JPH1030034A - Chloroprene copolymer latex composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising the aqueous dispersion of a chloroprene copolymer comprising chloroprene copolymerization units and ester monomer copolymerization units, capable of being substantially produced without using a solvent and capable of imparting a highly lustrous finish to an immersed product, etc. SOLUTION: This chloroprene copolymer latex composition comprises the aqueous dispersion of a chloroprene copolymer comprising (A) 75-95wt.% of chloroprene copolymerization units and (B) 5-25wt.% of the copolymerization units of at least one kinds of ester monomer selected from the group consisting of the 1-10C alkyl ester of (meth)acrylic acid, the 1-10C hydroxyl ester of the acid, and the 7-10C cycloalkyl ester of the acid. The total amount of the components A and B is at least 90wt.%. The chloroprene copolymer is prepared by subjecting the chloroprene and the ester to a releasing group emulsion copolymerization in the presence of a modifying agent comprising a mercaptan compound, a dialkylxanthogen disulfide or dialkoxyxanthogen disulfide to a polymerization degree of at least 90%. The solid content of the copolymer is 35-65wt.% based on the whole weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chloroprene / acrylate or chloroprene / methacrylic ester graft copolymer latex composition. In particular, the present invention relates to chloroprene / acrylic ester or chloroprene / methacrylic ester grafting, which is particularly useful in the manufacture of products having high surface gloss.
It relates to a copolymer latex composition.

[0002] The description in this specification is based on US Patent Application No. 60 / 013,492 (1), which is the priority of the present application.
(Filed on Mar. 15, 996), and the contents of the specification of the U.S. patent application constitute a part of the specification by reference to the number of the U.S. patent application. Shall be.

[0003]

2. Description of the Prior Art Conventional methods of manufacturing elastomeric products such as gloves, balloons and condoms involve, as a first step, a dip-forming form or object to be coated, in an organic solvent solution of the elastomer. Alternatively, the method includes a step of dipping in an elastomer latex. The coated dip-forming male or object is then lifted out of the coating medium, and the resulting elastomeric product or object coated with the elastomer is dried and optionally cured. Products manufactured by this method are known as dipping products.

[0004] Surface gloss is a desirable property in elastomeric products for aesthetic reasons. For immersion products,
Sufficient gloss can be obtained by an organic solvent immersion method. Gloves and other dipping products manufactured by such methods exhibit excellent surface appearance, but necessarily require large amounts of solvent, which has raised environmental and health concerns. The ultimate goal of the immersion product industry is an alternative that produces a glossy finish comparable to that produced by the solvent process, but with a substantially reduced amount of organic solvent or no use at all. Is to develop an elastomer product. For this reason, many aqueous latex systems have been used as alternatives to solvent-based systems, but unfortunately these alternative systems do not produce products with comparable gloss and appearance. Therefore, these alternative systems have not been employed in the immersion product industry.

[0005] Copolymers of chloroprene and alkyl acrylates or methacrylates are elastomeric compositions, which are commercially available in the form of solid or aqueous latexes. Generally, such compositions have been used in the manufacture of adhesives. It has now been found that certain chloroprene / alkyl acrylate graft copolymer latexes or chloroprene / alkyl methacrylate graft copolymer latexes can be produced and form highly glossy films on dipped products. Was.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to overcoming the above-mentioned problems of the prior art by preparing it substantially without solvents and, when used in the manufacture of dipped products, to a high degree. It is an object of the present invention to provide a latex composition capable of imparting a glossy finish to a latex composition, a method for producing the latex composition, a coated product that can be produced using the latex composition, and the production method.

[0007]

A chloroprene copolymer / latex composition for solving the above-mentioned problems comprises a copolymer of chloroprene having a copolymerization unit of 75 to 95% by weight and (i) a C ₁ -C ₁₀ alkyl ester of acrylic acid. , Acrylic acid C
C ₁ -C ₁₀ hydroxyalkyl esters of acrylic acid and C ₁ -C ₁₀ cycloalkyl esters of acrylic acid and (ii) C ₁ -C ₁₀ alkyl esters of methacrylic acid, C ₁ -C ₁₀ hydroxyalkyl esters of methacrylic acid and C of methacrylic acid ₁ -C ₁₀ least one copolymerized units aqueous chloroprene copolymer latex composition comprising an aqueous dispersion of a chloroprene copolymer containing a 5-25% by weight of the ester monomer selected from the group consisting of cycloalkyl esters Wherein the total weight percent of the copolymerized units of chloroprene and the copolymerized units of the ester monomer is at least 90% by weight, and the chloroprene polymer is a modified product of mercaptan, dialkylxanthogen disulfide or dialkoxyxanthogen disulfide. Of the modifier In the presence by free radical emulsion polymerization to a degree of polymerization of at least 90%, and wherein the copolymer solids content of the copolymer latex composition is 35-65, based on the total weight of the copolymer latex composition. % By weight.

