JP4744570B2 - Method for producing polymer composition - Google Patents

Description

The present invention relates to a method for producing a polymer composition.

In recent years, in order to reduce the burden on the environment, an example of using a biodegradable material also in a paint has been proposed. In addition, plant-derived raw materials are attracting attention because CO ₂ emissions and absorption are plus or minus zero in the life cycle and do not increase carbon dioxide in the atmosphere.

For example, in Patent Document 1, starch is used as a resin component for paint formation. However, when a solvent is used as a solvent, a large amount of volatile organic compounds are generated, and there is a concern about the burden on the environment. In addition, when water is used as a solvent, there is a problem in water resistance because acid groups remain in the coating film by modifying acid groups in starch.

Patent Document 2 contains starch as an acrylic curable composition, and Patent Document 3 contains starch as an antifouling paint composition, but it is a solvent-based material, so it generates a large amount of volatile organic compounds. Is concerned.

In Patent Document 4, starch is used for a coating agent having gas barrier properties, but it is necessary to adjust the number average molecular weight of starch by hydrolysis. Therefore, the usable starch is limited.

Patent Document 5 proposes a resin composition in which a starch derivative solution and an esterified natural resin and / or grafted natural resin solution are mixed. However, in this method, a commercially available starch derivative has a high solution viscosity and is difficult to blend. Further, it is not practical for general paints because of poor water resistance.

In Patent Document 6, a modified starch-containing resin aqueous dispersion is proposed for coatings. However, in order to obtain storage stability, a special esterified starch is used, which further contains a modified starch and a polymerizable unsaturated monomer. The average particle size of the mixture in the aqueous medium is 1000 nm or less. Reproduction was attempted using commercially available modified starch, but it could not be produced due to heat generation due to high energy resulting in gelation or generation of aggregates in the aqueous dispersion. This is considered that the starch particles sucked water and swollen, and the particles were aggregated. For this reason, the acquisition of starch and the formation of fine particles increase the cost.

In Patent Document 7 and Patent Document 8, when starch is used during the reaction, the starch is dissolved in water or the like. However, in this method, since a solvent is used when preparing the starch solution, a high concentration design cannot be performed. In addition, a starch solution having a large molecular weight has a very high viscosity and may be gelled. For this reason, the amount of starch used has been limited.

JP2004-224887 JP2003-165806 JP2006-233160 JP 2000-95994 JP2003-73501 JP2006-52338 JP 11-21380 JP 11-21529

This invention is made | formed in view of the above-mentioned background art, and aims at providing the manufacturing method of a polymer composition etc. which are kind to an environment.

According to this invention, in order to achieve the above-mentioned object, the configuration as described in the claims is adopted. Hereinafter, the present invention will be described in detail.

The first aspect of the present invention is:
A step of mixing a starch , a monomer and a sugar to obtain a monomer emulsion for emulsification;
The monomer emulsion is reacted, have a obtaining a polymer dispersion containing the polymer composition,
The sugar is a 10-mer or less,
The step of obtaining the polymer dispersion is not less than the gelatinization start temperature of the starch,
The step of obtaining the monomer emulsion is a method for producing a polymer composition , wherein the temperature is lower than the starch gelatinization start temperature .

According to this configuration, an environmentally friendly polymer composition using starch, sugar or the like for the reaction can be obtained.

The second aspect of the present invention is
2. The method for producing a polymer composition according to claim 1, wherein the starch is in a slurry form in the monomer emulsion.
It is in.

According to this structure, the restriction | limiting of the usage-amounts, such as starch, can be relieve | moderated largely, and the reaction excellent also from the environmental side can be performed now.

As another aspect of the present invention,
2. The method for producing a polymer composition according to claim 1, wherein the step of obtaining the polymer dispersion is at a higher temperature than the step of obtaining the monomer emulsion.
It may be.

According to this configuration, the dissolution of starch and the like proceeds with the reaction of the monomer, and the starch and the particles can be entangled well.

The third aspect of the present invention is
2. The method for producing a polymer composition according to claim 1, wherein the monomer is a copolymerizable unsaturated monomer.

As another aspect of the present invention,
Mixing at least one of the first starch and the first dextrin with the first monomer and the first sugar, emulsifying, and obtaining a core monomer emulsion;
Mixing at least one of the second starch and the second dextrin, the second monomer and the second sugar, emulsifying, and obtaining a shell part monomer emulsion; and
Reacting the core part monomer emulsion to obtain a polymer dispersion containing the core part polymer composition;
Wherein reacting the shell portion monomer emulsion, have a obtaining a polymer dispersion containing the core part polymer compositions shell formed around the polymer composition,
The method for producing a polymer composition, wherein the first sugar and the second sugar are 10-mer or less
It may be.

According to this structure, there exists an advantage of stabilization of the core structure by shell formation, or simultaneous use of the property of a core part and a shell part.

The fourth aspect of the present invention is
2. The method for producing a polymer composition according to claim 1, wherein the polymer composition is used for coating.

According to this configuration, an environmentally friendly paint can be obtained.

The fifth aspect of the present invention provides
2. The method for producing a polymer composition according to claim 1, wherein the polymer composition is used for an adhesive.

According to this configuration, an environmentally friendly adhesive can be obtained.

As another aspect of the present invention,
Monomer emulsion for emulsifying butyl acrylate, methyl methacrylate, acrylic acid, sodium polyoxyethylene alkyl ether sulfate, sucrose , esterified starch and water at a temperature below the gelatinization start temperature of esterified starch. And obtaining
A step of reacting the monomer emulsion in the presence of potassium persulfate at a temperature equal to or higher than the gelatinization start temperature of the esterified starch to obtain a polymer dispersion containing the polymer composition. Method for producing the composition
It may be.

Here, the starch is, for example, a carbohydrate (polysaccharide) having a molecular formula (C ₆ H ₁₀ O ₅ ) _n and refers to a natural polymer in which a number of α-glucose molecules are polymerized by glycosidic bonds. Starch crystals (starch granules) found in cells of higher plants and those collected by collecting them are also included in the starch.

