JP2010059239A - Curable ethylenic unsaturated monomer, one-component-curable polymer emulsion composition, and product made of resin using the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-component-curable polymer emulsion that has one-component curability as a polymer emulsion, produces a dry film excellent in water resistance and solvent resistance, and contains no toxic component, and to provide a product made of a resin using the polymer emulsion. <P>SOLUTION: An ethylenic unsaturated monomer that contains a 4,5-dihydroxy-2-imidazolidinone group is prepared by reacting an ethylenic unsaturated monomer having a urea group, which is obtained by a reaction of an ethylenic unsaturated monomer having an isocyanate group with an amine, with glyoxal under a condition of a pH 6-8. The one-component-curable polymer emulsion composition is produced by emulsion polymerization of a monomer composition which includes the 4,5-dihydroxy-2-imidazolidinone group-containing ethylenic unsaturated monomer, and another ethylenic unsaturated monomer. The product made of the resin using the emulsion composition is also disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a one-component cross-linking emulsion composition that is useful as a binder for paints, fibers, paper, pressure-sensitive adhesives, adhesives, and the like, and is excellent in water resistance and solvent resistance, and a resin processed product using the same.

  In recent years, there has been a strong interest in water-based resins that do not contain organic solvents from the viewpoint of resource saving and environmental conservation. Among these, polymer emulsions are widely used as binders for paints, fibers, paper, and the like because they have a high molecular weight, are relatively excellent in drying properties, and can be reduced in viscosity even when the solid content concentration is increased. However, these polymer emulsions use a relatively large amount of a water-soluble surfactant or dispersion stabilizer to stably disperse the oil-soluble polymer in water, so that the water resistance, solvent resistance, and chemical resistance of the dried film are reduced. There was an inferior problem.

  In order to solve this problem, a dry film having improved water resistance, solvent resistance, and chemical resistance is introduced by introducing a functional group into a polymer molecule of a polymer emulsion and causing a crosslinking reaction using the functional group. Many methods have been proposed for forming.

  As a polymer emulsion that forms a cross-linked film to improve water resistance, etc., a cross-linkable monomer is copolymerized in advance in the polymer molecule, or a cross-linking agent is added to a polymer emulsion having a certain kind of functional group. The two-part cross-linked polymer emulsions, which are formed by adding a cross-linking agent immediately before use, are classified into a one-part cross-linkable polymer emulsion that causes a cross-linking reaction when a dry film is formed.

  Among these, the two-component cross-linkable polymer emulsion has no problem in the storage stability of the main agent, but the workability is inferior because the cross-linking agent is added to the polymer emulsion immediately before use, and the pot after the cross-linking agent is added. Since there is a problem in life, a one-component crosslinked polymer emulsion is advantageous in actual use.

  One-pack crosslinkable polymer emulsions include those using a crosslinkable monomer such as N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide as a crosslinkable component. These crosslinkable components are heat-crosslinked polymer emulsions that generally require heat treatment after resin coating, and not only do they require thermal energy during the crosslinking reaction, but also formaldehyde, which is highly toxic during the crosslinking reaction. There was a problem of occurrence.

  Recently, a one-component cross-linking polymer emulsion using a hydrazine derivative as a cross-linking agent in an aldo group or keto group-containing polymer emulsion has been proposed (see, for example, Patent Document 1 and Patent Document 2). However, in this type of one-part crosslinked polymer emulsion, the hydrazine derivative coexisting in the system used as a crosslinking agent undergoes hydrolysis during storage to produce free hydrazine, and this hydrazine has a problem in terms of toxicity. .

  Further, as another one-component crosslinking polymer emulsion, a type in which a polyfunctional aldehyde derivative is used as a crosslinking agent in a urea group-containing polymer emulsion has been proposed (see, for example, Patent Document 3, Patent Document 4, and Patent Document 5). This type also shows room temperature crosslinkability similar to the crosslinking system of aldo group or keto group and hydrazine derivative, and various resistances of dry film, but the polyfunctional aldehyde derivative used as a crosslinker has mutagenesis. However, there is a problem in terms of toxicity of the crosslinking agent.