In the above composition, the solid content of the copolymer latex composition may be 40 to 60% by weight based on the total weight of the copolymer latex composition.

[0009] The above-mentioned composition comprises the above-mentioned chloroprene.
The copolymer is a C _{1 of} chloroprene and methacrylic acid.
Copolymerized units of -C ₁₀ alkyl esters may contain. In this case, the C ₁ -C ₁₀ alkyl ester of methacrylic acid may be methyl methacrylate.

The method according to the present invention is a method for producing a product having a glossy elastic surface, comprising: (a) a C ₁ -C ₁₀ alkyl ester of acrylic acid, a C ₁ -C ₁₀ hydroxyalkyl of acrylic acid. Esters and C ₁ -C ₁₀ cycloalkyl esters of acrylic acid and (ii) C ₁ -C ₁₀ alkyl esters of methacrylic acid, C ₁ -C ₁₀ hydroxyalkyl esters of methacrylic acid and C ₁ -C ₁₀ cycloalkyl of methacrylic acid. An aqueous chloroprene copolymer latex composition comprising an aqueous dispersion of a chloroprene copolymer containing from 5 to 25% by weight of copolymerized units of at least one ester monomer selected from the group consisting of alkyl esters, Total weight percent of the copolymerized units of the chloroprene and the copolymerized units of the ester monomer At least 90 wt%
Wherein the chloroprene polymer is a mercaptan,
At least 90% in the presence of a dialkyl xanthogen or dialkoxy xanthogen modifier
Water-based chloroprene, which is prepared by free-radical emulsion polymerization up to a polymerization rate of 35 to 65% by weight based on the total weight of the copolymer latex composition. Dipping the object to be coated in the copolymer latex composition; and (b) removing the object from the aqueous chloroprene for a time sufficient to allow a cohesive copolymer film to grow on the object. -A step of keeping the copolymer-latex composition retained; and (c) a step of removing the object from the aqueous chloroprene copolymer-latex composition.

In the above method, the solid content of the copolymer latex composition may be 40 to 60% by weight based on the total weight of the copolymer latex composition.

Further, the above-mentioned method comprises the steps of:
The copolymer is a C _{1 of} chloroprene and methacrylic acid.
Copolymerized units of -C ₁₀ alkyl esters may contain. In this case, the C ₁ -C ₁₀ alkyl ester of methacrylic acid may be methyl methacrylate.

A coated product according to the present invention is characterized in that it is manufactured by the above method.

A glove according to the present invention is a glove having a glossy finish, wherein the copolymerized unit of chloroprene has 7 units.
And 5 to 95 _{wt%, (i) C 1 ~C} 10 alkyl esters, C ₁ -C ₁₀ hydroxyalkyl esters and C ₁ -C ₁₀ cycloalkyl esters and (ii) methacrylic acid acrylic acid acrylic acid Acrylic acid And at least one ester monomer selected from the group consisting of C ₁ -C ₁₀ alkyl esters of methacrylic acid, C ₁ -C ₁₀ hydroxyalkyl esters of methacrylic acid, and C ₁ -C ₁₀ cycloalkyl esters of methacrylic acid has 5 copolymer units. Gloves comprising an outer layer of a chloroprene copolymer containing at least 90% by weight of said chloroprene copolymerized units and said ester monomeric copolymerized units, said chloroprene copolymer comprising at least 90% by weight. The polymer is
A glove prepared by free-radical emulsion polymerization to a polymerization rate of at least 90% in the presence of a mercaptan, dialkylxanthogen disulfide or dialkoxyxanthogen disulfide modifier, wherein the glove is prepared by the method described above. It is characterized by being manufactured.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The latex composition of the present invention is an aqueous suspension of a chloroprene / alkyl acrylate graft copolymer or a chloroprene / alkyl methacrylate graft copolymer. They are particularly useful in the manufacture of dipped products having a glossy finish by methods that use substantially no solvents.

