JPS6036543A - Chloroprene polymer composition - Google Patents

Abstract

PURPOSE:To provide titled composition in good balance between tensile strength and tensile elongation, suitable for coatings or adhesives for paper, leather, metal, textiles, resin, etc., comprising chloroprene polymer, acrylic polymer and hydrazine derivative having two or more hydrazine residues. CONSTITUTION:The objective composition comprising (A) 100pts.wt. of chloroprene polymer, (B) 0-300pts.wt. of an acrylic polymer (preferably, carbonyl group-contg. one derived from methyl methacrylate, etc.) and (C) 0.05-10pts.wt. of a hydrazine derivative having two or more hydrazine residues (pref. polycarboxylic acid dihydrazide).

Description

[Detailed description of the invention]

The present invention ν, 44℃, leather, metal, water conservancy, concrete,
Used as textiles, materials such as polyester, and adhesives
The rl-plane li coalescent composition is related to the proboscis. The coating film obtained from Akira Kigi's i'1↑ product has little yellowing and has a well-balanced tensile strength and tensile elongation. Since chloroprene rubber has excellent oil properties, flame resistance, and water resistance, its yellow sulfur modified product dissolved in an organic solvent is used for leather, paper, gold, and as an adhesive for resins. ing. 1. Disperse chloroprene nitrate in water with an emulsifier or stabilizer, emulsion polymerize it, and obtain a latex with a solid content of 34.5 to 60 parts by weight. If necessary, dilute with water and add a fiber binder. It is used in paper, commercial coating materials, and adhesives for tire tread fibers. Shape 1j2 IL 71' from this chlorobrene latex! i3. The membrane is fusible,
It has excellent water resistance, alkali resistance, and oil resistance. The molecular weight of the chloroprene rubber (polymer) of conochloroprene latex has a distribution of io, ooo to 950,000, with the largest part being said to be close to 1()(λ000) (edited by the Japan Rubber Association, "New "Introduction to Rubber Technology", 1972
November 1, 2017 [Refer to 1 revised i'tJ new edition, pages 38-43]
,. However, this chloroprene polymer is susceptible to aging, tends to change C° at high temperatures, and has the drawbacks of significant deterioration in mechanical properties. In order to improve these drawbacks of chlorobrene latex, it is conceivable to blend into chlorobrene latex an acrylic resin emulsion that causes less yellowing and provides a coating film with high mechanical strength. However, the elongation and strength of coating films obtained from mixtures of chlorobrene latex and acrylic resin emulsion are often lower than the average values of coating films obtained from both, and the yellowing improvement effect is also low. It turns out that there are few. Next, the present inventors used an acrylic polymer emulsion having a carbonyl group in the prisoner molecule and a crosslinked acrylic copolymer emulsion (containing 131 adipic acid dihydrazide at room temperature f20°C) as an acrylic resin emulsion. (Unexamined Japanese Patent Publication No. 11r (No. 54-110248,
No. 7-3850-, No. 57-3857, No. 58-96
643, Japanese Patent Application No. 58-44350), we attempted to further improve the heat resistance of the coating film by obtaining a crosslinked coating film. It was also found that the prevention of yellowing of the film was significantly improved.
7. Therefore, we found that when we used a normal acrylic copolymer instead of one that had crosslinked carbonyl groups as a single acrylic copolymer, the heat resistance was significantly improved even on the platform. Initially, in order to confirm the effects of hydrazine derivatives, it was discovered that mixing only adipic acid dihydrazide with chlorobrene latex (I~) also had an anti-yellowing effect and improved heat resistance, and the present invention was achieved. That is, the present specification is as follows: fAJ component: Chlorobrene polymer 100% W fsVI (Body component Niacrylic polymer 0-300% HWC) Component: 0.05-111% hydrazine derivative having at least two hydrazine residues Q! This invention provides a chloroprene polymer composition in which components 131 and 0 are blended in the above proportions. If necessary, a vinyl monomer such as styrene, butadiene, 2,3-dichlorobutadiene, acrylic acid lower ester, acrylic acid, acrylonitrile, methacrylic acid, itaconic acid, etc. is emulsified in water using an emulsifier, and in the presence of a tonaishiki. Chloroprene polymer 1o (
) Vulcanizing agent is 5 to 40 parts by weight based on heavy weight + western part, vulcanization acceleration'
t(, ('=0.1 to 10 parts by weight of the agent is blended as necessary. Examples of the vulcanizing agent include J3c, Ca, Mg,
ZnX5rXBa, Pb, (3e, Ti. Sn, Zr, 81), V, Co, Mo, Se
etc. (7) Metal (7) can be used as a compound, and zinc oxide, magnesium oxide, lead oxide, and calcium oxide are usually used because they are inexpensive.As vulcanization accelerators, 2-mercaptoimidacillin, Examples include luntril guanidine dicatecolvole I, 2,2,4,4-tetrahydroxydiphenyl sulfide, N-octadecyldisodium sulfosuccinate, N,N-diphenylthiourea, etc. Such vulcanization types The chloroprene latex is Neoprene 400.571.650.750. from Showa Denko ■.
842A, 60.450.572.950.635.7
It is sold under 35 product names. Next, the acrylic polymer as the il'l+ component that improves the strength of the coating film is selected from (a), methyl methacrylate, vinyl aromatic compounds (e.g. styrene), tert-butyl acrylate, halogenated vinylene, and ethylene. vinyl monomer 10
~75% by weight fb of alcohols with 1.2 to 16 carbon atoms,
Vinyl mono-7-□ selected from methyl acrylate, vinylnisder, i,3-dienes 90-2511j41: Section (mountain, acrylic^t, methacryl

