JP3789887B2 - Method for producing chitosan-containing composite emulsion, chitosan-containing resin composition and chitosan-containing paint obtained by this method - Google Patents

Description

【００６４】
【発明の効果】
この発明にかかるキトサン含有複合エマルジョンの製造方法は、ラジカル重合性単量体の乳化液を用いて、連続的又は断続的に反応系に滴下するので、重合反応の制御が行いやすく、安定的に重合を行いやすい。このため、系の固形分濃度を高めることができ、容積効率を向上させることができる。また、乳化液を滴下するので、滴下液内の重合速度が調整されて、ブツが生じにくくなり、得られるエマルジョンの品質をより向上させることができる。
【００６５】
また、このキトサン含有複合エマルジョンを用いた塗料組成物を塗布して得られる塗膜は、アンモニアやホルムアルデヒド等の低分子化合物の消臭機能を有するので、建築用資材の塗料として使用した場合、アンモニアやホルムアルデヒド等の低分子化合物の消臭が可能となり、シックハウス症候群に対する対応が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a chitosan-containing composite emulsion, and a chitosan-containing resin composition or chitosan-containing paint containing the chitosan-containing composite emulsion obtained by this production method.
[0002]
[Prior art]
Chitosan is a basic polysaccharide obtained from chitin present in crustacean crusts such as crabs and shrimps, and has been studied as various adsorbents, medical carriers, antibacterial agents and the like. In addition, using this chitosan as a component of a resin composition, skin cosmetics, hair cosmetics, pharmaceuticals, fiber treatment agents, deodorants, fragrances, cement additives, coating materials, bactericidal / bacteriostatic agents, Studies for use in agricultural chemicals and the like have been made (see Patent Document 1, paragraph [0001], etc.).
As a method for producing a resin composition containing chitosan as one component, a method in which chitosan is dissolved in methacrylic acid, an emulsifier or the like is added thereto and stirred to form an emulsion, and this is subjected to a polymerization reaction in a lump. A method is disclosed in which an emulsion containing methacrylic acid and an emulsifier is polymerized, and an aqueous solution of chitosan and methacrylic acid is dropped after a predetermined time (Patent Document 1, paragraphs [0042] to [0043], [0048]. Etc.).
[0003]
[Patent Document 1]
JP-A-11-286574
[0004]
[Problems to be solved by the invention]
However, when the emulsion containing chitosan and the monomer is polymerized in a lump as described above, the amount of heat generated at the time of polymerization increases, so that it is difficult to control the polymerization rate, and the reaction may run out of control. The resulting particles are often finer and the dispersion becomes highly viscous, making it difficult to handle. In order to control this polymerization rate, it is necessary to reduce the monomer concentration, resulting in a decrease in the volumetric efficiency of the reactor and a low concentration of the resulting dispersion.
[0005]
On the other hand, when the above dropping method is used, the polymerization rate can be easily controlled, so that a decrease in volumetric efficiency can be suppressed. However, since the dropping liquid is an aqueous solution of chitosan and methacrylic acid, the polymerization rate in the dropping liquid is increased, and as a result, agglomerates are likely to be generated, and a buttery substance is likely to be generated in the resulting dispersion. Become.
[0006]
Accordingly, an object of the present invention is to provide a method for producing a chitosan-containing composite emulsion that maintains high volumetric efficiency and has improved quality.
[0007]
[Means for Solving the Problems]
The present invention is characterized in that when the radical polymerizable monomer is polymerized in the presence of chitosan or a derivative thereof, an emulsion of the radical polymerizable monomer is continuously or intermittently added to the reaction system. .
[0008]
Since the radically polymerizable monomer emulsion is continuously or intermittently dropped into the reaction system, it is easy to control the polymerization reaction rate and to perform stable polymerization. For this reason, solid content of a system can be raised and volumetric efficiency can be improved. Moreover, since an emulsion is dripped, the polymerization rate in a dripping liquid is adjusted, it becomes difficult to produce a lump, and the quality of the obtained emulsion can be improved more.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
The method for producing a chitosan-containing composite emulsion according to the present invention is a method of polymerizing a radical polymerizable monomer in the presence of chitosan or a derivative thereof.
