sufficient strength cannot be obtained, while
If it exceeds 00, a gel-like substance may be formed during the sulfonation reaction, which is not preferable.

The sulfonic acid group-containing polymer of the present invention can be obtained by converting the above-mentioned base polymer into a known method, for example, edited by The Chemical Society of Japan, New Experimental Lecture (Vol. 14, III, pp. 1773), or JP-A-2-227403. Obtained by sulfonation according to the method described.

That is, the base polymer can be sulfonated at a double bond portion in the polymer using a sulfonating agent. In this sulfonation, the double bond is opened to form a single bond, or a hydrogen atom is replaced with a sulfonic acid (salt) while the double bond remains. When another monomer is used, for example, an aromatic unit may be sulfonated in addition to a diene unit portion in a double bond portion. The sulfonating agent in this case is preferably sulfuric anhydride, a complex of sulfuric anhydride and an electron donating compound, sulfuric acid, chlorosulfonic acid,
Fuming sulfuric acid, bisulfite (Na salt, K salt, Li salt, etc.)
Are used.

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.

The amount of the sulfonating agent is usually from 0.005 to 1.5 mol, preferably from 0.01 to 1.0 mol, in terms of sulfuric anhydride, relative to 1 mol of the diene unit in the base polymer.
If it is less than 0.005 mol, the desired sulfonation ratio cannot be obtained, so that the performance such as hydrophilicity, ion trapping property, ionic conductivity and adhesion may not be sufficient. If it exceeds 0.5 mol, the amount of unreacted sulfonating agent such as sulfuric anhydride increases, and after neutralization with an alkali, a large amount of sulfate is generated, and the purity is undesirably reduced.

In the sulfonation, a solvent inert to a sulfonating agent such as sulfuric anhydride can be used. Examples of the solvent include halogenated compounds such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene and dichloromethane. Hydrocarbons; nitromethane,
Nitro compounds such as nitrobenzene; and aliphatic hydrocarbons such as liquid sulfur dioxide, propane, butane, pentane, hexane, and cyclohexane. These solvents may be used as a mixture of two or more.

The reaction temperature for this sulfonation is usually -7
0 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. Thus, an intermediate (a sulfonate of the base polymer, hereinafter referred to as “intermediate”) in which a sulfonating agent such as sulfuric anhydride is bonded to the base polymer is produced.

In the sulfonic acid group-containing polymer of the present invention, the double bond is opened to form a single bond to which a sulfonic acid (salt) is bonded by reacting the intermediate with water or a basic compound, Alternatively, it is obtained by replacing a hydrogen atom with a sulfonic acid (salt) while leaving a double bond. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium methoxide, sodium ethoxide,
Alkali metal alkoxides such as potassium methoxide, sodium-t-butoxide and potassium-t-butoxide; carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; methyllithium, ethyllithium, n-butyllithium, sec-butyllithium; Organic metal compounds such as amyl lithium, propyl sodium, methyl magnesium chloride, ethyl magnesium bromide, propyl magnesium iodide, diethyl magnesium, diethyl zinc, triethyl aluminum, triisobutyl aluminum; aqueous ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine , Pyridine, aniline, piperazine and other amines; sodium, lithium, potassium, calcium, zinc and other metals Mention may be made of the compound. 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 and lithium hydroxide are particularly preferable.

The basic compound is used in an amount of 2 mol or less, preferably 1.3 mol, per 1 mol of the sulfonating agent used.
If it is less than 2 moles, and if it exceeds 2 moles, unreacted deterioration often increases, and the purity of the product is undesirably reduced. In the reaction between the intermediate and a basic compound, 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, in addition to the above various organic solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene;
Examples include 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 0 to + 120 ° C, more preferably +5
It is carried out at 0 to + 100 ° C, and can be carried out at normal pressure, reduced pressure or increased pressure. Further, the reaction time is usually 0.1 to 24 hours, preferably 0.5 to 24 hours.
5 hours.