When starch is suspended in water and heated, the starch granules absorb water and gradually expand. If heating is continued, the starch granules will eventually disintegrate and change into a gel (gelatinization). The temperature at which this gelatinization starts is called the gelatinization start temperature. At this time, the starch suspension gradually becomes transparent from the cloudy state and rapidly increases in viscosity. On the other hand, when the gelatinized starch solution is cooled, the paste liquid gradually becomes cloudy, releases water and becomes insoluble (aging). These states are also included in the starch. Starch includes, for example, corn starch (corn starch), waxy corn starch (mochi corn), high amylose corn starch (high amylose corn), wheat starch, rice starch, legumes (boiled beans, green beans, red beans, etc.), potato starch , Sweet potato starch and tapioca starch.

Dextrin is a general term for substances obtained by polymerizing several α-glucoses by glycosidic bonds, for example. Obtained by hydrolysis of starch. Sometimes referred to as a type of dietary fiber. The difference between dextrin and monosaccharide can also be indicated by an index DE (dextrose equivalent) indicating the degree of starch hydrolysis. Unhydrolyzed starch is zero, fully hydrolyzed monosaccharides (such as glucose) are 100, and commercially available dextrin is 4 or more and 20 or less. Dextrins include sugar chains that are branched (branched dextrin) and cyclized (cyclodextrin, cluster dextrin).

The sugar is, for example, the first oxidation product of a polyhydric alcohol and having one aldehyde group or ketone group. Includes aldoses with aldehyde groups and ketoses with ketone groups.

In addition, it is preferable to contain, for example, 5 to 85 parts of starch, preferably 5 to 70 parts, and more preferably 10 to 50 parts with respect to 100 parts by weight of the copolymerizable unsaturated monomer. For example, 0.5 to 100 parts of sugar, preferably 5 to 70 parts, and more preferably 10 to 50 parts of sugar are contained with respect to 100 parts by weight of copolymerizable unsaturated monomer.

According to the present invention, a method for producing an environmentally friendly polymer composition and the like can be obtained.

Other objects, features, or advantages of the present invention will become apparent from the detailed description based on the embodiments of the present invention described later and the accompanying drawings.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[Overview]

When starch was contained in the resin, saccharides were used to prevent starch aggregation and good storage stability was obtained. The composition at this time was a combination of starch (or modified starch), copolymerizable unsaturated monomer, sugar (oligosaccharide, modified sugar, etc.), surfactant and polymerization initiator.

In this embodiment, the starch currently used for industrial uses, such as a foodstuff and chemistry, can be used by using starch, a copolymerizable unsaturated monomer, and saccharide | sugar together. Therefore, the acquisition cost of starch can be reduced. In addition, pretreatment for using starch and special production equipment are not required, and costs can be reduced.

In addition, as said surfactant, although the anionic surfactant is mainly used by the following Example, it is not limited and a cation and a nonionic surfactant may be sufficient. The polymerization initiator may include a peroxide or a combination of a peroxide and a reduced product.

For example, when an experiment was conducted without using sugar, when starch having a large molecular weight was used, aggregates were generated in the aqueous dispersion, and a high quality product could not be produced. This is thought to be because starch particles absorb water and swell, and the particles aggregate.

In addition, when a starch having a low molecular weight was used and an experiment was carried out without using sugar, the resin could be produced, but the paint performance fell. By mixing the sugar, it is considered that the film-forming property of the starch composite emulsion system (emulsion) becomes good and contributes to the performance improvement.

First, the experimental method will be described in detail.

[Example a]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Take 25 parts of sucrose mixture (manufactured by Gunei Chemical Co., Ltd., trade name Three Sugar), 10 parts of esterified starch and 15 parts of deionized water, less than the gelatinization start temperature of this esterified starch (about 60 ° C.) The mixture was stirred and emulsified at 30 ° C.

At this time, the esterified starch was put in powder form, emulsified and dispersed, and reacted and dissolved while maintaining the dispersed state to prevent aggregation of the esterified starch. The esterified starch was not dissolved but made into a slurry. By doing so, it is possible to design a high concentration, and it is possible to prevent the starch solution having a large molecular weight from becoming very high and gelling. Therefore, the use of slurry-like starch makes it possible to greatly relax the restrictions on the amount of starch used, and provides an excellent advantage that an excellent reaction can be performed from the environmental aspect. It is done. These points are the same in the following embodiments.

Next, 50 parts of deionized water is charged into a reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel, and nitrogen is allowed to flow so that the gelatinization start temperature of starch and dextrin is not less than 80. The internal temperature is raised to 0 ° C., and 0.4 part of potassium persulfate dissolved in 5% with deionized water is charged. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

As described above, it is preferable to disperse starch, copolymerizable unsaturated monomer and water at a temperature lower than the gelatinization start temperature of starch and dextrin, and to react at a temperature higher than the gelatinization start temperature of starch and dextrin. . Above the gelatinization start temperature of starch and dextrin, starch dissolves and swells, making uniform dispersion difficult. In addition, when heat is applied during the reaction, starch dissolves with the reaction of the monomer, and the starch and the particles are intertwined well. Furthermore, when sugar (at least one of monosaccharide, disaccharide and oligosaccharide), especially 10-mer or less, preferably 5-mer or less, more preferably trimer or less, is added, the dispersibility of starch is increased. It has been found that the coating performance is improved. The particle size of the dispersion was 1000 nm or more.

In the above-described method, the esterified crosslinked starch may be changed to, for example, dextrin, urea phosphate starch, oxidized starch or cationic starch, and sucrose may be changed to, for example, oligosaccharide or maltose.