[0010]
The chitosan is a deacetylated product of chitin which is a compound having a (1-4) -2-acetamido-2-deoxy-β-D-glucan structure, that is, (1-4) -2-amino-2- A compound mainly composed of a compound having a deoxy-β-D-glucan structure.
[0011]
The chitosan derivative is a compound in which a part of the deacetylated amino group of chitosan or a part of the hydroxyl group of chitosan is chemically modified by acylation reaction, etherification reaction, esterification reaction, or other reaction. Say.
[0012]
In general, naturally occurring chitin is an amino group in which part of the acetamide group is not acetylated. For this reason, as chitosan or a derivative thereof used in the present invention, it is preferable to use one having a degree of deacetylation of 30% or more. Moreover, as chitosan or a derivative thereof used in the present invention, chitosan without chemical modification is preferable.
[0013]
The radical polymerizable monomer means a compound having a reactive vinyl group. When an acidic aqueous solution described later is used, when the polymerizable substance is used as an acid component in the acidic aqueous solution, the polymerizable substance is used. A compound copolymerizable with is preferred.
[0014]
Examples of this radical polymerizable monomer include styrene monomers such as styrene and divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and (meth) acrylic. Propyl acid, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Dodecenyl acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, hexadecenyl (meth) acrylate, stearyl (meth) acrylate, octadecenyl (meth) acrylate, behenyl (meth) acrylate, polyethylene glycol mono (Meth) acrylate, glycidyl (Meth) acrylic esters such as (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylamides such as diacetone (meth) acrylamide, vinyl acetates such as vinyl acetate, Examples thereof include fluorine-based monomers such as trifluoroethyl methacrylate, silicone macromonomers, and the like. These can use 1 type (s) or 2 or more types. In the present invention, “(meth) acryl” means “acryl or methacryl”.
[0015]
The polymerization is performed by continuously or intermittently adding an emulsion of the radical polymerizable monomer to the reaction system.
[0016]
The emulsion of the radical polymerizable monomer is an emulsion obtained by stirring in the presence of the radical polymerizable monomer, an aqueous medium such as water, and an emulsifier.
[0017]
Various known emulsifiers can be used as the emulsifier. Specific examples include cationic emulsifiers such as stearylamine hydrochloride, lauryltrimethylammonium chloride, trimethyloctadodecylammonium chloride, potassium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkanesulfonate, sodium alkylnaphthalenesulfonate. Anionic emulsifiers such as sodium dialkylsulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene alkyl allyl ether phosphate ester, polyoxyethylene alkyl ether , Polyoxyethylene alkyl allyl ether, polyoxyethylene oxy Propylene block polymers, polyethylene glycol fatty acid esters, nonionic emulsifiers such as polyoxyethylene sorbitan fatty acid esters, lauryl betaine, is amphoteric emulsifiers such as lauryl dimethyl amine oxide and the like.
[0018]
Further, a surfactant having a polymerizable carbon-carbon double bond in the molecule (hereinafter referred to as “reactive emulsifier”) can also be used. This reactive emulsifier is not only physically adsorbed to the emulsion particles like a normal emulsifier, but also becomes easy to be copolymerized and incorporated into the polymer chain during polymerization, so the emulsion obtained using the reactive emulsifier is an emulsifier Since there are few harmful effects due to the presence of water and it is uniformly present in the film, water resistance and adhesion to the substrate are also improved.
[0019]
The reactive emulsifier is a nonionic reactive emulsifier in which a radically polymerizable propenyl group is introduced into a hydrophobic group with polyoxyethylene alkylphenyl ether as a basic structure, and a sulfate ester salt of polyoxyethylene alkylphenyl ether as a basic structure. Examples include anionic reactive emulsifiers in which a radically polymerizable propenyl group is introduced into a hydrophobic group, and cationic reactive emulsifiers such as sodium alkylallylsulfosuccinate.
[0020]
Specific examples include: Asahi Denka Kogyo Co., Ltd .: trade names Adekaria Soap SE-10N, ER-20, ER-30, Kao Co., Ltd .: Trade Names Latemul S-180, Sanyo Chemical Industries, Ltd. : Trade name: Eleminol JS-2, manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Trade name: Aqualon HS-10, manufactured by Nippon Emulsifier Co., Ltd .: Trade name: Antox MS-60.