On the other hand, the sulfonic acid group-containing polymer of the present invention may be, for example, a sulfonic acid (salt) of a diene monomer or a sulfonic acid (salt) of a diene monomer and the other monomer described in JP-A-1-263103. The monomer component consisting of a combination of the above, in the presence of a radical polymerization initiator or an anionic polymerization initiator, usually -100 ° C. ~
It can also be obtained by carrying out (co) polymerization at + 150 ° C, preferably at 0 to 130 ° C. Here, the sulfonic acid (salt) of the diene monomer is preferably isoprenesulfonic acid (salt). In this case, other monomers that may be used in combination in this case include, in addition to the other monomers that may be used in the base polymer, acrylamide 2-methylpropanesulfonic acid (salt), styrenesulfonic acid (salt) And sulfonic acid group-containing monomers such as vinylsulfonic acid (salt) and methacrylsulfonic acid (salt). The weight average molecular weight of the sulfonic acid group-containing polymer thus obtained in terms of polystyrene is preferably 4,000 to 2,000,000, more preferably 5,
000 to 1,000,000. When the weight average molecular weight is less than 4,000, sufficient strength cannot be obtained, which is not preferable. On the other hand, when the weight average molecular weight exceeds 2000, 000, it is difficult to become water-soluble, which causes a problem in use.

The sulfonic acid (salt) group content of the sulfonic acid (salt) group-containing diene (co) polymer as described above is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more.
mmol / g or more, particularly preferably 0.5 to 5.5 mm
ol / g. If it is less than 0.1 mmol / g, functions such as adhesion to a substrate, hydrophilicity, and ion-capturing ability are hardly exhibited, which is not preferable.

The structure of the sulfonic acid (salt) group-containing diene (co) polymer of the present invention can be confirmed by the absorption of the sulfone group by an infrared absorption spectrum, and the composition ratio of these can be known by elemental analysis or the like. be able to. Also,
Its structure can be confirmed by a nuclear magnetic resonance spectrum. When the sulfonic acid (salt) group-containing diene-based (co) polymer of the present invention is a copolymer, by introducing a component based on a monomer other than the diene monomer, the coating property on the substrate is improved. Alternatively, the adhesion may be improved.

The (A) sulfonic acid group-containing polymer of the present invention can be used by dissolving it in an organic solvent to form an organic solution (hereinafter also referred to as “organic solution”). It is also possible to emulsify in water and emulsify (hereinafter, this emulsification process is also referred to as “re-emulsification”) before use.

Here, examples of the organic solvent that can be used in the formation of the organic solution include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and heptane, ketone solvents such as acetone and methyl ethyl ketone, tetrahydrofuran and dioxane. For example, ether solvents, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and amide solvents such as dimethylformamide are used. Even if these solvents are used alone,
There is no problem if two or more kinds are used in combination. The amount of the organic solvent used for forming the organic solution is preferably 10 to 1 with respect to 100 parts by weight of the sulfonic acid group-containing polymer.
000 parts by weight, more preferably 50 to 5,000
Parts by weight. If less than 10 parts by weight, the solution viscosity is high,
If a sufficient dispersing action cannot be obtained, on the other hand, if it exceeds 10,000 parts by weight, the amount of the solvent to be used increases, which is not economical.

The above-mentioned re-emulsification is obtained by stirring and mixing the above-mentioned sulfonic acid group-containing polymer or a solution of the polymer in an organic solvent with water, emulsifying the mixture, and removing the organic solvent while leaving water. Can be For this re-emulsification, a general method can be adopted. A method in which water is added to an organic solvent solution of the sulfonic acid group-containing polymer while stirring, or an organic solvent solution of a sulfonic acid group-containing polymer is added to water while stirring. There is no particular limitation on the method of adding water and the organic solvent solution of water and the sulfonic acid group-containing polymer at the same time and stirring. Here, as the organic solvent used for the re-emulsification, for example, the solvent used in the above-mentioned organic solution can be used. Even if these solvents are used alone,
There is no problem if two or more kinds are used in combination.

