JP2009191182A - Chloroprene-based polymer composition, adhesive composition and method for producing the chloroprene-based polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chloroprene-based polymer composition having a pale hue and excellent in photo-discoloration resistance. <P>SOLUTION: This chloroprene-based polymer composition having the pale hue and excellent in the photo-discoloration resistance is obtained by performing the emulsion polymerization of a 100 pts.mass chloroprene monomer and/or chloroprene with a monomer copolymerizable with chloroprene in the presence of 0.5 to 7 pts.mass of pale-colored rosin acid and/or a pale-colored rosin acid salt having a Hazen color number of ≤200. This chloroprene-based polymer composition can be suitably used as an adhesive. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a chloroprene polymer composition, an adhesive composition, and a method for producing a chloroprene polymer composition.

  Chloroprene-based polymers are suitably used as a raw material for solvent-type adhesives. The chloroprene polymer can be obtained by emulsion polymerization of a chloroprene monomer in the presence of an emulsifier. As the emulsifier, rosin acid, rosinate, etc. are preferably used from the viewpoint of having good strength at the time of freeze-coagulation drying after the completion of polymerization, and less excessive shrinkage and breakage at the time of drying the film etc. Yes. Of course, other than these, nonionic emulsifiers such as polyvinyl alcohol, and cationic emulsifiers such as quaternary ammonium salts are used.

  However, chloroprene polymers and adhesives using the same have a problem that they turn yellow or brown. As an attempt to solve such a problem, for example, Patent Document 1 discloses an alkali of disproportionated rosin acid in aqueous radical emulsion polymerization of chloroprene or a mixture of chloroprene and a monomer copolymerizable therewith. A technique using a water-soluble polymer containing a sulfonic acid group and / or a sulfate ester group introduced by a polymer reaction after addition polymerization and / or addition polymerization together with a metal salt is disclosed.

JP-A-8-269116.

  There is still room for improvement in the technology for producing a chloroprene polymer having a light hue and excellent light discoloration resistance while having adhesive properties when used as an adhesive or the like. Accordingly, the main object of the present invention is to provide a chloroprene polymer composition having a light hue and excellent light discoloration resistance.

First, in the present invention, 100 parts by mass of a chloroprene monomer and / or a chloroprene monomer and another monomer copolymerizable therewith, a light-colored rosin acid and / or a light-colored rosin having a color hazen of 200 or less. A chloroprene polymer composition obtainable by emulsion polymerization in the presence of 0.5 to 7 parts by mass of an acid salt is provided. Thereby, it can be set as the chloroprene-type polymer composition excellent in light discoloration resistance with a light hue.
And as an emulsifying dispersant, 0.05 to 1.0 parts by mass in total of one or more kinds of compounds selected from alkyl benzene sulfonate, polyoxyalkylene alkyl ether sulfonate and alkyl diphenyl ether sulfonate are used as a chloroprene system. A polymer composition can be obtained. Thereby, it can be set as the chloroprene-type polymer composition which was excellent in the light discoloration resistance with the hue of light color, and also excellent in adhesive performance.
Furthermore, it can be set as the chloroprene polymer composition which added the 1 or more types of compound chosen from the benzotriazole ultraviolet absorber, the hindered amine light stabilizer, and the phenol anti-aging agent. The light discoloration resistance can be further improved by using such a chloroprene polymer composition.
The present invention also provides an adhesive composition containing at least these chloroprene polymer composition and an organic solvent. By setting it as this adhesive composition, it can be set as the adhesive composition excellent in light discoloration resistance with a light hue.
In the present invention, 100 parts by mass of a chloroprene monomer and / or a chloroprene monomer and another monomer copolymerizable therewith is used as a light-colored rosin acid and / or light-colored rosin having a color hazen of 200 or less. Provided is a method for producing a chloroprene polymer composition which at least performs emulsion polymerization in the presence of 0.5 to 7 parts by mass of an acid salt. Furthermore, it is desirable to add one or more compounds selected from a benzotriazole ultraviolet absorber, a hindered amine light stabilizer, and a phenol antiaging agent during emulsion polymerization.

  According to this invention, it can be set as the chloroprene-type polymer composition which has the light hue and was excellent in photochromic resistance.