[Example b]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Taking 25 parts of sucrose mixture (trade name Three Sugar, manufactured by Gunei Chemical Industry Co., Ltd.), 10 parts of crosslinked starch and 15 parts of deionized water, the gelatinization start temperature of this crosslinked starch is less than about 75 ° C. The mixture was emulsified by stirring at room temperature. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 50 parts of deionized water, and nitrogen was introduced to an internal temperature of 80 ° C., which is higher than the gelatinization start temperature of the crosslinked starch. The temperature is raised and 0.4 part of potassium persulfate dissolved in 5% with deionized water is charged. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example c]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Take 10 parts of sucrose mixture (manufactured by Gunei Chemical Industry Co., Ltd., trade name Three Sugar), 10 parts of esterified starch and 15 parts of deionized water and stir at room temperature which is less than the gelatinization start temperature of the esterified starch And emulsified. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel is charged with 15 parts of sucrose mixture and 50 parts of deionized water, and nitrogen is allowed to flow, so that the gelatinization start temperature of the esterified starch is exceeded. The internal temperature is raised to 80 ° C., and 0.4 part of potassium persulfate dissolved in 5% with deionized water is charged. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 5,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example d]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, 5 parts of sodium dodecylbenzenesulfonate (trade name Neoperex G-25, manufactured by Kao Corporation), sucrose 10 parts of a mixture (trade name Three Sugar, manufactured by Gunei Chemical Industry Co., Ltd.), 10 parts of esterified starch, and 15 parts of deionized water are taken and emulsified by stirring at a room temperature below the gelatinization start temperature of the esterified starch. did. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel is charged with 15 parts of sucrose mixture and 50 parts of deionized water, and nitrogen is allowed to flow, so that the gelatinization start temperature of the esterified starch is exceeded. The internal temperature is raised to 80 ° C., and 0.4 part of potassium persulfate dissolved in 5% with deionized water is charged. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 5,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example e]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Then, 10 parts of esterified starch and 15 parts of deionized water were taken and emulsified by stirring at room temperature which is lower than the gelatinization start temperature of the esterified starch. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel was charged with 50 parts of deionized water and 25 parts of a sucrose mixture (manufactured by Gunei Chemical Industry Co., Ltd., trade name Three Sugar), nitrogen Is introduced, and the temperature is raised to an internal temperature of 80 ° C. which is higher than the gelatinization start temperature of the esterified starch, and 0.4 part of potassium persulfate dissolved in 5% with deionized water is charged. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example f]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) , Sucrose mixture (manufactured by Gunei Chemical Industry Co., Ltd., trade name Three Sugar) and 15 parts of deionized water were taken and emulsified by stirring at room temperature below the gelatinization start temperature of the esterified starch. While stirring, 10 parts of esterified starch is added and dispersed. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 50 parts of deionized water, and nitrogen was allowed to flow, so that the internal temperature was 80 ° C. or higher than the gelatinization start temperature of the esterified starch. To 0.4% potassium persulfate dissolved in 5% with deionized water. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example g]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, 4 parts of polyoxyethylene alkyl ether (trade name: Emulgen 1135S-70), Take 10 parts of sugar mixture (product name Three Sugar, manufactured by Gunei Chemical Industry Co., Ltd.), 10 parts of esterified starch and 15 parts of deionized water, and stir at room temperature which is less than the gelatinization start temperature of the esterified starch. Emulsified. In a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel, 15 parts of sucrose mixture, 3 parts of polyoxyethylene alkyl ether (trade name: Emulgen 1135S-70, manufactured by Kao Corporation), Charge 50 parts of deionized water, flow in nitrogen, raise the temperature to 80 ° C. which is higher than the gelatinization start temperature of esterified starch, and 0.4 parts of potassium persulfate dissolved in 5% with deionized water Prepare. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example h]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Take 25 parts of sucrose mixture (trade name Three Sugar, manufactured by Gunei Chemical Industry Co., Ltd.), 10 parts of esterified starch and 15 parts of deionized water and stir at room temperature which is less than the gelatinization start temperature of the esterified starch. And emulsified. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 50 parts of deionized water, and nitrogen was allowed to flow, so that the internal temperature was 80 ° C. or higher than the gelatinization start temperature of the esterified starch. The mixture is heated up to 0.8 parts of potassium persulfate dissolved in 5% with deionized water and 1 part of vitamin C dissolved in 10% with deionized water. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 4,500 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example i]

As a monomer mixture in a glass beaker, 50 parts of butyl acrylate, 50 parts of methyl methacrylate, 1.5 parts of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E-118B, manufactured by Kao Corporation) Take 25 parts of sucrose mixture (trade name Three Sugar, manufactured by Gunei Chemical Co., Ltd.), 10 parts of esterified starch, 0.3 part of silane coupling agent and 15 parts of deionized water, and gelatinize the esterified starch. The mixture was stirred and emulsified at room temperature, which was lower than the starting temperature. A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 50 parts of deionized water, and nitrogen was allowed to flow, so that the internal temperature was 80 ° C. or higher than the gelatinization start temperature of the esterified starch. To 0.4% potassium persulfate dissolved in 5% with deionized water. Subsequently, a pre-emulsified monomer emulsion was added dropwise over 2.5 hours, and in parallel, 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise. After completion of both droppings, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 6,000 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

[Example j (core shell)]

As a monomer mixture used as a core part in a glass beaker, 50 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.9 part of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (trade name: Latemul E, manufactured by Kao Corporation) -118B) Take 4.2 parts, sucrose mixture (manufactured by Gunei Chemical Industry Co., Ltd., trade name Three Sugar), esterified starch and deionized water 10 parts, room temperature below the gelatinization start temperature of esterified starch And emulsified with stirring. In addition, as a monomer mixture used in the shell part, 15 parts of butyl acrylate, 25 parts of methyl methacrylate, 0.6 part of acrylic acid, sodium polyoxyethylene alkyl ether sulfate (made by Kao Corporation, product) in a glass beaker Name Latemuru E-118B) 2.8 parts, sucrose mixture (manufactured by Gunei Chemical Industry Co., Ltd., trade name Three Sugar), 10 parts of esterified starch and 10 parts of deionized water, and gelatinization start temperature of esterified starch The mixture was emulsified by stirring at room temperature, which is less than A reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 50 parts of deionized water, and nitrogen was allowed to flow, so that the internal temperature was 80 ° C. or higher than the gelatinization start temperature of the esterified starch. To 0.48 parts of potassium persulfate dissolved in 5% with deionized water. Subsequently, a core monomer emulsion emulsified in advance was added dropwise over 1.5 hours, and 0.4 part of potassium persulfate diluted to 5% with deionized water was added dropwise in parallel. Subsequently, a shell part monomer emulsion previously emulsified was dropped over 1 hour, and 0.32 part of potassium persulfate dissolved in 10% with deionized water was dropped in parallel. After completion of dropping, the mixture was aged for 3 hours and then cooled to room temperature. An aqueous polymer dispersion having a solid content of 40.0%, a viscosity of 4,500 mPa · s, and a pH of 8.5 was obtained by adjusting with 2 parts of 25% aqueous ammonia and water.

