WO2007037376A1

WO2007037376A1 - Process for producing n-pyrrolidone graft polymer composition and n-pyrrolidone graft polymer composition

Info

Publication number: WO2007037376A1
Application number: PCT/JP2006/319480
Authority: WO
Inventors: Daisuke Imai; Keiko Izumi; Takashi Miyai
Original assignee: Nippon Shokubai Co., Ltd.
Priority date: 2005-09-30
Filing date: 2006-09-29
Publication date: 2007-04-05

Abstract

A process for producing an N-vinylpyrrolidone graft polymer which can have an improved degree of vinyl monomer grafting and can hydrophilize the surface of a plastic base, etc. The process for N-vinylpyrrolidone graft polymer production comprises the step of reacting an N-vinylpyrrolidone polymer with a vinyl monomer. In the process for producing an N-vinylpyrrolidone graft polymer, the N-vinylpyrrolidone polymer to be reacted as a raw material is regulated so as to have a 2-pyrrolidone content of 10,000 ppm or lower.

Description

Specification

Method for producing N_pyrrolidone-based graft polymer composition and N_pyrrolidone-based graph polymer composition

Technical field

[0001] The present invention relates to a method for producing an N-pyrrolidone-based graft polymer composition and an N-pyrrolidone-based graph polymer composition. More specifically, it has various characteristics such as hydrophilizing the surface of base materials such as plastics, improving stain resistance, and dispersing and stabilizing hydrophobic components in aqueous solutions. The present invention relates to a method for producing an N-pyrrolidone-based graft polymer composition and an N-pyrrolidone-based graft polymer composition.

Background art

[0002] An N-pyrrolidone-based graft polymer is formed by a graft polymerization reaction of an N-vininolepyrrolidone-based polymer containing polyvinylinolepyrrolidone or the like and a bull-based monomer. Such an N-bulylpyrrolidone-based graft polymer has the basic properties such as hydrophilicity of the N-bulylpyrrolidone-based polymer, and the graft imparts various properties possessed by the graft component. Therefore, it is used for various industrial applications.

[0003] As conventional N-pyrrolidone-based graft polymers, for example, polymethylpyrrolidone is used as a base, and examples of graft polymerization of methyl metatalylate and the like are disclosed (for example, see Patent Documents 1 to 4). ₀ ) Also, an aqueous emulsion in which (meth) acrylate or the like is grafted with N-burratatam as the main chain, such as bull pyrrolidone, is also disclosed (for example, see Patent Document 5).

[0004] However, polyvinyl pyrrolidone and the like obtained in these graft polymerizations are not related to a technique aiming to impart hydrophilicity to the surface of a plastic substrate or the like for stain resistance. When applied to plastics, it is required to improve the hydrophilicity of the surface of plastic substrates such as polysulfone and polyethersulfone. In addition, these technologies are not devised for improving the production method in graft polymerization of polybulurpyrrolidone or the like. It was.

Patent Document 1: US Pat. No. 6573313 (page 12)

Patent Document 2: US Pat. No. 5,705,553 (page 12)

Patent Document 3: Japanese Patent Publication No. 58-98319 (pages 124-125)

Patent Document 4: US Patent No. 3244658 (Page 12)

Patent Document 5: Japanese Patent Laid-Open No. 50-51189 (Pages 1-2)

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention has been made in view of the above situation, and can improve the graft ratio of the vinyl-based monomer, hydrophilize the surface of a plastic substrate, etc. It is an object of the present invention to provide a method for producing an N vinylpyrrolidone-based graft polymer composition that can be dispersed and stabilized in an aqueous solution, and an N-bulurpyrrolidone-based graft polymer composition.

Means for solving the problem

[0006] The inventors of the present invention have made various investigations on the production methods of an N-bulupyrrolidone-based graft polymer composition that involves a graft reaction. It was found that the graft ratio of the vinyl monomer is improved when the N-pyrrolidone graft polymer composition is produced by graft polymerization of the vinyl monomer. In addition, an N-bulurpyrrolidone-based graft polymer composition having a graft ratio of 13% or more is useful for various applications. For example, such a N-pyrrolidone-based graft polymer composition can be used to coat the surface of a plastic substrate or the like. It was found that the treatment can impart hydrophilicity, and the above problems can be solved brilliantly. Furthermore, the obtained N pyrrolidone-based graft polymer composition has been found to be able to disperse and stabilize a water-phobic component in the aqueous solution only by hydrophilizing the surface of the substrate. It has also been found that it can be suitably used for various applications such as cosmetic applications.

