JP6315625B2 - Method for producing surfactant, surfactant and aqueous coating resin - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for producing a surfactant, a surfactant, and an aqueous coating resin, and in particular, a method for producing a surfactant capable of imparting good water resistance and weather resistance to a resin coating film, the surfactant, and an aqueous coating resin. I will provide a.

The conventional emulsion polymerization reaction is an important method for preparing an aqueous dispersion polymer which may be, for example, a styrene resin or a propenyl resin. In addition, the stability of the emulsion polymerization reaction system (for example, aggregation rate, emulsion particle size or storage stability, etc.) varies depending on the surfactant used in the emulsion polymerization reaction, and affects the properties of the resulting polymer. (For example, refer to Patent Documents 1 and 2) .

US Pat. No. 6,265,495 US Pat. No. 6,362,364

  The above surfactants are generally anionic surfactants such as alkyl sulfates, alkylphenyl sulfates, polyoxyethylene alkyl sulfates, or polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl sulfates, and the like. Nonionic surfactants such as oxyethylene fatty acid esters may be used. However, defects such as too many emulsion bubbles during the reaction or remaining in the film in which the surfactant is formed in the free state after the reaction are all water resistance, weather resistance, heat resistance and adhesion of the resulting resin film. The film physical properties such as

  In order to effectively solve the above drawbacks, in general, a reactive group is introduced into the molecular structure of the surfactant to improve the reactivity between the surfactant and the reactive monomer, and further the polymerization of the emulsion polymerization reaction system. Increase stability. Thereby, after completion of the emulsion polymerization reaction, the surfactant does not remain in the film in a free state, and further, the physical properties, water resistance, adhesion, etc. of the obtained coating film do not deteriorate.

  However, when a reactive group is to be introduced into the molecular structure of the surfactant, a chemical modification reaction to the surfactant is required. However, this chemical modification reaction generally generates a bond between the reactive group and the surfactant using a solvent as a medium, particularly when the reactive group is an acrylic acid group. For this reason, this chemical modification reaction generates a large amount of waste solvent and further pollutes the environment. Furthermore, in order to improve the purity of the product, it is necessary to purify and purify the product resulting from the reaction (for example, alkali washing treatment and water washing treatment), and a large amount of waste alkaline liquid and waste water are generated. Give more load.

  In view of this, it is desired to provide a new method for producing a reactive surfactant and its use in which the conventional method for producing a surfactant and the disadvantages of its use are improved.

  Therefore, according to one embodiment of the present invention, a surfactant having a specific structure can be obtained by selective synthesis of a monomer, and can be used for an addition reaction of an unsaturated double bond monomer. Provided is a method for producing a surfactant that imparts excellent water resistance, weather resistance, glossiness and pigment dispersibility.

  Another aspect of the present invention provides a surfactant obtained by the above method.

  Still another embodiment of the present invention provides a polymer material obtained by a monomer mixture containing the above surfactant.

According to one aspect of the present invention, a method for producing a surfactant is provided. In this production method, first, a first reaction is performed on a mixture containing an aryl ether compound represented by the following formula (I) and a glycidyl ether compound represented by the formula (II) but not containing a solvent. 1 intermediate product is formed.


In formula (I), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and an oxygen atom and a hydrogen atom of R ₂ and R ₃ represent Combined, Y is


A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100.

In formula (II), R ₄ is


Wherein C═O is bonded to R ₅ , x is 0 or 1, and R ₅ is a group having a carbon-carbon double bond.

  Next, a second intermediate product is formed by performing a second reaction on the first intermediate product and the acid group compound.

  Subsequently, a surfactant is produced by performing a neutralization reaction on the second intermediate product.

  According to one embodiment of the invention, the above mixture comprises a catalyst.

  According to another embodiment of the present invention, the acid group compound includes a sulfonic acid compound, a phosphoric acid compound, or a carboxylic acid compound.

  According to still another embodiment of the present invention, the neutralizing agent for the neutralization reaction may include an alkali metal compound, an amine compound, an alkylamine compound, or an alkyl-substituted or unsubstituted alcoholamine compound.

