KR20130097281A - Composition for manufacturing water absorbent resin with natural polymer and manufactured water absorbent resin using the thereof - Google Patents

Abstract

PURPOSE: A natural polymer-containing composition for a moisture-absorbing resin is provided to reduce toxicity of a synthetic polymer while maintaining excellent moisture absorption. CONSTITUTION: A natural polymer-containing composition includes 100.0 parts by weight of an acrylic monomer, 5-50 parts by weight of a cellulose-based compound, 0.1-10 parts by weight of a carboxy(C1-C5)alkyl chitosan, and 0.01-3 parts by weight of cinnamon oil. The carboxy(C1-C5)alkyl chitosan is carboxymethyl chitosan or carboxymethyl chitosan. The composition additionally includes 10-30 parts by weight of a neutralizer, 0.1-1 parts by weight of a crosslinking agent, 1-3 parts by weight of an initiator, and 400-600 parts by weight of water per 100.0 parts by weight of the acrylic monomer.

Description

TECHNICAL FIELD [0001] The present invention relates to a water absorbent resin composition containing a natural polymer and a water absorbent resin prepared from the same,

The present invention relates to a water absorbent resin composition containing a natural polymer and a water absorbent resin prepared therefrom. More specifically, the present invention relates to a water absorbent resin composition comprising a natural polymeric cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil To a water absorbent resin containing a natural polymer capable of lowering the toxicity of a synthetic polymer while maintaining an excellent absorption power by polymerizing a composition for absorbent resin which is obtained by polymerizing a water absorbent resin.

Super Absorbent Polymer (SAP) is a synthetic polymer material having a function of absorbing moisture of several hundreds to several thousand times its own weight. When it enters the water in the present powder form, it instantaneously absorbs water and swells, Such a superabsorbent resin is mostly used for diapers, sanitary napkins for women, absorbent paper for medical use, and the like. BACKGROUND ART [0002] Acrylic water absorbent resins obtained from acrylic acid and / or its salt as monomers in water absorbent resin, which is a method of producing a macroreticular polymer crosslinked with a synthetic polymer, are most commonly used industrially due to high water absorption and low processing cost. Other commercially available water absorbent resins include polyacrylic acid partial neutralized crosslinked product, hydrolyzate of starch-acrylonitrile graft polymer, neutralized product of starch-acrylic acid graft polymer, neutralized product of vinyl acetate acrylic acid ester copolymer, A hydrolyzate of a nitrile copolymer, or a hydrolyzate of an acrylamide copolymer. These are produced by aqueous solution polymerization, suspension polymerization, reversed-phase suspension polymerization and the like.

Since such a water absorbent resin is mainly used as a disposable material, it has a characteristic of being easy to manufacture and having a low unit price, developed with a physical property such as a suction force for sucking moisture from a substrate containing an aqueous liquid, a liquid permeability, and a strength of a swollen gel Has come.

 However, in recent years, sanitary materials such as diapers and sanitary napkins including absorbent resins have not only absorbed urine, menstrual blood, body fluids, etc., but also can prevent erythema and itching in long- Function is also required.

Conventionally, when a sanitary material made of an absorbent resin is worn for a long time, volatile ammonia or the like, which is generated from byproducts generated by decomposition of urine, menstrual blood and the like in the sanitary material by microorganisms slowly comes into contact with the human body, It acts as a cause of skin rash and the like due to the toxicity of synthetic resin such as acrylic acid which is a raw material of the water absorbent resin.

In particular, Korean Patent No. 0226400 (Patent Document 1) discloses an absorbent structure formed by crosslinking a cellulose polymer fiber, which is a natural polymer, with a polyacrylic acid polymer. However, the problem that unreacted acrylic acid remains during crosslinking of the polyacrylic acid polymer In addition, US Patent No. 4842593 (Patent Document 2) proposes a method of adding an antimicrobial agent containing nitrogen to a water absorbent resin and a top sheet of a sanitary material, but there is a problem that the characteristics of the antimicrobial agent become insignificant when worn for a long period of time Respectively.

Therefore, there is a need for development of an absorbent resin for solving the problems of odor or dermatitis without causing adverse effects on the human body without lowering the physical properties such as the absorbency and the strength of the absorbent resin.

