JPS6154826B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel chlorinated polyolefin paint composition, and more specifically, a cyclopentadiene resin is blended into a room temperature drying paint containing a chlorinated polyolefin in a binder to improve adhesion, flexibility, and durability. This invention relates to a novel chlorinated polyolefin coating composition with improved impact resistance and alkali resistance. Chlorinated polyolefins have been widely used as binders for paints that dry at room temperature. Chlorinated polyolefin is a substance obtained by chlorinating polyolefin resin, and is chemically stable and resistant to acids and
It is not easily attacked by alkalis, etc., and its film has low permeability to water and water vapor. Chlorinated polyolefins are also known to dry quickly and provide very hard coatings. However, when this chlorinated polyolefin is used alone, it has the drawback of being brittle and having poor adhesion to substrates. Therefore, in order to take advantage of the advantages of chlorinated polyolefin, it is generally preferred to use a plasticizer in combination. Examples of such plasticizers include phthalate esters and chlorinated paraffins, but although the use of these improves flexibility and adhesion to substrates, it also impairs quick drying, hardness, and chemical stability. Sexuality etc. will be impaired. In addition, chlorinated polyolefin has quick drying properties, hardness,
It is also used as a modifier added to alkyd resin paints and oil-based paints to take advantage of its excellent properties such as chemical resistance and low water permeability. However, adding a large amount of chlorinated polyolefin causes problems such as increased cost, increased paint viscosity, and incompatibility with zinc-containing and aluminum-containing pigments. The present inventors have conducted studies to improve the adhesion, flexibility, and impact resistance of chlorinated polyolefin paints without sacrificing the characteristics of water resistance, corrosion resistance, and chemical resistance. As a result, they discovered that it is effective to blend a specific cyclopentadiene resin with chlorinated polyolefin, and have completed the present invention. The main object of the present invention is to provide a composition for a chlorinated polyolefin coating that dries at room temperature and has improved adhesion, flexibility, impact resistance, and alkali resistance. The object of the present invention is to provide a chlorinated polyolefin coating composition having excellent acid resistance and hardness. These objects of the present invention are to provide (i) per 100 parts by weight of chlorinated polyolefin (ii) a softening point of 50 to 160 obtained by thermal polymerization in a room temperature drying paint containing chlorinated polyolefin as a binder component.
5 to 100 parts by weight of cyclopentadiene resin at ℃ is added, and if desired, commonly used compounding agents such as pigments, plasticizers, solvents, stabilizers, and dispersants are added to prepare a composition for a paint that dries at room temperature. This is achieved by The cyclopentadiene resin used in the present invention contains 50 to 100 cyclopentadiene monomers.
% by weight, preferably 60-100% by weight, and 50-0% by weight, preferably 40-0% by weight of a diolefinic monomer, monoolefinic monomer or polar vinyl monomer copolymerizable therewith. A monomer component consisting of 200 to 300% of
℃, preferably 250 to 280℃ for 0.5 to 20 hours, preferably 1 to 10 hours in an autoclave, and then remove low-boiling substances such as unreacted substances by distillation or other ordinary polymer purification means. Softening point 50-160℃, preferably synthesized by
80-140℃, Gardner color number 10 or less. In addition, cyclopentadiene resins are hydrogenated using conventional methods to reduce the coloration of the resin and improve weather resistance, and cyclopentadiene resins are modified by adding ethylenically unsaturated carboxyl compounds such as maleic anhydride. These cyclopentadiene resins can also be used as the cyclopentadiene resin in the present invention. In this case, if a resin with too low a cyclopentadiene monomer content is used, the compatibility with the chlorinated polyolefin may be insufficient, resulting in poor paint drying, film hardness, flexibility, and water resistance. It is also inferior in performance, and is not preferred as a compounding agent for paints. Furthermore, if the softening point of the cyclopentadiene resin is too high, the compatibility with the chlorinated polyolefin will be poor. Cyclopentadiene monomer means cyclopentadiene or its derivatives, and includes cyclopentadiene, lower alkyl-substituted cyclopentadiene such as methyl-substituted and ethyl-substituted cyclopentadiene, and dimers, trimers, and codimers thereof. It may also be a lower Diels-Alder adduct such as a body, as well as mixtures thereof. Among these, cyclopentadiene exists stably as dicyclopentadiene at room temperature, so cyclopentadiene and dicyclopentadiene are usually handled in exactly the same way. On the other hand, diolefinic monomers include conjugated diene compounds such as 1,3-butadiene, isoprene, and 1,3-pentadiene, as well as non-conjugated diene compounds such as 1,4-pentadiene and 1,5-hexadiene. , and monoolefinic monomers include styrene, α-methylstyrene, ethylene, propylene, butene, pentene, and the like. Furthermore, the polar monoolefinic monomer is a vinyl monomer having a polar group, and includes organic unsaturated cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl acetate, vinyl propionate, allyl acetate, methalyl acetate, and propionic acid. allyl,
Lower fatty acid esters of unsaturated alcohols such as metaallyl propionate, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and esters of the unsaturated carboxylic acids and lower alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, glycide, and ethylene glycol. , acrolein,
Unsaturated aldehydes such as methacrolein, monohydric to polyhydric unsaturated alcohols such as allyl alcohol, crotyl alcohol, 1,4-butenediol, 3-hexene-2,5-diol, and other allylglucidyl ethers. It means an unsaturated ether such as On the other hand, the chlorinated polyolefin used in the present invention is generally used as a binder for paint compositions that dry at room temperature, and is obtained by chlorinating polyethylene or polypropylene in a conventional manner. Specific examples of the chlorinated polyolefin used include chlorinated polyethylene and chlorinated polypropylene, which have a chlorine content of 55% by weight or more and are soluble in toluene, and the viscosity of a 40% by weight toluene solution at 25°C is 20 ~10000 centipoise is preferred. In the present invention, it is essential to contain a chlorinated polyolefin as a component of the binder, but the content of the chlorinated polyolefin is usually 20% by weight or more, preferably 30% by weight or more of the total binder component. , other binder ingredients,
For example, if a small amount of chlorinated polyolefin is added as a modifier to a paint whose main binder is natural drying oil or alkyd resin, even if a cyclopentadiene resin is added to the paint, there will be no noticeable improvement. cannot be effective. In the present invention, chlorinated polyolefin 100
Cyclopentadiene resin 5 to parts by weight
It is necessary to add 100 parts by weight, preferably 10 to 70 parts by weight. If the amount of cyclopentadiene resin added is too small, the effect of improving the adhesion, flexibility, impact resistance, and alkali resistance of the coating film will be small; on the other hand, if it is too large, the drying speed and hardness of the coating film will decrease. Therefore, it is not desirable. In carrying out the present invention, the chlorinated polyolefin and cyclopentadiene resin are dissolved in commonly used coating solvents such as toluene, xylene, solvent naphtha, etc., and if desired, alkyd resin, natural drying oil, etc. Other binders like amino resin, acrylic resin etc., pigments like titanium oxide, red lead, Bengara, zinc dust, calcium carbonate, talc etc., plastics like dioctyl phthalate, dioctyl sebacate, chlorinated paraffin etc. A coating composition is prepared by adding stabilizers such as phenyl glycidyl ether, epoxidized soybean oil, and the like. The composition is applied to the substrate by conventional methods, such as brushing, spraying, or other methods, and is cured at room temperature or under forced drying up to about 100°C if necessary to shorten drying time. By doing so, a film with excellent hardness, adhesion, flexibility, impact resistance, gloss, water resistance, corrosion resistance, and chemical resistance can be formed. The present invention will be explained in more detail with reference to Examples below. In addition, parts and percentages in the examples are based on weight unless otherwise specified. Example 1 A monomer mixture of 70 parts of dicyclopentadiene and 30 parts of isoprene was heated at 260°C in the presence of xylene solvent.
A cyclopentadiene resin with a softening point of 125°C obtained by thermal polymerization for 3 hours was blended with chlorinated polyethylene (chlorine content 63% by weight) etc. according to the following formulation to prepare a coating composition. . After thoroughly mixing this composition in a ball mill, it was applied to a degreased mild steel plate using a bar coater using piano wire with a diameter of 1 mm, and was dried and cured for one week in an atmosphere of 25°C and 60% relative humidity. Create a coating film and evaluate its performance
Evaluation was made according to JISK-5400. The results are shown in Table-1. Compounding Process Cyclopentadiene resin 0-55 (parts) Chlorinated polyethylene (Adekaprene manufactured by Asahi Denka Co., Ltd.)
CE-505) 100-45 Chlorinated paraffin (Empara 65 manufactured by Ajinomoto Co.)
75 Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipeiku R-
550) 120 Epoxidized soybean oil (Adekasizer manufactured by Asahi Denka Co., Ltd.)
O-120) 5.5 Xylene 150