According to another aspect of the invention, a surfactant is provided. This surfactant may be produced by the above method and have a structure represented by the following formula (III).


In Formula (III), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and the oxygen atoms of R ₂ and R ₃ are each —CH ₂ — Or R ₆ and R ₄ is


Wherein C═O is bonded to R ₅ and x is 0 or 1, R ₅ is a group having a carbon-carbon double bond, and R ₆ is an anionic group. , Y is


A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100.

According to one embodiment of the present invention, anionic groups _mentioned, -SO _{3 M,} -PO 3 M 2, but may include _-PO 3 MH or -COOM, but are not limited to, and M is , A hydrogen atom, an alkali metal atom, an ammonium group, an alkylammonium, or an alkyl-substituted or unsubstituted ammonium alcohol group.

  According to yet another aspect of the invention, a polymeric material is provided. This polymer material is produced by performing a polymerization reaction with a monomer mixture containing an unsaturated compound and a surfactant. However, this polymerization reaction may be an emulsion polymerization reaction, a solution polymerization reaction, a suspension polymerization reaction, and a photocuring polymerization reaction.

  According to one embodiment of the present invention, the unsaturated compound includes an acrylic resin or styrene.

  The production method using the surfactant of the present invention and the use thereof include the synthesis of a surfactant having a specific structure by a specific monomer, and the addition of the surfactant by a terminal double bond group and an unsaturated compound. By generating a reaction and forming a covalent bond, good weather resistance can be imparted to the resin material.

The following description made with reference to the accompanying drawings is intended to make the embodiments of the present invention and merits thereof easier to understand. It should be noted that each feature is for illustration purposes only and is not drawn to scale. The description of the related drawings is as follows.
It is a flowchart which shows the manufacturing method of surfactant based on one Example of this invention.

  In the following, the production and use of embodiments of the present invention will be discussed in detail. However, it should be understood that the embodiments provide a number of usable inventive concepts that may be implemented in a variety of specific contexts. The particular embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the invention.

  Please refer to FIG. FIG. 1 is a flowchart showing a method for producing a surfactant according to one embodiment of the present invention. In one example, the manufacturing method 100 first forms a first intermediate product by performing a first reaction on the mixture, as shown in step 110.

The above mixture comprises an aryl ether compound represented by formula (I) below and a glycidyl ether compound represented by formula (II) below.


In formula (I), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and an oxygen atom and a hydrogen atom of R ₂ and R ₃ are bonded to each other. , Y is


A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100.

  Specific examples of the alkylenoxy group having 2 to 4 carbon atoms include ethyleneoxy group, propyleneoxy group, isopropenyloxy group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, or any combination of the above functional groups. However, it is not limited to these.

The R ₂ and R ₃ segments described above can effectively improve the hydrophilicity of the obtained surfactant, and further the emulsifying ability of the surfactant with respect to the reaction monomer (monomer) and the physical properties of the resulting resin coating film. (For example, chemical stability of resin emulsion) is improved.

When the carbon number of R ₂ or R ₃ is larger than 4, the resulting surfactant has the disadvantage that it is too lipophilic, reduces the emulsifying ability of the surfactant to the reactive monomer, and reduces the aggregation rate. In addition, the polymerization reaction by the surfactant is made difficult. When the carbon number of R ₂ or R ₃ is smaller than 2, the resulting surfactant has a disadvantage that it is too hydrophilic, and lowers the water resistance of the formed photocured film. R ₂ and R ₃ each preferably represent an alkylenoxy group having 2 to 3 carbon atoms.

  When the sum of m and n is less than 2, the resulting surfactant has a high viscosity, which reduces its hydrophilicity and further significantly reduces its emulsifying ability with respect to the reactive monomer. This lowers the stability of the reaction system, and causes disadvantages such as too many emulsion polymerization aggregates, a large particle size of emulsion particles and a decrease in conversion.