  In addition to these, various types of one-component cross-linked polymer emulsions have been proposed, but none are satisfactory in terms of cross-linkability, water resistance of dry film, solvent resistance, and toxicity. There is a strong demand for the development of a new type of one-part crosslinked polymer emulsion.

JP-A-2-175742 Japanese Patent Laid-Open No. 10-168380 US Pat. No. 5,468,800 German Patent No. 4439457 JP 2002-265749 A

  In view of such a situation, the present invention has a one-part crosslinkability as a polymer emulsion, and the obtained dry film is excellent in water resistance and solvent resistance and does not contain a toxic component. It aims at providing the resin processed product using it.

  The inventors of the present invention have a one-component crosslinkability, and the obtained dry film is excellent in water resistance and solvent resistance, and does not contain a toxic component, and a resin processed product using the same We made extensive studies with the aim of providing As a result, the 4,5-dihydroxy-2-imidazolidinone group-containing copolymer emulsion has no generation of toxic components and is used for resin processing to obtain a resin processed product having excellent water resistance and solvent resistance. Based on this finding, the present invention has been completed.

（式中、Ｒ^１はＨ又はメチル基であり、Ｒ^２は直鎖状又は分岐鎖状の炭素数１〜８のアルキル基であり、炭素に結合している水素が水酸基で置換されていてもよい）で表される４，５−ジヒドロキシ−２−イミダゾリジノン基を有するエチレン性不飽和単量体に関する。 That is, the present invention provides the formula (1):

(In the formula, R ¹ is H or a methyl group, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms, and hydrogen bonded to carbon is substituted with a hydroxyl group. The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group represented by:

  The present invention also provides a reaction between an ethylenically unsaturated monomer having a urea group obtained from the reaction of an ethylenically unsaturated monomer having an isocyanate group and an amine with glyoxal at a pH of 6-8. And an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group.

  The ethylenically unsaturated monomer having an isocyanate group is preferably (meth) acrylic acid 2-isocyanate alkyl.

  Furthermore, the present invention is obtained by emulsion polymerization of a monomer composition comprising an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group and another ethylenically unsaturated monomer. The present invention relates to a one-component crosslinked polymer emulsion composition.

  The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group may be a monomer obtained from a reaction between an ethylenically unsaturated monomer having a urea group and glyoxal. preferable.

  The ethylenically unsaturated monomer having a urea group is preferably a monomer obtained from a reaction between an ethylenically unsaturated monomer having an isocyanate group and an amine.

  The ethylenically unsaturated monomer having a urea group is preferably a monomer obtained from the reaction of 2-methacrylic acid 2-isocyanate alkyl with an amine.

  The amount of the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group is preferably 0.1 to 10 mol% of the monomer composition.

  The present invention relates to a processed resin product using the one-part crosslinking polymer emulsion composition.

  According to the present invention, a one-component cross-linkable polymer emulsion having a one-component cross-linkability and excellent in water resistance and solvent resistance and containing no toxic components, and a resin processed product using the same Can be provided.

  The present invention is described in detail below. The one-part crosslinked polymer emulsion of the present invention is obtained by emulsion polymerization of an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group and another ethylenically unsaturated monomer. The one-pack crosslinked polymer emulsion of the present invention is one in which hydroxyl groups between 4,5-dihydroxy-2-imidazolidinone groups in a polymer undergo dehydration condensation and are crosslinked.