The amount of the organic solvent used in the re-emulsification 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 sulfonic acid group-containing polymer. is there. When the amount is less than 20 parts by weight, a stable re-emulsified product cannot be obtained. On the other hand, when the amount exceeds 5,000 parts by weight, productivity is disadvantageously deteriorated. The amount of water used in the re-emulsification is preferably 50 to 10,000 based on 100 parts by weight of the sulfonic acid group-containing polymer.
0 parts by weight, more preferably 100 to 5,000 parts by weight. When the amount is less than 50 parts by weight, a stable re-emulsified product cannot be obtained. On the other hand, when the amount exceeds 10,000 parts by weight, productivity becomes poor and there is a problem.

In the re-emulsification, 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. And 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 may be used after being dissolved or dispersed in an organic solvent solution of the sulfonic acid group-containing polymer, or may be used after being dissolved or dispersed in water. The amount of the surfactant to be used is generally 10 parts by weight or less, preferably 6 parts by weight or less, based on 100 parts by weight of the sulfonic acid (salt) group-containing diene (co) polymer.

Further, in order to adjust the pH in the system, an alkali compound such as sodium hydroxide and 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 re-emulsified emulsion of the sulfonic acid group-containing polymer thus obtained is usually from 10 to
It is 1,000 nm, preferably 20-500 nm.
The solid content of the obtained sulfonic acid group-containing polymer emulsion is usually 5 to 50% by weight, preferably 1 to 50% by weight.
The content is 0 to 40% by weight, which can be appropriately selected depending on use conditions, storage conditions, and the like.

Next, the crosslinking agent (B) used in the present invention comprises at least one compound selected from a radical generator, a vulcanizing agent and a vulcanization accelerator. 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, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2-4-dimethyl Valeronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2- (carbamoylazo) isobutyronitrile, hydrochloride of 2,2'-azobis-2-amidopropane, and the like.

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 (B) is usually 0.1% by weight based on the sulfonic acid group-containing polymer (A).
Not less than 15% by weight, preferably not less than 0.5% by weight and not more than 10%.
% By weight. If the amount is less than 0.1% by weight, sufficient cross-linking is not performed, and the cross-linked product is not preferable because of poor solvent resistance and low mechanical strength. On the other hand, when the content is 15% by weight or more, unreacted radical generator, vulcanizing agent, and vulcanization accelerator remain in the crosslinked product, and various physical properties may be deteriorated.

The crosslinked composition of the present invention contains the above (A) to
In addition to the component (B), other additives can be used in combination. For example, a reducing substance can be added to ease the crosslinking conditions described below or to carry out a crosslinking reaction at a lower temperature. The reducing substance is not particularly limited, but is preferably, for example, one that can be used as a redox initiator. For example, inorganic reducing agents such as iron sulfate and hydrogen sulfite, organic reducing agents such as alcohol, tertiary amine, naphthenate, mercaptans, and polyamine, and organic metal compounds such as triethylaluminum, triethylboron, and diethylzinc are used. it can. The amount of the reducing substance used is usually 0.01 to 200% by weight based on the radical generator of the component (B).

In order to promote the crosslinking more efficiently,
Polyfunctional monomers can also be used. Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Known ones such as methylenebisacrylamide and divinylbenzene are exemplified. The amount of polyfunctional monomer used is
It is usually at most 30% by weight, preferably at most 15% by weight, based on the component (A).

In order to improve the physical properties of known crosslinked products,
Other polymers can be used in combination. Examples of other polymers include known polymers such as urethane resins, phenol resins, acrylic resins, polyester resins, polyamide resins, polyethers, polystyrene, polyester amide, polycarbonate, polyvinyl chloride, and diene polymers such as SBR polymers. Can be There is no problem if these other polymers are used in a solvent system or an emulsion system. The amount of the other polymer used is
It is usually 1,000% by weight or less based on the component (A).

Further, an organic filler or an inorganic filler can be dispersed and used together. 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 properties, light absorption properties, photochromic properties, ultraviolet absorption properties, infrared absorption properties, light resistance, antibacterial properties, vibration damping properties, sound insulation properties, moisture absorption properties, gas absorption properties, oil absorption properties, Those that impart radiation absorption or the like can be used.