Korean Patent No. 0226400 United States Patent No. 4842593

Disclosure of the Invention The present invention has been made to solve the problems of the prior art, and it is an object of the present invention to provide a water absorbent resin by polymerizing a composition for a water absorbent resin containing a cellulose polymer as a natural polymer, carboxy (C1-C5) alkyl chitosan and cinnamon oil, It is an object of the present invention to provide a composition for a water absorbent resin containing a natural polymer capable of lowering the toxicity of a synthetic polymer while maintaining its absorption power.

It is also an object of the present invention to provide an absorbent resin including the above water absorbent resin composition.

In order to achieve the above object, the present invention provides a composition for an absorbent resin comprising an acrylic monomer, a cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil.

The present invention also provides an absorbent resin characterized by being manufactured by including the above water absorbent resin composition.

INDUSTRIAL APPLICABILITY According to the water absorbent resin composition containing the natural polymer of the present invention and the water absorbent resin prepared therefrom, it is possible to polymerize a water absorbent resin composition comprising a natural polymeric cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil, There is an advantage that it is possible to provide an absorbent resin having low toxicity of skin with reduced skin rash and the like in a human body contacting portion by lowering the toxicity of the synthetic polymer while maintaining an excellent absorbent power.

1 is a graph showing an infrared spectroscopy (FT-IR) spectrum of the water absorbing polymer prepared in Example 1 of the present invention, (a) carboxymethylcellulose, (b) carboxymethylchitosan, Fig.
2 is a SEM image showing the morphology of the water absorbing polymer according to Comparative Example 1 of the present invention.
3 is a SEM image showing the morphology of the water absorbing polymer according to Example 1 of the present invention.
4 is a graph showing swelling degree according to the drying method of the water absorbent polymer according to Example 1 of the present invention.

Best Mode for Carrying Out the Invention Hereinafter, a preferred embodiment of the composition for a water absorbent resin containing a natural polymer and a water absorbent resin produced therefrom and a method for measuring a physical property will be described in detail. The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

The water absorbent resin composition of the present invention preferably contains an acrylic monomer, a cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil.

The acrylic monomer may be any conventional monomers used in the water absorbent resin and may be one or two selected from the group consisting of anionic monomers containing anionic acrylic monomers and salts thereof, (Meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide-2-methylpropanesulfonic acid, and 2- (Meth) acrylate, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol (N, N) -dimethylaminoethyl (meth) acrylate, (N, N) -dimethylaminopropyl (meth) acrylamide or a mixture thereof. May be not less than illustrated, it is most effective to preferably comprises acrylic acid or acrylamide.

Also. Among the natural polymers, the cellulose-based compound is an environmentally friendly natural fiber capable of completely biodegrading and is added in order to produce a highly absorbent polymer which is non-toxic to the human body, and in particular, cellulose derivatives such as methylcellulose, ethylcellulose, propylcellulose, carboxymethylcellulose, Cellulose, methylhydroxyethylcellulose, methylhydroxypropylcellulose or ethylhydroxyethylcellulose, and more preferably one or more selected from the group consisting of carboxymethylcellulose and hydroxyethylcellulose .

The content of the cellulose compound is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the acrylic monomer. The cellulose concentration is closely related to the swelling property. If the amount is less than 5 parts by weight, the absorption rate may be low. If the amount is more than 50 parts by weight, the absorption rate of the produced absorbent polymer is not improved any more.

Among natural polymers, chitosan substituted with carboxy (C1-C5) alkyl is added to impart antimicrobial properties to the water absorbent resin and has a chain structure similar to that of cellulose, and is preferably carboxymethyl chitosan or carboxyethyl chitosan .

The content of carboxy (C1-C5) alkyl chitosan is preferably 0.1 to 30 parts by weight, more preferably 1.0 to 10 parts by weight, per 100 parts by weight of the acrylic monomer. If the content of carboxyl (C1-C5) alkyl chitosan is less than 0.1 parts by weight, there may be a problem that does not appear antimicrobial, if more than 10 parts by weight, the structure of chitosan is dense, it is difficult to produce a super absorbent polymer have. In addition, when the water absorbent resin is prepared by incorporating carboxy (C1-C5) alkyl chitosan in the optimum amount in the above range, the effect of the antimicrobial is increased.