  The present invention will be described below, but the following is an example of the present invention and should not be construed as being limited thereto. The chloroprene polymer composition according to the present invention is a light-colored chloroprene monomer and / or chloroprene monomer and 100 parts by mass of another monomer copolymerizable therewith, and an emulsifier having a color tone hazen of 200 or less. It is a chloroprene polymer composition obtainable by emulsion polymerization in the presence of 0.5 to 7 parts by mass of rosin acid and / or light-colored rosin acid salt.

  The chloroprene-based polymer that can be used in the present invention is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene), or a chloroprene monomer and another monomer copolymerizable therewith. A copolymer with the body.

  The type of other monomer copolymerizable with the chloroprene monomer is not limited, but for example, ethylenically unsaturated carboxylic acid, acrylic acid such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Esters of acid, esters of methacrylic acid such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl ( Examples include hydroxy (meth) acrylates such as (meth) acrylate, 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile and the like. Two or more types can be used in combination.

  The type of rosin acid is not limited. Of the mixture. In addition, fatty acids such as oleic acid, stearic acid, and octadecenoic acid may be included.

  Examples of the metal salt of rosin acid include, but are not limited to, alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium, and ammonium salts. Preferably, sodium salt or potassium salt is used from the viewpoint of easy handling.

  The light-colored rosin acid can be obtained, for example, by subjecting the rosin acid to a hydrogenation reaction and / or a disproportionation reaction, followed by purification. A light-colored rosinate can be obtained in the same manner. In the present invention, a light-colored rosin acid (light-colored rosin acid salt) having a color tone Hazen of 200 or less may be used, and the light-coloring method of rosin acid (rosin acid salt) is not limited. Can be lightened.

The method for the hydrogenation reaction can be carried out by a known method and is not particularly limited. For example, it can be carried out by heating unpurified rosin acid or rosinate under hydrogen pressure in the presence of a hydrogenation catalyst. The hydrogenation catalyst is not particularly limited, and a known catalyst such as a supported catalyst such as palladium carbon, rhodium carbon, or platinum carbon, a metal powder such as nickel or platinum, or an iodide such as iodine or iron iodide may be used. it can. The catalyst is usually 0.01 to 5% by mass, the hydrogenation pressure is about 50 to 200 kg / cm ² , and the reaction temperature is 100 to 300 ° C.

The method of disproportionation reaction can be performed by a known method and is not particularly limited. For example, the above-mentioned unpurified rosin acid or rosinate can be heated without supplying hydrogen in the presence of a disproportionation catalyst. The disproportionation catalyst is not particularly limited, and known catalysts such as supported catalysts such as palladium carbon, rhodium carbon and platinum carbon, metal powders such as nickel and platinum, iodine and iron iodide can be used. The catalyst is usually 0.01 to 5% by mass, the hydrogenation pressure is about 50 to 200 kg / cm ² , and the reaction temperature is 100 to 300 ° C.

  And the refinement | purification process which removes impurities, such as an unsaponified substance and a high molecular weight substance, from the unpurified rosin acid and rosinate which carried out the hydrogenation reaction and / or the disproportionation reaction is performed. This purification method can be carried out by a known method, for example, by an operation such as distillation, recrystallization or extraction. Industrially, distillation under conditions of a temperature of 200 to 300 ° C. and a pressure of 1 to 10 mmHg is often used.

  Light-colored rosin acid and light-colored rosinate can be used as an emulsifier for emulsion polymerization of a chloroprene monomer, and the color tone hazen is 200 or less in order to suppress coloring of the chloroprene polymer. is required. Preferably it is 150 or less. The color tone hazen is also called a platinum-cobalt color method or an APHA method, and is measured according to ASTM D1209. Since it is performed using a liquid layer that is thicker than the Gardner color number or the like according to ASTM D-154, it is possible to more accurately evaluate a light-colored rosin acid (rosinate). The lightened rosin acid (rosinate) can have a Gardner color value of 1 or less.

  The addition amount of the light-colored rosin acid or light-colored rosin acid salt is 100 parts by weight in total, or 100 parts by weight in total of the chloroprene monomer and other monomers copolymerizable therewith. The range of 0.1-10 mass parts is good, Preferably the range of 1-7 mass parts is good. If it is less than 0.1 parts by mass, stable polymerization of the chloroprene monomer is impossible, and if it is added in excess of 10 parts by mass, the adhesive performance of the adhesive containing the chloroprene polymer may be deteriorated.