  When the sum of the above m and n is larger than 100, the segment length of the alkylenoxy group is too long, the content of the anionic group of the resulting surfactant is reduced, and the surfactant is a nonionic surfactant. This lowers the stability of the emulsion polymerization reaction, thereby causing adverse effects such as an increase in emulsion polymerization aggregates, an increase in emulsion particle size and poor storage stability.

  In one embodiment, the sum of m and n may be an integer of 5 to 50, and more preferably an integer of 5 to 30. In another embodiment, the sum of a and b may preferably be 6.

The aryl ether compound shown in formula (I) may be a polyoxyethylene polyaryl ether, but due to its compound structure, the individual numbers m and n cannot be reliably defined. However, from the NMR spectrum of the aryl ether compound represented by formula (I), those skilled in the art can clearly define the total content of R ₂ and R ₃ in the aryl ether compound (that is, the sum of m and n).

In formula (II), R ₄ is


Wherein C═O is bonded to R ₅ , x is 0 or 1, and R ₅ is a group having a carbon-carbon double bond.

  When x = 0, the obtained surfactant has an olefin group structure, and when x = 1, the obtained surfactant has an acrylic group structure. However, when x = 0 or 1, an olefin group or an acrylic group having a double bond structure may undergo an addition reaction with an unsaturated monomer, thereby binding a subsequent unsaturated monomer to a surfactant. Further, the water resistance, weather resistance and adhesiveness of the resulting resin coating film are improved.

  The group having a carbon-carbon double bond may include an alkenyl group that is substituted or unsubstituted with at least one group and has 2 to 4 carbon atoms, provided that the at least one group is an ethenyl group. , Propenyl groups, isobutenyl groups, acrylates, methacrylates or other suitable groups.

  The group having a carbon-carbon double bond may preferably include an alkenyl group having 2 to 4 carbon atoms. The group having a carbon-carbon double bond may more preferably be an alkenyl group having 3 carbon atoms.

  The glycidyl ether compound represented by formula (II) may include, but is not limited to, allyl glycidyl ether, glycidyl methacrylate, isobutenyl glycidyl ether, other suitable glycidyl ether compounds, or any combination of the above compounds.

  The amount of the glycidyl ether compound represented by the formula (II) used may be 1.0 part by weight to 15.0 parts by weight with respect to 100 parts by weight of the aryl ether compound represented by the formula (I). The amount is preferably 5.0 parts by weight to 10.0 parts by weight, and more preferably 6.0 parts by weight to 8.0 parts by weight.

  In one embodiment, according to the reaction mechanism of the first reaction, by cleaving the cyclic structure of the glycidyl ether compound represented by formula (II) and further forming a bond with the allyl ether compound represented by formula (I) A first intermediate product can be formed.

  When performing the first reaction, the mixture may contain a catalyst so as to reduce the reaction temperature and reaction time in order to increase the reaction rate. The above catalyst may include, but is not limited to, boron trifluoride, boron trifluoride etherate, potassium hydroxide, sodium hydroxide, alumina, triethylamine, quaternary ammonium salts or other suitable catalysts. Not.

  The amount of the catalyst used may be 0.1% by weight to 8.0% by weight with respect to 100% by weight of the aryl ether compound represented by the formula (I), and 2.0% by weight to 6. 0 weight% is preferable and 3.0 weight%-5.0 weight% is more preferable.

  When the above mixture contains a catalyst, the reaction temperature of the first reaction may be 60 ° C. to 90 ° C., and the reaction time may be 4 hours to 20 hours. Preferably, the reaction temperature of the first reaction is 70 ° C. to 85 ° C., and the reaction time is 4 hours to 10 hours. More preferably, the reaction temperature of the first reaction is 70 ° C. and the reaction time is 8 hours.

  In one embodiment, the above mixture does not contain an organic solvent, does not require a solvent removal purification step, and more effectively reduces reaction waste and reduces environmental pollution. Gently saves energy. Furthermore, since the epoxide ring-opening reaction is performed with the aryl ether compound and the glycidyl ether compound after the first reaction, the first intermediate product formed by the first reaction has high purity, It does not require a purification and purification process such as an alkali washing process and a water washing process, and further achieves energy saving and waste reduction, thereby reducing energy consumption. Therefore, the production method of the present invention is a new process that is natural and environmentally friendly.

