JPS636102B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly reactive solvent-free chlorinated polyethylene liquid resin composition. Chlorinated polyethylene is originally chemically inert and has excellent chemical resistance, weather resistance, oil resistance, heat resistance, and flame retardancy, and these properties can be used to make it into other resins. Blended in solid form, it has been used as an improvement material for improving the impact resistance and aging of polyvinyl chloride, and as a flame retardant material for polyethylene, polypropylene, polystyrene, ABS, etc. In addition, as liquid resin compositions of chlorinated polyethylene, organic solvent solutions of so-called solvent-processed chlorinated polyethylene, which are obtained by chlorinating relatively low molecular weight polyethylene in organic solvents, are used as paints, adhesives, etc. However, this chlorinated polyethylene was hard and brittle due to its high chlorine content, and its properties such as flexibility and elongation could not be expected. The applicant has previously discovered that a chlorinated polyethylene solution obtained by dissolving chlorinated polyethylene obtained by an aqueous suspension chlorination method in an organic solvent under specific conditions has a coating film that is higher than that of the above-mentioned solvent-based chlorinated polyethylene. was found to be very flexible and useful as adhesives, paints, etc. (Japanese Patent Application Laid-open Nos. 54-26839 and 153853-1983), but this material requires a large amount of organic solvent. When used, there were problems with environmental pollution and restrictions on handling. The present inventors dissolve the chlorinated polyethylene obtained by the above-mentioned aqueous suspension chlorination method in a reactive compound without using an organic solvent to obtain a liquid resin composition that can be 100% cured. As a result of various studies, we found that a certain reactive compound has good compatibility with chlorinated polyethylene, and both become transparent liquids, and this liquid is hardened by a curing catalyst and becomes flexible. The present invention was achieved by discovering that a cured product having elasticity can be obtained. That is, the present invention provides (a) a molecular weight of 10,000 to 100,000;
Chlorinated copolymers based on polyethylene with other monomers in aqueous suspension with a chlorine content of 25
~50% by weight rubbery chlorinated polyethylene resin 10
~50% by weight of (b) esters of acrylic acid or methacrylic acid and monohydric aliphatic alcohols having 1 to 10 carbon atoms, diacrylates or dimethacrylates having 1 to 14 ethylene glycol units, acrylates or methacrylates of phenol derivatives, 1 selected from the group consisting of diacrylate or dimethacrylate of bisphenol A, triacrylate or trimethacrylate of trimethylolpropane, acrylate or methacrylate of cyclohexanol, acrylate or methacrylate of benzyl alcohol, glycidyl acrylate, glycidyl methacrylate, and epoxy acrylate species or two
(a) dissolved in 50-90% by weight of more than one reactive compound;
This is a solvent-free liquid resin composition with high reactivity, characterized in that the total amount of (b) and (b) is 100% by weight. The chlorinated polyethylene resin as component (a) in the present invention is a rubber-like resin obtained by chlorinating polyethylene or a copolymer containing ethylene as a main component with another monomer as a raw material polymer under aqueous suspension. chlorinated polymer. The raw material polyethylene or ethylene copolymer preferably has a molecular weight of 10,000 to 100,000.
Chlorinated polyethylene resins obtained from those having a molecular weight of less than 10,000 do not provide favorable results as elastomers in terms of tensile strength, elongation, thermal stability, etc. In addition, it is difficult to dissolve chlorinated polyethylene resin obtained from raw materials with a molecular weight exceeding 100,000 in reactive compounds, and even if it is obtained, the viscosity of this liquid composition is abnormally high, making it difficult to handle. Poor workability. In order to improve workability, the resin concentration must be significantly lowered, making it impractical. The chlorine content in chlorinated polyethylene resin is 25~