According to this method, there is an advantage that the core structure can be stabilized by shell formation, or the properties of the core part and the shell part can be used simultaneously.

[Other examples]

Many other combinations were tested. The results are shown in the table. Although the table is divided for convenience of space, it is originally a single table.

Here, the numerical value of the usage fee indicates “part by weight”. The following are used as abbreviations for the monomers.
BA: Butyl acrylate
MMA: Methyl methacrylate
2EHA: 2-ethylhexyl acrylate
CHMA: cyclohexyl acrylate
BMA: Butyl methacrylate
St: Styrene

Moreover, the composition of the oligosaccharide of the present Example is as follows.
Glucose 24%
Maltose 8%
Isomaltose 15%
Marto Triose 1%
Panose 15%
Isomalt triose 5%
Other isomaltooligosaccharides 32%
(Total isomalt-oligosaccharides 67%)

KPS used as an oxidizing agent indicates potassium persulfate.

This composition is an example of an Example and is not limited to this.

Hereinafter, the method of resin evaluation, the method of coating and performance evaluation, etc. in the table will be described.

[Resin evaluation method]

Storage stability: 250 mL of resin was placed in a 250 mL sample bottle and stored at room temperature for 1 month. Thereafter, the state in the container was visually observed and evaluated according to the following criteria.
○: No change (no separation / coloring)
(Triangle | delta): Although creaming is recognized, it becomes uniform by stirring.
X: Separation or gelation is observed.

Particle size: This is the value when the sample is diluted with ion-exchanged water using F-PAR1000 (trade name, manufactured by Otsuka Electronics Co., Ltd., a concentrated particle size analyzer) and measured at 25 ° C.

Aggregate evaluation method: Based on JISK6828-3, 100 g of the sample was diluted twice with ion-exchanged water, filtered through a stainless steel wire mesh (180 μm), and the filtration residue was washed. The sample was dried for about 30 minutes in a drier at 105 ± 2 ° C., weighed, and evaluated.
When the amount of coarse particles (filtration residue) [%] = (mass of filtration residue [g]) / (mass of sample [g]) × 100,
○: Coarse particle amount ≦ 3%
×: Coarse particle amount> 3%

[Painting and performance evaluation method]

The method of blending, coating, etc. will be described.

(A) Glossy paint First, the case of glossy paint is assumed.

<Adjustment of pigment paste>

After mixing the said raw material with a stainless steel container, it stirred and disperse | distributed for 20 to 40 minutes with the disper using glass beads, and the pigment paste was manufactured.

<Manufacture of paints>

With the above composition, the mixture was mixed and stirred for 30 minutes with a disper to produce a paint.

<Evaluation test method>

・ Paint condition (in container)
Based on 4.1.2a of JIS K 5600-1-1, it carried out as follows.
If the mouth of the container is open and the surface is covered with skin, remove it and stir the contents with a spatula or a stick. Even if some of the ingredients sink to the bottom of the container, there is no particularly hard lump, scrape the bottom part little by little to dissolve the precipitate, and stir until the contents are easily uniform throughout. Sometimes it is uniform without a hard mass.
○ No abnormalities are observed × There are hard lumps, lumps, etc.

・ Coating state (coating appearance)
Nippe Ultra Sealer III (Nippon Paint Co., Ltd. styrene-acrylic resin-based sealer) is applied to a flexible board (JIS A 5430 compliant) at a coating amount of 100 g / m ² using a brush and left for 16 hours (temperature 23) Thereafter, the evaluation paint was applied ^twice with a brush at a coating amount of 100 g / m ² and a paint interval time of 3 hours. Then, after leaving for 24 hours, the state of the coating film surface was observed and evaluated (visually).
○ No abnormalities are observed in the coating film × Abnormalities such as cracks, itchiness and pinholes are observed

・ Nippe Ultra Sealer III (Nippon Paint Co., Ltd. styrene-acrylic resin-based sealer) coated on a water-resistant flexible board (JIS A 5430) with a brush at a coating amount of 100 g / m ² and left for 16 hours (Temperature 23 ° C., 50% humidity) After that, the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a coating interval time of 3 hours. Thereafter, the film was dried and cured for 7 days to prepare a water resistance test plate, and immersed in water at 20 ° C. for 7 days. After taking out and washing with water, the state of the coating film surface was observed and evaluated within 30 minutes.
A: The coating film immersed in water has no swelling, cracking, peeling, etc. B: The coating film immersed in water has a swelling area of less than 3%, cracking, peeling, etc.
△: Coating area immersed in water 3% or more but less than 10% swells, cracks, peeling, etc. ×: Coating area immersed in water 10% or more swells to less than 30%, cracks, peeling, etc. XX: Coat area immersed in water More than 30% swells, cracks, peels, etc.

・ Nippe Ultra Sealer III (styrene-acrylic resin-based sealer having a carboxyl group manufactured by Nippon Paint Co., Ltd.) was applied to an alkali-resistant flexible board (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m ² and left for 16 hours. (Temperature 23 ° C., 50% humidity) After that, the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a coating interval time of 3 hours. Then, it was dried and cured for 7 days to prepare an alkali resistance test plate, and immersed in a 3% aqueous solution of sodium hydroxide at 20 ° C. for 7 days. After taking out and washing with water, the state of the coating film surface was observed and evaluated within 30 minutes.
A: The coating film immersed in water has no swelling, cracking, peeling, etc. B: The coating film immersed in water has a swelling area of less than 3%, cracking, peeling, etc.
△: Coating area immersed in water 3% or more but less than 10% swells, cracks, peeling, etc. ×: Coating area immersed in water 10% or more swells to less than 30%, cracks, peeling, etc. XX: Coat area immersed in water More than 30% swells, cracks, peels, etc.

-Cleaning resistance It was carried out according to the glossy synthetic resin emulsion paint standard defined in JIS K 5660. The equipment has the function of 6.3 wet abrasion test equipment of JIS K 5600-5-11, and consists of a test tank, a soap bath, a brush, etc., and the brush reciprocates on the coating film of the test piece. Was used. The test piece was applied to a hard vinyl chloride sheet (specified in JIS K 6734) with an evaluation paint using a 6 mil applicator, and dried and cured for 7 days to prepare a wash resistance test plate.