The first intermediate product obtained above may have a structure represented by the following formula (IV).


In formula (IV), the definitions of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Y, a, b, m and n are as described above and will not be described here.

After performing step 110, as shown in step 120, the second reaction shown in the following formula (V) is performed by performing the second reaction on the first intermediate product and the acid group compound. An intermediate product is obtained.


In formula (V), the definitions of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Y, a, b, m and n are as described above and will not be described here. However, depending on the different acid group compounds used, R ₇ may represent different acid groups.

  The acid group compounds may include, but are not limited to, sulfonic acid compounds, sulfuric acid compounds, phosphoric acid compounds, carboxylic acid compounds, other suitable acid group compounds, or any combination of the above compounds. The acid group compound is preferably a sulfonic acid compound.

  When the above acid group compound is a sulfonic acid compound, a sulfuric acid compound, a phosphoric acid compound and a carboxylic acid compound, the obtained surfactant may have an anionic property, and is an emulsifier or a solution polymerization reaction in an emulsion polymerization reaction. The polymer resin may be further modified, and the polymer resin may be further modified, whereby different interface characteristics (for example, lowering the interfacial tension of the polymer resin and the polymer resin) To improve functions such as hydrophilicity, wettability, pigment dispersibility, and water resistance, weather resistance and adhesion of the resulting coating film).

  This acid group compound may undergo an esterification reaction with an unterminated hydroxyl group of the first intermediate product, and the second intermediate product has an acid group.

In one embodiment, R ₇ may represent a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, a carboxylic acid group, other suitable acid groups, or any combination of the above groups.

  The total amount of the first intermediate product used is 100 parts by weight, and the amount of the acid group compound used may be 1.0 to 15.0 parts by weight, preferably 2.0 parts by weight to 10.0 parts by weight, more preferably 4.0 parts by weight to 7.0 parts by weight.

  When the amount of the acid group compound used is smaller than 1.0 part by weight, the anionization conversion rate of the obtained surfactant becomes insufficient during the reaction, and the anion content of the surfactant is decreased. Further, the aggregate during the emulsion polymerization reaction increases, and as a result, the conversion rate of the emulsion polymerization reaction decreases. When the amount of the acid group compound used is larger than 15.0 parts by weight, the time for achieving the predetermined conversion rate can be shortened, but the resulting second intermediate product is difficult to filter and the yield is low. , Waste increases.

After step 120, as shown in step 130 and step 140, the second intermediate product is neutralized to obtain a surfactant represented by the following formula (III).


In formula (III), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Y, a, b, m and n are as described above, and will not be described here. R ₆ represents an anionic group.

  In one embodiment, the neutralizing agent for the neutralization reaction may be ammonia water, alkali metal compounds, amine compounds, alkylamine compounds, alkyl-substituted or unsubstituted alcoholamine compounds, other suitable basic compounds, or any of the above materials. Mixtures may be included.

When the acid group compound and neutralizing agent in the second reaction are different, R ₆ may represent —SO ₃ M, —PO ₃ M ₂ , —PO ₃ MH, or —COOM, where M is a hydrogen atom , An alkali metal atom, an ammonium group, an alkyl ammonium, or an alkyl-substituted or unsubstituted ammonium alcohol group.

  The above neutralization reaction can neutralize the terminal acid group of the second intermediate product, so that the stability of the resulting surfactant can be improved and can be stably applied to high temperature and high humidity environments. , Can improve the stability of products used effectively. Next, the neutralized surfactant has an anionic group and can be modified with respect to the resin, and more effectively the water resistance, weather resistance, glossiness, pigment dispersibility and storage stability of the resin. Etc., and the interface characteristics of the resin can be adjusted to satisfy various usage needs.

  In one embodiment, when the neutralizing agent is aqueous ammonia, ammonia gas release (escape) due to the neutralization reaction occurs, but the resulting surfactant can still have good water resistance.

