JP7085415B2 - Cartridge for water purifier and water purifier for softening - Google Patents

Description

The present invention relates to a water purifier for softening that purifies and softens tap water and a cartridge for a water purifier used therein.

The effects of soft water are (a) mellowing the taste of tea and coffee, (b) preventing scale generation in cooking utensils, (c) improving the foaming of soap, and (d) water in containers such as glasses. There are measures such as suppressing the generation of marks. Therefore, conventionally, a water purifier having a softening function has been widely used.

As a method for softening water, (1) a method using a cation exchange resin, (2) a method using an NF (Nanofiltration; nanofiltration) or RO (Reverse Osmosis; reverse osmosis) membrane, and (3) adding an alkaline agent. There is a method of removing the sedimented material. Among these, the method using the cation exchange resin described in (1) above is superior in terms of energy efficiency and maintenance of the device.

When a method using a cation exchange resin is selected as the water purifier for softening, not only the hardness removal performance is emphasized, but also the elution of impurities from the cation exchange resin itself does not impair the quality of the treated water. is important.

As a measure against elution from the cation exchange resin itself, for example, Japanese Patent Application Laid-Open No. 7-204631 (Patent Document 1) discloses a water purifier in which a cation exchange resin and activated carbon are mixed.

Further, Japanese Patent Application Laid-Open No. 2016-22443 (Patent Document 2) is filled with a strong acid cation exchange resin having a degree of cross-linking of 16 to 24% in order to suppress the elution of formaldehyde from the strong acid cation exchange resin. Cartridges for water purifiers are disclosed.

Japanese Unexamined Patent Publication No. 7-204631 Japanese Unexamined Patent Publication No. 2016-22443

However, among the eluates from the cation exchange resin, formaldehyde is difficult to be adsorbed on the activated carbon, so that the water purifier of Cited Document 1 did not sufficiently remove formaldehyde from the cation exchange resin.

Further, even in the case of the water purifier cartridge of Cited Document 2, there is a problem that formaldehyde eluted from the strong acid cation exchange resin is insufficiently removed. There was a problem that the amount of formaldehyde elution was large.

Therefore, an object of the present invention is to provide a water purifier cartridge capable of reducing formaldehyde eluted from a strongly acidic cation exchange resin and a water purifier for softening in which the cartridge is used.

Such a problem is solved by the following invention.
That is, the present invention (1) includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
It has a softening material layer filled in a filling area of the softening material in the cartridge container.
The softening treatment material layer is formed of a mixture of a salt-type strongly acidic cation exchange resin and a polyamine-type anion exchange resin composed of a granular polyvinylamine crosslinked polymer, and the polyvinylamine crosslinked polymer is formed. Being a weakly basic anion exchange resin with at least a primary amine ,
It is intended to provide a cartridge for a water purifier, which is characterized by the above.
Further, the present invention (2) includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
It has a softening material layer filled in a filling area of the softening material in the cartridge container.
The softened material layer is composed of a salt-type strongly acidic cation resin layer laminated on the upstream side and a polyamine type anion exchange resin layer composed of a granular polyvinylamine crosslinked polymer laminated on the downstream side. The polyvinylamine crosslinked polymer which is formed is a weakly basic anion exchange resin having at least a primary amine.
It is intended to provide a cartridge for a water purifier, which is characterized by the above.

Further, the present invention ( 3 ) is characterized in that the granular polyvinylamine crosslinked polymer is a hydrolyzate of a suspension polymer of N-vinylcarboxylic acid amide and a crosslinkable monomer (1). Alternatively, the cartridge for the water purifier of (2) is provided.

Further, in the present invention ( 4 ), the granular polyvinylamine crosslinked polymer is a hydrolyzate of a suspended polymer of N-vinylcarboxylic acid amide, a crosslinkable monomer, and acrylonitrile. The present invention provides a cartridge for a water purifier according to ( 1 ) or (2) , wherein the crosslinkable monomer is a polyvinyl compound .