[0021]
Since the chitosan has a polycationic property, when an anionic emulsifier is used, aggregation or the like is likely to occur. On the other hand, when a cationic or nonionic emulsifier is used, aggregation hardly occurs and emulsification is easy. And the emulsified state tends to exist stably. For this reason, as the emulsifier, the above cationic emulsifier, nonionic emulsifier, cationic reactive emulsifier, or nonionic reactive emulsifier is preferably used. Furthermore, from the viewpoint that there are few adverse effects due to the presence of the emulsifier and it exists uniformly in the film, it is more preferable to use the above-mentioned cationic reactive emulsifier or nonionic reactive emulsifier.
[0022]
Polymerization is performed by continuously or intermittently adding the emulsion of the radical polymerizable monomer to the reaction system. By adding the radical polymerizable monomer continuously or intermittently, the amount of heat generated by the polymerization can be adjusted, and the polymerization rate can be adjusted. For this reason, it can polymerize more stably. Furthermore, even if the amount of the radical polymerizable monomer in the final reaction system is increased, the polymerization becomes possible, the nonvolatile content in the reaction system can be increased, and the volumetric efficiency can be improved.
[0023]
The time for continuously or intermittently adding the emulsion of the radical polymerizable monomer to the reaction system is preferably added over 40% or more of the total reaction time, and is added over 50% or more. Is more preferable. If it is less than 40%, it becomes difficult to control the polymerization rate, the weight average molecular weight of the resulting polymer increases, and aggregates are likely to be generated.
[0024]
The time point at which the polymerization is started refers to the time point when the emulsion of the radical polymerizable monomer is added, and the time point at which the polymerization is completed is a time point when the amount of residual monomer in the reaction system is 1% by weight or less. And The total reaction time is the time from the start of weight to the end of weight.
[0025]
The chitosan or derivative thereof may be supplied to the reaction system in a solid state, but the radical polymerization is preferably performed by supplying the reaction system as an aqueous solution dissolved in an acidic aqueous solution (hereinafter referred to as “chitosan aqueous solution”). It is more preferable because it is easily incorporated into a polymer composed of a polymerizable monomer.
[0026]
As the acidic substance used in the acidic aqueous solution, any acidic substance can be used as long as it is water-soluble, but if an acidic monomer copolymerizable with the radical polymerizable monomer is used, It is more preferable because an acidic site can be incorporated into the polymer comprising the radical polymerizable monomer, and the chitosan or derivative thereof can be bound thereto by ionic bond. An example of such an acidic monomer is (meth) acrylic acid.
[0027]
The chitosan or derivative thereof may be used as an emulsion (hereinafter referred to as “chitosan emulsion”) not only in the state of the chitosan aqueous solution but also suspended in an acidic aqueous solution and an emulsifier. By using a chitosan emulsion, the amount of the chitosan or derivative thereof or acidic monomer in the chitosan emulsion can be increased compared to the case of the chitosan aqueous solution, and a larger amount of the chitosan or derivative thereof can be obtained. Can be used. Moreover, since the emulsion state which is a place of superposition | polymerization with the said radically polymerizable monomer can be hold | maintained without destroying, it is more preferable.
[0028]
As the above-mentioned emulsifier, the above-mentioned emulsifier can be used, and for the reasons described above, it is preferable to use a cationic emulsifier, a nonionic emulsifier, a cationic reactive emulsifier, or a nonionic reactive emulsifier, and the above cation It is more preferable to use a reactive emulsifier of the system or a nonionic reactive emulsifier.
[0029]
As a method for charging the above chitosan or derivative thereof, chitosan aqueous solution and / or chitosan emulsion into the reaction system, any one of a method of charging into the reactor before the reaction and a method of adding continuously or intermittently A method may be adopted.
[0030]
That is, the above chitosan or derivative thereof, chitosan aqueous solution and / or chitosan emulsion, and the radical polymerizable monomer emulsion may be separately added to the reaction system, respectively, Alternatively, after the derivative, chitosan aqueous solution and / or chitosan emulsion is charged into the reactor, the radical polymerizable monomer emulsion may be added. In any case, since the radical polymerizable monomer that is the main component of the polymerization is added continuously or intermittently, the polymerization can be easily controlled.