（式中、Ｒ^１はＨ又はメチル基であり、Ｒ^２は直鎖状又は分岐鎖状の炭素数１〜８のアルキル基であり、炭素に結合している水素が水酸基で置換されていてもよい）で表される４，５−ジヒドロキシ−２−イミダゾリジノン基を有するエチレン性不飽和単量体であることが好ましい。式（１）中、Ｒ^２は直鎖状又は分岐鎖状の炭素数１〜８のアルキル基であり、炭素数が８より大きいと、他のエチレン性不飽和単量体に不溶となる傾向にある。 Examples of the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group include formula (1):

(In the formula, R ¹ is H or a methyl group, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms, and hydrogen bonded to carbon is substituted with a hydroxyl group. The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group represented by In the formula (1), R ² is a linear or branched alkyl group having 1 to 8 carbon atoms, and when the carbon number is larger than 8, it tends to be insoluble in other ethylenically unsaturated monomers. It is in.

  The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group of the present invention is obtained from the reaction of an ethylenically unsaturated monomer having a urea group and glyoxal.

  The ethylenically unsaturated monomer having a urea group of the present invention can be obtained by reacting an ethylenically unsaturated monomer having an isocyanate group with an amine as a simple synthesis method.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include (meth) acryloyl isocyanate, (meth) acrylic acid 2-isocyanate alkyl, (meth) acryloyloxyphenyl isocyanate, and an ethylenically unsaturated monomer having a hydroxyl group. And an adduct of diisocyanate and the like. Examples of the ethylenically unsaturated monomer having a hydroxyl group include glycols (meth) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples include acrylates, allyl alcohol, and monoallyl ether of polyhydric alcohol. Among these, (meth) acrylic acid 2-isocyanate alkyl is preferable.

  Examples of amine compounds that react with an ethylenically unsaturated monomer having an isocyanate group to generate a urea group include primary amines such as methylamine, ethylamine, propylamine, butylamine, octylamine, cyclohexylamine, and ethanolamine, dimethyl Secondary amines such as amine, diethylamine and diethanolamine are used. Of these, ethanolamine is preferable in terms of solubility in other unsaturated monomers. The amount of amine used is preferably equimolar to the ethylenically unsaturated monomer having an isocyanate group.

（式中、Ｒ^１はＨ又はメチル基であり、Ｒ^２は直鎖状又は分岐鎖状の炭素数１〜８のアルキル基であり、炭素に結合している水素が水酸基で置換されていてもよい）で表される、ウレア基を有するエチレン性不飽和単量体が得られる。そして、ウレア基を有するエチレン性不飽和単量体と、グリオキザールとの反応により、式（１）で表される４，５−ジヒドロキシ−２−イミダゾリジノン基を有するエチレン性不飽和単量体が得られる。 By reaction of an ethylenically unsaturated monomer having an isocyanate group (isocyanate alkyl (meth) acrylate) with an amine, the formula (2):

(In the formula, R ¹ is H or a methyl group, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms, and hydrogen bonded to carbon is substituted with a hydroxyl group. It is also possible to obtain an ethylenically unsaturated monomer having a urea group. An ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group represented by the formula (1) is obtained by reacting an ethylenically unsaturated monomer having a urea group with glyoxal. Is obtained.

  The reaction between the ethylenically unsaturated monomer having an isocyanate group and the amine is carried out in an organic solvent that is relatively easy to distill off, such as ethyl acetate and methylene chloride. After completion of the reaction, the organic solvent is removed by concentration under reduced pressure. The

  The reaction between the ethylenically unsaturated monomer having a urea group and glyoxal is carried out under conditions where the pH is 6-8. When the pH is lower than 6, the addition reaction rate of glyoxal decreases, and when the pH is higher than 8, the system tends to be colored. In addition, the reaction temperature between the ethylenically unsaturated monomer having a urea group and glyoxal is preferably 40 to 60 ° C, and when the temperature is lower than 40 ° C, the addition reaction rate of glyoxal is decreased and higher than 60 ° C. The system tends to be easily colored.

  The amount of glyoxal used is preferably equimolar to the ethylenically unsaturated monomer having a urea group.