Further, the present invention ( 5 ) provides a cartridge for a water purifier according to ( 3 ) or ( 4 ), wherein the crosslinkable monomer is divinylbenzene.

Further, the present invention ( 6 ) includes a cartridge for a water purifier according to any one of (1) to ( 5 ).
A housing for storing the water purifier cartridge and
It is intended to provide a water purifier for softening, which is characterized by having.

According to the present invention, it is possible to provide a water purifier cartridge capable of reducing formaldehyde eluted from a strongly acidic cation exchange resin and a water purifier for softening in which the cartridge is used.

The cartridge for a water purifier of the present invention includes a cartridge container in which a tap water supply port and a softened water discharge port are formed.
It has a softening material layer filled in a filling area of the softening material in the cartridge container.
The softened material layer is formed of a mixture of a salt-type strongly acidic cation exchange resin and a polyamine-type anion exchange resin composed of a granular polyvinylamine crosslinked polymer, or is laminated on the upstream side. It is formed of a salt-type strongly acidic cation resin layer and a polyamine-type anion exchange resin layer composed of granular polyvinylamine crosslinked polymers laminated on the downstream side.
It is a cartridge for a water purifier characterized by. In the present invention, the upstream side refers to the supply side of tap water in the filled region of the softened material, and the downstream side refers to the discharge side of the softened water in the filled region of the softened material.

The cartridge for a water purifier of the present invention has a cartridge container in which a tap water supply port and a softening water discharge port are formed, and a softening treatment material layer filled in a filling region of the softening treatment material in the cartridge container. .. In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier are connected, and the softened water discharge port and the softening water purification water are connected. It is installed in the housing of the water purifier for softening so as to be connected to the discharge path of the softened water formed in the housing of the vessel.

The softening treatment material layer according to the cartridge for a water purifier of the present invention is formed of a mixture of (A) a salt-type strongly acidic cation exchange resin and a polyamine-type anion exchange resin composed of a granular polyvinylamine crosslinked polymer. Or (B) formed of a salt-type strongly acidic cation resin layer laminated on the upstream side and a polyamine type anion exchange resin layer composed of a granular polyvinylamine crosslinked polymer laminated on the downstream side. Has been done. That is, the softening material layer according to the cartridge for a water purifier of the present invention is formed of a mixture of (A) a salt-type strong acid cation exchange resin and a polyamine-type anion exchange resin, or (B) upstream. It is formed of a salt-type strong acid cation resin layer laminated on the side and a polyamine-type anion exchange resin layer laminated on the downstream side, and the softened material layer of (A) or ( The polyamine type anion exchange resin constituting the softening treatment material layer of B) is a granular polyvinylamine crosslinked polymer. Therefore, the softening material layer according to the cartridge for a water purifier of the present invention is formed of a mixture of (A) a salt-type strongly acidic cation exchange resin and a granular polyvinylamine crosslinked polymer, or (B). It is formed of a salt-shaped strongly acidic cation resin layer laminated on the upstream side and a granular polyvinylamine crosslinked polymer layer laminated on the downstream side.

In the softening treatment material layer of (A), even if formaldehyde is eluted from the strongly acidic cation exchange resin, the eluted formaldehyde is rapidly adsorbed on the granular polyvinylamine crosslinked polymer existing in the vicinity. Therefore, the softening material layer (A) according to the cartridge for a water purifier of the present invention is excellent in the ability to remove formaldehyde eluted from the strongly acidic cation exchange resin.

In the softening treatment material layer (B), a polyamine type anion exchange resin layer made of a granular polyvinylamine crosslinked polymer having a high formaldehyde adsorption capacity is present immediately after the strongly acidic cationic resin layer which is a source of formaldehyde. Therefore, even if formaldehyde elutes from the strongly acidic cation exchange resin, it is rapidly adsorbed on the polyamine type anion exchange resin layer made of the granular polyvinylamine crosslinked polymer. Therefore, the softening material layer (B) according to the cartridge for a water purifier of the present invention is excellent in the ability to remove formaldehyde eluted from the strongly acidic cation exchange resin.