  Preferably, when the neutralizing agent is an alkyl-substituted or unsubstituted alcohol amine compound, the alkyl-substituted or unsubstituted alcohol amine compound has more preferable stability, so that the neutralization reaction may release ammonia gas ( Escape) does not occur, effectively reduces damage to the operator and the environment due to the process, and has favorable weather resistance.

  When the alkyl-substituted or unsubstituted alcohol amine compound is a secondary alcohol amine compound, the resulting alkylenoxy group derivative has more preferable temporal stability.

  In the obtained surfactant, a polycyclic structure composed of a functional group bonded to a benzene ring having an aryl ether structure contributes to an improvement in pigment dispersibility by the surfactant. Therefore, when this surfactant is used in the coating process, the pigment added to the coating can be uniformly dispersed in the coating to improve the appearance of the coating.

  In one embodiment, the resulting surfactant may be used in an emulsion polymerization reaction to synthesize an aqueous paint resin as an emulsifier, the emulsion polymerization reaction reacts with a reactive monomer mixture, and This reaction monomer mixture contains the unsaturated compound and the resulting surfactant.

  In the above emulsion polymerization reaction process, this unsaturated compound undergoes an addition reaction with the terminal double bond group of the emulsifier (ie, the surfactant of the present invention), so that the unsaturated compound and the surfactant of the present invention are converted. By forming a bond, the surfactant of the present invention is not liberated in the emulsion system, and the stability of the emulsion polymerization reaction and the water resistance and weather resistance of the resulting resin coating can be improved.

  In one use evaluation example, the unsaturated compound is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, methyl methacrylate, methacrylic acid. Ethyl, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, styrene, dimethyl styrene, tert-butyl styrene, other suitable unsaturated compounds or any combination of the above compounds Although it may include, it is not limited to these.

  In one embodiment, the surfactants of the present invention may be used in reaction mechanisms that can cause addition reactions to solution polymerization reactions, suspension polymerization reactions, photocuring reactions or other unsaturated double bonds. .

  However, the amount of the surfactant used may be 0.5 to 5.0 parts by weight, or 1.0 to 4 parts by weight with respect to 100 parts by weight of the total amount of unsaturated compounds. It is preferably 0.0 parts by weight, and more preferably 1.5 parts by weight to 3.0 parts by weight.

  In the above polymerization addition reaction of the reaction monomer mixture, when the amount of the surfactant used is less than 0.5 parts by weight, the amount of the surfactant used is too small and the reaction system stability is likely to be deteriorated. The phenomenon that the conversion rate decreases due to the excessive amount of aggregates appears, and further affects the physical properties of the entire resin coating film to be obtained.

  When the usage-amount of surfactant is larger than 5.0 weight part, too much surfactant will reduce the surface characteristic of the resin coating film obtained. However, when this polymer emulsion is used to form a polymer film by coating, the surfactant migrates to the surface of the polymer film over time and forms bonds with the remaining unsaturated compounds. Reduce the surface properties of the molecular film.

  In one embodiment, the obtained resin emulsion is coated on the surface of a substrate and forms a continuous coating layer by heat drying and curing.

  In one embodiment, the substrate may comprise an optical film, glass substrate, plastic substrate, wood board substrate, solar panel, other suitable substrate or any mixture of the above substrates, It is not limited to.

  The surfactant of the present invention has an anionic group, and the double bond group at the end of the surfactant may form a bond with the unsaturated compound. In that case, the resulting resin coating film is good It has excellent water resistance and weather resistance.

  In one example of use, the reactive surfactant of the present invention may be used in the paint industry to synthesize an emulsifier used in an aqueous resin emulsion polymerization reaction or used in a solution polymerization reaction of an oil-containing resin. By synthesizing the modifier, it is possible to impart excellent physical properties such as water resistance, weather resistance, and adhesiveness to the resulting resin coating film.

  Hereinafter, the use of the present invention will be described by way of examples, but this is not intended to limit the present invention, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Can be added.