  Then, an emulsifying dispersant may be added. The emulsifying dispersant can be used for maintaining the stability of the chloroprene polymer in each step, and the type thereof is not particularly limited. In general, aromatic naphthalene formalin condensate or the like is used as an emulsifying dispersant. However, in order to more effectively suppress the coloring of the chloroprene polymer, one or more compounds selected from alkylbenzene sulfonate, polyoxyalkylene alkyl ether sulfonate and alkyl diphenyl ether sulfonate are used. It is preferable to do.

Specific examples of the emulsifying dispersant include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium alkyldiphenyl ether sulfonate, potassium alkyldiphenyl ether sulfonate, polyoxyethylene alkyl ether sodium sulfonate, polyoxypropylene alkyl ether sulfone. Examples include sodium acid, potassium polyoxyethylene alkyl ether sulfonate, potassium polyoxypropylene alkyl ether sulfonate, and the like.
In addition, although dodecylbenzene sulfonate has a linear type and a side chain type, it is more preferable to use a linear type from a viewpoint of the influence on an environment.

  The addition amount of the emulsifying dispersant is not limited, but it is 0.05 in total with respect to 100 parts by mass of the chloroprene monomer or 100 parts by mass of the chloroprene monomer and other monomers copolymerizable therewith. It is good that it is -1.0 mass part. By setting it as this numerical range, it can be set as the chloroprene-type polymer which has the adhesiveness outstanding when it was set as the adhesive agent, having sufficient stability.

  Examples of the polymerization reaction catalyst include inorganic peroxides such as potassium persulfate, organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, and diacyl peroxides. be able to. Among these, potassium persulfate is preferably used from the viewpoint of performing a stable polymerization reaction. The catalyst is preferably used in an aqueous solution of 0.1 to 5% by mass.

  In order to improve the activity of the catalyst, sodium sulfite, potassium sulfite, iron (II) oxide, anthraquinone, sodium β-sulfonate, formamidine sulfonic acid, L-ascorbic acid and the like can be added.

  The chain transfer agent is not particularly limited as long as it can be usually used in the production of a chloroprene polymer. For example, chain transfer agents such as long-chain alkyl mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and n-octyl mercaptan, dialkyl xanthogen disulfides such as diisopropyl xanthogen disulfide and diethyl xanthogen disulfide, and iodoform can be used.

  The polymerization inhibitor is not particularly limited as long as it can be used for producing a chloroprene polymer. For example, polymerization inhibitors such as thiodiphenylamine, diethylhydroxylamine, hydroquinone, pt-butylcatechol, 1,3,5-trihydroxybenzene, hydroquinone methyl ether, and the like can be used.

  The final polymerization rate is not particularly limited and can be appropriately determined. The lower limit value of the final polymerization rate is preferably 55% or more, and the upper limit value is preferably 95% or less. Adhesive strength suitable for practical use can be obtained by setting it to 55% or more, and generation of gel unnecessary for the solvent can be suppressed by setting it to 95% or less, so that it can be suitably used as an adhesive. . The polymerization rate can be calculated by the following formula.

  And the Mooney viscosity etc. of a chloroprene-type polymer can also be controlled by controlling the kind, usage-amount, polymerization rate, etc. of these chain transfer agents.

  The polymerization temperature is preferably in the range of 0 to 55 ° C. from the viewpoint of easy control of the reaction. From the viewpoint of performing the polymerization reaction more smoothly and safely, it is desirable that the lower limit value of the polymerization temperature is 5 ° C. or higher and the upper limit value is 45 ° C. or lower. In order to further improve the adhesive properties as an adhesive, it is more desirable that the lower limit of the polymerization temperature is 10 ° C. or higher and the upper limit is 20 ° C. or lower.

  A chloroprene polymer is obtained by subjecting a chloroprene monomer and / or a monomer capable of copolymerization with the chloroprene monomer to emulsion polymerization in the presence of the aforementioned emulsifier, dispersant, catalyst or chain transfer agent. It is obtained by adding a polymerization inhibitor when the polymerization rate is reached. The obtained chloroprene polymer is exposed to a high temperature by a steam flash method or a concentration method to remove unreacted monomers and the like. Since the chloroprene polymer from which the monomers are removed is alkaline, the pH is adjusted to neutral by adding an aqueous acetic acid solution, etc., and finish processing is performed by a method such as freezing coagulation or salting out. A molded product such as a chip is used.

  Furthermore, it is preferable to add one or more compounds selected from benzotriazole ultraviolet absorbers, hindered amine light stabilizers, and phenol aging inhibitors. Thereby, the light discoloration resistance of the chloroprene polymer can be further improved.

  Examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl- 1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-t-butylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6 (T-butyl) phenol, 2,4-di-t-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di -T-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl-3- (3- (2H-ben Zotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazol-2-yl) -4-methylphenol and the like.

  The addition amount of the benzotriazole ultraviolet absorber is preferably in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the chloroprene polymer. If it is less than 0.01 part by mass, the light discoloration-resistant effect due to the addition may not be obtained, and if it exceeds 1.0 part by mass, the adhesive performance of the adhesive containing the chloroprene polymer is deteriorated. There is a fear.

  Examples of hindered amine light stabilizers include N, N ′, N ″, N ″ ″-tetrakis- [4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethyl). Piperidin-4-yl) amino) -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,2) 6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperdyl) butylamine polycondensate, poly [{6- ( 1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene { (2,2,6,6-tetramethyl-4-pipe Zyl) imino}], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperzine ethanol, bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperzyl) sebacate and the like can be mentioned.

  The addition amount of the hindered amine light stabilizer is preferably in the range of 0.01 to 1.0 part by mass with respect to 100 parts by mass of the chloroprene polymer. If it is less than 0.01 part by mass, the light discoloration-resistant effect due to the addition may not be obtained, and if it exceeds 1.0 part by mass, the adhesive performance of the adhesive containing the chloroprene polymer is deteriorated. There is a fear.

  Examples of the phenol aging inhibitor include 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 2,6-diphenol. -T-butyl-4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis-3- (3 5-di-t-butyl-4-hydroxyphenylpropionamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyles , Diethyl [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t- Butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m -Tolyl) poropionate] and the like.

  As the addition amount of the phenol anti-aging agent, addition of 0.01 to 1.5 parts by mass with respect to the chloroprene polymer is preferable. If the amount is less than 0.01 parts by mass, the light discoloration-inhibiting effect due to the addition may not be obtained. If the amount exceeds 1.5 parts by mass, the adhesive performance of the adhesive containing a chloroprene polymer will deteriorate. There is a fear.

  The step of adding the benzotriazole ultraviolet absorber, hindered amine light stabilizer and phenol anti-aging agent is not particularly limited, and may be added to the monomer before polymerization or the chloroprene heavy polymer obtained by polymerization. It may be a step of adding to the coalescence. Furthermore, from the viewpoint of improving the dispersion state in the chloroprene polymer, after dissolving in the chloroprene monomer to make a chloroprene polymer, a method of degassing and removing with the unreacted chloroprene monomer, and addition of these A method in which an agent emulsified with a surfactant is added to a chloroprene polymer latex.

  The chloroprene polymer composition of the present invention can be dissolved in an organic solvent to form an adhesive composition. The kind of organic solvent is not limited, For example, organic solvents, such as toluene, xylene, acetone, methyl ethyl ketone, n-hexane, cyclohexane, methylcyclohexane, cyclopentane, isopropyl acetate, and ethyl acetate, can be used. You may use an organic solvent individually or in mixture of multiple types. Furthermore, an acrylic monomer such as methyl methacrylate can be graft-polymerized and used as a graft-type adhesive or the like.

  Furthermore, metal oxidizing agents such as zinc white and magnesia, phenolic resins, rosin resins, tackifying resins such as coumarone resins and petroleum resins, formaldehyde catchers, various fillers, etc. can be added to the adhesive composition. .

  The use of the adhesive composition that can be obtained in the present invention is not limited, and paper, wood, cloth, leather, jersey, leather, leather, rubber, plastic, foam, earthenware, glass, mortar, cement-based material, ceramic, It can be used for bonding various members such as metals. Furthermore, it can be used not only for the same type but also for bonding different types of members.

  Hereinafter, the present invention will be described in more detail with reference to examples. These examples do not limit the invention. Unless otherwise specified, “part” and “%” are based on mass.