The substrate of the salt-type strong acid cation exchange resin is a styrene-divinylbenzene copolymer. When the resin material forming the substrate of the salt-type strong acid cation exchange resin comes into contact with tap water, it generates formaldehyde and releases formaldehyde into the water to be treated.

The salt-type strong acid cation exchange resin may have any of a gel-type structure, a macroporous type structure, and a porous type structure. The structure of the salt-type strong acid cation exchange resin is preferable because the gel-type structure has a high exchange capacity and therefore a large amount of hardness adsorption.

The cation exchange group of the salt-type strong acid cation exchange resin is a sulfonic acid group. The salt form of the salt form of the strongly acidic cationic resin is Na form or K form.

Examples of the salt-type strong acid cation exchange resin include Amberjet 1220Na manufactured by Dow Chemical and Imac HP1220Na manufactured by Sumika Chemtex. Further, as the salt-type strong acid cation exchange resin, a strong acid cation exchange resin such as Amber Jet 1020H manufactured by Dowex may be converted into Na type or K type.

The wet ion exchange capacity of the salt-type strong acid cation exchange resin is preferably 1.5 to 3.0 (eq / L-R), particularly preferably 1.7 to 2.7 (eq / L-R). ).

The harmonic mean diameter of the salt-type strong acid cation exchange resin is preferably 400 to 900 μm, particularly preferably 500 to 800 μm.

The anion exchange resin used in the cartridge for a water purifier of the present invention is a polyamine type anion exchange resin composed of a granular polyvinylamine crosslinked polymer. That is, the anion exchange resin used in the water purifier cartridge of the present invention is a granular polyvinylamine crosslinked polymer among the polyamine type anion exchange resins. Polyamine-type anion exchange resins generally have the ability to adsorb formaldehyde, and the present inventors have found that, among them, the polyvinylamine crosslinked polymer is particularly excellent in formaldehyde adsorption performance. It is presumed that the granular polyvinylamine crosslinked polymer has excellent formaldehyde adsorption performance because the proportion of primary amine in the amino groups introduced into the polymer can be increased.

The granular polyvinylamine crosslinked polymer is a polymer having a primary amino group and having a crosslinked polymerized structure crosslinked by a crosslinkable monomer.

The granular polyvinylamine crosslinked polymer may have any of a gel type structure, a macroporous type structure, and a porous type structure. The structure of the granular polyvinylamine crosslinked polymer is preferably a macroporous type.

The granular polyvinylamine crosslinked polymer has at least a primary amino group as an anion exchange group. In addition to the primary amino group, the granular polyvinylamine crosslinked polymer further contains one or more of a secondary amino group, a tertiary amino group and a quaternary ammonium group. You may have. The primary amino group, secondary amino group, tertiary amino group and quaternary ammonium group are not particularly limited as long as they are groups usually used for polyamine type anion exchange resins. The amino group in the granular polyvinylamine crosslinked polymer may be converted to the hydrochloric acid form.

It is preferable that the granular polyvinylamine crosslinked polymer is partially in the form of hydrochloric acid in that the pH of the softened water, which is the treated water, can be easily adjusted to around 7. The ratio of the amino groups converted into the hydrochloric acid form in the granular polyvinylamine crosslinked polymer is appropriately selected depending on the type of amino group, the amount introduced, and the like.

The wet ion exchange capacity of the granular polyvinylamine crosslinked polymer is preferably 2 to 4 (eq / L-R), particularly preferably 2.5 to 3.5 (eq / L-R). When the ion exchange capacity of the granular polyvinylamine crosslinked polymer is within the above range, the formaldehyde adsorption performance is enhanced.

The harmonic mean diameter of the granular polyvinylamine crosslinked polymer is preferably 300 to 1200 μm, particularly preferably 500 to 1000 μm.