(Preparation of surfactant)
[Preparation Example S-1]
First, 100.0 parts by weight of polyoxyethylene polyaryl ether, 6.5 parts by weight of glycidyl methacrylate and 3.0 parts by weight of potassium hydroxide were added to the reaction flask. Next, the temperature was raised to 70 ° C. to carry out the first reaction. After 6 hours to 10 hours, the first intermediate product of Preparation Example S-1 was obtained. Subsequently, 5.5 parts by weight of sulfamic acid (NH ₂ SO ₃ H) was added to the first intermediate product, and the temperature was raised to 80 ° C. to carry out a second reaction. After 6-8 hours, a second intermediate product was obtained. The second intermediate product was neutralized with 0.5 part by weight of ammonia water (NH ₄ OH) to obtain the surfactant of Preparation Example S-1 represented by the following formula (III-1).


In formula (III-1), the definitions of R ₁ and Y are as described above and will not be described here. a represents 2, b represents 2, and the sum of m and n was 30.

[Preparation Example S-2]
First, 100.0 parts by weight of polyoxyethylene polyaryl ether, 9.5 parts by weight of glycidyl methacrylate and 3.0 parts by weight of potassium hydroxide were added to the reaction flask. Next, the temperature was raised to 70 ° C. to carry out the first reaction. After 6 to 10 hours, the first intermediate product of Preparation Example S-2 was obtained. Subsequently, 8.0 parts by weight of sulfamic acid (NH ₂ SO ₃ H) was added to the first intermediate product, the temperature was raised to 80 ° C., and a second reaction was performed. After 6-8 hours, a second intermediate product was obtained. The surfactant in Preparation Example S-2 represented by the following formula (III-2) was obtained by neutralizing the second intermediate product with 0.5 part by weight of ammonia water (NH ₄ OH).


In formula (III-2), the definitions of R ₁ and Y are as described above and will not be described here. a represents 2, b represents 2, and the sum of m and n was 20.

[Preparation Example S-3]
First, 100.0 parts by weight of polyoxyethylene polyaryl ether, 12.0 parts by weight of glycidyl methacrylate and 3.5 parts by weight of potassium hydroxide were added to the reaction flask. Next, the temperature was raised to 70 ° C. to carry out the first reaction. After 6 hours to 10 hours, the first intermediate product of Preparation Example S-3 was obtained. Subsequently, 9.5 parts by weight of sulfamic acid (NH ₂ SO ₃ H) was added to the first intermediate product, the temperature was raised to 80 ° C., and a second reaction was performed. After 6-8 hours, a second intermediate product was obtained. The surfactant in Preparation Example S-3 represented by the following formula (III-3) was obtained by neutralizing the second intermediate product with 0.8 part by weight of aqueous ammonia (NH ₄ OH).


In formula (III-3), the definitions of R ₁ and Y are as described above and will not be described here. a represents 2, b represents 2, and the sum of m and n was 10.

[Preparation Example S-4]
First, 100.0 parts by weight of polyoxyethylene polyaryl ether, 15.0 parts by weight of glycidyl methacrylate and 3.5 parts by weight of potassium hydroxide were added to the reaction flask. Next, the temperature was raised to 70 ° C. to carry out the first reaction. After 6 hours to 10 hours, the first intermediate product of Preparation Example S-4 was obtained. Subsequently, 12.0 parts by weight of sulfamic acid (NH ₂ SO ₃ H) was added to the first intermediate product, and the temperature was raised to 80 ° C. to carry out a second reaction. After 6-8 hours, a second intermediate product was obtained. The surfactant of Preparation Example S-4 represented by the following formula (III-4) was obtained by neutralizing the second intermediate product with 1.0 part by weight of aqueous ammonia (NH ₄ OH).


In formula (III-4), the definitions of R ₁ and Y are as described above and will not be described here. a represents 2, b represents 2, and the sum of m and n was 5.

[Evaluation of Reactive Surface Active Emulsion Polymerization Performance of the Present Invention]
The polymer film of the present invention is formed by performing an emulsion polymerization reaction with a monomer compound. In addition, the usage-amount of each composition of the monomer compound used for Example 1- Example 8 and Comparative Example 1- Comparative Example 4 and its kind are shown in Table 1, and it does not explain here.