The chloroprene / acrylic acid ester and chloroprene / methacrylic acid ester-grafted polymer constituting the polymer component of the latex composition are a mercaptan-modified polymer, a dialkylxanthogen-modified polymer, or a dialkoxyxanthogen disulfide. It is a modified polymer. They comprise at least 90%, preferably 99%, of chloroprene and at least one C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ hydroxyalkyl or C ₁ -C ₁₀ cycloalkyl ester of acrylic or methacrylic acid. % By polymerization. C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ hydroxyalkyl or C ₁ -C ₁₀ cycloalkyl ester of acrylic acid or methacrylic acid
It means that the alkyl, hydroxyalkyl or cycloalkyl group of the ester function contains 1 to 10 carbon atoms. Typical ester comonomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate.
Butyl, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. Methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate are preferred. Optionally, the chloroprene / acrylate copolymer or chloroprene / methacrylate copolymer may contain up to 10% by weight of other vinyl monomers. However, preferably, the copolymer is a dipolymer.
Examples of suitable vinyl monomers include 2,3-dichloro-1,3-butadiene, 1,3-butadiene, methacrylic acid, acrylonitrile, and styrene. Copolymers whose polymer backbone contains 75-95% by weight of copolymerized units of chloroprene and 5-25% by weight of C ₁ -C ₁₀ alkyl esters of acrylic acid or methacrylic acid are used in formulations for dipped products (i.e. , An aqueous latex composition comprising a copolymer latex and a conventional additive).

The graft copolymer is prepared by combining an aqueous emulsion of chloroprene, an acrylate or methacrylate comonomer, and any additional vinyl monomers with an anionic surfactant and a molecular weight modifier [ie, a modifier. ) Or chain transfer agent]
Can be prepared by free-radical polymerization in the presence of
During the copolymerization reaction, the alkyl acrylate or alkyl methacrylate monomer is copolymerized with chloroprene,
Form a polymer backbone. In addition, acrylate or methacrylate monomers also graft copolymerize to the copolymer backbone. Usually, about half of the acrylate or methacrylate monomer units are present in the grafted side chains.

Graft copolymerization is when the surfactant is one whose cation has one of the following structures:
Effectively achieved. That is, triethanolammonium, tri (2-propanol) ammonium, diethanol ammonium, and C ₁ -C ₃ alkyl diethanol ammonium. The anion of the surfactant is
Preferred are those derived from strong acids such as organic sulfonic acids and sulfates. Preferred surfactants are
Diethanolammonium dodecylbenzenesulfonate and triethanolammonium dodecylbenzenesulfonate.

The reaction is carried out in the presence of a polymerization initiator, preferably a redox pair based polymerization initiator.
Typical redox pairs include sodium sulfite / potassium persulfate, sodium sulfite / ammonium persulfate, and sodium metabisulfite / potassium persulfate.

The graft copolymerization is carried out at a temperature of from 10 to 60 ° C. to a conversion of at least 90%, preferably higher than 99%. The polymerization is carried out in the presence of 0.05 to 0.8 parts mercaptan, dialkyl xanthogen disulfide or dialkoxy xanthogen disulfide chain transfer agent per 100 parts of monomer. The presence of a chain transfer agent during polymerization prevents the formation of very high molecular weight copolymers (ie, gels) that tend to crosslink or become insoluble. In preparing the graft copolymer component of the present invention, it is common practice to add all of the acrylate or methacrylate monomer to the chloroprene monomer at the beginning of the reaction.
Usually, about 5 to 25 parts of acrylate or methacrylate monomer per 100 parts of monomer is used. The copolymerization is performed until the chloroprene monomer is exhausted. Next, excess acrylate or methacrylate monomers are grafted onto the copolymer backbone. The graft copolymer can be easily prepared by methods well known in the art.
Details regarding the preparation can be found, for example, in U.S. Pat.
Nos. 5,399,625 and 5,407,933.