[0007] That is, the present invention is a method for producing an N vinylpyrrolidone-based graft polymer composition comprising a step of reacting an N-bululpyrrolidone-based polymer with a bull-based monomer. The production method is a method for producing an N-vinylpyrrolidone-based graft polymer composition in which the content of 2-pyrrolidone in the starting N-butyrpyrrolidone-based polymer is 10 OOOppm or less.

The present invention is described in detail below.

[0008] The method for producing an N-bulupyrrolidone-based graft polymer composition of the present invention includes a step of reacting a vinyl monomer with an N-bulupyl lididone-based polymer. By this step, grafting is carried out on a monomer component N-Burpyrrolidone-based polymer containing a beryl monomer.

The method of adding the vinyl monomer in the above step is not particularly limited. For example, a method of adding a vinyl monomer after producing an N-butyrpyrrolidone polymer, an N-vinylpyrrolidone polymer, The method of adding a vinyl-type monomer during manufacture of this is mentioned.

[0009] The N-vinylpyrrolidone-based polymer is obtained by polymerizing monomer components using an initiator. Usually, N-Buylpyrrolidone is hydrolyzed during polymerization, and 2-pyrrolidone is an impurity. Generate as In the process of the present invention, the reaction is carried out with the content of 2-pyrrolidone in the N-vinylpyrrolidone polymer used for graft copolymerization being lOOOOppm or less. By setting the content of 2-pyrrolidone to lOOOOppm or less, the graft ratio of the bull monomer can be improved. If it exceeds lOOOOppm, the grafting rate will not be improved sufficiently, and the effect of imparting properties by grafting may not be obtained sufficiently. More preferably, it is 5000 ppm or less, More preferably, it is 3000 ppm or less, Most preferably, it is 2000 ppm or less.

As a method of setting the content of 2-pyrrolidone in the N-vinylpyrrolidone polymer used as the above raw material to ΙΟΟΟΟρ pm or less, use an azo initiator and an organic peroxide as a peroxide in an aqueous solvent. The polymerization is preferably carried out while maintaining the pH of the polymerization system at about 7-9. Details of the manufacturing method will be described later. For polymerization of general PVP (especially those with a low K value: K value of 40 or less), a method of polymerizing in an aqueous solvent using an initiator of hydrogen peroxide Z ammonia Z metal catalyst is often used. . According to this method, 2-pyrrolidone is normally generated at 10,000 ppm or more. According to the above-described polymerization method, a polymer having a small amount of 2-pyrrolidone (the content of 2-pyrrolidone is 100 OOppm or less) is suitably obtained. be able to. The graft ratio is an index showing how much the monomer component that is a side chain charged in the main chain of the polymer is polymerized and bonded in the graft reaction, and is obtained as follows. .

The obtained polymerization liquid emulsion is diluted so as to have a solid content of about 10% by mass, and applied to a high-speed centrifugal separator (Hitachi Koki, himac CP60E) (40000 rpm × 2 hours, 25 ° C.). Measure the solid content of the diluted solution and the supernatant before centrifugation (120 ° C X I. 5 hours), and obtain the graph rate according to the following formula.

Graft ratio (mass%) = [(AX B- C) Z (AX B)] X 100

A: Charge PVP amount during polymerization Z (charge PVP amount during polymerization + VM amount)

B: Solid content of the diluent

C: Solid content of supernatant

In the above A, PVP represents an N-bulurpyrrolidone polymer, and VM represents a bulle monomer. As the bur monomer, for example, MMA (methyl (meth) acrylate) and BA (butyl acrylate) are suitable. The higher the numerical value obtained, the higher the graft ratio.

The present invention also provides an N-bulupyrrolidone-based graft polymer composition of an N-bulupyrrolidone-based polymer and a bull-based monomer, wherein the N-bulupyrrolidone-based graft polymer composition has a graft ratio. It is also an N-vinylpyrrolidone-based graft polymer composition having a content of 13% or more. Such an N-bulylpyrrolidone-based graft polymer composition has the characteristics of a vinyl monomer while having the hydrophilic properties of the N-bulylpyrrolidone-based polymer, and is therefore useful for various applications. For example, by treating the surface of a plastic substrate or the like with such an N-vinylpyrrolidone-based graft polymer composition, sufficient hydrophilicity can be imparted to have stain resistance. . If it is less than 13%, sufficient hydrophilicity may not be imparted to the surface of a plastic substrate or the like. More preferably, it is 14% or more, and further preferably 15% or more. The N-butylpyrrolidone-based graft polymer composition includes a polymer that is grafted to a polymer and may be composed of only the grafted polymer. . The N-vinylpyrrolidone-based graft polymer composition is not particularly limited as long as the graft ratio is 13% or more, but the 2-pyrrolidone in the N-vinylpyrrolidone-based polymer used as the raw material described above is not limited. It is preferable to obtain it by a method for producing an N-bulu pyrrolidone-based graft polymer that is reacted at a content of 1 OOOOppm or less.