[0031]
In addition, when the chitosan emulsion and the emulsion of the radical polymerizable monomer are separately added to the reaction system, the addition of the chitosan emulsion should be completed by the end of the reaction. Good.
[0032]
Furthermore, as another preparation method to the reaction system of the chitosan or derivative thereof, chitosan aqueous solution and / or chitosan emulsion, the chitosan or derivative thereof and / or chitosan aqueous solution and the radical polymerizable monomer may be used. After mixing, an emulsifier is added and emulsified to prepare a preliminary emulsified liquid, which may be added to the reaction system. At this time, when using the chitosan or derivative thereof as chitosan or a derivative thereof and / or chitosan aqueous solution, the acidic substance is added in addition to the above. That is, the preliminary emulsion contains the chitosan or derivative thereof, an acidic substance such as (meth) acrylic acid, an emulsifier, and water. Even when this preliminary emulsified liquid is used, the radical polymerizable monomer is polymerized in an emulsified state, and the polymerization rate can be controlled in the same manner as described above.
[0033]
A chitosan-containing resin composition produced by the above method can be obtained by incorporating the chitosan-containing composite emulsion in another resin composition.
Any other resin composition can be selected according to the application. Examples of such applications include fiber treatment agents, deodorants, fragrances, cement additives, coating materials, disinfecting / bacteriostatic agents, agricultural chemicals, architectural finishing paints, and the like.
[0034]
When the above-mentioned paint is selected as the application, the chitosan-containing paint can be obtained by including the chitosan-containing composite emulsion produced by the above-described method in the resin composition for paint. When this chitosan-containing paint is applied to the product, a coated product with a coating film obtained from the chitosan-containing paint is obtained, but this coated product can adsorb low-molecular substances such as formaldehyde and ammonia. An odor effect can be exhibited.
[0035]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. First, raw materials used in Examples and Comparative Examples, tests and evaluation methods performed in Examples and Comparative Examples, and each component used will be described.
[0036]
<Raw materials>
(Chitosan)
-Chitosan: Kyowa Technos Co., Ltd .: C-60M
(Acid substance)
Acrylic acid: manufactured by Mitsubishi Chemical Corporation (used as 80% aqueous solution) (hereinafter abbreviated as “AA”)
[0037]
(Radical polymerizable monomer)
・ Methyl methacrylate: Mitsubishi Rayon Co., Ltd. (hereinafter abbreviated as “MMA”)
Cyclohexyl methacrylate: manufactured by Asahi Kasei Corporation (hereinafter abbreviated as “CHMA”)
2-ethylhexyl acrylate: manufactured by Mitsubishi Chemical Corporation (hereinafter abbreviated as “2EHA”)
[0038]
(emulsifier)
Nonionic reactive emulsifier: manufactured by Asahi Denka Kogyo Co., Ltd .: Adekaria soap ER-20 (non-volatile content 65% by weight) (hereinafter abbreviated as “ER20”)
Nonionic reactive emulsifier: manufactured by Asahi Denka Kogyo Co., Ltd .: ADEKA rear soap ER-30 (non-volatile content: 75% by weight) (hereinafter abbreviated as “ER30”)
[0039]
(Polymerization catalyst)
Azobis-2-aminodipropane dihydrochloride: manufactured by Otsuka Chemical Co., Ltd .: V-50 (hereinafter abbreviated as “V50”)
[0040]
<Test and evaluation method>
[viscosity]
Using a Brookfield type (B type) viscometer (BM type, manufactured by Tokimec Co., Ltd.), the viscosity of the emulsion was measured according to JIS K6828-1996.
[0041]
[Emulsion stability]
The obtained emulsion was put in a plastic container and allowed to stand in a drier at 50 ° C. for 7 days. The presence or absence of aggregates and the change in viscosity were evaluated according to the following criteria.
○: No aggregate and no change in viscosity
Δ: No aggregate and some viscosity change
X: A large amount of aggregates were found or gelled
[0042]
[Filterability]
The state of the residue when the obtained emulsion was filtered with a 100 mesh filter cloth (made of nylon) was evaluated according to the following criteria.
○: No residue is seen
Δ: Some residue is observed
×: Many residues are seen
[0043]
[Adhesion]
The degree of adhesion of the stirring blade and the polymerization vessel after polymerization was evaluated according to the following criteria.