[Example 1]
Production of chloroprene polymer Light-colored rosin ("Pine Crystal KR-85", manufactured by Arakawa Chemical Co., Ltd.) 4.0 having a water volume of 120 liters and a color tone of Hazen of 150 or less using a reactor having an internal volume of 5 liters. Parts by weight, 0.3 parts by weight of sodium dodecylbenzenesulfonate (“Neopelex G-65”, manufactured by Kao Corporation), 0.8 parts by weight of sodium hydroxide and 0.3 parts by weight of sodium hydrogen sulfite as other additives After dissolution, 100 parts by mass of chloroprene monomer and 0.1 part by mass of n-dodecyl mercaptan were added with stirring. Polymerization was carried out at 10 ° C under a nitrogen atmosphere using 0.1 parts by mass of potassium persulfate as a catalyst. When the final polymerization rate reached 70%, an emulsion of phenothiazine was added to stop the polymerization, and the reaction was not performed under reduced pressure. The monomer was removed.
No abnormality such as generation of precipitates was observed in the obtained chloroprene polymer. The pH of this chloroprene polymer was adjusted to 7 with dilute acetic acid. Also here, no abnormalities such as generation of coagulum were observed. A sheet of a chloroprene polymer was obtained by a freeze coagulation drying method.

Hue b Value The obtained chloroprene polymer sheet was subjected to a color tone inspection using a colorimetric test apparatus (manufactured by Nippon Denshoku Industries Co., Ltd., “Z-Σ80 color difference meter”). The hue b value indicates the yellow degree on the (+) side and the blue degree on the (−) side, and a value showing a value of 2.5 or less was regarded as acceptable.

Light Resistance The appearance of the obtained chloroprene polymer sheet after being irradiated with a xenon weather meter at a black panel temperature of 63 ° C. for 15 hours was confirmed. Pale yellow is indicated by “◯” and dark yellow is indicated by “Δ”.

Manufacture of graft-type adhesive Using a reactor with an internal volume of 10 L, 100 parts by mass of chloroprene polymer, 400 parts by mass of toluene, 200 parts by mass of methyl ethyl ketone, 60 parts by mass of methyl methacrylate, 0.5 parts by mass of benzoyl peroxide In addition, graft polymerization was carried out at 80 ° C. After 5 hours, phenothiazine was added and cooled to 15 ° C. to complete the polymerization. The polymerization rate was 35%.

Color Tone The obtained graft adhesive solution was put in a glass bottle and visually observed for color tone. Almost transparent was designated as “◎”, pale yellow as “◯”, and dark yellow as “Δ”.

Tack The obtained graft adhesive solution was applied to cellophane with a brush under the conditions of 23 ° C. and 50 RH%, and the tackiness after standing for 5 minutes was evaluated by finger feeling. “Good” indicates a good feeling of adhesion, and “No” indicates a defect.

Adhesive peel strength Adhesive was applied at 200 g / m ^{2 on} each of two canvases (25 × 150 mm), and an open time was taken for 30 minutes, followed by 5 reciprocations with a hand roller. Initial strength after 3 hours set time and normal strength after 10 days were measured at a tensile speed of 200 mm / min.

[Example 2]
Before emulsion polymerization of the chloroprene monomer and removal of the unreacted monomer in the same manner as in Example 1, 2,6-di-t-butyl-4-methylphenol (“Sumilyzer BHT”) was used as an anti-aging agent. Manufactured by Sumitomo Chemical Co., Ltd.) 0.1 parts by mass, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (t-butyl) phenol (“tinuvin” as an ultraviolet absorber 326 ", manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.15 parts by mass and bis (2,2,6,6-tetramethyl-4-piperzyl) sebacate (" Tinuvin 770 ", Ciba Specialty Chemicals) as a light stabilizer (Chemical Co., Ltd.) 0.15 parts by mass of the mixed emulsion was added. Thereafter, unreacted monomers were removed under reduced pressure in the same manner as in Example 1, pH adjustment and freeze-coagulation drying were performed to obtain a sheet of chloroprene polymer. Evaluation was performed in the same manner as in Example 1.

[Example 3]
A chloroprene polymer was prepared by changing sodium dodecylbenzenesulfonate as a dispersant in Example 1 to sodium alkyldiphenyl ether sulfonate (“Perex SSH”, manufactured by Kao Corporation), and evaluated in the same manner as in Example 1. .

[Example 4]
A chloroprene-based polymer was prepared by changing the sodium dodecylbenzenesulfonate of the dispersant in Example 1 to sodium polyoxyethylene lauryl ether sulfonate (“Emar 20C”, manufactured by Kao Corporation), and evaluated in the same manner as in Example 1. Went.