[0011] Preference is given to the above-mentioned vinyl-based monomers! / The form of hydrophobic vinyl-based monomers and hydrophilic bull-based monomers may be offset, but they are hydrophobic. It is preferable to produce an N-vinylpyrrolidone-based graft polymer using a bulle monomer because it is advantageous for the affinity with the surface of a plastic substrate or the like.

Examples of the hydrophobic bur monomer include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate. (Meth) acrylates such as butyl acetate; beryl esters such as propionate butyl; butyl ethers such as methyl butyl ether and ethyl butyl ether

Styrene; olefins such as propylene, otaten and the like, and one or more of these are preferably used. Of these, from the viewpoint of polymerizability, (meth) acrylates, buresters, and methyl methacrylate, with (meth) acrylates being more preferred with styrene, and butyl acrylate being the most preferred.

[0012] The present invention further relates to an N-bulupyrrolidone-based graft polymer composition of an N-bulupyrrolidone-based polymer and a bull-based monomer, the N-bulupyrrolidone-based graft polymer composition comprising: Gel permeation chromatography elution curve force It is also an N-bulylpyrrolidone-based graft polymer composition having a single peak.

The measurement conditions for gel permeation chromatography (GPC) of the N-bulupyrrolidone-based graft polymer composition are as follows.

[GPC measurement method]

Column: Showa Denko Co., Ltd. Shodex KD-G, Shodex LF804, Shodex KD 801

Eluent: 0.1% Lithium bromide dimethylformamide solution

Eluent flow rate: 0.8mLZ min

Injection volume: Column oven: 40 ° C

Detector: Differential refractometer (RI)

Sample concentration: 1.0%

Analysis software: System Instruments SIC480II

Data processing parameter setting of analysis software

[1] Up slope: 5, Down slope: 5

[2] Minimum peak width: 20 sec

[3] Base sensitivity: 1 point

[4] Minimum peak area: 10000

[5] Calculation range: 0—22min

The above elution curve has “single peak” means that the portion of the retention time of 0 to 22 minutes corresponding to the polymer elution curve under the above measurement conditions does not have two or more peaks but only one peak. It means having.

The N-vinylpyrrolidone-based graft polymer composition is not particularly limited as long as the gel permeation chromatography elution curve has a single peak. Power In the N-vinylpyrrolidone-based polymer used as the raw material described above It is preferable to obtain it by a method for producing an N-vinylpyrrolidone-based graft polymer that is reacted with a 2-pyrrolidone content of 1 OOOOppm or less. The vinyl monomer is preferably the same as described above.

In the process for producing the N-vinylpyrrolidone-based graft polymer in the present invention, the weight ratio of the N-butyropyrrolidone-based polymer to the vinyl monomer is preferably 10Z90 or more, more preferably 20Z80 or more. It is more preferable that it is 30Z70 or more. The upper limit is preferably 70Z30 or less, preferably 65Z35 or less, more preferably 60Z40 or less, and still more preferably 50Z50 or less. Thereby, in the above process, the graft ratio of the bull monomer can be sufficiently improved. If the weight ratio of the N-bulurpyrrolidone polymer to the vinyl monomer is outside the above range, the characteristics of the N vinylpyrrolidone polymer and the characteristics of the vinyl monomer may not be compatible. Also, when it becomes smaller than 10Z90, There is a possibility that the degree of rotation cannot be sufficiently improved.

[0014] The method of the graft polymerization reaction for obtaining the N-vinylpyrrolidone-based graft polymer is not particularly limited, and may be performed by a method such as solution polymerization, emulsion polymerization, suspension polymerization, or precipitation polymerization. Can do.

Examples of the solvent used in the above polymerization reaction include one or more of water, lower alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, etc., and particularly water is used. It is preferable to do.