When tap water is treated with a salt-type strongly acidic cation exchange resin as the softening treatment material, when tap water is continuously distributed through the softening treatment material, the water to be treated and the strong acid cation exchange resin are used. Since the contact time is very short, even if formaldehyde is eluted from the strongly acidic cation exchange resin, the concentration of formaldehyde in the softened water, which is the treated water, is very low, and the elution of formaldehyde does not become a problem. Further, when the flow of tap water to the softened material is stopped for a short time, the amount of formaldehyde eluted into the softened water is small, so that the elution of formaldehyde is less likely to be a problem. On the other hand, if the tap water is left to stand for a certain period of time without being circulated to the softened material, the water to be treated and the strongly acidic cation exchange resin are formed in the filled area of the softened material of the water purifier cartridge. Since the contact time is long, the amount of formaldehyde that elutes and accumulates in the softened water in the filling region of the softening treatment material increases. Therefore, after standing for a certain period of time, the concentration of formaldehyde in the softened water at the initial stage of resuming water flow becomes high, which causes a problem of elution of formaldehyde into the softened water.

In the cartridge for a water purifier of the present invention, a mixture of a salt-type strongly acidic cation exchange resin and a granular polyvinylamine crosslinked polymer, or a salt-type strongly acidic cation resin layer laminated on the upstream side and laminated on the downstream side. Since the granular polyvinylamine crosslinked polymer layer is filled in the packed region, even if the water to be treated and the strongly acidic cation exchange resin come into contact with each other for a long time, the formaldehyde eluted from the strongly acidic cation exchange resin will be present in the vicinity. Since it is immediately adsorbed on the existing polyvinylamine crosslinked polymer or the polyvinylamine crosslinked polymer in the polyvinylamine crosslinked polymer layer existing immediately after that, the removability of the eluted formaldehyde is improved.

Further, among the cartridges for water purifiers of the present invention, when a mixture of a salt-type strongly acidic cation exchange resin and a granular polyvinylamine crosslinked polymer is filled in the filling region of the softening material, a strong acid having a negative charge. Since the positive cation exchange resin and the positively charged polyamine type anion exchange resin electrically aggregate and clamp, and the volume expands, it becomes necessary to increase the volume of the cartridge container. On the other hand, in the water purifier cartridge of the present invention, the salt-shaped strongly acidic cation resin layer laminated on the upstream side and the granular polyvinylamine crosslinked polymer layer laminated on the downstream side are filled in the packed region. If this is the case, the volume of the cartridge does not become too large because clamping due to electrical aggregation between the strongly acidic cation exchange resin and the granular polyvinylamine crosslinked polymer which is a polyamine type anion exchange resin does not occur.

The granular polyvinylamine crosslinked polymer is subjected to suspension polymerization in salt water containing N-vinylcarboxylic acid amide and a crosslinkable monomer in the presence of a dispersant to obtain a granular crosslinked polymer, and then. Examples thereof include a granular polyvinylamine crosslinked polymer obtained by hydrolyzing a granular crosslinked polymer (hereinafter, also referred to as a granular polyvinylamine crosslinked polymer (1)). For example, the granular polyvinylamine crosslinked polymer (1) can be produced by the method for producing polyvinylamine crosslinked polymer particles disclosed in Japanese Patent Publication No. 2016/042846. Hereinafter, the manufacturing method will be described.

The suspension polymerization according to the granular polyvinylamine crosslinked polymer (1) is a generally used suspension polymerization. That is, the suspension polymerization according to the granular polyvinylamine cross-linked polymer (1) includes an N-vinylcarboxylic acid amide, a crosslinkable monomer, and a monomer capable of copolymerizing with N-vinylcarboxylic acid amide, if necessary. It is carried out by suspending the polymerization initiator and the dispersant in salt water, stirring with arbitrary strength to generate monomer droplets, and performing radical polymerization. The particle size of the monomer droplets is controlled by the dispersant and the stirring intensity, but is 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm.