○: Adhesion of polymer is not seen
Δ: Slight adhesion of polymer is observed
X: Adhesion of polymer is often observed
[0044]
[Low temperature stability]
When the obtained emulsion was cooled to −5 ° C., it was evaluated whether or not the emulsion had deteriorated, such as precipitation and aggregation. The measuring method was performed according to JIS K 5663 (1995).
○: Not altered
×: Altered
[0045]
[Coating test]
Acrylic resin primer (manufactured by Tsunewa Chemical Industry Co., Ltd .: Eco Sealer White) is applied to gypsum board (30cm x 20cm), dried for several hours, and the resulting coating composition is diluted to a viscosity that is easy to apply with clean water. Then, it was applied with a brush and a medium hair roller. Moreover, it spray-coated by using a universal gun (caliber 4 mm diameter) on another gypsum board which was similarly ground-treated. At this time, the following requirements were evaluated according to the following criteria. In addition, the measuring method followed or conformed to JIS K 5663 (1995).
[0046]
▲ 1 ▼ Paint workability
It was evaluated whether the painting workability of brush painting, roller coating or spraying was easy.
○: Easy in all painting methods
X: Coating workability was not good in at least one painting method
[0047]
(2) Drying time evaluation
The length of the drying time was evaluated according to the following criteria.
(Drying at 20 ° C)
○: Drying time within 2 hours
X: Drying time over 2 hours
(Dry at 5 ° C)
○: Drying time within 4 hours
×: Drying time over 4 hours
Table 1 shows one evaluation for each example and comparative example. This is because the same result was obtained in any of the coating methods.
[0048]
(3) Appearance of coating film
The appearance of the coating film was evaluated according to the following criteria.
○: In all painting methods, the coating film is smooth and no spots are seen
X: In at least one coating method, large unevenness is observed in the coating film
[0049]
(4) Concealment rate
Nippon Denshoku Industries Co., Ltd .: Whiteness was measured using a colorimetric color difference meter ZE-2100.
[0050]
(5) Alkali resistance test
The gypsum board on which the coating film was formed was immersed in an aqueous calcium hydroxide solution for 18 hours, and the properties of the coating film when it was pulled up were evaluated according to the following criteria.
Y: No change
X: Change is seen in coating film
[0051]
▲ 6 ▼ Cleaning resistance
The properties of the coating film after 100 washing tests were evaluated according to the following criteria.
Y: No change
X: The coating film is torn
[0052]
[Deodorization test]
The gypsum board on which the coating film was formed was placed in a Tedlar bag, and after deaeration, ammonia gas or formaldehyde gas was injected to adjust the concentration in the Tedlar bag to 100 ppm (ammonia gas) or 80 ppm (formaldehyde gas). Next, the concentration of each gas in the Tedlar bag after 2 hours, 7 hours, and 24 hours was measured with a Kitagawa type gas detector tube, and the remaining amount was measured.
[0053]
(Example 1) (Drip of preliminary emulsion)
Into a reaction vessel equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel, and nitrogen gas introduction tube, the raw materials shown in Table 1 were charged, and nitrogen gas was introduced while raising the temperature to 60 ° C. did.
Next, the emulsifier shown in Table 1 was dissolved in water, chitosan was gradually added, and an acidic substance was added and dissolved. After confirming that it was sufficiently dissolved, a predetermined amount of each of the monomers shown in Table 1 was added and pre-emulsified with an emulsifier at a stirring speed of 1000 to 1500 rpm to prepare a preliminary emulsion (Drip 1 in Table 1). Produced.
[0054]
Then, with the reaction temperature kept at 60 ° C., the preliminary emulsion was dropped into the reaction vessel over 2 hours. After completion of the dropping, aging was performed at a reaction temperature of 70 ° C. After 2 hours, it was judged that the polymerization reaction was completed, and it was cooled. The physical properties of the obtained emulsion were evaluated by the above methods. The results are shown in Table 1.
The determination of the completion of the polymerization was performed by collecting the reaction solution in the reaction solution and measuring the residual monomer amount by gas chromatography to confirm that the residual monomer amount was 1% by weight or less.