  Other monomers copolymerizable with the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group include methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2- (meth) acrylic acid 2- Examples include ethyl hexyl, (meth) acrylic acid esters such as lauryl (meth) acrylate, stearyl (meth) acrylate, styrene, vinyl acetate, vinyl propionate, and the like. Moreover, in order to improve the emulsion polymerization stability or mechanical stability of the aqueous emulsion obtained, (meth) acrylic acid 2-hydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Alkyl, (meth) acrylamide, (meth) acrylonitrile, glycidyl (meth) acrylate, and the like can be used. Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and half esters of these unsaturated dicarboxylic acids. These 1 type or 2 types or more may be mixed and used.

  Furthermore, in order to further improve the solvent resistance of the obtained one-part cross-linked polymer emulsion, a crosslinkable polyfunctional monomer having two or more unsaturated groups such as divinylbenzene and ethylene glycol di (meth) acrylate, or molecular weight Mercaptan, thioglycolic acid and its ester, β-mercaptopropionic acid and its ester, etc. may be used to adjust the pH.

  Examples of the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group in the one-part crosslinked polymer emulsion of the present invention include 0.1 to 0.1% of all monomers constituting the copolymer. It is used in the range of 10 mol%, preferably in the range of 0.5 to 5 mol%. When the amount used is less than 0.1 mol%, the degree of crosslinking of the 4,5-dihydroxy-2-imidazolidinone group in the polymer emulsion is low, and the resulting resin processed product has poor water resistance and solvent resistance. It will be enough. On the other hand, when it exceeds 10 mol%, the reactivity and stability at the time of emulsion polymerization decrease, which is not preferable.

  As the surfactant used in the emulsion polymerization of the present invention, a normal anionic surfactant, cationic surfactant, or nonionic surfactant is used. As anionic surfactant, alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, etc. are used, and as cationic surfactant, alkyl trimethyl ammonium chloride, etc. are used, and nonionic As the surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene alkyl ether is used.

（式中、Ｒはアルキル基、ｎは１０又は２０）で表される反応性界面活性剤、式（４）：

（式中、ｎは９又は１１、ｍは５又は１０）で表される反応性界面活性剤、式（５）：

（式中、ＲはＣ_１２Ｈ_２５又はＣ_１８Ｈ_３６Ｆで表される基、ＭはＮＨ_４又はＮａで表される基）で表される反応性界面活性剤があげられる。これらの反応性界面活性剤は、乾燥皮膜の耐水性に優れるという点で好ましい。 In addition, a radically polymerizable reactive surfactant can be used in the emulsion polymerization. The reactive surfactant is not particularly limited as long as it is reactive, but a more preferable reactive surfactant is represented by the formula (3):

(Wherein R is an alkyl group and n is 10 or 20), a reactive surfactant represented by formula (4):

(Wherein n is 9 or 11, m is 5 or 10), a reactive surfactant represented by formula (5):

(Wherein, R represents a group represented by C ₁₂ H ₂₅ or C ₁₈ H ₃₆ F, and M represents a group represented by NH ₄ or Na). These reactive surfactants are preferable in that they are excellent in water resistance of the dry film.

  The amount of the surfactant used is preferably 0.1 to 5% by weight based on the total weight of the ethylenically unsaturated monomer composition. If the amount of the surfactant used is less than 0.1% by weight, emulsion polymerization is difficult, and even if emulsion polymerization is possible, there is a problem in polymerization stability, and the particle system of the obtained aqueous emulsion becomes large. It is not preferable in terms of storage stability. Moreover, when the usage-amount of surfactant exceeds 5 weight%, the hot water resistance of resin falls, and there exists a problem in the hot water resistant adhesion as a resin processed product, and is unpreferable.

  Examples of radical polymerization initiators used in emulsion polymerization include ammonium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, azobisamidinopropane hydrochloride, and the like. A redox system using a reducing agent such as sodium sulfite, Rongalite or ascorbic acid may be applied.