The washing resistance test was performed as follows in accordance with the provisions of JIS K 5660, 6.13. That is, the test piece is fixed horizontally on the test stand of the test tank of the detergency test apparatus with the coating surface facing upward. Place a brush fully soaked with 0.5% soap solution on the coated surface of the test piece, drop 0.5% soap solution on the surface to be rubbed, and keep the wet surface while always brushing the painted surface. And then rub 1000 times. Thereafter, the test piece was taken out, washed with water and dried, and then the state of the coating film surface was observed and evaluated (visually).
○ With 1000 brush strokes, the paint film is not torn in the rubbed area, and the substrate is not exposed due to wear.
X: The brush was torn 1000 times, and the paint film was torn in the rubbed area and the substrate was exposed due to wear.

-Nippe Ultra Sealer III (styrene-acrylic resin-based sealer having a carboxyl group manufactured by Nippon Paint Co., Ltd.) is applied to a flexible plate with wet and cold repeatability (conforming to JIS A 5430) using a brush at a coating amount of 100 g / m ² . After standing for 16 hours (temperature: 23 ° C., humidity: 50%), the evaluation paint was applied twice at a coating interval of 3 hours using a brush at a coating amount of 100 g / m ² . Thereafter, the sample was dried and cured for 7 days to prepare a wet and cold repeatability test body, and the test was conducted according to JIS K 5600-7-4. After immersing the test piece in water at 23 ± 2 ° C. for 18 hours, immediately cool it in a thermostat kept at −20 ° C. ± 2 ° C. for 3 hours, and then in another thermostat kept at 50 ± 2 ° C. for 3 hours. Warm up. After repeating this operation seven times, the state of the coating film surface was observed and evaluated (visually).
○ There is no swelling, cracking, peeling, etc. on the coating film △ There is swelling, cracking, peeling, etc. locally on the coating film × Overall swelling, cracking, peeling, etc. on the coating film

・ Accelerated weather resistance Nippe Ultra Sealer III (styrene-acrylic resin-based sealer having a carboxyl group manufactured by Nippon Paint Co., Ltd.) is applied to a flexible board (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m ² for 16 hours. After standing (temperature: 23 ° C., humidity: 50%), the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a paint interval of 3 hours. After that, drying and curing for 7 days to prepare an accelerated weathering test plate, the specimen was taken out after 480 hours of irradiation according to JIS K 5600-7-7 (xenon lamp method), and left in the room for 1 hour. The state of the surface was observed and evaluated (visually). The chalking grade is in accordance with JIS K 5600-8-6.
○ There is no swelling, peeling, cracking, etc. when the chalking grade is 1 or less, and there is no significant change in color compared to the sample board. × Chalking grade is 2 or more, or peeling, cracking, or color change. large

-It measured in the state of evaluation paint 25 degreeC using the viscosity Stormer viscometer.

・ Gloss evaluation paint was applied to a glass plate with an applicator of 6 mil under the conditions of a temperature of 23 ° C. and a humidity of 50%, and then allowed to stand for 24 hours under the same conditions to measure the gloss value (60 degree gloss value). Here, a gloss value measuring instrument (micro-TRI-gloss manufactured by Big Chemie) was used.

(B) Matte paint Next, matt paint is assumed.

<Adjustment of pigment paste>

The above raw materials were mixed in a stainless steel container, and stirred and dispersed with a disper for 30 minutes to produce a pigment paste.

<Manufacture of paints>

With the above composition, the mixture was mixed and stirred for 30 minutes with a disper to produce a paint.

<Evaluation test method for matte paint>

・ Paint condition (in container)
Based on 4.1.2a of JIS K 5600-1-1, it carried out as follows.
If the mouth of the container is open and the surface is covered with skin, remove it and stir the contents with a spatula or a stick. Even if some of the ingredients sink to the bottom of the container, there is no particularly hard lump, scrape the bottom part little by little to dissolve the precipitate, and stir until the contents are easily uniform throughout. Sometimes it is uniform without a hard mass.
○ No abnormalities are observed × There are hard lumps, lumps, etc.

・ Coating state (coating appearance)
Nippe Ultra Sealer III (Nippon Paint Co., Ltd. styrene-acrylic resin-based sealer) is applied to a flexible board (JIS A 5430 compliant) at a coating amount of 100 g / m ² using a brush and left for 16 hours (temperature 23) Thereafter, the evaluation paint was applied ^twice with a brush at a coating amount of 100 g / m ² and a paint interval time of 3 hours. Then, after leaving for 24 hours, the state of the coating film surface was observed and evaluated (visually).
○ No abnormalities are observed in the coating film × Abnormalities such as cracks, itchiness and pinholes are observed

・ Nippe Ultra Sealer III (Nippon Paint Co., Ltd. styrene-acrylic resin-based sealer) coated on a water-resistant flexible board (JIS A 5430) with a brush at a coating amount of 100 g / m ² and left for 16 hours (Temperature 23 ° C., 50% humidity) After that, the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a coating interval time of 3 hours. Thereafter, the film was dried and cured for 7 days to prepare a water resistance test plate, and immersed in water at 20 ° C. for 7 days. After taking out and washing with water, the state of the coating film surface was observed and evaluated within 30 minutes.
A: The coating film immersed in water has no swelling, cracking, peeling, etc. B: The coating film immersed in water has a swelling area of less than 3%, cracking, peeling, etc.
△: Coating area immersed in water 3% or more but less than 10% swells, cracks, peeling, etc. ×: Coating area immersed in water 10% or more swells to less than 30%, cracks, peeling, etc. XX: Coat area immersed in water More than 30% swells, cracks, peels, etc.