The graft polymerization is preferably carried out in such a way that the copolymer solids content is in the range from 35 to 65% by weight, preferably from 40 to 60% by weight, based on the total weight of the reaction mixture. In such a method, it is not necessary to adjust the solids content of the latex to form the latex composition of the present invention. However, usually, the solids content of the non-isolated chloroprene copolymer latex obtained from the copolymerization reaction is adjusted to form the latex composition of the present invention. The solid content of the latex composition is 35
%, The film strength was found to be unacceptably low in use.

The weight percent of acrylate or methacrylate comonomer units in the chloroprene / (meth) acrylate copolymer directly affects the quality of coatings made from the latex of the present invention. . Prepared from latex containing a C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ hydroxyalkyl or C ₁ -C ₁₀ chloroprene graft copolymer having less than 5 wt% copolymerized units of cycloalkyl esters of acrylic acid or methacrylic acid Paints lack gloss. Similarly, the acrylic acid or methacrylic acid C
₁ -C ₁₀ alkyl, C ₁ -C ₁₀ hydroxyalkyl or C ₁ -C ₁₀ paint prepared cycloalkyl esters from the latex containing a chloroprene copolymer having 25 wt% or more, even lacks this property. The gloss grade is a numerical value indicating the intensity of light reflection on the surface of the object. Gloss is determined by comparing the value obtained using a standard plate with the intensity of light reflected on the measurement object.

The chloroprene / (meth) acrylate graft copolymer latex of the present invention may optionally contain additives conventionally used in rubber latex processing, for example, other polymers, fillers and the like. , Antioxidants, metal oxides, curing agents, surfactants, and plasticizers. Typical fillers include hard clay, chalk, carbon black, and silica. Typical antioxidants include Neozone D (phenyl-β-naphthylamine), Santowhite Crystals (Santowhite Crysta).
ls) [4,4'-thio-bis-6 (6-t-butyl-m
-Cresol)] and Wingstay L
(Polymeric hindered phenol). Conventional metal oxides include zinc oxide, lead oxide and magnesium oxide. Curing agents include tetraethylthiuram disulfide, sodium dibutyldithiocarbamate, sulfur, thiocarbanilide, and diphenylguanidine. Examples of surfactants include sodium lauryl sulfate, Darvan® SMO
And Lomar® dispersants. Typical plasticizers include naphthalene oil and esters. Usually such additives are present in an amount of 0.1 to 20% by weight, based on the weight of the polymer solids.

The present invention is further directed to a method of producing a dipped product having a glossy appearance without a substantial amount of organic solvents. A male mold for dip molding in the shape of the final product (for
m; hereinafter often referred to simply as "male". ) (Which is usually hard) is coated by dipping it in an aqueous dispersion of the chloroprene / (meth) acrylic acid graft copolymer latex of the present invention. The male mold is then pulled up in such a way as to leave a uniform film of the copolymer latex dispersion on the male mold. Normally,
It takes about 10 seconds to 5 seconds to form a film of appropriate strength.
Immersion times in the range of minutes are required. The thickness of the coating to be applied may be increased by performing a subsequent dipping step. After a moderate thickness and strength coating is formed, the coated product is dried, optionally leached and vulcanized. As an optional additional step, the coated male mold may be immersed in a coagulant solution such as Ca (NO ₃ ) ₂ dissolved in ethanol. However, preferably, it is not immersed in the coagulant, but is air-dried or dried in an oven.
The polymer may be cured by heating or left uncured, depending on the particular application for which the product is to be used. For example, products that require maximum flexibility are typically not cured, while products that require strength and elasticity are usually cured.

In many cases, the method of the present invention is used to coat male molds that have been previously coated with a thick layer of another polymer that provides strength, flexibility, chemical resistance and rub resistance. . The coated male mold is then dipped in the chloroprene / (meth) acrylate copolymer latex of the present invention. Alternatively, the male mold may be coated with the latex of the present invention and may be coated with a layer of another polymer. It is also possible to produce the final product using only the chloroprene graft copolymer. In each case, the outermost layer of the dipped articles (goods article) must be formed of a chloroprene graft copolymer to achieve a highly glossy surface. It is also within the scope of the present invention to provide a product in which the layer closest to the male mold is a chloroprene / (meth) acrylate polymer, which is removed and turned upside down before use.

Products made from the latex of the present invention include gloves, bladders, balloons or condoms. This latex is particularly suitable for producing gloves with a glossy finish.