[0015] When performing the above polymerization reaction, for example, reaction conditions such as reaction temperature and pressure are not particularly limited. For example, the reaction temperature is 60 to 100 ° C, and the pressure in the reaction system is normal pressure. Alternatively, pressurization is preferable. In the graft polymerization reaction for obtaining an N-butylpyrrolidone-based graft polymer that is useful in the present invention, the initiator is not particularly limited, and is not limited to hydrogen peroxide, an azo-based initiator, ammonium persulfate or the like. Examples thereof include sulfates and organic peroxides, and it is preferable to use persulfates.

As said initiator, only 1 type may be used and 2 or more types may be used together.

[0016] Hereinafter, the N-butylpyrrolidone polymer will be described.

The monomer component forming the N-vinylpyrrolidone polymer is not particularly limited as long as it contains at least N-vinylpyrrolidone. For example, N-vinylpyrrolidone may be used alone, Use a polymerizable monomer copolymerizable with N-Buylpyrrolidone. In the case of copolymerizing a polymerizable monomer other than N-Buylpyrrolidone, the content of N-Buylpyrrolidone in the monomer component is not particularly limited. For example, N-Buylpyrrolidone in the monomer component is not limited. The content of bullpyrrolidone is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.

[0017] The polymer monomer component copolymerizable with N-vinylpyrrolidone is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylic acid esters such as cyclohexyl (meth) acrylate and hydroxyethyl (meth) acrylate; (meth) acrylic acid amide, and N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide , N, N,-(Meth) acrylamide derivatives such as dimethyl (meth) acrylamide; dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) Basic unsaturated monomers such as acrylamide, vinyl pyridine and buriumidazole and their salts or quaternized compounds; buramides such as buluformamide, buracetoamide, buroxazolidone; (meth) acryl Carboxylic group-containing unsaturated monomers such as acid, itaconic acid, maleic acid, fumaric acid and the like; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; Bull esters; Bull ethylene strength-Bonates and derivatives thereof; Styrene and derivatives thereof; (Meth) acrylic acid-2-ethyl sulfonate and derivatives thereof; Bull sulfonic acid and derivatives thereof; Methyl vinyl ether, Ethyl vinyl ether, Butyl Vinyl ethers such as vinyl ether; ethylene, propylene, otaten, butadiene, etc. Olefin compounds, and the like. Of these, (meth) acrylic acid esters, (meth) acrylamides, (meth) acrylamide derivatives, basic unsaturated monomers and their or Quaternized compounds, buramides, carboxyl group-containing unsaturated monomers and salts thereof, bulule esters, burethylene carbonate and derivatives thereof are particularly suitable. Only one of these may be used, or two or more may be mixed and copolymerized with N-butylpyrrolidone.

[0018] The method of the polymerization reaction for obtaining the N-vinylpyrrolidone-based polymer is not particularly limited, and may be performed by methods such as solution polymerization, emulsion polymerization, suspension polymerization, and precipitation polymerization, for example. it can.

As the solvent used for the polymerization reaction, water is most preferable. Solvents that are soluble in water, for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanolanolol, diethylene glycol, and the like can be used by mixing with water. In particular, it is preferable to use a solvent such as isopropyl alcohol and n-butyl alcohol mixed with water from the viewpoint of suppressing side reactions.

When performing the above polymerization reaction, for example, reaction conditions such as reaction temperature and pressure are not particularly limited. For example, the reaction temperature is 20 to 150 ° C., and the pressure in the reaction system is normal pressure. Or, pressurization is preferred. In the polymerization reaction for obtaining the vinylpyrrolidone polymer useful in the present invention, it is preferable to use an azo initiator or an organic peroxide initiator because 2-pyrrolidone is hardly generated. [0020] Examples of the azo initiator include 4, 4'-azobis 4-ciano valeric acid, 2, 2 'azobis [2-methyl-N- (2- (1-hydroxybutyl)) propionamide], 2 , 2, 1-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2, 2, 1-azobis [N— (2-probe) 2-methylpropionamide], 2, 2 , -Azobis [N-butyl 2-methylpropionamide], 2, 2'-Azobis [N-cyclohexyl 2-methylpropionamide], 2, 2, -azobis [2-(2-imidazoline 2-yl) propane] Dihydrochloride, 2, 2, -azobis [2- (2-imidazoline-2-yl) propane] disulfate, 2, 2, -azobis [2- (2-imidazoline-2-yl) propane] disulfate Dihydrate, 2, 2, -azobis [2- (3, 4, 5, 6-tetrahydropyridine-2-yl) propane] dihydrochloride , 2, 2, —azobis [2— (1— (2-hydroxyethyl) —2—imidazoline—2—yl) propane] dihydrochloride, 2, 2, azobis [2— (2—imidazoline 2— Yl) propane] dihydrochloride, 2,2, -azobis (2-aminodipropane) dihydrochloride, 2,2, -azobis [2— (N— (2—force ruboxetyl) amidino) propane] dihydrochloride, Examples thereof include dimethyl-2,2'-azobis (2-methylpropionate), and among these, 4,4, -azobis-4-cyananovaleric acid and dimethyl-2,2, -azobis (2-methylpropionate) are preferable. These may use only 1 type and may use 2 or more types together.