・ Nippe Ultra Sealer III (styrene-acrylic resin-based sealer having a carboxyl group manufactured by Nippon Paint Co., Ltd.) was applied to an alkali-resistant flexible board (JIS A 5430 compliant) with a brush at a coating amount of 100 g / m ² and left for 16 hours. (Temperature 23 ° C., 50% humidity) After that, the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a coating interval time of 3 hours. Then, it was dried and cured for 7 days to prepare an alkali resistance test plate, and immersed in a 3% aqueous solution of sodium hydroxide at 20 ° C. for 7 days. After taking out and washing with water, the state of the coating film surface was observed and evaluated within 30 minutes.
A: The coating film immersed in water has no swelling, cracking, peeling, etc. B: The coating film immersed in water has a swelling area of less than 3%, cracking, peeling, etc.
△: Coating area immersed in water 3% or more but less than 10% swells, cracks, peeling, etc. ×: Coating area immersed in water 10% or more swells to less than 30%, cracks, peeling, etc. XX: Coat area immersed in water More than 30% swells, cracks, peels, etc.

-Washing resistance It was carried out in accordance with the synthetic resin emulsion paint standard defined in JIS K 5663. The equipment has the function of 6.3 wet abrasion test equipment of JIS K 5600-5-11, and consists of a test tank, a soap bath, a brush, etc., and the brush reciprocates on the coating film of the test piece. Was used. The test piece was applied to a hard vinyl chloride sheet (specified in JIS K 6734) with an evaluation paint using a 6 mil applicator, and dried and cured for 7 days to prepare a wash resistance test plate.

The washing resistance test was performed as follows in accordance with the provisions of 7.12 of JIS K 5663. That is, the test piece is fixed horizontally on the test stand of the test tank of the detergency test apparatus with the coating surface facing upward. Place a brush fully soaked with 0.5% soap solution on the coated surface of the test piece, drop 0.5% soap solution on the surface to be rubbed, and keep the wet surface while always brushing the painted surface. Cycle 500 times and rub. Thereafter, the test piece was taken out, washed with water and dried, and then the state of the coating film surface was observed and evaluated (visually).
○ After 500 reciprocations of the brush, the paint film is torn in the rubbed area, and no exposed substrate due to wear is observed. × With the 500 reciprocations of the brush, the paint film is torn in the rubbed area and exposed to the substrate due to wear. Is accepted

・ Nippe Ultra Sealer III (styrene-acrylic resin-based sealer having a carboxyl group manufactured by Nippon Paint Co., Ltd.) is applied to the accelerated weather-resistant flexible board (JIS A 5430) with a brush at a coating amount of 100 g / m ² for 16 hours. After standing (temperature: 23 ° C., humidity: 50%), the evaluation paint was applied twice with an application amount of 100 g / m ² using a brush for a paint interval of 3 hours. Thereafter, drying and curing for 7 days to prepare an accelerated weathering test plate, the specimen was taken out after 240 hours of irradiation according to JIS K 5600-7-7 (xenon lamp method), and left in the room for 1 hour. The state of the surface was observed and evaluated (visually). The chalking grade is in accordance with JIS K 5600-8-6.
○ There is no swelling, peeling, cracking, etc. when the chalking grade is 1 or less, and there is no significant change in color compared to the sample board. × Chalking grade is 2 or more, or peeling, cracking, or color change large

-It measured in the state of evaluation paint 25 degreeC using the viscosity Stormer viscometer.

・ Gloss evaluation paint was applied to a glass plate with an applicator of 6 mil under the conditions of a temperature of 23 ° C. and a humidity of 50%, and then allowed to stand for 24 hours under the same conditions to measure the gloss value (60 degree gloss value). Here, a gloss value measuring instrument (micro-TRI-gloss manufactured by Big Chemie) was used.

Next, various other examples will be described.

[Other examples]

<About starch>

Anything is applicable. Examples include corn starch, waxy corn starch, high amylose corn starch, tapioca starch, potato starch, sweet potato starch, wheat starch, rice starch and the like, processed starch, dietary fiber, and the like.

Here, the processed starch includes a derivative in which a functional group is introduced into an anhydroglucose residue of a raw material starch, and a starch whose viscosity is reduced by acid treatment or the like. An example is shown below.

Etherified starch: Hydrophilic groups introduced to improve stability in aqueous solution, hydrophobic groups introduced to make the starch film water resistant, or lipophilic groups introduced, and ions introduced There are things with improved ionicity. Depending on the type of functional group, it can be divided into carboxymethyl starch, hydroxyalkyl starch, cationic starch and the like.

Esterified starch: A derivative obtained by reacting starch with an organic acid, an inorganic acid, or a salt thereof to bond a functional group. Depending on the type of acid used, it can be divided into starch acetate, phosphate starch and the like.

Cross-linked starch: A derivative in which polyfunctional groups are bonded between hydroxyl groups of two or more starches. Epichlorohydrin cross-linked starch, phosphate cross-linked starch, etc.

Graft copolymerized starch: A starch obtained by chemically combining starch with other organic polymer materials such as polyacrylamide, polyacrylic acid, polyvinyl acetate, polyacrylonitrile.

The processed starch also includes low-viscosity starch that has been subjected to oxidation, hydrolysis, roasting, and physical processing, such as oxidized starch, acid-treated starch, and dextrin.

<Molecular weight of starch>

The weight average molecular weight was adopted as the starch molecular weight. The molecular weight was measured by the GPC method under the following conditions.
Column: shodex OHpack SB-860M HQ x2
Guard column: shodex OHpack SB-G
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 1.0 mL / min Injection volume: 50 μL
Sample: 0.5 w / w% sample dissolved in 50 mM sodium nitrate aqueous solution Standard: Pullulan

<About sugar>

Monosaccharides such as D-glucose, D-fructose, D-mannose and D-galactose, oligosaccharides such as maltose, sugar (sucrose), panose, maltotriose and isomaltotriose (consisting of 2 to 6-mer) Oligosaccharides) and modified products thereof can be mentioned as examples. Examples of sugars are not particularly limited, and sugars, sugar alcohols such as sugar, glucose, isomerized sugar, maltose, trehalose, sorbitol, maltitol, lactitol, erythritol, various oligosaccharides, and mixtures thereof are used. be able to. Examples of the oligosaccharides include maltooligosaccharides (preferably having a polymerization degree of 3 to 7), nigerooligosaccharides, isomaltoligosaccharides, panose oligosaccharides, gentiooligosaccharides, fructooligosaccharides, galactooligosaccharides, xylooligosaccharides, whey oligosaccharides and their A syrup etc. can also be mentioned.

<About the monomer having a copolymerizable functional group>

Examples of the carboxyl group-containing monomer (monomer) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid and the like.