[Table] From the results, the composition of the present invention was improved in terms of adhesion, Erichsen test, impact resistance, alkali resistance, etc. compared to the composition without cyclopentadiene resin (Experiment No. 1). It can be seen that However, when the amount of cyclopentadiene resin is blended in a larger amount than that of chlorinated polyethylene (experiment number 4), a decrease in hardness, Erichsen test, bending resistance, etc. is observed, which is not preferable. Example 2 A cyclopentadiene resin with a softening point of 125°C obtained by thermally polymerizing a mixture of 75 parts of dicyclopentadiene and 25 parts of vinyl acetate at 260°C for 3 hours in the presence of a xylene solvent was subjected to the following compounding treatment. A coating composition was prepared by blending with chlorinated polypropylene (chlorine content: 63% by weight) according to the method, and its performance was evaluated in the same manner as in Example 1. The results are shown in Table-2. Compounding Process Cyclopentadiene resin 0-55 (parts) Chlorinated polypropylene (Adekaprene CP-100, manufactured by Asahi Denka Co., Ltd.) 100-45 Chlorinated paraffin (Manufactured by Ajinomoto Co., Ltd., Empara 65)
75 Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Taipeiku R-
550) 120 Epoxidized soybean oil (Adekasizer manufactured by Asahi Denka Co., Ltd.)
O-120) 5.5 Xylene 150