[0027]

【Example】

(Test Method for Gloss) Method 1 To accurately measure the gloss without being affected by the polymer layer being subbed, an aliquot of latex (optionally containing compounding additives) was placed on a glass microscope. On glass slides. The glass microscope slide is first immersed in isopropanol and dried, then the slide is immersed in the latex for 10 seconds, pulled up, and immersed again.
A total of four dippings in latex are performed. The slide is then air dried at room temperature for 72 hours. The dried slides are immersed in water for 1/2 hour and air dried for 1 hour. The coated slides are then cured at 121 ° C. for 時間 hour. The gloss of the coated slide glass is Horiba
Measure with IG-310 gloss checker. Gloss is reported as the average of three individual gloss measurements of the coated slide. A higher gloss value indicates a glossier surface. Using this method, the gloss was measured in Example 1 and Comparative Examples A to D.

Method 2 The gloss of the copolymer layer obtained by depositing the latex on a microscope slide previously coated with a polychloroprene rubber layer is measured as follows. That is, neoprene L which is a commercially available polychloroprene latex
−671A (Neoprene L-671A) (DuPont Dow Elastomer
s, LLC) with the components shown in Table 1.

[0029]

[Table 1]

Glass microscope slides are washed by dipping in isopropanol and drying.
The slide is then immersed in a coagulant solution of 400 g of calcium nitrate dissolved in 640 g of ethanol. After dripping large droplets of the coagulant solution, the slide glass is immersed in the blended neoprene L-671A latex. The coated slides are immersed again in this coagulant solution, removed and air-dried at room temperature for 24 hours. Dry slide glass in water 1/2
Soak for hours and air dry for 1 hour. The coated glass slide cures at 121 ° C. for 時間 hour. Some of the cured glass slides are then treated with the latex to be tested by dipping them. Gloss of coated slide glass,
Measure with a Horiba IG-310 gloss checker. Gloss is reported as the average of four individual measurements of the gloss of the coated glass slide. Higher gloss indicates a glossier surface. This method is described in Example 2
4 and Comparative Examples E and F were used to determine gloss.

Example 1 A chloroprene / methyl methacrylate graft copolymer latex was prepared as follows. That is, a solution of 1575.0 parts of chloroprene, 225.0 parts of methyl methacrylate, and 3.6 parts of n-dodecyl mercaptan was prepared, followed by 1980.0 parts of deionized water, 90.0 parts of deionized water. 60% triethanol ammonium dodecylbenzenesulfonate, 7.2 parts of 87.6
% KOH and a solution containing 5.4 parts Na ₂ SO ₃ using an Eppenbach homomixer (Eppenbach).
Homomixer) for 3 minutes. The emulsion was introduced into a reaction vessel in a nitrogen atmosphere, and the temperature of the emulsion was adjusted to 40 ° C. Polymerization was initiated by slow addition of an initiator solution of 5% potassium persulfate / 0.125% sodium 2-anthraquinone sulfonate. After adding 28 parts of the initiator solution over 3.5 hours, the specific gravity of the emulsion is 1.083 g /
cm ³ . The temperature of the emulsion was raised to 48 ° C. and another 43 parts of the initiator solution were added over 3 hours to a specific gravity of 1.086 g / cm ³ . The emulsion was then cooled and 40.0 parts of 85% diethanolamine was added. The solids content of this latex is 4
6.29%. The residual chloroprene monomer content was 0.009% and the residual methyl methacrylate content was 0.350%. The overall monomer conversion was 99.2%. This emulsion is
It was blended with the components shown in Table 2.

[0032]

[Table 2]

The compounded latex was filtered through four layers of cheesecloth and the resulting latex was tested for gloss. When tested according to Method 1 above, the average gloss was 133.3.

Comparative Example A A chloroprene / methyl methacrylate copolymer was prepared in the same manner as described in Example 1 except that 900 parts of chloroprene and 900 parts of methyl methacrylate were used.
A latex was prepared. The final solids content of the latex is 4
7.00%. The residual chloroprene content was 0.004%, and the residual methyl methacrylate content was 0.138%. The overall monomer polymerization rate was 99.7%. The latex was formulated as in Example 1 and deposited on a glass slide. When tested according to Method 1 above, the average gloss of the three glass slides was 13.0. This example demonstrates that copolymers having an alkyl acrylate content higher than 25% lack gloss.