【";in,
0 to 10 carboxylic acids selected from itaconic acid, maleic anhydride, maleic acid, and crotonic acid; An aqueous emulsion is used.The method for producing such an acrylic resin emulsion is described in [Pu2 Stitch, Rikuryo Toza 8 Acrylic Nanpo], written by Megumi Kita, published by Kogyo Shinbunsha, I-1, 1976, 6. Monthly 15 H issue) i ]-51 to L57 pages. Such acrylic resin emulsion is produced by oil-based Verdinone (acronal 290.295.1).
It is sold under product names such as i55. The acrylic copolymer emulsion obtained by emulsion polymerization of this fat, (+)) and (non-forming monomer)
The tensile strength of the coating film obtained from the composition blended in a ratio of 50 to 150 parts by weight, preferably 50 to 150 parts by weight, is certainly improved by 1 to 1. In general, to judge the aging resistance of chloroprene rubber, the tensile strength jW at room temperature (20°C) and the elongation at high temperature (8
It is said that the aging resistance is excellent because there is little decrease in tensile strength and elongation at 0°C) and there is little yellowing of chloroprene rubber due to heat treatment at 80°C. Generally, commercially available chloroprene latex tends to yellow due to high-temperature treatment, but it should be noted that (as the acrylic polymer of the B+ component, the above-mentioned JP-A No. 54-110248, No. 57-3850, No. 58-96643) It was found that when the acrylic copolymer having a carbonyl group disclosed in the above publication was used, the tensile strength of the coating film at high temperature was higher than the tensile strength of the coating film at room temperature. An aqueous emulsion of a group-containing acrylic copolymer is prepared from (a) methyl methacrylate, vinyl aromatic compound, tert-butyl acrylate, vinyl halide, and ethylene. body 10
~75, (bl) acrylic acid of an alcohol having 2 to 16 carbon atoms. 25 to 90% weight, at least one Aldo JN or 1F keto group and one FC molecule.
a carbonyl group-containing monomer having 2 polymerizable divalent bonds;
I4J is obtained by emulsion polymerization of monomers consisting of 71 monomer o, i to 20 monomers, and (Sanno saturated carboxylic acid monomer 11F 0 to 10 iTi' (ji group) (see the above-mentioned publications), Its monomers (such as al), methyl methacrylate, vinyl aromatic compounds (such as styrene), tert-butyl acrylate, vinyl halides (such as vinyl chloride, vinylidene chloride, etc.), and ethylene In emulsion polymerization, tp-mer fal is used.
The copolymerization ratio of is usually 10 to 75 with respect to all units Ii:
The amount of nails is preferably 30 to 70. monomer f
When aJ is used in conjunction with the second type line ``2'', it becomes sharp. monomer fa
t acts to impart hardness to the coating film of the composition of the present invention. acrylic acid or (methacrylic acid) alcohols having 2 to 16 carbon atoms, methyl norate, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.) ], ]3-dienes (for example, butadiene, etc.) are used, and mono;!4'' bodies (1
)), (F combination ratio is H7 for all cars, usually 2 for the body)
5-90, IH, j, preferably V, 30-701
F stitching is poor. It is also possible to use two or more types of single substance (1). Single: The piece (l) has the effect of imparting flexibility to the coating. ζ1. :ij": As wood fcl, a carbonyl group-containing monomer containing at least one aldo group or keto group and one polymerizable double bond in the molecule is used. Compounds having only a bond (-C-0-) or carboxyl Au (-C-OI-I) are not included in this monomer fcl.Specific examples of monomers (C1 include acrolein, diacetone acrylamide,
Formylstyrene, vinyl alkyl ketone with 4 to 7 carbon atoms (T&:I' vinyl methyl ketone, vinyl ethyl ketone, vinyl ethyl ketone'-7)
General formula (in the formula, 1.L'H or 5J C!-13, I?, "i
-;l: l l Acrylic (or methacrylic) oxyargylprobanal, diacetone methacrylate, diacetone methacrylate, acetonitrile acrylate, 2-hydroxypropyl acrylate-acetylacetate, butanediol-1 , 4-acrylate-acetylacetate and the like. Particularly preferred are diacetone acrylamide, acrolein and vinylmethylken. The copolymerization ratio of monomer + c+ in emulsion polymerization is usually 0.1 to 1 to 1, based on the total monomers.
~7% by weight. The monomer (c) acts to provide a carbonyl group (that is, an aldo group or a keto group) to the carbonyl group-containing copolymer, and the carbonyl group reacts with the organic hydrazine derivative to form a crosslinked structure. The physical properties of the coating film, especially the water resistance of the coating film, can be improved by giving
Contributes to improving chemical properties, blocking resistance, etc. Examples of the monomer (d) include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid, acrylamide, methacrylamide, and N-methylol. Methacrylamide is opened, 4jh' + rest (d) +
-1: Two or more types may be used in combination. 7 as described below
Preferred single 11 (isomer (d) for f11 is itaconic acid, itaconic acid and acrylic acid, itaconic acid and methacrylic acid, or itaconic acid and acrylic acid and methacrylic acid.)
1lr,, J・1 body (the copolymerization ratio of cD is usually 0 to 1