【table】

[Table] From the results, the composition of the present invention was improved in terms of adhesion, Erichsen test, impact resistance, alkali resistance, etc. compared to the composition without cyclopentadiene resin (Experiment No. 5). It can be seen that However, if the amount of cyclopentadiene resin is greater than that of chlorinated polypropylene (Experiment No. 8), hardness, adhesion, Erichsen test, impact resistance, etc. will deteriorate, which is not preferable.

Claims (1)

[Scope of Claims] 1. In a room temperature drying paint containing chlorinated polyolefin as a component in the binder, (i) per 100 parts by weight of chlorinated polyolefin, (ii) a softening point of 50 to 160 obtained by thermal polymerization. 1. A chlorinated polyolefin coating composition comprising 5 to 100 parts by weight of a cyclopentadiene resin having a temperature of 5 to 100 parts by weight. 2. The composition according to claim 1, wherein the content of chlorinated polyolefin in the binder is 20% by weight or more. 3. The composition according to claim 1, wherein the chlorinated polyolefin is chlorinated polyethylene or chlorinated polypropylene. 4 Cyclopentadiene resin is obtained by thermally polymerizing a monomer component consisting of 50 to 100% by weight of a cyclopentadiene monomer and 50 to 0% by weight of a comonomer copolymerizable therewith. The composition according to claim 1, which is a composition according to claim 1. 5. The composition according to claim 4, wherein the cyclopentadiene monomer is cyclopentadiene, alkylcyclopentadiene, or a dimer, trimer, or codimer thereof. 6. The composition according to claim 4, wherein the copolymer is a diolefinic monomer, a monoolefinic monomer, or a polar vinyl monomer.