A 50% by weight rubbery material is preferred in this invention. If the chlorine content is less than 25% by weight, it is difficult to eliminate the crystals in the raw material polymer by chlorination, and the remaining crystals adversely affect the solubility of reactive compounds, making it difficult to form a uniform liquid. Furthermore, if the chlorine content exceeds 50% by weight, the thermal stability of the chlorinated polyethylene resin deteriorates, leading to problems of coloring or corrosion to other materials. Copolymers whose main component is ethylene, which is the raw material for chlorinated polyethylene resins, include various comonomers such as propylene, butene, pentene, hexene, vinyl chloride, vinyl acetate, and acrylic esters. Although copolymers having various component proportions can be used, copolymers with an ethylene content of 60% by weight or more, preferably 80% by weight or more are particularly desirable in the present invention. If the ethylene content is particularly low, the melting point of the copolymer is low, making it difficult to perform aqueous suspension chlorination smoothly, and the thermal stability of the obtained chlorinated product is also not very favorable. In the present invention, the reactive compound (b) that dissolves the chlorinated polyethylene resin is one or more compounds selected from acrylic ester compounds and methacrylic ester compounds. Such compounds include esters of acrylic acid or methacrylic acid and monohydric aliphatic alcohols having 1 to 10 carbon atoms, diacrylates or dimethacrylates having 1 to 14 ethylene glycol units, acrylates or methacrylates of phenol derivatives, and bisphenols. A diacrylate or dimethacrylate, trimethylolpropane triacrylate or trimethacrylate, cyclohexanol acrylate or methacrylate, benzyl alcohol acrylate or methacrylate, glycidyl acrylate, glycidyl methacrylate, and epoxy acrylate. The ratio of the chlorinated polyethylene resin as the component (a) and the reactive compound as the component (b) in the composition of the present invention is as follows:
10 to 50% by weight of chlorinated polyethylene resin and 50 to 90% by weight of reactive compound in the total amount of component (a) and component (b)
A range of is appropriate. If the chlorinated polyethylene resin is less than 10% by weight, it will not be sufficient to impart the excellent properties of the rubbery chlorinated polyethylene resin, and if the reactive compound is less than 50% by weight, the viscosity of the liquid composition will decrease. This is not preferable because it becomes extremely high and the workability deteriorates. The chlorinated polyethylene resin is dissolved in the reactive compound by heating it in a closed container with stirring, usually at 50 to 120°C. The above-mentioned melting temperature is appropriately selected depending on the type of reactive compound. Although strong stirring is required in the dissolution step, long-term stirring using a rotary blade stirrer is usually sufficient. Since dissolution is carried out at high temperatures, a polymerization inhibitor is added in an amount of 0.1 to 1% by weight based on the amount of the reactive compound in order to suppress polymerization of the reactive compound. Such polymerization inhibitors include pyrogallol, quinone, hydroquinone, methoxyquinone,
Examples include methylene blue. The composition of the present invention can be cured by various methods such as thermosetting, electron beam curing, and ultraviolet curing. The composition of the present invention can be used for coatings, paints, adhesives, additives, and photosensitive materials. A cured product with impact resistance and elongation properties is obtained. Furthermore, by adding a polymerization catalyst to the composition of the present invention, about 30% of the reactive compound is polymerized, and the composition can be used as a polymerized liquid varnish. The present invention will be explained below with reference to Examples. Example 1 Polyethylene with a molecular weight of 30,000, ethylene-vinyl acetate copolymer (vinyl acetate content 15% by weight),
Using ethylene-ethyl acrylate copolymer (ethyl acrylate content: 18% by weight) as a raw material, each is chlorinated in aqueous suspension to produce rubber-like chlorinated polyethylene with a chlorine content of 43% by weight, chlorinated ethylene-
A vinyl acetate copolymer and a chlorinated ethylene-ethyl acrylate copolymer were obtained. Using n-butyl acrylate, decyl methacrylate, trimethylolpropane trimethacrylate, and benzyl methacrylate as reactive compounds with the chlorinated polyethylene resin, adding 0.2% by weight of hydroquinone to the reactive compounds,
Put both into a separable flask with a stirrer and add
It was dissolved under the dissolution conditions shown in the table. When we observed the dissolution state of liquid compositions with chlorinated polyethylene resin concentrations of 20% and 40% by weight, both were transparently dissolved, and the viscosity of these liquid compositions at 40°C was that of chlorinated polyethylene resin. Bright density 20
The weight percentage was 500 to 1000 poise, and the 40 weight percent was 1000 to 1500 poise. Benzoyl peroxide was added to the above liquid composition in an amount of 2% by weight based on the reactive compound, and this was applied to a mild steel plate (50% by weight).
× 150 × 1 mm) and heated at 70℃ in a constant temperature bath for 4
After curing for a while, a cured film with a thickness of 200 microns was obtained. The physical properties of the cured film are pencil hardness, bending test,
The impact resistance was also as shown in Table 1.