[Example 1]
Add 153 grams of unsaturated compound (M-1), 2.5 phm of the surfactant from Preparation Example S-1 above and 0.3 phm of initiator to 153 grams of water and mix evenly. The monomer compound of Example 1 was obtained. However, the unsaturated compound (M-1) is copolymerized with n-butyl acrylate, methyl methacrylate and acrylic acid, and the proportion of n-butyl acrylate, methyl methacrylate and acrylic acid is 49:49. : 2.

  Next, the polymer film of Example 1 was obtained by coating the monomer compound so as to form a film and performing an emulsion polymerization reaction. The obtained polymer film was evaluated by the following evaluation methods such as agglomeration rate, solid content, conversion rate, average particle size, viscosity, and water resistance, and the obtained results are shown in Table 1.

[Examples 2 to 8 and Comparative Examples 1 to 4]
Examples 2 to 8 and Comparative Examples 1 to 4 use the same preparation method as that for the polymer film of Example 1, but the type of unsaturated compound and surfactant in the monomer compound And the composition and evaluation results are shown in Table 1 and will not be described here. The unsaturated compound (M-2) of Examples 5 to 8 and Comparative Example 1 was copolymerized with n-butyl acrylate, styrene and acrylic acid, and n-butyl acrylate, styrene and The proportion of acrylic acid was 49: 49: 2.

〔Evaluation item〕
1. Aggregation rate Monomer polymerization reaction was performed on the monomer compounds of Examples 1 to 8 and Comparative Examples 1 to 4 to form an emulsion by polymerization, and the weight (Wi) was measured. Next, the emulsion obtained in each Example and Comparative Example was filtered with a 100-mesh metal mesh, and the residue in the metal mesh was washed with water.

Subsequently, the residue was dried at 105 ° C., and after 2 hours, its weight (Wf) was measured, and the aggregation rate was calculated by the following formula (VI).

2. Solid content A monomer polymerization reaction was performed on the monomer compounds of Examples 1 to 8 and Comparative Examples 1 to 4, and an emulsion was formed by polymerization. Then weigh exactly 3 grams of emulsion and make an aluminum cup (size: upper diameter is 7.0 centimeters, lower diameter is 4.5 centimeters and height is 1.3 centimeters) ).

Subsequently, the aluminum cup was placed in a circulation oven set at a temperature of 130 ° C., and after 30 minutes, the aluminum cup was weighed, and the solid content was calculated by the following formula (VII).


In the formula (VII), Wt represents the total weight of the emulsion and aluminum cup after drying, Wc represents the weight of the aluminum cup, and Ws represents the weight of the emulsion before drying.

3. Conversion Rate The calculated value of the solid content and the ratio (%) of the theoretical solid content were the conversion rates of the emulsion polymerization reaction of each Example and Comparative Example.

4). Average particle diameter An emulsion polymerization reaction was performed on the monomer compounds of the above Examples and Comparative Examples to form an emulsion.

  Next, the average particle diameter of the emulsion was measured at 25 ° C. with a particle size distribution meter (manufactured by COULTER, whose model number is LS230).

5. Viscosity At 25 ° C., viscometer (manufactured by BROOKFIELD) and No. The viscosity of the emulsions obtained in each of the above Examples and Comparative Examples was measured using a 31 rotor.

6). Water Resistance The emulsion obtained in each of the above Examples and Comparative Examples was coated on a glass plate, and a polymer film having a thickness of 10 μm was formed through a film forming step.

Next, the glass plate is immersed in a test water tank (water temperature is set at 25 ° C.) for water whitening resistance, and after 1 day and 7 days, the glass plate is taken out and polymer film is visually observed. The degree of whitening was observed and evaluated according to the following standards.
A: The polymer film was transparent and was in close contact with the glass plate.
○: The polymer film was a blue transparent film and was in close contact with the glass plate.
□: The polymer film was partially whitened, but was in close contact with the glass plate.
(Triangle | delta): The polymer film was a part whitened film, and there existed the condition which peels around the film.
X: The polymer film was completely whitened or peeled off from the glass plate.