Among natural polymers, cinnamon oil is added to improve the treatment and antimicrobial effect against secondary infection of skin irritation caused by residual unreacted acrylic monomer, and it is preferable that cinnamon oil is added in an amount of 0.01 to 3 Is preferably added in an amount of 0.01 to 2 parts by weight, more preferably 0.01 to 2 parts by weight.

If the amount of cinnamon oil is less than 0.01 part by weight, the anti-inflammatory and antimicrobial effects of the water absorbent resin may be insignificant. If the content of the cinnamon oil is more than 3 parts by weight, the hydrolytic component of cinnamon oil may be difficult to form a superabsorbent polymer Lt; / RTI > In addition, when cinnamon oil is contained in an optimum amount of the above range to produce an absorbent resin, the effect of anti-inflammation and antibacterial is enhanced.

It is also preferable that the composition for absorbent resin further comprises a neutralizing agent, a crosslinking agent, an initiator and water.

The neutralizing agent is added for partial neutralization of the acrylic monomer. The neutralizing agent is not limited as long as it is a compound capable of neutralizing acrylic acid by making an alkaline aqueous solution. In particular, sodium hydroxide, potassium hydroxide, ammonium hydroxide or lithium hydroxide can be used, It is effective to use sodium or potassium hydroxide.

The content of the neutralizing agent is preferably 10 to 30 parts by weight, more preferably 17 to 25 parts by weight, per 100 parts by weight of the acrylic monomer. When the content of the neutralizing agent is less than 17 parts by weight, the neutralization becomes too weak and the water absorbency of the water absorbent resin is reduced. When the amount of the neutralizing agent is more than 25 parts by weight, the neutralization is too much, Problems can arise.

In addition, the crosslinking agent is added in order to absorb the water absorption rate of the water absorbent resin and to maintain the stable gel strength in the swollen state by absorbing water. The crosslinking agent used in the present invention is not particularly limited as long as it is a crosslinking agent capable of crosslinking an acrylic monomer. Particularly, a crosslinking agent such as N, N'-methylenebisacrylamide, ethylene glycol, propylene glycol, glycerin, trimethylpropane, polyethylene glycol, Diacrylate or triacrylate, and alkylenebisacrylamide, and it is more effective to use N, N'-methylenebisacrylamide.

The content of the crosslinking agent is preferably 0.1 to 1 part by weight, more preferably 0.3 to 0.6 part by weight based on 100 parts by weight of the acrylic monomer. When the amount of the cross-linking agent is less than 0.1 part by weight, the gel strength of the water absorbent resin is weak and the water absorbing speed is slowed down. When the amount is more than 1 part by weight, the absorbency is significantly reduced.

The initiator is added to initiate the reaction of the acrylic monomer. The initiator is preferably added after adding the cross-linking agent to the partially neutralized acrylic monomer. Any initiator may be used without limitation as long as it is a water-soluble radical polymerization initiator. Particularly, a water-soluble peroxide such as potassium persulfate or ammonium persulfate is effective, and the content of the initiator is preferably 1 to 3 parts by weight, more preferably 1.5 to 2 parts by weight, per 100 parts by weight of the acrylic monomer Is effective. When the content of the initiator is less than 1 part by weight, the gel strength of the water absorbent resin becomes weak. When the content of the initiator exceeds 3 parts by weight, the water absorbability is deteriorated.

In addition, water is added by adding the water absorbent resin by suspension polymerization or reversed-phase suspension polymerization, and it is effective for the uniform reaction to include 400 to 600 parts by weight based on 100 parts by weight of the acrylic monomer.

Hereinafter, the method of producing the water absorbent resin will be described in detail.

Mixing a composition for absorbent resin comprising the acrylic monomer, the cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil;

Polymerizing the composition for absorbent polymer to form a polymer;

And drying the polymer.

The composition for absorbent resin composition preferably contains 5 to 50 parts by weight of a cellulose compound, 0.1 to 10 parts by weight of carboxy (C1-C5) alkyl chitosan and 0.01 to 3 parts by weight of cinnamon oil, based on 100 parts by weight of the acrylic monomer Do.