[0055]
52 parts by weight of the emulsion obtained above, 20 parts by weight of calcium carbonate (manufactured by Maruo Calcium Co., Ltd .: heavy calcium carbonate), 0.1 part by weight of a cellulose thickener (manufactured by RHEOX: Benaqua 1000), non-silicone 0.4 part by weight of an aqueous antifoaming agent (manufactured by San Nopco: SN deformer 777), 1.0 part by weight of a rheology control agent (manufactured by RHEOX: rheorate 216), 25 parts by weight of titanium dioxide (manufactured by DuPont: R-706) 1 part by weight, 1.0 part by weight of a nonionic wetting agent (Asahi Denka Co., Ltd .: Adekatol TN-100) and 0.5 part by weight of an anionic dispersant (Kao Co., Ltd .: Poise 521) Was sufficiently stirred until it became uniform to prepare a coating composition.
Said evaluation was performed using the obtained coating composition. The results are shown in Table 1.
[0056]
(Example 2) (Individual addition of chitosan aqueous solution and monomer-containing emulsion)
Into a reaction vessel equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel, and nitrogen gas introduction tube, the raw materials shown in Table 1 were charged, and nitrogen gas was introduced while raising the temperature to 60 ° C. did.
Next, the emulsifiers shown in Table 1 were dissolved in water, a predetermined amount of each of the monomers shown in Table 1 was added, and pre-emulsified with an agitation speed of 1000 to 1500 rpm with an emulsifier to prepare Drop 1.
Moreover, the dripping liquid 2 was obtained by adding chitosan and an acidic substance to the quantity of water shown in Table 1 gradually and dissolving them.
[0057]
And the said dripping liquid 1 and the dripping liquid 2 were dripped at reaction container over 2 hours in the state which hold | maintained reaction temperature at 60 degreeC, respectively. After completion of the dropping, aging was performed at a reaction temperature of 70 ° C. After 2 hours, it was judged that the polymerization reaction was completed, and it was cooled. The physical properties of the obtained emulsion were evaluated by the above methods. The results are shown in Table 1.
Moreover, the coating composition was produced by the method similar to Example 1 using the obtained emulsion. Said evaluation was performed using the obtained coating composition. The results are shown in Table 1.
[0058]
(Example 3) (A chitosan aqueous solution is charged into a reaction vessel and a monomer-containing emulsion is added) A reaction vessel equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel, and nitrogen gas introduction tube Inside, the emulsifier shown in Table 1 was dissolved in water, chitosan was gradually added, and an acidic substance was added and dissolved. After confirming sufficient dissolution, nitrogen gas was introduced while raising the temperature to 60 ° C.
Next, the emulsifiers shown in Table 1 were dissolved in water, a predetermined amount of each of the monomers shown in Table 1 was added, and pre-emulsified with an agitation speed of 1000 to 1500 rpm with an emulsifier to prepare Drop 1.
[0059]
And the said dripping liquid 1 was dripped over 2 hours in the state which hold | maintained reaction temperature at 60 degreeC. After completion of the dropping, aging was performed at a reaction temperature of 70 ° C. After 2 hours, it was judged that the polymerization reaction was completed, and it was cooled. The physical properties of the obtained emulsion were evaluated by the above methods. The results are shown in Table 1.
Moreover, the coating composition was produced by the method similar to Example 1 using the obtained emulsion. Said evaluation was performed using the obtained coating composition. The results are shown in Table 1.
[0060]
(Comparative Example 1) (All of chitosan and monomer are charged into a reaction vessel)
In a reaction vessel equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel, and nitrogen gas inlet tube, dissolve the emulsifiers shown in Table 1 in water, gradually add chitosan, and add the acidic substance. In addition, it was dissolved. After confirming that it was sufficiently dissolved, a predetermined amount of each of the monomers shown in Table 1 was added and stirred to form a pre-emulsion. And nitrogen gas was introduce | transduced, heating up to 60 degreeC.
Then, the polymerization reaction was carried out while maintaining the reaction temperature at 60 ° C. After 4 hours, it was judged that the polymerization reaction was completed, and it was cooled. The physical properties of the obtained emulsion were evaluated by the above methods. The results are shown in Table 1.
In addition, since the obtained emulsion had poor emulsion stability and filterability, no coating composition was prepared, and low-temperature stability, a coating test, and a deodorization test were not performed.