0rB loading, preferably 0.5 to 5.0% by weight, more preferably 0.8 to 2.5% by weight. In order to obtain the cold-crosslinkable carbonyl group-containing copolymer dispersion of component ω) in the present invention, at least the above (a) to
In this emulsion polymerization, Ji')i\ bodies consisting of each monomer (d) are
In addition to the monomers 'l~(d), t) of 111''
It is possible to copolymerize one body. Such parties, 11
Other monomers that can be combined include, for example, butanediol diacrylate, butanediol monoacrylate, acrylonitrile, methacrylaterile, various hydramides, hydroxides, and hydroxides.
,? Ami1-''(7) N-alkyl and/or tJ-argyrol derivatives (e.g. acrylamide, N-mef
-ylacrylamide, N-isobutylacrylamide,
Examples include N-methylolacrylamide and N-methacrylamide. The carbonyl group of this o'3) component, τ, containing co-J[F, emulsion polymerization to obtain a combined aqueous dispersion 1 portion = k 1 per C';
1 person is well known. Examples of emulsifiers used in the emulsion polymerization include anionic surfactants such as alkyl sulfates, argylbenzene sulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkylphenol ether sulfates, polyoxyethylene alkyl ethers, Examples include nonionic surfactants such as polyoxyethylene alkylphenol ether, ethylene oxide propylene oxide block copolymer, and norbitane derivatives. As discussed below, particularly preferred emulsifiers are alkyl sulfates, alkyl sulfonates and alkylbenzene sulfonates, or combinations of these surfactants with polyoxyethylene alkylphenol ether sulfate. In addition, as a polymerization initiator in emulsion polymerization, for example, persulfates such as potassium persulfate and ammonium persulfate,
Examples include organic peroxides such as hydrogen oxide, benzoyl peroxide, cumene hydroperoxide, and tertiary butyl hydroperoxide, and azobisisobutyronitrile. /l? ? Preferred are water-soluble initiators and resox-type initiators, and ω) Component acrylic polymer to 100 parts by weight of chloroprene polymer! n: kl', 300 1 part or less is preferable because the decrease in elongation of the coating film can be suppressed to a small extent. Next, as an organic hydrazine derivative having at least two hydrazine residues added to prevent the horns (ψ,: of the chloroprene polymer), for example, organic hydrazine derivatives containing from 2 to IC, especially from 4 to 6 carbon atoms may be added. Examples include dihydrazides of dicarboxylic acids such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, and inophthalic acid dihydrazide. Examples include aliphatic water-soluble dihydrazines having 2 to 4 carbon atoms, such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4-dihydrazine. Dihydrazine, etc. Particularly preferable organic hydrazine derivatives are adipic acid dihydrazide, isoso-A taric acid dihydrazide, and sebacic acid dihydrazide. When it is a copolymer, when the solvent (e.g. water) evaporates and forms a coating film,
03) The carbonyl group of component (C) and the hydrazine group of component (C) form a hydrogen bond to form a crosslinked polymer. () ■ The heat resistance of the coating film “1” obtained by the formation of this cross-linked polymer,
It is assumed that this is the reason for the improvement in the pull [2] strength. This (C) component, the icohydrazine dicenter, has a prisoner component (
7) Add 0.05 to 10 molar parts of 7'v'n3g combined 100 Tr+ to the installed parts. However, when using the aqueous content ti'<dy of the carbonyl group-containing acrylic copolymer in component (J3) and 1-2, in the above water utilization reaction, the carbonyl group (total of aldo group and keto group) of component 03) ) chopped into 1 mol L2, the hydrazine derivative is consumed at a rate of 0.02 to 1 mol; c,
, (y) to determine the blend rl. If the blend F1 of component C) is small, the effect of preventing yellowing and improving the strength of the coating film will be small. This (C) component may be mixed with the ■ component and the ω) component in the same volume 1, or the (4) component and the (C) component may be mixed in L7.
After that, it may be mixed with component Q'3). Of course, the components (B) and C) may be mixed and then combined with the component (4). A room-temperature crosslinking emulsion in which component (C) a hydrazine derivative is blended with an emulsion of a carbonyl group-containing acrylic copolymer as component (I3) is Acronal YJ-2715D1 from Yuka Verdice ■.
2720D, YJ-27401). The film-forming resin moisture 7jl liquid composition of the present invention contains zinc sulfate, manganese sulfate, water-soluble acetate of zinc, manganese, cobalt or lead, 1j of nitric acid, 1j of nitric acid, zinc monoxide, and A small amount of lead nitrate etc. can be added. Furthermore, the film-forming water-absorbing dispersion composition of the present invention contains pigments that are generally known in the field of compounding technology for paints, adhesives, etc., such as calcium carbonate, talc, clay, and mica powder. , extender pigments such as palite; potassium, sodium or ammonium salts of condensed phosphoric acids such as hexametaphosphoric acid; sodium or ammonium salts of polyacrylic acid; customary anionic or nonionic surfactants: methylcellulose, Dispersants such as ethyl cellulose, flobyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol; various components such as thickeners; and adhesives such as petroleum resins, rosin, and terpene-phenol copolymers can be blended. The film-forming resin aqueous dispersion composition is a PI! agent for surface treatment of paper, cloth, etc., which is the application of chloroprene Radex.