It is also preferable that 10 to 30 parts by weight of a neutralizing agent, 0.1 to 1 part by weight of a crosslinking agent, 1 to 3 parts by weight of an initiator and 400 to 600 parts by weight of water are contained in 100 parts by weight of the acrylic monomer.

In the mixing step, it is preferable to mix the composition except for the initiator first at a room temperature by a commonly used mixing method, more preferably by mixing using an agitator in an inert atmosphere such as nitrogen or helium. The mixing time is preferably 10 minutes to 60 minutes, more preferably 20 to 40 minutes.

It is also preferable to include a step of polymerizing the composition for absorbent resin to form a polymer. It is effective that the initiator is added to the composition for absorbent resin subjected to the mixing step and then heat-polymerized at 60 to 100 캜.

Further, it is preferable to include a step of drying the water absorbent resin polymer formed through the polymer forming step, and it is effective that the drying is performed by heat drying or lyophilization.

It is preferable that the water absorbent resin containing the above-mentioned composition for a water absorbent resin and containing a natural polymer produced by the above production method has a swelling degree of the following formula (1).

[Formula 1]

(Where Ws is the weight of the swollen sample and Wd is the weight of the dried sample).

Accordingly, the absorbent resin containing the natural polymer having low skin toxicity can be produced by reducing the toxicity of the synthetic polymer while maintaining the excellent absorbency of the conventional acrylic water absorbent resin.

Hereinafter, characteristics of the water absorbent resin containing the natural polymer of the present invention were evaluated by the following test method, and the results are shown in Figs. 1 to 4 and Table 1.

1) FT-IR analysis

According to the examples and comparative examples, a certain amount of the water absorbent resin was mixed with KBr while being mixed, and 200 mg of the water absorbent resin was pressed into pellets by applying pressure, and analyzed by fourier transform infrared spectroscopy (FT-IR, Shimadazu, 8201PC) The results are shown in Fig.

2) Observation of morphology

The absorbent resin prepared in Examples and Comparative Examples was vacuum-coated with Au-Pd for 60 seconds using an automatic coater (Sputter Coater 108auto, Cressington Scientific Instruments Inc.), and then subjected to a scanning electron microscope (SEM, JEOL, JSM-5400A ), And morphology was observed at 15 kV. The results are shown in FIG. 2 and FIG.

3) Swelling degree measurement

The water absorbent resin prepared according to the above Examples and Comparative Examples was immersed in distilled water at room temperature, and the weight change was observed after 15 hours. The degree of swelling was calculated from the following formula 1, and the results are shown in Table 1 below Respectively. The degree of swelling measured according to the drying method is shown in Fig.

[Formula 1]

(Where Ws is the weight of the swollen sample and Wd is the weight of the dried sample).

4) Patch test

The absorbent resin prepared according to the above Examples and Comparative Examples was immersed in distilled water for 30 minutes and then patched and placed in the arms of 30 adult males and women for 24 hours. On average, when itching, rashes, A case where an oscillation occurred, and a case where there was no abnormality were marked with a circle.

[ Example  One]

4 mL of acrylic acid (Sigma-Aldrich), 15 mL of a 5 wt% aqueous solution of carboxymethylcellulose (Sigma-Aldrich), 0.1 g of carboxymethyl chitosan (Sigma-Aldrich), cinnamon ( Cinnamonum zeylanicum Blume extract, , 2.13 g of acrylamide (Tokyo chemical industry Co.), 0.0143 g of N, N-methylenebisacrylamide (Tokyo chemical industry Co.) as a crosslinking agent, 0.92 g of caustic soda and 19.6 mL of water were mixed to prepare a water absorbent resin composition . Thereafter, the water absorbent resin composition was stirred at room temperature for 30 minutes in a stream of nitrogen, and the temperature was gradually raised to 70 deg. 71.3 mg of ammonium peroxodisulfate (Sigma-Aldrich) as an initiator was added and polymerization was carried out for 3 hours under a nitrogen stream. The obtained polymer was thermally dried at 70 DEG C for 12 hours to obtain a superabsorbent resin.

[Example 2]

Except that 10 mL of a 5 wt% carboxymethylcellulose aqueous solution (Sigma-Aldrich) was used.

[Example 3]

Except that 30 mL of a 5 wt% aqueous carboxymethylcellulose solution (Sigma-Aldrich) was used.