[0021] Examples of the organic peroxide initiator include diisopropyl peroxydicarbonate, dicumyl peroside, di-t-butyl peroxyhexahydroterephthalate, di-t-butyl peroxide, t-butyl hydroper Oxide, t-butylperoxypivalate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and the like. Among these, t-butyl hydroperoxide and t-butyl peroxybivalate are preferable. These may use only 1 type and may use 2 or more types together.

[0022] The azo initiator and the organic peroxide-hydrogen initiator may be used in combination. The amount of the initiator used is not particularly limited, but is preferably 0.01% to 10% by weight, more preferably 0.1 to 5% by weight, based on the secondary monomer component. 5 to 3% by weight is more preferable.

When carrying out the above polymerization reaction, the polymerization reaction is promoted or N In order to prevent this, a basic pH adjuster can also be used. Addition of the pH regulator can be carried out by any method. For example, it may be charged into the system from the beginning of the polymerization, or may be added successively during the polymerization. Specific examples of the pH regulator include ammonia, aliphatic amines, aromatic amines, sodium hydroxide, potassium hydroxide, and the like. Among these, ammonia is particularly preferable. These may use only 1 type and may use 2 or more types together. In the case of using a pH regulator, the amount used is not particularly limited, and it is preferable that the solution during polymerization be in the pH range of 5 to 10. More preferably, it should be used in a pH range of 7-9.

[0023] When the polymerization reaction is performed, a transition metal salt can be used for the purpose of promoting the polymerization reaction. Specific examples of the transition metal salt include strong rubonic acid salts and chlorides such as copper, iron, cobalt, and nickel. These may be used alone or in combination of two or more. When the above transition metal salt is used, the amount used is not particularly limited, and it is preferably 0.1 to 20000 ppb force S, more preferably 1 to 5000 ppb in weight it with respect to the monomer component. In carrying out the polymerization reaction, a chain transfer agent, a buffering agent and the like can be used in addition to the polymerization initiator, the pH adjuster, and the transition metal salt.

In the above polymerization reaction, the method of adding a pH regulator, transition metal, etc. is not particularly limited, and any method such as a batch system or a continuous system can be used.

[0024] The N value of the N-butylpyrrolidone polymer is preferably 100 or less. More preferably, it is 60 or less, and more preferably 40 or less. If such a polymer is used, it can contribute to the improvement of the grafting ratio of the bull monomer in the N-bull pyrrolidone graft polymer. If the K value exceeds 100, the graft ratio of the vinyl monomer in the N-vinylpyrrolidone-based graft polymer may not be improved. The K value serves as an index indicating the molecular weight of the polymer, and can be determined, for example, as follows.

The polymer is dissolved in water at a concentration of 1% by mass, and the viscosity of the solution is measured at 25 ° C using a capillary viscometer.

(log 7?) / C = [(75Ko ² ) / (l + l. 5KoC)] + Ko K = 1000Ko

(Where C represents the number of grams of polymer in 100 ml of solution. Η is the viscosity of the solution relative to the solvent.

rel

Represents degrees. ). The higher the numerical value obtained, the higher the molecular weight.

[0025] The method for producing an N-bulupyrrolidone-based graft polymer of the present invention comprises the above-described configuration, and produces an N-bulupyrrolidone-based graft polymer in which the graft ratio of the vinyl monomer as a graft component is improved. can do. In addition, since such a N-butylpyrrolidone-based graft polymer can impart a sufficient hydrophilicity to the surface of the base material because the plastic base material has a stain-proof function, the N-bulu of the present invention The method for producing a pyrrolidone-based graft polymer is industrially useful.

Brief Description of Drawings

[0026] Fig. 1 is a GPC chart of N-Buylpyrrolidone-based graft polymer 1.

[FIG. 2] FIG. 2 is a GPC chart of N-Burpyrrolidone Graft Polymer 4. BEST MODE FOR CARRYING OUT THE INVENTION

[0027] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” means “parts by weight”, “%

"Means"% by mass ".