  As the emulsion polymerization method of the one-part cross-linked polymer emulsion of the present invention, a polymerization method in which the components are charged in a batch, a method in which each component is polymerized while being continuously supplied, and the like are applied. The polymerization is usually carried out at a temperature of 30 to 90 ° C. with stirring. In the present invention, when an unsaturated carboxylic acid is used, a basic substance is added during the polymerization or after completion of the polymerization to adjust the pH so that the polymerization stability, mechanical stability, and chemical stability during the emulsion polymerization can be achieved. Can be improved. In addition, the additive miscibility when adding a film-forming aid to a polymer emulsion having a high Tg can be significantly improved. In this case, it is preferable to adjust the pH of the resulting one-pack crosslinked polymer emulsion to 7 or higher. As the basic substance used in this case, ammonia, ethylamine, ethanolamine, caustic soda and the like can be used.

  In order to further improve the leveling agent, antifoaming agent, preservative, and weather resistance, an ultraviolet absorber, a light stabilizer, and the like can be added to the one-pack crosslinked polymer emulsion of the present invention as necessary.

  Although it does not specifically limit as a use of the one-pack bridge | crosslinking type polymer emulsion of this invention, It uses suitably as binders, such as a coating material, a fiber, paper, an adhesive, and an adhesive agent.

  The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group of the present invention can be suitably used for emulsion polymerization, but other polymerization methods such as suspension polymerization and solution polymerization. Thus, it is possible to obtain a cross-linked polymer by polymerizing with another copolymerizable monomer.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are not intended to limit all of the present invention, and all the examples carried out without departing from the contents of the present description are within the scope of the present invention. Included in the technical scope. Moreover, part and% show a mass part and the mass%, respectively, unless there is particular notice.

  The performance evaluation test method for the dried film and the resin processed product will be described below.

(1) Water resistance and solvent elution rate of dried film The obtained polymer emulsion was dried at 23 ° C. and 65% RH for 7 days to prepare a dried film. Each of the prepared dry films was immersed in water or toluene for 1 day, and the water elution rate and solvent elution rate were measured. The water elution rate and solvent elution rate were calculated by the following formulas.

(2) Strength measurement of resin processed product The obtained polymer emulsion was diluted to 10%, impregnated with filter paper (Toyo Filter Paper Co., Ltd .: qualitative filter paper for analysis No. 2) at 25 g / m ² , and at 110 ° C. for 10 minutes Dried. The prepared resin processed product is heat-treated in an oven at 150 ° C. for 5 minutes, and then the tensile strength (normal strength) of the resin processed product and the tensile strength (wet strength) of the resin processed product immediately after being immersed in water at 23 ° C. for 10 minutes. ) Was measured. (Tensile speed 200mm / min)

(3) Measurement of contained formaldehyde and amount of glyoxal The obtained polymer emulsion was measured using gas chromatography (manufactured by Shimadzu Corporation / gas chromatograph GC-14B).

(I) Synthesis of ethylenically unsaturated monomer (UMA-1G) having 4,5-dihydroxy-2-imidazolidinone group Ethyl acetate was added to a separable flask having a thermometer, a stirrer, a drying tube and a dropping funnel. 225 parts and 2-isocyanatoethyl methacrylate 53.5 parts were charged and cooled to 5-10 ° C. Subsequently, a mixture of 21 parts of ethanolamine and 20 parts of ethyl acetate was added dropwise over 2 hours with stirring, and the mixture was maintained for 3 hours after the addition. Thereafter, the mixture was concentrated under reduced pressure to remove ethyl acetate, and an ethylenically unsaturated monomer having a urea group was obtained.

  A separable flask having a thermometer, a stirrer, a condenser tube and a dropping funnel was charged with 13.8 parts of 40% glyoxal and 9.5 parts of water, the pH in the system was adjusted to 7 with caustic soda, and the temperature was raised to 40 ° C. . Subsequently, an ethylenically unsaturated monomer having a urea group synthesized while stirring was dropped over 4 hours, and held for 2 hours after the completion of dropping to obtain UMA-1G.