[0061]
(Comparative Example 2) (All the monomers were charged into a reaction vessel, and an aqueous chitosan solution was added dropwise)
Pre-emulsions were added to the reaction vessels equipped with a stirrer, temperature controller, thermometer, reflux condenser, dropping funnel, and nitrogen gas introduction pipe, and a predetermined amount of each of water and the monomers shown in Table 1 was added. Turned into. And nitrogen gas was introduce | transduced, heating up to 60 degreeC.
Moreover, the dripping liquid 2 was obtained by adding chitosan and an acidic substance to the quantity of water shown in Table 1 gradually and dissolving them.
And in the state which hold | maintained reaction temperature at 60 degreeC, the said dripping liquid was dripped over 2 hours, performing polymerization reaction. After completion of the dropping, the reaction temperature was raised to 70 ° C., and after 2 hours, the polymerization reaction was judged to be complete, and cooling was performed. The physical properties of the obtained emulsion were evaluated by the above methods. The results are shown in Table 1.
In addition, since the obtained emulsion had poor emulsion stability and filterability, no coating composition was prepared, and low-temperature stability, a coating test, and a deodorization test were not performed.
[0062]
(Comparative example 3) (Blank example which does not use chitosan)
An emulsion was obtained in the same manner as in Example 1 except that chitosan and an acidic substance were not used, and a coating composition was prepared. Table 1 shows the physical properties and the results of the evaluation test.
[0063]
[Table 1]

[0064]
【The invention's effect】
In the method for producing a chitosan-containing composite emulsion according to the present invention, a radically polymerizable monomer emulsion is continuously or intermittently dropped into the reaction system, so that the polymerization reaction is easily controlled and stably performed. Easy to polymerize. For this reason, the solid content concentration of the system can be increased, and the volumetric efficiency can be improved. Moreover, since an emulsion is dripped, the polymerization rate in a dripping liquid is adjusted, it becomes difficult to produce a lump, and the quality of the obtained emulsion can be improved more.
[0065]
In addition, since the coating film obtained by applying a coating composition using this chitosan-containing composite emulsion has a deodorizing function for low molecular compounds such as ammonia and formaldehyde, when used as a coating material for building materials, ammonia It is possible to deodorize low molecular weight compounds such as formaldehyde and formaldehyde, and to cope with sick house syndrome.

Claims (9)

Upon polymerizing a radical polymerizable monomer in the presence of chitosan or a derivative thereof, and chitosan or a chitosan aqueous solution of a derivative thereof in an acidic aqueous solution, by adding emulsifier after mixing the radical-polymerizable monomer Emulsifying to prepare a pre-emulsion, and continuously or intermittently adding the pre-emulsion to the reaction system, and starting the polymerization from the start of the addition of the emulsion of the radical polymerizable monomer. A method for producing a characteristic chitosan-containing composite emulsion. 2. The method for producing a chitosan-containing composite emulsion according to claim 1 , wherein the acidic aqueous solution is a (meth) acrylic acid aqueous solution. When polymerizing a radical polymerizable monomer in the presence of chitosan or a derivative thereof, the radical polymerizable monomer is added to an aqueous solution in which an emulsifier, (meth) acrylic acid, chitosan or a derivative thereof and water are mixed and dissolved, Stirring to prepare a preliminary emulsion, adding the preliminary emulsion continuously or intermittently to the reaction system, and starting the polymerization from the start of addition of the radical polymerizable monomer emulsion. A method for producing a characteristic chitosan-containing composite emulsion. 4. The method for producing a chitosan-containing composite emulsion according to any one of claims 1 to 3, wherein the preliminary emulsion is added over 40% or more of the total reaction time. Upper Kichichi agent, method for producing a chitosan-containing composite emulsion according to any one of claims 1 to 4, characterized in that a nonionic or cationic reactive emulsifying agent. The radical polymerizable monomer, (meth) method for producing a chitosan-containing composite emulsion according to any one of claims 1 to 5, characterized in that it comprises an acrylic acid ester monomer. The chitosan containing resin composition containing the chitosan containing composite emulsion obtained by the manufacturing method in any one of Claims 1 thru | or 6 . A chitosan-containing paint containing the chitosan-containing resin composition according to claim 7 . A coated product having a coating film obtained from the chitosan-containing paint according to claim 8 .