[0028] (Example 1)

Base PVP synthesis

In a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line, and a thermometer, 100 parts of ion-exchanged water was added and nitrogen was introduced to form a nitrogen atmosphere. After heating the polymerization vessel to an internal temperature of 98 ° C, while stirring, 60 parts of N-Buylpyrrolidone, 1.8 parts of 30% hypophosphorous acid solution, 0.7 parts of 25% aqueous ammonia solution, 10 parts of ion-exchanged water 10 5 parts of monomer solution and 4, 4'-azobis-4 cyanovaleric acid (NC-25, manufactured by Niho Chemical Co., Ltd.) 0.37 parts, triethanolamine 0.42 parts ion-exchanged water 29.2 parts The initiator solution dissolved in each was continuously added dropwise over 1 hour. Further, while continuing stirring for 1 hour, add an initiator solution prepared by dissolving 0.07 parts of NC-25 and 0.08 parts of triethanolamine in 1. 3 parts of ion-exchanged water in two portions. Poly Mer solution 1 was obtained. The obtained polymer solution 1 had a solid content of 30.1%, a K value of 28.5, and the amount of 2-pyrrolidone was 2518 ppm based on the solid content.

[0029] Graft polymerization

Add 80 parts of polymer solution 1, 82.8 parts of ion exchanged water, and 7.2 parts of methyl metatalylate to a polymerization vessel equipped with a condenser, nitrogen introduction line, and thermometer, and introduce nitrogen while stirring. A nitrogen atmosphere was established. The polymerization vessel was heated to an internal temperature of 80 ° C., and an initiator solution in which 0.18 part of ammonium persulfate was dissolved in 1 part of ion-exchanged water was added. Subsequently, 28.8 parts of methyl metatalylate was added over 60 minutes, and when heating and stirring were continued for 90 minutes, a milky white emulsion was obtained. For this N-butylpyrrolidone-based graft polymer 1, the above-mentioned graft ratio was found to be 16.6%. As a result of measuring molecular weight distribution by GPC, a single peak was observed as shown in Fig. 1.

[0030] (Example 2)

Base PVP synthesis

In a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line, and a thermometer, 700 parts of ion-exchanged water was added and nitrogen was introduced to create a nitrogen atmosphere. After heating the polymerization vessel to bring the internal temperature to 90 ° C, the stirring force S et al., 300 parts of N-Buylpyrrolidone, 1.2 parts of 25% aqueous ammonia solution, 0.2 part of 0.200% copper sulfate pentahydrate aqueous solution 0. 3 parts of the monomer solution and 69 parts of 69% t-butyl nanodrop 1-year-old oxide were continuously added dropwise over 1 hour. While the mixture was further stirred for 5 hours, 2.1 parts of 69% t-butyl hydride peroxide was added in 4 portions to obtain polymer solution 2. The obtained polymer solution 2 had a solid content of 30.2%, a K value of 54.5, 2-pyrodide, and an amount of 3200 ppm based on the solid content.

[0031] Graft polymerization

To a polymerization vessel equipped with a condenser, a nitrogen introduction line, and a thermometer, 667 parts of polymer solution 2 and 190 parts of ion-exchanged water were added, and nitrogen was introduced while stirring to create a nitrogen atmosphere. The polymerization vessel was heated to an internal temperature of 80 ° C, and an initiator solution in which 1.5 parts of ammonium persulfate was dissolved in 2 parts of ion-exchanged water was added. Subsequently, 133 parts of butyl acrylate were added over 60 minutes, and further heating and stirring were continued for 90 minutes. As a result, milky white emulsion was obtained. With respect to this N-butylpyrrolidone-based graft polymer 2, the above-mentioned graft ratio is calculated as 15 4%.

[0032] (Example 3)

Base PVP synthesis

In a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line, and a thermometer, 148 parts of ion-exchanged water was added and nitrogen was introduced to form a nitrogen atmosphere. After heating the polymerization vessel to an internal temperature of 90 ° C, stirring, N-vinylpyrrolidone 60 parts, 1N sodium hydroxide aqueous solution 16 parts, 3-mercaptopropionic acid 1.6 parts, ion-exchanged water 44 parts Powerful monomer solution and 2,2, -azobis (2-aminodipropane) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) 1. Initiator solution prepared by dissolving 2 parts in 29 parts of ion-exchanged water It was dripped continuously over 2 hours. Further, while the stirring was continued for 3 hours, an initiator solution prepared by dissolving 0.24 parts of V-50 in 5.8 parts of ion-exchanged water was added in two portions to obtain a polymer solution 3. The obtained polymer solution 3 had a solid content of 21.1%, a K value of 16.1, and a 2-pyrrolidone content of 5397 ppm based on the solid content.