Comparative Example B A chloroprene / methyl methacrylate copolymer latex was prepared in substantially the same manner as described in Example 1, except that 1125 parts of chloroprene and 675 parts of methyl methacrylate were used. The final solids of the latex was 46.67%. The residual chloroprene content was 0.008%, and the residual methyl methacrylate content was 0.109%. The overall monomer polymerization rate was 99.7%. Latex Example 1
And deposited on glass slides. When tested according to Method 1 above, the average gloss of the three glass slides was 60.3. This example further demonstrates that copolymers having an alkyl acrylate content higher than 25% lack gloss.

Comparative Example C A chloroprene copolymer latex was prepared in substantially the same manner as described in Example 1, except that 1800 parts of chloroprene were used and no methyl methacrylate was used. The final solids content of the latex is 47.2
It was 0%. The residual chloroprene content is 0.2
It was 91%, and the monomer polymerization rate was 99.4%.
The latex was formulated as in Example 1 and deposited on a glass slide. When tested according to Method 1 above, the average gloss of the three glass slides was 91.
It was 3. This example demonstrates that the homopolymer lacks gloss.

Comparative Example D "Neoprene latex 750" (DuPont Dow Elast)
(Chloroprene copolymer latex from omers, LLC) was compounded as in Example 1 and deposited on glass slides as in Example 1. The average gloss of the three slide glasses was 86.0. "Neoprene latex 750" contains the potassium salt of disproportionated rosin acid as a stabilizer. When compared to the latex of Example 4, the gloss data of this comparative composition (tested according to Method 1 above) shows that the surfactant system of the latex does not strongly affect the gloss of the film.

Example 2 A chloroprene / methyl methacrylate graft copolymer latex was prepared as follows. That is, a solution of 1503.0 parts of chloroprene, 297.0 parts of methyl methacrylate, and 3.6 parts of n-dodecyl mercaptan was prepared, followed by 1980.0 parts of deionized water, 90.0 parts of deionized water. 60% triethanol ammonium dodecylbenzenesulfonate, 7.2 parts of 87.6
% KOH and a solution containing 5.4 parts of Na ₂ SO ₃ were emulsified in an Eppenbach homomixer for 4 minutes. This emulsion was introduced into a reaction vessel in a nitrogen atmosphere, and then 5% potassium persulfate /
Polymerization was initiated by slow addition of a solution of 0.125% sodium 2-anthraquinone sulfonate.
After the addition of 32 parts of the initiator solution over 5 hours, the specific gravity of the emulsion was 1.080 g / cm ³ . The temperature of the emulsion was raised to 48 ° C. and
Parts of the initiator solution over 4 hours to give a specific gravity of 1.0
It was 88 g / cm ³ . The emulsion was then cooled. The residual chloroprene monomer content was 0.005%, the residual methyl methacrylate monomer content was 0.360%, and the overall monomer polymerization rate was 99.2%. This latex is listed in Table 3.
And the components shown in Table 1.

[0039]

[Table 3]

No coagulant solution was used. This compound was filtered through four layers of cheesecloth before use.
One sample was applied to the cured neoprene layer as described in Test Method 2 above. The gloss was 67.

Example 3 A chloroprene / methyl methacrylate graft copolymer latex was prepared as follows. That is, a solution of 1503.0 parts of chloroprene, 297.0 parts of methyl methacrylate, and 3.6 parts of n-dodecyl mercaptan was prepared, followed by 1980.0 parts of deionized water, 90.0 parts of deionized water. 60% triethanol ammonium dodecylbenzenesulfonate, 7.2 parts of 87.6
% KOH and a solution containing 5.4 parts of Na ₂ SO ₃ were emulsified in an Eppenbach homomixer for 4 minutes. This emulsion was introduced into a reaction vessel in a nitrogen atmosphere, and then the temperature of the emulsion was adjusted to 15 ° C., and 5% potassium persulfate / 0.125% 2
-Polymerization was initiated by slow addition of a solution of sodium anthraquinone sulfonate. 1 for 3 hours
After the addition of 6 parts of the initiator solution, the specific gravity of the emulsion was 1.067 g / cm ³ . The temperature of the emulsion was raised to 48 ° C. and an additional 58 g of initiator solution was added over 4 hours to give a final specific gravity of 1.088 g / c.
It was in m ^3. The emulsion was then cooled. No residual chloroprene monomer was detected and the content of residual methyl methacrylate monomer was 0.15.
0%, and the overall monomer conversion was 99.7%. This latex was blended with the components shown in Table 4 and applied to the cured neoprene layer as described in Test Method 2 above. The gloss was 80.3.