In addition to adhesives, fiber binders, backing materials for fabrics, binders for elastography, asphalt modifiers, acrylic Ji
J, I Mastikko which is the use of fat emulsion)・
Materials, 5" mono-mastic mastic intermediate coating, 9Jll (Zj" mastic topcoat l-shrine, floor finishing material, automobile exterior body paint, anti-vibration coating 1, slate coating 1-4:,
It is useful as a coating phase for coatings such as I, Kinbako J1, and as a binder for pressure-sensitive adhesives, adhesive binders for labels, binders for non-woven fabrics, and adhesive sealants.臥1”1久4′[、面1.1″”(
Provides a coating film with excellent modification properties. Above, water-based emulsions have been described 7, but the composition of the present invention is a bath agent 7 in which the dispersion medium is not water but dissolved using a solvent such as toluene or xylene.
;J, it goes without saying that even if a non-vulcanized chloroprene polymer is used, it is effective in preventing yellowing and improving the mechanical properties of the coating film. Hereinafter, the present invention will be further explained in detail by giving Examples and Comparative Examples. Parts and parts in these examples are by weight unless otherwise specified. Example 1 Production of acrylic copolymer water 1'1 emulsion of component The following materials were placed in a reaction vessel: 200 parts water, reacted with 20 moles of ethylene oxide, 35 parts aqueous solution of Nisder's sodium salt (anionic emulsifier) of p-phenylphenol in sulfuric acid, 10 parts alkyl sulfate sodium salt. The following mixture was prepared as Feed I in 1.5 parts: 200 parts water; 35 parts aqueous solution of anionic/sexual emulsifier 20 parts styrene 15 m parts -2-ethylhexyl acid 17
A solution was prepared in which 2.5 parts of 4 parts of methyl methacrylate x 4 f wound potassium were dissolved. After purging the inside of the reaction vessel containing the above-mentioned materials with nitrogen gas, 10 g of feed material (2) was added and heated to 90°C.
Then 10% of Feed H was injected. While heating and stirring at 90° C., feed (1) and the remainder of feed (2) were uniformly fed into the reactor little by little over a period of 3 to 3.5 hours. After the supply was completed, the reactor was kept at 90° C. for another 1.5 hours and reacted while stirring, and then the inside of the reactor was cooled to room temperature. Aqueous ammonia was added to the resulting dispersion to adjust I) to 7 to 8 to obtain an aqueous copolymer dispersion with a solid content of 50. Examples 2 to 4 An aqueous dispersion of an acrylic 41ζ polymer was obtained in the same manner as in Example 1, except that the component ratio of the vinyl monomer was changed as shown in Table 1. (Leaving space below) Example 1, Comparative Example 1 Vulcanized Chlorobu 1/Lane Lax “Neoprene 842 A (Product Name)” manufactured by Showa Denko (Solid content: 50%)
100 parts of adipine rj2 dihydrazide (A I)
-) I) was blended in an amount of 0.35 parts to form a coating composition (Example IA). This coating composition was poured onto a framed glass plate so as to obtain a wall thickness of 800 microns, and left at 20° C. for one week to form a coating film. The color difference (ΔE) of this coating film is 25°3, the tensile strength at 20°C is about 60 Kg/zf or more, and the elongation is 9
It was more than 00%. This coating film was left in a constant temperature bath at 80°C for 70 minutes, and the color difference was changed again.
Tensile strength and elongation were determined. The results are shown in Table 2. For comparison, Table 2 shows the physical properties of a neoprene film (Comparative Example 1) prepared by 842 people who did not mix adipic acid dihydrosidide. Note that the larger the difference between the color difference at 80°C and the color difference at 20°C, the more advanced the yellowing is. Table 2 *Adipic acid dihydrazide' 10,000 f·t[i<Y112-7, Comparative Examples 2-4 A coating film was obtained in the same manner as in Example 1, except that the coating components shown in Table 3 were used. The physical properties of this coating 1:f (are shown in Table 3. (The following is a blank space) Example 8, Comparative Example 5 A coating film was obtained in the same manner as in Example 1 using a coating composition having the composition shown in Table 4 below. The stress/strain curves of the membrane were measured after storage at 20°C for 7 days and at 80°C for 7 days.The results are shown in Figure 1. In the figure, a shows the film stored at 20°C, and b shows the 80°C film.
Those stored at 0°C are shown. Table 4 Examples 9 to IO1 Comparative Examples 6 to 7 In Example 3, a coating composition containing Neoprene 842A, the acrylic copolymer emulsion obtained in Example 3, and adipic acid dihydrazide in the proportions shown in Table 5 was prepared. A coating film was obtained in the same manner except that it was used. The physical properties of the coating film are shown in the same table. (Margin below)