See Table 1. In Table 1, the surfactant used in Examples 1 to 8 has an unsaturated group, can generate an addition reaction with an unsaturated compound, and further forms a covalent bond. Have sex. Therefore, the resin film of the present invention is good because the resin film is not whitened and the polymer film is not peeled off even after being placed in the test water tank for 7 days. It has excellent water resistance.
On the other hand, the surfactant (S-5, polyoxyethylene aryl ether sulfate) used in Comparative Example 1 has a large viscosity due to the influence of its structure, and the obtained resin The water resistance of the coating film was lowered.

  As a result, the surfactant of the present invention can react with the reactive monomer having an unsaturated double bond, does not remain in the emulsion, and does not show a “migration” phenomenon in the resin coating film. Surface characteristics (for example, water resistance, weather resistance, etc.) can be imparted.

  Next, the first reaction of the surfactant of the present invention does not require the use of a separate solvent, and the product of the first reaction does not require alkaline washing treatment and water washing treatment. The effect of reduction can be produced.

  Although the embodiments of the present invention have been disclosed as described above, this is not intended to limit the present invention, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention is based on what is specified in the following claims.

100 Method 110 Step of forming a first intermediate product by performing a first reaction on the mixture 120 Step of performing a second reaction on the first intermediate product and the acid group compound Step 130 for forming the intermediate product of 2 Step 140 for performing the neutralization reaction on the second intermediate product 140 A surfactant is obtained.

Claims (8)

A first intermediate product is obtained by conducting a first reaction on a mixture comprising an aryl ether compound represented by formula (I) below and a glycidyl ether compound represented by formula (II) below, but not containing a solvent. Forming a step;

(In Formula (I), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and an oxygen atom and a hydrogen atom of R ₂ and R ₃ are bonded to each other. Y is
A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100)

(In formula (II), R ₄ is
Wherein C═O is bonded to R ₅ , and x is 0 or 1, and R ₅ is a group having a carbon-carbon double bond)
Forming a second intermediate product by performing a second reaction on the first intermediate product and the acid group compound;
Performing a neutralization reaction on the second intermediate product to obtain a surfactant having a structure represented by the following formula (III):

(In Formula (III), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and the oxygen atoms of R ₂ and R ₃ are each —CH _2. -Or R ₆ and R ₄ is
Wherein C═O is bonded to R ₅ , and x is 0 or 1, and R ₅ is a group having a carbon-carbon double bond, and R ₆ is an anionic group Y is
A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100)
A method for producing a surfactant.   The method for producing a surfactant according to claim 1, wherein the mixture includes a catalyst.   The method for producing a surfactant according to claim 1, wherein the acid group compound includes a sulfonic acid compound, a sulfuric acid compound, a phosphoric acid compound, or a carboxylic acid compound.   The method for producing a surfactant according to claim 1, wherein the neutralizing agent for the neutralization reaction is an alkali metal compound, an amine compound, an alkylamine compound, or an alkyl-substituted or unsubstituted alcoholamine compound. It has the structure shown in the following formula (III)
(In Formula (III), R ₁ represents a methylene group, R ₂ and R ₃ each represent an alkylenoxy group having 2 to 4 carbon atoms, and the oxygen atoms of R ₂ and R ₃ are each —CH _2. -Or R ₆ and R ₄ is
Wherein C═O is bonded to R ₅ , and x is 0 or 1, and R ₅ is a group having a carbon-carbon double bond, and R ₆ is an anionic group Y is
A and b each represent an integer of 1 to 4, and the sum of m and n is an integer of 2 to 100)
Surfactant. The anionic group is selected from the group consisting of —SO ₃ M, —PO ₃ M ₂ , —PO ₃ MH and —COOM, and M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylammonium or alkyl-substituted or The surfactant according to claim 5, which represents an unsubstituted ammonium alcohol group. An unsaturated compound;
The surfactant according to claim 5 or claim 6,
An aqueous paint resin having a reactive monomer mixture containing   The water-based paint resin according to claim 7, wherein the unsaturated compound includes an acrylic resin or styrene.