Examples of this include carbon black, Ketjen black, graphite, charcoal powder, carbon fiber, iron, silver,
Copper, lead, nickel, silicon carbide, tin oxide, iron oxide, titanium oxide, magnesium oxide, zinc oxide, cerium oxide, calcium oxide, zirconium oxide, antimony oxide, ferrite, alumina, aluminum hydroxide, magnesium hydroxide, titanic acid Potassium, 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, zeolite, sepiolite, zonotolite, activated clay, polymer beads And the like. The amount of the organic / inorganic filler is usually 1,500% by weight based on the component (A).
Is below

The crosslinked composition of the present invention is used by mixing the above components (A) and (B) and, if necessary, other components. Upon mixing, it is preferable to use the solvent after dissolving or dispersing it in a solvent. Examples of the solvent include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and heptane, ketone solvents such as acetone and methyl ethyl ketone, and tetrahydrofuran. And ether solvents such as dioxane, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and water. As a solvent to be used, an organic solvent is used if the sulfonic acid (salt) group-containing diene (co) polymer as the component (A) is soluble in an organic solvent, and water is used if it is soluble in water. Is preferred. In the case of a re-emulsified product, it is preferable to use water. These solvents can be used alone or in combination of two or more.

The crosslinking reaction of the crosslinked composition of the present invention is preferably carried out by heating. After forming these compositions into a sheet or film, a method of performing a heat treatment or applying the composition of the present invention to a substrate as described below, and applying a temperature to a solvent such as an organic solvent or water. There is no particular limitation such as evaporation while performing a crosslinking reaction at the same time. The heating temperature varies depending on the vulcanizing agent or peroxide (radical generator) used, or the thickness of the film, but is usually 40 to 200 ° C, preferably 60 to 180 ° C.
It is. When the temperature is lower than 40 ° C., the crosslinking reaction does not proceed sufficiently. On the other hand, when the temperature is higher than 200 ° C., the crosslinked product may be undesirably colored. The time required for crosslinking is generally 1 to 120
Minutes, preferably 5 to 60 minutes. The crosslinked composition of the present invention can be crosslinked by ultraviolet rays or electron beams. In particular, in electron beam crosslinking, a graft reaction to a substrate is likely to occur, which leads to improvement in adhesion and the like. Combination with heat crosslinking is also possible.

The crosslinked composition of the present invention is usually used after being coated on a substrate. 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.

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 such as a nonwoven fabric.

Here, examples of the porous material include a nonwoven fabric, a woven fabric, and a knitted fabric, 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.
It is 0.5 to 30 g / m ² , preferably 1 to 10 g / m ² . If it is less than 0.5 g / m ² , the desired performance such as hydrophilicity and ion trapping property is hardly exhibited, while 30 g / m 2
^If it exceeds ² , the mechanical strength of a porous material such as a coated nonwoven fabric is undesirably reduced.

The crosslinked composition of the present invention is particularly effective for modifying the surface of a substrate, and is excellent in water resistance, solvent resistance and durability. In particular, by coating on a hydrophobic surface, it becomes 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. Further, by coating the surface of the battery separator, the affinity with the battery electrolyte is improved, and the effect of leading to improvement in battery characteristics such as self-discharge characteristics can be expected. Furthermore, the crosslinked product composition of the present invention has 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. Furthermore, it is one of the features to highly disperse the filler,
There is also a feature that the properties of each filler can be sufficiently exhibited.