[0042]

[Table 4]

Example 4 A chloroprene / methyl methacrylate graft copolymer latex was prepared as follows. That is, a solution of 1440.0 parts of chloroprene, 360.0 parts of methyl methacrylate, and 3.6 parts of n-dodecyl mercaptan was prepared, followed by 1980.0 parts of deionized water, 90.0 parts of 60% triethanol ammonium dodecylbenzenesulfonate, 7.2 parts of 87.6
% KOH and a solution containing 5.4 parts of Na ₂ SO ₃ were emulsified in an Eppenbach homomixer for 4 minutes. This emulsion was introduced into a reaction vessel under a nitrogen atmosphere, and then the temperature of the emulsion was adjusted to 40 ° C. The polymerization was 5% potassium persulfate / 0.1%.
Started by the slow addition of a solution of 125% sodium 2-anthraquinone sulfonate. After adding 47 parts of the initiator solution over 5 hours, the specific gravity of the emulsion was 1.086 g / cm ³ . The temperature of the emulsion was raised to 48 ° C. and an additional 15 g of initiator solution was added over 4 hours to give a final specific gravity of 1.088 g
/ Cm ³ . The emulsion was then cooled. The residual chloroprene monomer content is 0.0
The content of the remaining methyl methacrylate monomer was 0.153%, and the overall monomer conversion was 99.6%. This latex was blended with the components shown in Table 5 and applied to the cured neoprene layer as described in Test Method 2 above. The gloss was 70.

[0044]

[Table 5]

Comparative Example E A glass slide glass was blended in the manner shown in Table 1 above as in "Neoprene latex L-671".
A ". No chloroprene / methyl methacrylate graft copolymer latex was coated on the glass slide. The average gloss was 34. From this example, it can be seen that the chloroprene homopolymer lacks gloss.

Comparative Example F "Neoprene latex L-671A" was blended with the components shown in Table 6.

[0047]

[Table 6]

The compound was filtered through four layers of cheesecloth before use. Glass microscope slides were first washed by immersion in isopropanol and drying. The glass slide is then 640
Immersed in 400 parts of a coagulant solution of calcium nitrate dissolved in 1 part of ethanol. After dripping large droplets of the coagulant solution, the slide glass is immersed in the blended neoprene L-671A latex. The coated slides were immersed again in this coagulant solution, removed and air dried at room temperature for 24 hours. The dried slides were immersed in water for 1/2 hour and air dried for 1 hour. 121 ° C coated slide glass
For 1/2 hour. From this example, it can be seen that the ingredients used in Examples 2, 3 and 4 do not contribute to the measured high gloss at all.

[0049]

As described above, the chloroprene / acrylic ester or chloroprene / methacrylic ester copolymer latex composition according to the present invention substantially uses a solvent which has hitherto been regarded as an environmental and health problem. And it is particularly useful in applications to dipped products. In addition, the copolymer
When a dipped product is manufactured using the latex composition, a product having a glossy surface can be manufactured.

────────────────────────────────────────────────── ⁶ Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location // C08J 5/02 C08J 5/02 (71) Applicant 597035953 300 Bellevue Parkway Wilmington, DE 19809 U.S.A. S. A.

Claims (10)