Examples of the N-vinylcarboxylic acid amide according to the granular polyvinylamine crosslinked polymer (1) include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, and N. -Vinylpropionamide, N-methyl-N-vinylpropionamide, N-vinylbutylamide, N-vinylisobutylamide and the like can be mentioned, with preference given to N-vinylformamide and N-vinylacetamide. The N-vinylcarboxylic acid amide may be one kind or a combination of two or more kinds.

A monomer capable of copolymerizing with the N-vinylcarboxylic acid amide according to the granular polyvinylamine crosslinked polymer (1) is used as needed, and (meth) acrylonitrile, (meth) acrylamide, and N-alkyl (meth) are used. Alkali metal salt or ammonium salt of acrylamide, N, N'-dialkyl (meth) acrylamide, N, N'-dialkylaminoalkyl (meth) acrylamide, (meth) acrylamide alkanesulphonic acid, alkali metal salt of (meth) acrylic acid Or ammonium salt, hydroxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acryloyloxyalkyl-trimethylammonium salt, alkali metal or ammonium salt of (meth) acryloyloxyalkanesulfonic acid, N-vinylpyrrolidone. , Dialyl-dialkylammonium salt, vinylpyridine, vinylimidazole, vinylpentyltrialkylammonium salt, alkali metal salt of vinylsulfonic acid, ammonium salt and the like, and acrylonitrile is preferable. The monomer capable of copolymerizing with N-vinylcarboxylic acid amide may be one kind or two or more kinds.

Examples of the crosslinkable monomer according to the granular polyvinylamine crosslinked polymer (1) include aromatic polyvinyl compounds such as divinylbenzene, trivinylbenzene and divinyltoluene; ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate. Poly (meth) acrylates such as glycerol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; methylenebisacrylamide; triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, tetraallyloxyetane and , Pentaerythritol diallyl ether, pentaerythritol triallyl ether, allyl ether compounds such as pentaerythritol tetraallyl ether; poly (meth) allyloxyalkane and the like, aromatic divinyl compounds and allyl ether compounds are preferable, and divinylbenzene is particularly preferable. preferable.

The amount of the crosslinkable monomer added is 0.1 to 50% by mass, preferably 0.1 to 20% by mass, based on the total amount of the monomers. If the amount of the crosslinkable monomer added exceeds 5% by mass with respect to all the monomers, it becomes difficult to obtain spherical particles only with N-vinylcarboxylic acid amide, so that copolymerization with N-vinylcarboxylic acid amide can be performed. It is preferable that a possible monomer is used in combination. The amount of the monomer copolymerizable with the N-vinylcarboxylic acid amide is preferably 0.1 to 50% by mass with respect to all the monomers.

Examples of the polymerization initiator according to the granular polyvinylamine crosslinked polymer (1) include azo-based and peroxide-based polymerization initiators, for example, 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2 '-Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylpropionitrile), 2, 2'-azobis-2-amidinopropane hydrochloride, 4, 4' -Azobis-4-cyanovaleric acid, 2,2'-azobis [2- (5-methyl-imidazolin-2-yl) propane] hydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) ) Propane] Hydrochloride, etc., ammonium peroxodisulfate or potassium, hydrogen peroxide, benzoylperoxide, lauroylperoxide, octanoylperoxide, succinicperoxide, t-butylperoxy-2-ethylhexanoate, etc. may be mentioned. .. As the polymerization initiator, an oil-soluble initiator such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) is preferable. The polymerization initiator may be one kind or a combination of two or more kinds. The amount of the polymerization initiator added is usually 0.02 to 5% by mass, preferably 0.05 to 2% by mass, based on all the monomers.

Examples of the salt according to the granular polyvinylamine crosslinked polymer (1) include ammonium sulfate, sodium sulfate, ammonium chloride, sodium chloride, calcium chloride and the like, and among these, ammonium sulfate is preferable. The salt may be one kind or a combination of two or more kinds. In salt water, the amount of salt added is 30 to 100% by mass, preferably 50 to 90% by mass, and particularly preferably 60 to 90% by mass with respect to water. When the amount of salt added in the salt water is less than 30% by mass with respect to water, the N-vinylcarboxylic acid amide does not separate into two phases, and the amount of salt added in the salt water is 100 with respect to water. If it is by mass%, the effect of salt can be sufficiently obtained, and if it exceeds 100% by mass, it becomes uneconomical.