The ¹³ CNMR spectrum of the obtained UMA-1G was measured with an FTNMR apparatus (manufactured by JEOL Ltd./JNM-EX270). ^{The 13} C NMR spectrum is shown in FIG. As a result of the ¹³ C NMR spectrum of FIG. 1, it can be seen that UMA-1G has the structural formula shown in FIG. FIG. 2 is a diagram showing the correspondence between the structural formula of UMA-1G and each peak of the ¹³ C NMR spectrum. The peak at 172 ppm in FIG. 1 relates to the carbon atom indicated by h in FIG. 2, and the peak at 162 ppm is the carbon atom indicated by c, the peak at 138 ppm is the carbon atom indicated by j, and the peak at 129 ppm. Is the carbon atom indicated by k, the peak at 87 ppm is the carbon atom indicated by e and d, the peak at 66 ppm is the carbon atom indicated by g, the peak at 62 ppm is the carbon atom indicated by a, the peaks at 45 ppm and 41 ppm are f Alternatively, the carbon atom represented by b and the peak at 20 ppm relate to the carbon atom represented by i.

(II) Synthesis of UMA-2G UMA-2G was subjected to the same reaction as UMA-1G, except that the amine was changed from 21 parts of ethanolamine to 25 parts of n-butylamine to obtain UMA-2G.

(III) Synthesis of UMA-3G In the synthesis of UMA-3G, the same reaction as UMA-1G was performed, except that 53.5 parts of 2-isocyanate ethyl methacrylate was changed to 48.7 parts of 2-isocyanate ethyl acrylate, UMA-3G was obtained.

[Example 1]
A separable flask having a condenser, thermometer, stirrer, and dropping funnel was charged with 100 parts of water and 0.4 part of sodium dodecyl sulfate, and the temperature was raised to 80 ° C. Immediately after adding 0.5 parts of ammonium persulfate, 180 parts of water, 3.6 parts of sodium dodecyl sulfate, 99.5 parts of methyl methacrylate, 97.1 parts of butyl acrylate, 2.5 parts of UMA-1G (to monomer) 0.5 mol%) was added dropwise over 3 hours. At the same time, a solution prepared by dissolving 0.5 part of ammonium persulfate in 20 parts of water was added dropwise over 3 hours. Thereafter, the inner temperature was maintained at 80 ° C. for 1 hour and cooled. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Example 2]
The same operation as in Example 1 was performed except that UMA-1G was changed to UMA-2G to obtain a one-pack crosslinked polymer emulsion. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Example 3]
Except that UMA-1G was changed to UMA-3G, the same operation as in Example 1 was performed to obtain a one-pack crosslinked polymer emulsion. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Examples 4 to 6]
The same operation as in Example 1 was performed except that the amount of UMA-1G used was changed to obtain a one-pack crosslinked polymer emulsion. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Example 7]
The same operation as in Example 1 was carried out except that sodium dodecyl sulfate was changed to the reactive emulsifier of formula (3) to obtain a one-pack crosslinked polymer emulsion. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Comparative Example 1]
The same operation as in Example 1 was carried out except that an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group was not used, to obtain a one-pack crosslinked polymer emulsion. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Comparative Example 2]
The same operation as in Example 1 was carried out except that the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group was changed to N-methylolacrylamide (2.5 mol% to monomer), A one-pack crosslinked polymer emulsion was obtained. Table 1 shows the water resistance and solvent elution rate of the dried film of the obtained one-component cross-linked polymer emulsion, and Table 2 shows the evaluation results of the resin processed products.