The crosslinked composition of the present invention can be applied to various uses. When applied to porous materials, for example, cationic dyeing aids for fibers, water-absorbent nonwoven fabrics, nonwoven fabrics for wet tissues, nonwoven fabrics for sealing materials, antifouling materials, ion exchange fibers, hydrophilizing agents for battery separators, ammonia Filter applications such as air purifying filters to remove ionic substances, water purifying filters, etc., leukocyte removing filters, pollen allergen removing materials, water vapor permeable materials, antibacterial materials, deodorant fibers, deodorant paints, deodorants Paper,
Humidity control materials such as anti-fog materials and anti-condensation materials, anti-static materials,
Examples include anticorrosion materials, oxygen absorbers, sanitary articles, surface modification of activated carbon, and the like. 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, by combining the crosslinked composition of the present invention with various fillers, it can be applied to various uses. For example, general paint, paint for circuit boards, conductive materials,
Battery materials such as binders for solid electrolytes or carbon compounds for electrodes, electromagnetic wave shielding materials, antistatic paints, sheet heating elements, electrochemical reaction electrode plates, electrical contact materials, friction materials, antibacterial materials, sliding materials, Abrasive materials, magnetic recording media, thermosensitive recording materials, electrochromic materials, light diffusion films, water-blocking materials for communication cables, light-blocking films, sound-insulating sheets, plastic magnets, X-ray intensifying screens, printing inks, pesticide granules, electrophotography Toner. 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.

[0047]

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.

Total Sulfonic Group Content Sulfonic Group-Containing Polymer Soluble in Solvent The re-emulsified 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, sulfate,
After removing insolubles such as hydroxide with a filter, 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. Water-soluble sulfonic acid group-containing polymer Prepare a 20% aqueous solution of each sulfonic acid group-containing polymer,
Dialysis membrane [manufactured by Hanui Chemical Co., Ltd., Cellulose
Diolizer Tubing-VT351] to remove low molecular weight substances. This sample was subjected to cation exchange resin [Amberlite IR-118, manufactured by Organo Corporation].
H], and the sulfonic acid content was determined by potentiometric titration.

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. Weight average molecular weight (Mw ) Base polymer The weight average molecular weight (Mw ) of the base polymer was measured by gel permeation chromatography (GPC) using polystyrene as a standard sample. Sulfonic acid group-containing polymer Weight average molecular weight (Mw) of sulfonic acid group-containing polymer
By gel permeation chromatography (GPC)
As a result, polystyrene sulfonic acid N
It measured using a.

Measurement of Gel Content At the ratios shown in Tables 4 to 10, the components (A), (B), other components and the solvent, (A) + (B) + (other components) become 20%. Was mixed as follows. 10 g of this mixture is 50
It was weighed in a cc beaker and left in a thermostat at 120 ° C. for 1 hour to remove the solvent and perform a crosslinking reaction. Then, it was taken out of the thermostat, 20 cc of the same solvent was added, and the mixture was stirred with a stirrer for 30 minutes. After stirring, the insolubles were filtered, dried, and weighed. The progress of crosslinking was determined using the ratio of the insoluble content to the solid content in the beaker initially as the gel content.

Adhesion Measurement The compositions shown in Tables 4 to 10 were applied to a copper plate using an applicator, and dried in a thermostat at 100 ° C. for 30 minutes to obtain evaluation samples. The adhesion to the copper plate was evaluated by a cross-cut adhesive tape (using cellophane tape) peel test. Tables 4 to 10 show the numbers of non-peeled pieces among the 100 grids.

Evaluation of hydrophilicity The compositions shown in Tables 4 to 10 were further diluted 10-fold with the same solvent. A 10 cm square nonwoven fabric (made of polypropylene) was dipped in this solution. Then, it dried at 100 degreeC for 1 hour in the thermostat, and was set as the evaluation sample. The amount of coating was calculated from the weight increase before and after coating due to dipping. Distilled water was poured onto the coated non-woven fabric, and the extent to which the distilled water soaked into the non-woven fabric was qualitatively observed. ○ those with relatively good penetration
Those that did not easily penetrate were evaluated as x.

Ammonia adsorption amount The composition shown in Table 10 was further diluted 10 times with the same solvent. A 10 cm square nonwoven fabric (made of polypropylene) was immersed in this solution and dipped. Then 1
The sample was dried in a thermostat at 00 ° C. for 1 hour to obtain an evaluation sample. Next, the non-woven fabric of this evaluation sample was allowed to stand in ammonia-saturated steam at 25 ° C. overnight. After the standing, vacuum drying was performed at 50 ° C. for 5 hours in order to simply remove the attached ammonia. After drying, the nonwoven fabric was immersed in a mixture of 2 g of a 0.1N aqueous sodium hydroxide solution and 50 cc of water, and shaken in a sealed state. By this operation, the ammonia adsorbed on the nonwoven fabric was released and dissolved in water. This aqueous phase is used as a trace total nitrogen analyzer [Mitsubishi Chemical Corporation]
TN-05 type], and the amount of ammonia adsorbed on the nonwoven fabric was determined.