[Example 5]
The anti-aging agent 2,6-di-t-butyl-4-methylphenol in Example 2 was replaced with 2,2-methylenebis-4-ethyl-6-t-butylphenol (“NOCRAK NS-5”, Ouchi Shinsei Chemical). Made by UV absorber 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (t-butyl) phenol into 2- (2H-benzotriazole-2) -Il) -4,6-di-t-pentylphenol ("Tinuvin 328", manufactured by Ciba Specialty Chemicals) and light stabilizer bis (2,2,6,6-tetramethyl-4-piperzyl) ) Sebacate is bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate (“T Bin 144 ", instead each manufactured by Ciba Specialty Chemicals Co., Ltd.) to prepare a chloroprene polymer was evaluated in the same manner as in Example 1.

[Example 6]
A chloroprene polymer was prepared by changing the sodium dodecylbenzenesulfonate of the dispersing agent in Example 2 to a sodium salt of β-naphthalenesulfonic acid formalin condensate (“Demol NL”, manufactured by Kao Corporation). Evaluation was performed in the same manner.

[Examples 7 to 9]
Chloroprene-based polymers were prepared under the conditions shown in Table 1 while changing the amount of rosin acid, and evaluated in the same manner as in Example 1.

[Example 10]
As for the monomers, copolymers were prepared using chloroprene monomer and 2,3-dichloro-1,3-butadiene under the conditions shown in Table 1, and evaluated in the same manner as in Example 1.

[Examples 11 and 12]
A chloroprene polymer was prepared under the conditions shown in Table 1 while changing the amount of the dispersant, and evaluated in the same manner as in Example 1.

[Comparative Example 1]
In Example 2, a light-colored rosin as an emulsifier was changed to a normal disproportionated rosin (“Longis 3R”, manufactured by Arakawa Chemical Co., Ltd.) to prepare a chloroprene polymer, and evaluation was performed in the same manner as in Example 1.

[Comparative Example 2]
A chloroprene polymer was prepared under the conditions shown in Table 2 while changing the prescription amount of the light-colored rosin as an emulsifier and evaluated in the same manner as in Example 1.

[Comparative Example 3]
A chloroprene polymer was prepared under the conditions shown in Table 2 while changing the amount of the emulsifier light-colored rosin to 7.1 parts by mass, and evaluated in the same manner as in Example 1.

  These results are shown in Tables 1 and 2.

As can be seen from the results shown in Table 1, any chloroprene polymer that can be obtained using 0.5 parts by weight (Example 7) to 7.0 parts by weight (Example 9) of light-colored rosin is a hue. b value, light resistance, etc. were favorable (Examples 1-12).
On the other hand, as can be seen from the results shown in Table 2, Comparative Example 1 in which the lightened rosin is not used, Comparative Example 2 in which the prescription amount of the lightened rosin is 0.4 parts by mass, and 7.1 parts by mass Comparative Example 3 and the like all had poor hue b value, light resistance and the like (Comparative Examples 1 to 3).
From the above, it has been shown that according to the present invention, a chloroprene polymer composition having a light hue and excellent light discoloration resistance can be obtained and can be suitably used as an adhesive composition.

Claims (6)

  100 parts by mass of chloroprene monomer and / or chloroprene monomer and other monomer copolymerizable therewith, light-colored rosin acid and / or light-colored rosinate having a color tone of 200 or less A chloroprene polymer composition obtainable by emulsion polymerization in the presence of 7 parts by mass.   Furthermore, as an emulsifying dispersant, 0.05 to 1.0 parts by mass in total of one or more kinds of compounds selected from alkylbenzene sulfonate, polyoxyalkylene alkyl ether sulfonate and alkyl diphenyl ether sulfonate are obtained. The chloroprene polymer composition according to claim 1, wherein   The chloroprene polymer composition according to claim 1 or 2, further obtained by adding one or more kinds of compounds selected from a benzotriazole ultraviolet absorber, a hindered amine light stabilizer and a phenol anti-aging agent. .   An adhesive composition comprising at least the chloroprene polymer composition according to any one of claims 1 to 3 and an organic solvent.   100 parts by mass of chloroprene monomer and / or chloroprene monomer and other monomer copolymerizable therewith, light-colored rosin acid and / or light-colored rosinate having a color tone of 200 or less The manufacturing method of the chloroprene-type polymer composition which performs at least emulsion polymerization in presence of 7 mass parts.   6. The chloroprene polymer composition according to claim 5, wherein at least one compound selected from a benzotriazole ultraviolet absorber, a hindered amine light stabilizer, and a phenol antioxidant is added during the emulsion polymerization. Production method.