Examples of the styrene monomer include styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, vinyltoluene and the like.

Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples include -to, 2,3-dihydroxypropyl (meth) acrylate, glycerol (meth) acrylate and the like.

Examples of (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Examples include isobornyl (meth) acrylate, benzyl (meth) acrylate and the like.

Examples of the sulfonic acid group-containing monomer include 2- (meth) acryloxyethyl-1-sulfonic acid, 3- (meth) acryloxypropyl-1-sulfonic acid, and 3- (meth) acryloxy-2-hydroxypropyl- Examples include 1-sulfonic acid, 2-acrylamido-2-methylpropane-1-sulfonic acid, aryl sulfonic acid, and metal sulfonic acid.

Examples of the acid amide group- or N-alkyl group-substituted amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N Examples include methylol (meth) acrylamide, methylenebis (meth) acrylamide, and the like.

Examples of amino group-containing monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-methylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, An example is N-diethylaminopropyl (meth) acrylamide.

Examples of the carbonyl group-containing monomer include acrolein, diacetone acrylamide, diacetone (meth) acrylate, vinyl methyl ketone, and the like.

Other monomers having a functional group include (meth) acryloyloxyethyl acid phosphate, acid phosphooxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, 3,4 Epoxy cyclohexyl (meth) acrylate, divinylbenzene having 2 to 3 polymerizable double bonds, diallyl phthalate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylo -Lumetanetetra (meth) acrylate etc. That.

Examples of vinyl monomers include (meth) acrylonitrile, vinyl acetate, vinyl propionate, vinyl versatate, and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, glycidyl (meth) allyl ether, 3,4-epoxycyclohexyl (meth) acrylate, and the like.

<Glass transition temperature>

The glass transition temperature (Tg) of the above monomer is preferably selected from −50 to 50 ° C. from the viewpoint of the film forming properties of the formed coating film and the properties of the coating film such as water resistance and durability.

The glass transition temperature (absolute temperature) is a value calculated from the following equation.
1 / Tg = W ₁ / T ₁ + W ₂ / T ₂ +... W _n / T _n
Here, W ₁ , W ₂ ... W _n in the formula are the weight% of each monomer (= (blending amount of each monomer / total weight of monomer) × 100), and T ₁ , T _{2. n} is the glass transition temperature (absolute temperature) of the homopolymer of each monomer.

<About surfactants>

(Anionic)
Examples of the anionic surfactant include oleate, laurate, dodecylbenzenesulfonate, alkylnaphthalenesulfonate, dialkylsulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl allyl ester. Examples include -tersulfate, polyoxyethylene dialkyl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, and the like.

(Cationic)
Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, triethanolamine difatty acid quaternary salt, N-hydroxyethyl-N-methylpropanediamine fatty acid monoester amide salt, alkylbenzyldimethylammonium salt, Examples thereof include alkyl ammonium salts.

(Nonionic)
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, poly (oxyethylene-oxypropylene) block copolymer, polyethylene glycol fatty acid ester, polyoxyethylene sorbitan. A fatty acid ester etc. can be mentioned as an example.

(Reactivity)
Examples of reactive surfactants include polyethylene glycol mono (meth) acrylates of various molecular weights (different EO addition moles), polyoxyethylene alkylphenol ether (meth) acrylates, 2- Examples thereof include ammonium (meth) acryloyloxyethyl sulfonate, monomaleic acid ester of polyoxyethylene glycol and derivatives thereof, polyoxyalkylene, alkyl ether, and phosphoric acid ester.

(Polymer)
Examples of the polymeric surfactant include polyvinyl alcohol and its derivatives, polyacrylamide, poly (meth) acrylic acid neutralized product, polyhydroxyethyl (meth) acrylate, polyhydroxypropyl (meth) acrylate. Examples thereof include casein and casein.

(Bisexual)
Examples of amphoteric surfactants include amidopropyl betaine, carboxybetaine, sulfobetaine, aminocarboxylic acid, imidazoline derivatives, phospholipids, and phosphate esters containing tertiary nitrogen.

<About polymerization initiator>

The emulsion polymerization reaction can be reacted using a radical polymerization initiator. Radical polymerization initiators generate radicals by heat or reducing substances to cause addition polymerization of vinyl monomers. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds, etc. is there. For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroxide, t-butyl peroxybenzoate, 2.2-azobisisobutyronitrile, 2.2-azobis (2-diaminopropane) ) Hydrochloride, 2.2-azobis (2.4-dimethylvaleronitrile), etc., preferably a water-soluble polymerization initiator. If acceleration of polymerization rate or low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous sulfate, ferrous chloride, vitamin C, formaldehyde sulfooxylate salt is used in combination with a radical polymerization initiator. be able to.

<About the neutralizing agent>

The resin composition of the present invention can be used even without being neutralized. Further, the resin composition of the present invention can be used even after neutralization. Both storage stability was good. Examples of neutralizing agents that can be used include ammonia, inorganic salts of alkali metal hydroxides, and organic bases such as organic amines. Specific examples include aqueous ammonia, sodium hydroxide, potassium hydroxide, monoethanolamine, dietanolamine, triethanolamine, morpholine and the like.

<About additives>

In the resin composition of the present invention, film forming aids, plasticizers, fillers, pigments, viscosity modifiers, antifoaming agents, preservatives, dispersants, antioxidants, freezing, which are known additives as necessary. Inhibitors, flameproofing agents, flame retardants, rustproofing agents and the like can be blended and used within a range not impairing the effects of the present invention.

<Silane coupling agent>

Examples of the silane coupling agent that is copolymerized with the monomer component constituting the acrylic copolymer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ- (meth) acryloxypropylmethyldimethoxy. Examples include silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and the like.

Epoxy group-containing silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, epoxy group-containing alkoxysilane oligomer and the like can be mentioned as examples.

Examples of mercapto group-containing silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethyldimethoxysilane, γ-mercaptopropyltrimethyldiethoxysilane, mercapto group-containing alkoxysilane oligomers, etc. As an example.

Examples of amino group-containing silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl). ) -Γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

Examples of the isocyanate group-containing silane coupling agent include γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.