[Claims] (1) a copolymer unit of chloroprene having a copolymerization ratio of 75 to 95;
And _{weight%, (i) C 1 ~C} 10 alkyl esters of acrylic acid, C ₁ to C ₁ -C ₁₀ cycloalkyl esters and (ii) methacrylic acid C ₁ -C ₁₀ hydroxyalkyl esters and acrylic acid Acrylic acid A copolymer unit of at least one ester monomer selected from the group consisting of a C ₁ to C ₁₀ alkyl ester, a C _{1 to} C ₁₀ hydroxyalkyl ester of methacrylic acid and a C _{1 to} C ₁₀ cycloalkyl ester of methacrylic acid is 5 to 25 weight% An aqueous chloroprene copolymer latex composition comprising an aqueous dispersion of a chloroprene copolymer comprising:
The total weight percent of the chloroprene copolymerized units and the ester monomer copolymerized units is at least 90%
% By weight, wherein the chloroprene polymer is in the presence of a mercaptan, dialkyl xanthogen disulfide or dialkoxy xanthogen disulfide modifier,
It is prepared by free-radical emulsion polymerization to a degree of polymerization of at least 90%, and the copolymer solids content of the copolymer latex composition is 35 to 65% by weight based on the total weight of the copolymer latex composition. A composition comprising: 2. The composition of claim 1, wherein the solids content of the copolymer latex composition is 40 to 60% by weight based on the total weight of the copolymer latex composition. 3. The chloroprene copolymer of claim 1, wherein the chloroprene copolymer contains copolymerized units of C ₁ -C ₁₀ alkyl esters of chloroprene and methacrylic acid.
Composition. 4. The composition according to claim 3, wherein the C ₁ -C ₁₀ alkyl ester of methacrylic acid is methyl methacrylate. 5. A method for producing a product having a glossy elastic surface, comprising: (a) 75 to 95% by weight of chloroprene copolymerized units;
If, (i) C ₁ ~C ₁₀ alkyl esters of acrylic acid, C ₁ ~ of C ₁ -C ₁₀ cycloalkyl esters and (ii) methacrylic acid C ₁ -C ₁₀ hydroxyalkyl esters, and acrylic acid Acrylic acid C ₁₀ alkyl ester,
Chloroprene the C ₁ -C ₁₀ hydroxyalkyl esters and C ₁ -C ₁₀ of copolymerized units of at least one ester monomer selected from the group consisting of cycloalkyl esters of methacrylic acid methacrylic acid containing a 5 to 25 wt% An aqueous chloroprene copolymer latex composition comprising an aqueous dispersion of a copolymer, wherein the total weight percent of the copolymerized units of the chloroprene and the copolymerized units of the ester monomer is at least 90% by weight; Is at least 9 in the presence of a mercaptan, dialkylxanthogen disulfide or dialkoxyxanthogen disulfide modifier.
An aqueous system prepared by free-radical emulsion polymerization to a polymerization rate of 0% and wherein the copolymer solids content of the copolymer latex composition is 35 to 65% by weight based on the total weight of the copolymer latex composition Dipping the object to be coated in the chloroprene copolymer latex composition; and (b) removing the object for a time sufficient to grow a coherent copolymer film on the object. A method comprising: maintaining the aqueous chloroprene copolymer latex composition in the aqueous chloroprene copolymer latex composition; and (c) removing the object from the aqueous chloroprene copolymer latex composition. 6. The method of claim 5, wherein the solids content of the copolymer latex composition is 40 to 60% by weight based on the total weight of the copolymer latex composition. 7. The chloroprene copolymer contains copolymerized units of a C ₁ -C ₁₀ alkyl ester of chloroprene and methacrylic acid.
the method of. 8. The method of claim 7 wherein the C ₁ -C ₁₀ alkyl methacrylate is methyl methacrylate. 9. A coated product produced by the method of claim 5. 10. A glove having a glossy finish, wherein the copolymerized unit of chloroprene is 75 to 95.
And _{weight%, (i) C 1 ~C} 10 alkyl esters of acrylic acid, C ₁ to C ₁ -C ₁₀ cycloalkyl esters and (ii) methacrylic acid C ₁ -C ₁₀ hydroxyalkyl esters and acrylic acid Acrylic acid A copolymer unit of at least one ester monomer selected from the group consisting of a C ₁ to C ₁₀ alkyl ester, a C _{1 to} C ₁₀ hydroxyalkyl ester of methacrylic acid and a C _{1 to} C ₁₀ cycloalkyl ester of methacrylic acid is 5 to 25 weight% % Gloves comprising an outer layer of a chloroprene copolymer containing at least 9% by weight of the chloroprene copolymerized units and the ester monomer copolymerized units.
0% by weight, wherein said chloroprene polymer is prepared by free-radical emulsion polymerization to a conversion of at least 90% in the presence of a mercaptan, dialkylxanthogen disulfide or dialkoxyxanthogen disulfide modifier. A glove, wherein the glove is manufactured by the method of claim 5.