As the dispersant according to the granular polyvinylamine crosslinked polymer (1), a polymer dispersant is preferable. The polymer dispersant may be either ionic or nonionic, but ionic ones are preferable. Examples of the ionic polymer dispersant include those obtained by polymerizing (meth) acryloyloxyethyltrimethylammonium chloride, dimethyldiallylammonium chloride, etc., which are cationic monomers, and these cationic monomers and nonionic monomers. And the copolymer with. Examples of the nonionic monomer include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N, N'-dimethylacrylamide, acrylonitrile, diacetoneacrylamide, 2-hydroxyethyl (meth) acrylate and the like. .. Examples of the nonionic polymer dispersant include polyvinyl alcohol and polyethylene glycol polyacrylamide. The weight average molecular weight of the ionic polymer dispersant is 50 to 5 million, preferably 50,000 to 3 million. The weight average molecular weight of the nonionic polymer dispersant is 1,000 to 100,000, preferably 1,000 to 50,000. The amount of the polymer dispersant added is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass, based on water.

The polymerization reaction temperature in suspension polymerization is usually 30 ° C. to 100 ° C., and the polymerization reaction time is usually 1 to 15 hours. After suspension polymerization, salts, dispersants, unreacted monomers and the like can be removed by washing with water.

Then, suspension polymerization is carried out to obtain a granular crosslinked polymer. The granular crosslinked polymer obtained by suspension polymerization is a granular N-vinylcarboxylic acid amide crosslinked polymer.

Then, the granular N-vinylcarboxylic acid amide crosslinked polymer obtained by suspension polymerization is hydrolyzed. Hydrolysis of the granular N-vinylcarboxylic acid amide crosslinked polymer can be carried out under basic or acidic conditions, but in order to obtain a free polyvinylamine crosslinked polymer, hydrolysis is carried out under basic conditions. It is preferable to do so. In order to obtain salt-type polyvinylamine crosslinked polymer particles, it is preferable to hydrolyze them under acidic conditions.

The base used for hydrolysis is not particularly limited as long as it can have a pH of 8 to 14 during hydrolysis, and examples thereof include aqueous solutions of sodium hydroxide, potassium hydroxide, and ammonia. The amount of the base added is 0.05 to 2.0 equivalents, preferably 0.4 to 1.2 equivalents, relative to the formyl group of the N-vinylcarboxylic acid amide crosslinked polymer.

The acid used for hydrolysis is not particularly limited as long as the pH can be set to 0 to 5 during hydrolysis, and inorganic acids such as hydrohalogenate, sulfuric acid, nitric acid, and phosphoric acid, and carbon. Examples thereof include monos of numbers 1 to 5 or organic acids such as dicarboxylic acid, sulfonic acid, benzenesulfonic acid and toluenesulfonic acid, and hydrogen halide and hydrogen halide gas are preferable, and hydrohalogen acid is particularly preferable. The amount of the acid added is 0.05 to 2.0 equivalents, preferably 0.4 to 1.2 equivalents, relative to the formyl group of the N-vinylcarboxylic acid amide crosslinked polymer.

Granular polyvinylamine crosslinked polymers can be obtained by washing with water or the like after hydrolysis. In the case of base hydrolysis, a granular free polyvinylamine crosslinked polymer is obtained, and in the case of acid hydrolysis, a granular salted polyvinylamine crosslinked polymer is obtained.

In the water purifier cartridge of the present invention, the tap water supply port and the tap water supply path formed in the housing of the softening water purifier of the present invention are connected, and the softened water discharge port and the present invention are used. It is installed in the housing of the water purifier for softening of the present invention so as to be connected to the discharge path of the softened water formed in the housing of the water purifier for softening.