<Chain transfer agent>

As chain transfer agents, methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid and esters thereof, 2-ethylhexylthio Mercaptans such as glycol and octyl thioglycolate; Alcohols such as methanol, ethanol, propanol, n-butanol, isopropanol, t-butanol, hexanol, benzyl alcohol and allyl alcohol; Halogenated carbonization such as chloroethane, fluoroethane and trichloroethylene Hydrogens: acetone, methyl ethyl ketone, cyclohexanone, acetophenone, acetaldehyde, propio Aldehydes, n- butyraldehyde, furfural, carbonyls, such as benzaldehyde; methyl-4-cyclohexene-1,2-dicarboxylic acid anhydride, such as α- methylstyrene may be mentioned by way of example.

<Crosslinking agent>

Polyglycidyl compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane Examples thereof include trimethylolpropane polyglycidyl ether and diglycerol polyglycidyl ether.

Examples of polyisocyanate compounds include tolylene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and prepolymers modified from these.

Examples of the polyaziridine compound include 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridylurea, 1,1 ′-(hexamethylene) bis-3,3-aziridylurea, ethylenebis- (2-aziridinylpropionate), tris (1-aziridinyl) phosphine oxide, 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris- (2-aziridinylpropio) Example).

<Core shell>

About the starch containing resin composition of this invention, a core part and a shell part can also be provided by the method generally called a core / shell type emulsion. By giving a difference in the resin composition of each layer, or by making a difference in the set Tg at the core portion / shell portion, it is possible to form a film with less stickiness while maintaining low temperature film-forming properties, etc. It is possible to create a high-performance film.

At this time, the Tg of the core part and the shell part is preferably −50 ° C. or more and 80 ° C. or less, and the total is preferably −50 ° C. or more and 50 ° C. or less.

<Regarding the coating composition>

The coating composition using the emulsion resin in the present embodiment, in addition to the emulsion resin, if necessary, a curing agent, a color pigment, an extender pigment, a pigment dispersant, an antifoaming agent, a thickener, an ultraviolet absorber, Light stabilizers, antifreezing agents, film-forming aids, fungicides, preservatives and the like can also be included.

The curing agent is not limited, and those well known by those skilled in the art, which are capable of crosslinking reaction with reactive functional groups of the emulsion resin, such as isocyanate compounds, adipic dihydrazide, carbodiimide group-containing compounds, epoxy group-containing compounds, etc. You can choose. Two or more of these may be used.

The color pigment is not particularly limited, and examples thereof include inorganic pigments such as chrome yellow, yellow iron oxide, iron oxide, carbon black, and titanium dioxide; azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo Examples thereof include organic pigments such as pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. Examples of the extender pigment include calcium carbonate, precipitated barium, clay, talc, and diatomaceous earth.

<Formation method of coating film>

The base material is not particularly limited, for example, iron, stainless steel, aluminum and the like, metal materials of the surface treatment product, cement base materials such as cements, limes, gypsums, polyvinyl chlorides, polyesters, polycarbonates, Examples thereof include plastic base materials such as acrylics and biodegradable polylactic acids, and buildings, building materials, and structures made of these.

The application method is not particularly limited, and can be performed on various substrates by, for example, brush coating, roller coating, roll coater, curtain flow coating, spray coating, knife edge coating, dip coating, electrodeposition coating, or the like. . After coating, the coating film can be obtained by drying at room temperature or heating. The coating amount, the coating film thickness, and the drying time can be arbitrarily set according to the type of coating material, the base material to be applied, and the like.

[Usage]

Provided is a starch-containing resin composition having a low environmental load that can be used in various applications such as coating agents such as paints, films, plastics, glass, paper, fibers, leather, adhesives, adhesives, and the like.

It is not limited as a paint use, For example, it can be used for undercoat, intermediate coat, and topcoat. It can be used not only in the field of construction and building materials, but also in automobiles / industrial, interior or exterior. Examples of the form of the paint include clear paint, enamel paint, filler and the like. As described above, it can be applied to various coating methods. Examples include brush coating, roller coating, porous roller coating, tampo coating, spatula coating, trowel coating, air spray coating, airless spray coating, curtain flow coating, flow coating, roll coater coating, iron coating, rolling coating, Examples thereof include centrifugal coating, electrostatic coating, and electrodeposition coating. The present embodiment can also be used to provide a role of painting such as a sealer, a primer, a filler, and a top coat. Furthermore, anticorrosion, antiseptic, antifungal, antproof, antifouling, waterproof, sterilization, chemical resistance, fire resistance, aesthetics, smoothing, gloss, coloring, pattern, design, landscape creation, functional addition, heat insulation, water repellent The present embodiment can also be used for purposes such as fluorescence, camouflage, and adsorption of harmful chemical substances.

[Interpretation of rights, etc.]

The present invention has been described above with reference to specific embodiments. However, it is obvious that those skilled in the art can make modifications or substitutions of the embodiments without departing from the gist of the present invention. That is, the present invention has been disclosed in the form of exemplification, and the contents described in the present specification should not be interpreted in a limited manner. In order to determine the gist of the present invention, the claims section described at the beginning should be considered.

It will also be appreciated that illustrative embodiments of the invention achieve the above objects, but that many modifications and other examples can be made by those skilled in the art. The elements or components of each embodiment described in the claims, specification, drawings, and description may be employed in combination with one or more other elements. The claims are intended to cover such modifications and other embodiments, which are within the spirit and scope of the present invention.

Claims (5)

A step of mixing a starch , a monomer and a sugar to obtain a monomer emulsion for emulsification;
The monomer emulsion is reacted, have a obtaining a polymer dispersion containing the polymer composition,
The sugar is a 10-mer or less,
The step of obtaining the polymer dispersion is not less than the gelatinization start temperature of the starch,
The method for producing a polymer composition , wherein the step of obtaining the monomer emulsion is less than the starch gelatinization start temperature . 2. The method for producing a polymer composition according to claim 1, wherein the starch is in a slurry form in the monomer emulsion. 2. The method for producing a polymer composition according to claim 1, wherein the monomer is a copolymerizable unsaturated monomer. 2. The method for producing a polymer composition according to claim 1, wherein the polymer composition is used for coatings. 2. The method for producing a polymer composition according to claim 1, wherein the polymer composition is used for an adhesive.