[Brief explanation of the drawing]

Figure 1 shows the stress/strain curve of the coating film. In the figure, a is measured at 20°C, and b is measured at 80°C.
This is the paint film after a week. l Chamberlain Applicant Yuka Bar 1 Isocie Co., Ltd. Agent Patent Attorney Hidetoshi Ukawa Agent Patent Attorney Masahisa Hase

Claims (1)

[Claims] 1), West component: 100 parts by weight of chloroprene polymer (131 components: 0 to 300 parts by weight of niacryl-based polymer (0 components: 0.05 to 10 parts by weight of hydrazine derivative having at least two hydrazine residues) A chloroprene polymer composition in which the above components (13) and Ω component are blended in the above proportions in parts by weight. 2) Claims characterized in that the hydrazine derivative of component 0 is a polyhydric carboxylic acid dihydrazide. Chloroprene polymer composition 1 according to claim 1. 31. The chloroprene according to claim 1, wherein the acrylic polymer of component 131 is an acrylic copolymer containing a carbonyl group. Polymer composition. , i), (131 component carbonyl 7+% f-γ acrylic copolymer, at least (a+ medyl methacrylate, vinyl aromatic compound, acrylic acid, vinyl chloride, halogenated vinyl) and ethylene monomer 1
Methyl acrylate, vinyl ester to acrylic acid or methacrylic acid ester of alcohol with 0 to 75 carbon atoms, (bl 2 to 16 carbon atoms) 3:+1
and monomers 25 to 90 selected from 1,3-dienes
jTt-b'r, (I have at least one aldo group or keto group and one polymerizable double bond in C1 molecule)
- carbonyl group-containing monomer o, i~2 (1+7j
"u" (regret, The chloroprene copolymer J14 composition according to claim 3, which is an aqueous dispersion. The chloroprene polymer composition according to item 3,