Then, tap water is supplied into the softening water purifier of the present invention, is supplied into the filling region of the softening treatment material via the tap water supply path in the housing of the softening water purifier of the present invention, and is softened. The liquid is passed through the material layer. When the tap water passes through the softening treatment material layer, the softening treatment material causes Ca ions and Mg ions, which are hardness components in the tap water, to be Na ions or K of the salt-type strongly acidic cation exchange resin of the softening treatment material. It is exchanged for ions and the tap water is softened. The softened treated water is discharged to the outside of the softening water purifier of the present invention through the softened water discharge path inside the housing of the softened water purifier of the present invention, and is used as softened water.

The water purifier for softening of the present invention is a water purifier for softening, which comprises a cartridge for the water purifier of the present invention and a housing for accommodating the cartridge for the water purifier of the present invention.

The water to be treated by the water purifier for softening of the present invention is tap water.

Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.

(Manufacturing Example 1)
216 g of demineralized water, 144.0 g of ammonium sulfate, and 9.0 g of polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20% by mass, weight average molecular weight 800,000) were put into a 500 mL four-necked flask, and the mixture was stirred and dissolved. , A polymer bath. N-vinylformamide 49.8 g, divinylbenzene 4.20 g, acrylonitrile 6.00 g, azo-based polymerization initiator 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, Wako Pure Chemical Industries, Ltd.) (Made by Yakuhin Kogyo Co., Ltd.) 0.60 g was mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed, and the inside of the flask was replaced with nitrogen while stirring at 150 rpm. After 30 minutes, the temperature was raised and polymerization was carried out at 50 ° C. for 3 hours, followed by 70 ° C. for 2 hours. After the polymerization, it was filtered, washed with water and filtered to obtain 136.9 g of polymer spherical particles in a water-containing state. The solid content was 42.0%. 100.0 g of the reaction product thus obtained was placed in a 4-neck flask, 143.0 g of desalinated water and 143.0 g of a 48 mass% sodium hydroxide aqueous solution were added, and the mixture was hydrolyzed at 100 ° C. for 6 hours with stirring. .. It was washed with water and filtered to obtain 106.8 g of polyvinylamine crosslinked polymer spherical particles in a water-containing state. As a result of microscopic observation, spherical particles of 50 μm to 2 mm were observed.
The physical characteristics of the obtained polyvinylamine crosslinked polymer spherical particles were measured and found to have an ion exchange capacity of 3.2 (eq / L-R, wet state) and a harmonic mean diameter of 600 μm.

<Measuring method of harmonic mean diameter of ion exchange resin>
The measurement was performed using a laser diffraction / scattering method particle size distribution measuring device (trade name: LS 13 320 (wet system)) manufactured by Beckman Coulter.

(Example 1)
Na-type strongly acidic cation exchange resin (Amberjet 1220Na, Dow Chemical) with an ion exchange capacity of 2.2 (eq / L-R, wet state) and a harmonized average diameter of 610 μm in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. A cartridge was prepared by filling 900 mL with a mixture of 900 mL and 18 mL of the polyvinylamine crosslinked polymer spherical particles obtained in Production Example 1.
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the car ridge, it was left for 24 hours in a room adjusted at 23 ° C.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the formaldehyde concentration of the treated water was analyzed. The results are shown in Table 1.

(Example 2)
Na-type strongly acidic cation exchange resin (Amberjet 1220Na, Dow Chemical) with an ion exchange capacity of 2.2 (eq / L-R, wet state) and a harmonized average diameter of 610 μm in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. A cartridge was prepared by filling 900 mL of (manufactured by the same company) on the upstream side with 18 mL of the polyvinylamine crosslinked polymer spherical particles obtained in Production Example 1 in a laminated manner on the downstream side.
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the car ridge, it was left for 24 hours in a room adjusted at 23 ° C.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the formaldehyde concentration of the treated water was analyzed. The results are shown in Table 1.