[0033] Graft polymerization

In a polymerization vessel equipped with a cooling pipe, nitrogen introduction line, and thermometer, 114 parts of polymer solution 3, 48.8 parts of ion-exchanged water, and 7.2 parts of methyl metatalylate are added and nitrogen is added while stirring. The nitrogen atmosphere was introduced. The polymerization vessel was heated to an internal temperature of 80 ° C., and then an initiator solution in which 0.18 part of ammonium persulfate was dissolved in 1 part of ion-exchanged water was added. Subsequently, 28.8 parts of methyl methacrylate were added over 60 minutes, followed by further heating and stirring for 90 minutes. As a result, milky white emulsion was obtained. In this N-butylpyrrolidone-based graft polymer 3, the aforementioned graft ratio was determined to be 14.3%.

[0034] (Comparative Example 1)

Base PVP synthesis

N-vinylpyrrolidone 90 parts and ion-exchanged water 206 parts were added to a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line, and a thermometer, and nitrogen was introduced to form a nitrogen atmosphere. While stirring at room temperature, 0.045 parts of a 0.1% aqueous copper sulfate solution, 0.5 parts of a 25% aqueous ammonia solution and 2.1 parts of a 30% aqueous hydrogen peroxide solution were added to initiate polymerization. After the internal temperature rose due to the polymerization heat, stirring was continued for 1.5 hours at 80 ° C. Next, after adding 1.0 part of 30% aqueous hydrogen peroxide, Further, heating was continued for 1 hour to obtain a polymer solution 4. The obtained polymer solution 4 had a solid content of 30.0%, a K value of 29.8, and an amount of 2-pyrrolidone of 16599 ppm based on the solid content.

[0035] Graft polymerization

Add 80 parts of Polymer Solution 4, 82.8 parts of ion-exchanged water, and 7.2 parts of methylmetatalylate to a polymerization vessel equipped with a condenser, nitrogen introduction line, and thermometer, and introduce nitrogen while stirring. A nitrogen atmosphere was established. The polymerization vessel was heated to an internal temperature of 80 ° C., and an initiator solution in which 0.18 part of ammonium persulfate was dissolved in 1 part of ion-exchanged water was added. Subsequently, 28.8 parts of methyl metatalylate was added over 60 minutes, and when heating and stirring were continued for 90 minutes, a milky white emulsion was obtained. For this N-butylpyrrolidone-based graft polymer 4, the above-mentioned graft ratio was 10.3%. As a result of measuring molecular weight distribution by GPC, two peaks were observed as shown in Fig.2.

[Comparative Example 2]

Base PVP synthesis

In a polymerization vessel equipped with a condenser, a nitrogen introduction line, and a thermometer, 60 parts of ion exchange water and 1 part of 0.01% aqueous copper sulfate solution were charged into the reaction vessel, and the temperature was raised to 100 ° C. while blowing nitrogen. While stirring, 30 parts of N-butylpyrrolidone and 10 parts of a 1% aqueous hydrogen peroxide solution were added dropwise over 1 hour. During the dropping, the pH of the reaction system was adjusted to a range of 7.5 to 8.5 while adding ammonia water as appropriate. After completion of the dropwise addition, the reaction was continued for 2 hours while maintaining the temperature at 100 ° C. to obtain a polymer solution 5. The obtained polymer solution 5 had a solid content of 29.9%, a K value of 29.6, and an amount of 2-pyrrolidone of 11204 ppm based on the solid content.

[0037] Graft polymerization

A milky white emulsion was obtained in the same manner as in Comparative Example 1 except that the polymer solution 5 was used instead of the polymer solution 4. In this N-butylpyrrolidone-based graft polymer 5, the above-mentioned graft ratio was 11.0%.

[0038] (Comparative Example 3)

Base PVP synthesis

Polymerization was carried out in the same manner as in Comparative Example 1 except that 2 parts of 25% aqueous ammonia solution and 10 parts of 30% aqueous hydrogen peroxide solution were used to obtain polymer solution 6. Of the resulting polymer solution 6 Solids [or, 30. 1 ^_0/0 kappa value ί or 16.0, the flashing with 35369ppm against 2-pyrrolidone amount ί or solids.