Example 4

Was prepared in the same manner as in Example 1, except that 0.3 g of carboxymethyl chitosan (Sigma-Aldrich) was used.

[ Comparative example  One]

Except that 5 wt% carboxymethyl cellulose aqueous solution (Sigma-Aldrich), carboxymethyl chitosan (Sigma-Aldrich), cinnamon ( Cinnamonum zeylanicum Blume extract, Euroaroma) oil was not used .

Comparative Example 2

Carboxymethyl chitosan (Sigma-Aldrich), cinnamon ( Cinnamonum zeylanicum Blume extract, Euroaroma) oil was not used, and was prepared in the same manner as in Example 1.

[Comparative Example 3]

Cinnamon ( Cinnamonum zeylanicum Blume extract, Euroaroma) was prepared in the same manner as in Example 1 except that no oil was used.

[Table 1]

1 is a graph showing an infrared spectroscopy (FT-IR) spectrum of the water absorbing polymer prepared in Example 1 of the present invention, (a) carboxymethylcellulose, (b) carboxymethylchitosan, As shown in (d), the water absorbing polymer according to the present invention is a water absorbent polymer having a group -OH (3500 cm ^-1 ) group by hydrogen bonding between a hydroxy group of carboxymethyl cellulose and a hydroxy group and an amino group of carboxymethyl chitosan Of the total amount of the water-absorbent resin.

2 and 3 are SEM image photographs showing the morphology of the fms absorbent polymer according to Comparative Example 1 and Example 1 of the present invention. It is shown that uniform pores are formed in the water absorbent resin by the inclusion of a natural polymer, Is significantly improved.

FIG. 4 is a graph showing the swelling degree according to the drying method of the water absorbing polymer according to Example 1 of the present invention, and it was confirmed that the water absorbing resin prepared by freeze drying than that prepared by heat drying at 70 ° C improved the absorbency to some extent there was.

In addition, as shown in Table 1, when the natural polymer is added in an optimum amount, the absorbency is improved more than when the natural polymer is not contained, and as shown in the patch test, the toxicity is remarkably reduced, I could.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Claims (10)

An absorbent resin composition comprising an acrylic monomer, a cellulose compound, carboxy (C1-C5) alkyl chitosan and cinnamon oil.
The method of claim 1,
The acrylic monomer may be selected from the group consisting of acrylic acid, methacrylic acid, 2-methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, 2- (meth) acrylamide- (Meth) acrylate, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol , N) -dimethylaminoethyl (meth) acrylate, (N, N) -dimethylaminopropyl (meth) acrylamide or mixtures thereof.
The method of claim 1,
The cellulose-based compound is one or two or more selected from methyl cellulose, ethyl cellulose, propyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose or ethyl hydroxyethyl cellulose. A water absorbent resin composition, characterized by the above-mentioned.
The method of claim 1,
Wherein said chitosan substituted with carboxy (C1-C5) alkyl is carboxymethyl chitosan or carboxyethyl chitosan.
The method of claim 1,
In 100 parts by weight of the acrylic monomer,
5 to 50 parts by weight of the cellulose-based compound, 0.1 to 10 parts by weight of the carboxy (C1-C5) alkyl chitosan, and 0.01 to 3 parts by weight of the cinnamon oil.
The method of claim 1,
The water-absorbent resin composition further comprises 10-30 parts by weight of a neutralizing agent, 0.1-1 part by weight of a crosslinking agent, 1-3 parts by weight of an initiator, and 400-600 parts by weight of water, based on 100 parts by weight of the acrylic monomer. A water absorbent resin composition.
A water absorbent resin, comprising the composition for water absorbent resins according to any one of claims 1 to 6.
8. The method of claim 7,
Wherein the degree of swelling of the water absorbent resin satisfies the following formula (1).
[Formula 1]

(Where Ws is the weight of the swollen sample and Wd is the weight of the dried sample).
8. The method of claim 7,
Wherein the water absorbent resin is prepared by polymerizing at 60 to 100 DEG C for 1 to 5 hours.
8. The method of claim 7,
The water absorbent resin is a water absorbent resin, characterized in that produced by heat drying or freeze drying at 70 ℃.

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