[Comparative Example 3]
A separable flask having a condenser, a thermometer, a stirrer, and a dropping funnel was charged with 100 parts of water and 0.4 part of sodium dodecyl sulfate and heated to 80 ° C. Immediately after adding 0.5 parts of ammonium persulfate, 180 parts of water, 3.6 parts of sodium dodecyl sulfate, 99.5 parts of methyl methacrylate, 97.1 parts of butyl acrylate, an ethylenically unsaturated monomer having a urea group An emulsion prepared in advance from 2 parts (based on 0.5 mol% of monomer) of (an adduct of 2-isocyanatoethyl methacrylate and ethanolamine at the time of UMA-1G synthesis) was added dropwise over 3 hours. At the same time, a solution prepared by dissolving 0.5 part of ammonium persulfate in 20 parts of water was added dropwise over 3 hours. Thereafter, the inner temperature was maintained at 80 ° C. for 1 hour and cooled. To the resulting polymer emulsion, 2.5 parts of 40% glyoxal was added as a crosslinking agent to obtain a crosslinked polymer emulsion. The water resistance and solvent elution rate of the dry film of the cross-linked polymer emulsion are shown in Table 1, and the evaluation results of the processed resin products are shown in Table 2.

[Comparative Example 4]
A crosslinked polymer emulsion was prepared in the same manner as in Comparative Example 3 except that the amount of 40% glyoxal added as a crosslinking agent was changed to 0.068 parts (1 equivalent of urea group and 0.1 equivalent of aldehyde group). Got. The water resistance and solvent elution rate of the dry film of the cross-linked polymer emulsion are shown in Table 1, and the evaluation results of the processed resin products are shown in Table 2.

[Comparative Example 5]
A cross-linked polymer emulsion was obtained in the same manner as in Comparative Example 3 except that the amount of 40% glyoxal added as a cross-linking agent was changed to 1.33 parts (the same amount used as glyoxal used in Example 1). The water resistance and solvent elution rate of the dry film of the cross-linked polymer emulsion are shown in Table 1, and the evaluation results of the processed resin products are shown in Table 2.

  From the results of Examples 1 to 7 and Comparative Examples 1 to 5, it can be seen that the dry film obtained from the one-part cross-linked polymer emulsion of the present invention is excellent in water resistance and solvent resistance and does not contain a toxic component.

It is a figure which shows the ¹³ CNMR spectrum of UMA-1G. It is a figure which shows the correspondence of the structural formula of UMA-1G, and each peak of a ¹³ CNMR spectrum.

Claims (9)

Formula (1):

(In the formula, R ¹ is H or a methyl group, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms, and hydrogen bonded to carbon is substituted with a hydroxyl group. Or an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group. 4, obtained by reacting an ethylenically unsaturated monomer having a urea group obtained from the reaction of an ethylenically unsaturated monomer having an isocyanate group with an amine, and glyoxal under conditions of pH 6-8. An ethylenically unsaturated monomer having a 5-dihydroxy-2-imidazolidinone group. The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group according to claim 2, wherein the ethylenically unsaturated monomer having an isocyanate group is 2-isocyanate alkyl (meth) acrylate. . One-part cross-linked polymer obtained by emulsion polymerization of a monomer composition comprising an ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group and another ethylenically unsaturated monomer Emulsion composition. The ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group is a monomer obtained from a reaction between an ethylenically unsaturated monomer having a urea group and glyoxal. 5. A one-component cross-linked polymer emulsion composition according to 4. 6. The one-component cross-linked polymer emulsion composition according to claim 5, wherein the ethylenically unsaturated monomer having a urea group is a monomer obtained from a reaction between an ethylenically unsaturated monomer having an isocyanate group and an amine. object. The one-component cross-linked polymer emulsion composition according to claim 6, wherein the ethylenically unsaturated monomer having a urea group is a monomer obtained from a reaction of 2-isocyanate alkyl (meth) acrylate with an amine. The amount of the ethylenically unsaturated monomer having a 4,5-dihydroxy-2-imidazolidinone group is 0.1 to 10 mol% of the monomer composition. The one-component cross-linking polymer emulsion composition according to any one of the above. A resin processed product using the one-component cross-linking polymer emulsion composition according to any one of claims 4, 5, 6, 7 and 8.

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