[0039] Graft polymerization

A milky white emulsion was obtained in the same manner as in Comparative Example 1 except that the polymer solution 6 was used instead of the polymer solution 4. With respect to this N-butylpyrrolidone-based graft polymer 6, the aforementioned graft ratio was determined to be 9.3%.

[0040] Substrate hydrophilization test

The N-butylpyrrolidone-based graft polymer emulsions obtained in Example 1 and Comparative Example 1 were each dried at 120 ° C. for 1 hour to obtain powder. Using the obtained N-butylpyrrolidone graft polymer, a polyethersulfone hydrophilization test was conducted.

Polyethersulfone (Sumitomo Chemical Co., Ltd .: SUMIKAETACEL PES 5400P) 5 parts, 1 part of N-Burpi-Lidone Graft Polymer is dissolved in 20 parts of N, N-dimethylacetamide, and 0.07 mm applicator is used To form a film on a glass plate. Next, when this glass plate was immersed in ion-exchanged water, a white thin film was obtained. This thin film was further immersed in ion-exchanged water for 1 hour, then attached on a silicon sheet, and air-dried under conditions of 25 ° C and 60% humidity for 24 hours. The contact angle between the obtained thin film and water was measured. Here, the contact angle was evaluated by using a contact angle measuring device (“FACE contact angle meter CA-X” manufactured by Kyowa Interface Chemical Co., Ltd.) as the contact angle with water 30 seconds after dropping. In addition, as a blank test, a film was formed and dried in the same manner even under conditions in which no N-butylpyrrolidone-based graft polymer was used, and a contact angle was measured. The results are shown in Table 1.

[0041] [Table 1]

It is considered that when N-bulylpyrrolidone-based graft polymer 1 having a high graft ratio is used, the contact angle becomes smaller and the hydrophilicity of the surface is greatly improved. Thus, the hydrophilicity of the surface has been improved, and an improvement in stain resistance can be expected. By using a polymer with a high graft rate, the polymer fixing rate to the surface of the polyethersulfone substrate is improved, and as a result, it is considered that the polymer has been made hydrophilic.

[0043] [Emulsification dispersion test]

DL-α-tocophenol 0.1 part was added to 10 parts of the N-bulylpyrrolidone-based graft polymer emulsion obtained in Examples and Comparative Examples prepared at 20% by mass, and the mixture was stirred at room temperature for 5 minutes. The appearance of the later solution was visually confirmed. The results are shown in Table 2.

No release of DL α tocopherol was confirmed.

DL α Tocopherol release confirmed X

[0044] [Table 2]

[0045] From Table 2, the release of DL-a tocophenol was not confirmed in the examples and the effect of stabilizing the dispersion of tocophenol was observed, but the release was confirmed in the comparative example. In other words, in the examples where the graft ratio forces were 6%, 15.4%, and 14.3%, a sufficient dispersion stabilizing effect was observed, while the graft ratios were 10.3%, 11.0%, 9 In the comparative example of 3%, a sufficient dispersion stabilizing effect was not observed, and there was a large difference in the dispersion stabilizing effect between the example and the comparative example, and it was clear that the utility was significantly different industrially. Became.

Industrial applicability

[0046] The method for producing an N-bulupyrrolidone-based graft polymer of the present invention comprises the above-described configuration, and produces an N-bulurpyrrolidone-based graft polymer in which the graft ratio of the vinyl monomer as a graft component is improved. can do. In addition, since such a N-butylpyrrolidone-based graft polymer can impart a sufficient hydrophilicity to the surface of the base material because the plastic base material has a stain-proof function, the N-bulu of the present invention The method for producing a pyrrolidone-based graft polymer is industrially useful.

Claims

The scope of the claims

[1] A method for producing an N-bulupyrrolidone-based graft polymer composition comprising a step of reacting an N-bulupyrrolidone-based polymer with a bull-based monomer,

The production method is a method for producing an N-vinylpyrrolidone-based graft polymer composition, wherein the reaction is carried out with the content of 2-pyrrolidone in the raw material N-butylpyrrolidone-based polymer being lOOOOppm or less.

[2] An N-bulupyrrolidone-based graft polymer composition of an N-bulupyrrolidone polymer and a bull monomer,

The N-vinylpyrrolidone-based graft polymer composition has a graft ratio of 13% or more.

[3] An N-bulupyrrolidone-based graft polymer composition of an N-bulupyrrolidone-based polymer and a bull-based monomer,

The N-vinylpyrrolidone-based graft polymer composition is characterized in that the dissolution curve of gel permeation chromatography has a single peak.