(Comparative Example 1)
Na-type strong acid cation exchange resin (Amberjet 1220Na, Dow Chemical) with an ion exchange capacity of 2.2 (eq / L-R, wet state) and a harmonized average diameter of 610 μm in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. A cartridge was prepared by filling a mixture of 900 mL (manufactured by Purolite) and 18 mL of a polyamine type anion exchange resin (Purolite A830W, manufactured by Purolite).
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the car ridge, it was left for 24 hours in a room adjusted at 23 ° C.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the formaldehyde concentration of the treated water was analyzed. The results are shown in Table 1.

(Comparative Example 2)
Na-type strongly acidic cation exchange resin (Amberjet 1220Na, Dow Chemical) with an ion exchange capacity of 2.2 (eq / L-R, wet state) and a harmonized average diameter of 610 μm in an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm. 900 mL on the upstream side, ion exchange capacity 3.0 (eq / L-R, wet state), polyamine type anion exchange resin with harmonized average diameter of 850 μm, Purolite A830W, Purolite) 18 mL on the downstream side The cartridge was prepared by filling in a laminated form.
Next, tap water having a water temperature of 23 ° C. was passed through the cartridge at SV60BV / hr for 15 minutes. Then, with tap water accumulated in the car ridge, it was left for 24 hours in a room adjusted at 23 ° C.
After leaving it for 24 hours, tap water having a water temperature of 23 ° C. was passed through again at SV60BV / hr for 1 minute, and the treated water during that period was collected. Then, the formaldehyde concentration of the treated water was analyzed. The results are shown in Table 1.

(Comparative Example 3)
In an acrylic column with an inner diameter of 4.6 cm and a height of 100 cm, 900 mL of Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.), a specific surface area of 1400 m ² / g, and a particle size of 0.18 to 0. The same procedure as in Example 1 was carried out except that 100 mL of granular activated carbon (Taiko activated carbon CW480PGR, manufactured by Futamura Chemical Co., Ltd.) having a range of 355 mm was mixed. The results are shown in Table 1.

(Comparative Example 4)
The same procedure as in Example 1 was carried out except that only 900 mL of a Na-type strong acid cation exchange resin (Amberjet 1220Na, manufactured by Dow Chemical Co., Ltd.) was filled in an acrylic column having an inner diameter of 4.6 cm and a height of 100 cm. The results are shown in Table 1.

Claims (6)

A cartridge container in which a tap water supply port and a softened water discharge port are formed,
It has a softening material layer filled in a filling area of the softening material in the cartridge container.
The softening treatment material layer is formed of a mixture of a salt-type strongly acidic cation exchange resin and a polyamine-type anion exchange resin composed of a granular polyvinylamine crosslinked polymer, and the polyvinylamine crosslinked polymer is formed. Being a weakly basic anion exchange resin with at least a primary amine ,
Cartridge for water purifier featuring. A cartridge container in which a tap water supply port and a softened water discharge port are formed,
It has a softening material layer filled in a filling area of the softening material in the cartridge container.
The softened material layer is composed of a salt-type strongly acidic cation resin layer laminated on the upstream side and a polyamine type anion exchange resin layer composed of a granular polyvinylamine crosslinked polymer laminated on the downstream side. The polyvinylamine crosslinked polymer which is formed is a weakly basic anion exchange resin having at least a primary amine .
Cartridge for water purifier featuring. The cartridge for a water purifier according to claim 1 or 2 , wherein the granular polyvinylamine crosslinked polymer is a hydrolyzate of a suspension polymer of N-vinylcarboxylic acid amide and a crosslinkable monomer. The granular polyvinylamine crosslinked polymer is a hydrolyzate of a suspended polymer of N-vinylcarboxylic acid amide, a crosslinkable monomer, and acrylonitrile, and the crosslinkable monomer is a polyvinyl compound. The cartridge for a water purifier according to claim 1 or 2 , wherein the cartridge is provided. The cartridge for a water purifier according to claim 3 or 4 , wherein the crosslinkable monomer is divinylbenzene. The water purifier cartridge according to any one of claims 1 to 5 .
A housing for storing the water purifier cartridge and
A water purifier for softening, which is characterized by having.