【table】

[Table] Comparative Example 1 When dissolution treatment was carried out under the same conditions except that the chlorinated polyethylene resin concentration in Table 1 of Example 1 was changed to 5% by weight and 55% by weight, the resin concentration was 55%.
% by weight, the chlorinated polyethylene resin was only in a swollen state and did not become a liquid state. Additionally, 2% by weight of azobisisobutyronitrile was added to the liquid composition with a resin concentration of 5% by weight based on the reactive compound, and this was applied onto the same mild steel plate as in Example 1 and heated to 60°C in a constant temperature bath. and cure for 5 hours, thickness
A cured film of 200 microns was obtained. The physical properties of the cured film are a pencil hardness of 2H to 4H and Example 1.
It was harder, with a bending test of 10 mmφ or more, and impact resistance (load of 200 g) of 30 cm or less. Example 2 Polyethylene having a molecular weight of 50,000 was used as a raw material and was chlorinated under aqueous suspension to obtain a rubber-like chlorinated polyethylene having a chlorine content of 50% by weight. 20 parts by weight of the above chlorinated polyethylene, 30 parts by weight of benzyl acrylate, 50 parts by weight of diethylene glycol diacrylate, and 0.2 parts by weight of methoxyquinone were placed in a separable flask with a stirrer, and heated at 70°C for 4 hours.
The mixture was heated for an hour to dissolve it. After cooling, 1 part by weight of azobisisobutyronitrile was added thereto, and this was applied to a mild steel plate in the same manner as in Example 1 and cured at 80°C for 3 hours to obtain a cured film with a thickness of 150 microns.
The obtained cured film has a pencil hardness of HB and a bending strength of 3 mm.
φ, impact resistance (load 200g) was 50cm. Example 3 An ethylene-vinyl acetate copolymer having a molecular weight of 70,000 (vinyl acetate content: 20% by weight) was chlorinated in aqueous suspension as a raw material to obtain a rubbery chlorinated ethylene-vinyl acetate copolymer having a chlorine content of 45% by weight. 20 parts by weight of the above chlorinated copolymer, 10 parts by weight of decyl acrylate, 20 parts by weight of trimethylolpropane trimethacrylate, phenol derivative acrylate (“P-200A” manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
50 parts by weight and 0.3 parts by weight of methoxyquinone were placed in a separable flask equipped with a stirrer and heated at 80°C for 3 hours to dissolve them. After cooling, 10 parts by weight of titanium oxide and 10 parts by weight of calcium carbonate were added thereto and mixed in a ball mill for 5 hours. Further, 1.5 parts by weight of benzoyl peroxide was added thereto, and the mixture was applied to a mild steel plate in the same manner as in Example 1 and baked at 120°C for 30 minutes to obtain a cured film with a thickness of 100 microns. The obtained cured film has a pencil hardness of HB, bending diameter of 4 mm, and impact resistance (load of 200 g).
It was 40cm long. Example 4 Polyethylene with a molecular weight of 10,000 was chlorinated in aqueous suspension to obtain rubber-like chlorinated polyethylene with a chlorine content of 30% by weight. 40 parts by weight of the above chlorinated polyethylene, 10 parts by weight of n-butyl acrylate, 50 parts by weight of bisphenol A diacrylate, and 0.2 parts by weight of hydroquinone were placed in a separable flask with a stirrer and heated at 60°C for 3 hours to dissolve them. Ta. After cooling, 1 part by weight of benzoin was added, and this was applied onto the same mild steel plate as in Example 1, and cured by irradiation with a UV lamp (high-pressure mercury lamp, 110 W/cm) at an irradiation distance of 20 cm for 1 minute. The cured film was 100 microns thick, and an acetone spot test confirmed that it was sufficiently cured. The pencil hardness of this cured film was 2B, bending was less than 2 mmφ, and impact resistance (load: 200 g) was 80 cm. Example 5, Comparative Examples 2 to 5 Chlorinated polyethylenes each having a chlorine content of 40% by weight were obtained by an aqueous suspension chlorination method using polyethylene having a molecular weight of 50,000 and polyethylenes having molecular weights of 4,000 and 150,000. Similarly, polyethylene with a molecular weight of 50,000 was chlorinated to obtain chlorinated polyethylenes with a chlorine content of 55% by weight and 20% by weight. A heat resistance test was conducted on each of the above chlorinated polyethylenes, and changes in dehydrochlorination due to thermal decomposition at a heating rate of 10° C./min were measured using a thermobalance. The results are shown in Table 2. In addition, each of the above chlorinated polyethylenes was prepared in the same manner as in Example 1, using propyl acrylate and benzyl acrylate to give a resin concentration of 20% by weight.
The solubility was examined by heating at 70°C for 3 hours, and the results are also shown in Table 2. The evaluation of solubility in Table 2 is as follows. 〇...Good solubility ×...Poor solubility

[Table] As is clear from Table 2, Comparative Example 2, which uses polyethylene with a molecular weight of 4,000 as a raw material, has poor heat resistance, and Comparative Example 3, which uses polyethylene with a molecular weight of 150,000 as a raw material, has poor solubility. was only in a swollen state. In Comparative Example 3, a uniform liquid was obtained only when the chlorinated polyethylene concentration was 5 weight and heated at 80° C. for 4 hours. Furthermore, in Comparative Examples 4 and 5, when the chlorine content exceeds the range of the present invention, there is a problem in heat resistance, and when it is low, solubility deteriorates, and in Comparative Example 5, the liquid became cloudy and a large amount of insoluble matter was present.

Claims (1)

[Claims] 1 (a) Polyethylene with a molecular weight of 10,000 to 100,000 or a copolymer containing ethylene as a main component with other monomers, chlorinated in aqueous suspension with a chlorine content of 25 to 50
Weight% rubbery chlorinated polyethylene resin 10~50
(b) Esters of acrylic acid or methacrylic acid and monohydric aliphatic alcohol having 1 to 10 carbon atoms, diacrylates or dimethacrylates with 1 to 14 ethylene glycol units, acrylates or methacrylates of phenol derivatives, bis One member selected from the group consisting of phenol A diacrylate or dimethacrylate, trimethylolpropane triacrylate or trimethacrylate, cyclohexanol acrylate or methacrylate, benzyl alcohol acrylate or methacrylate, glycidyl acrylate, glycidyl methacrylate, and epoxy acrylate. Or 2
(a) dissolved in 50-90% by weight of more than one reactive compound;
A solvent-free liquid resin composition with high reactivity, characterized in that the total amount of (b) is 100% by weight.