Reference Example (A) Preparation of Sulfonic Acid Group-Containing Polymers A to M A prescribed amount of dioxane (400 g) was placed in a glass reaction vessel.
And a specified amount of sulfuric anhydride (A; 6.0 g, B;
11.0 g, C; 7.0 g, D; 13.7 g, E;
3g, F; 54.4g, G; 67.1g, H; 6.0
g, I: 11.0 g, J: 11.0 g, K: 6.0 g,
L; 6.0 g, M; 79.1 g) were added while keeping the internal temperature at 25 ° C, and the mixture was stirred for 2 hours to obtain a sulfuric anhydride-dioxane complex. The complex obtained above was added to a dioxane solution (concentration = 25%) of the base polymer (100 g) shown in Table 1 while maintaining the internal temperature at 25 ° C., and stirring was further continued for 2 hours. For A to J, a prescribed amount of sodium hydroxide (A; 3.6 g, B;
7.2 g, C; 4.6 g, D; 8.2 g, E; 2.0
g, F: 28.6 g, G: 35.2 g, H: 3.6 g,
I; 7.2 g, J; 7.2 g) in 100 g of water and methanol (50 g) were added.
Stirred at C for 1 hour. After stirring, water and the solvent were distilled off under reduced pressure to obtain a sulfonic acid group-containing polymer. Tables 1 and 2 show the measurement results of the sulfonic acid group content and Mw.

In the case of re-emulsification, 50 g of a sulfonic acid group-containing polymer corresponding to the component (A) synthesized above was used.
To tetrahydrofuran / isopropyl alcohol (90
/ 10 weight ratio). Water 5 in the flask
Then, 1 g of an anionic / nonionic surfactant [Sandet EN, manufactured by Sanyo Chemical Co., Ltd.] was added thereto, and the mixture was further stirred for 1 hour. Thereafter, 800 g of water was added, and the entire 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 was 20%. Table 2 shows the particle size of these emulsions.

(A) of the sulfonic acid group-containing polymers X to Z
Prepared pressure-resistant container was charged with Na isoprene sulfonate (and other monomers) at the ratio shown in Table 3 for a total of 200 g and water 7
Then, the temperature was raised to 80 ° C. Then 30%
Add 40 g of hydrogen peroxide, raise the internal temperature to 100 ° C,
Polymerization was performed for 3 hours. After completion of the polymerization, water was removed under reduced pressure to obtain a sulfonic acid group-containing polymer. Table 3 shows the results.

Examples 1 to 16, Comparative Examples 1 to 5 Crosslinked products were prepared according to the formulations shown in Tables 4 to 10. The results are shown in Tables 4 to 10. The crosslinked product composition of the present invention has a high gel content, and is excellent in solvent resistance and water resistance. It is also excellent in hydrophilicity and high adhesion to a substrate.
Therefore, it can be applied to various uses such as a binder resin, a coating material, a surface treatment agent, and a surface modifier.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

The crosslinked composition of the present invention is effective in modifying the surface of a substrate. In particular, by coating on a hydrophobic surface, it becomes possible to develop or maintain hydrophilicity and hygroscopicity. Further, for example, when coated on a porous material such as a nonwoven fabric, it exhibits a weak base such as ammonia or amine present in the air or water, or an ionic substance, and enhances affinity with the compound. . Furthermore, the crosslinked product composition of the present invention has excellent characteristics that it has high adhesion to various substrates, hardly peels off the coating film from the substrates, and can maintain stable performance for a long period of time.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Katsuhiro Ishikawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (1)

[Claims] 1. A diene (co) polymer having a sulfonic acid (salt) group, (B) a radical generator,
At least one selected from the group of vulcanizing agents and vulcanization accelerators
A crosslinked composition comprising, as a main component, a species compound.