JPS6235435B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil-based coating composition with improved film properties, and more particularly, it contains a natural drying oil-based film-forming component modified with a cyclopentadiene-based polymer and a petrolatum oxide-based rust inhibitor as vehicle components. The present invention relates to an oil-based coating composition suitable for temporary rust prevention of metal materials. Oil-based varnishes and oil-based paints that use natural drying oils or their processed oils as film-forming ingredients have been widely used for a long time, but they have the disadvantage of poor drying properties and corrosion resistance. A method of modifying with a cyclopentadiene polymer (Japanese Unexamined Patent Publication No. 13717/1983, Japanese Patent Application No. 159359/1982, etc.), a natural drying oil film-forming component modified with a cyclopentadiene polymer is further modified with a phenol resin. How to
No. 100867-100867-Patent Application No. 3209-1983), etc. have been developed. These methods show far superior drying properties and corrosion resistance compared to conventional methods, but on the other hand,
There was a new problem in that the coating film was susceptible to coating defects such as wrinkles and peeling, and further improvements in drying properties were desired. Therefore, the present inventors conducted intensive studies to improve the shortcomings of the conventional technology, and found that when a specific rust preventive agent was mixed with a natural drying oil-based film-forming component modified with a cyclopentadiene-based polymer, an unexpected result was found. The present inventors have discovered that these drawbacks can also be overcome, and have completed the present invention. Thus, according to the present invention, a natural drying oil-based film-forming component modified with a cyclopentadiene-based polymer
An oil-based coating composition is provided which contains a mixture of (A) and a petrolatum oxide rust inhibitor (B) as a vehicle component. Component (A) used in the present invention is obtained by mixing a cyclopentadiene polymer () with a natural drying oil-based film-forming component () or by subjecting it to a heating reaction. The component () used is a natural drying oil or a processed oil thereof, which has been conventionally known as a vehicle component for oil-based varnishes or oil-based paints. Specific examples of natural drying oils include linseed oil, tung oil, and safflower oil. 100 iodine value, such as dehydrated castor oil, soybean oil, fish oil, etc.
The above-mentioned oils are exemplified, and the processed oils include stand oil, boiled oil, and the like. On the other hand, the component () used as a modifier may be either oily or resinous; in the former case, the viscosity at 25°C is usually 100 centipoise or more, preferably 200 centipoise or more; in the latter case, usually has a softening point of 160°C or lower, preferably 150°C or lower. At this time, if the viscosity of the polymer is too low, the distillation loss during the heating reaction tends to increase and the effect of improving drying properties tends to decrease; Compatibility decreases and gelation tends to occur during heating reaction. In addition, the composition of such a polymer is selected as appropriate, but
Usually, it is a homopolymer or copolymer having a cyclopentadiene monomer content of 30% by weight or more, preferably 40% by weight or more. The higher the cyclopentadiene monomer content, the better the reactivity with component (), but conversely the compatibility decreases, so copolymers with a cyclopentadiene monomer content of 40 to 90% by weight are preferred. Ru. The cyclopentadiene monomers used in polymerization include cyclopentadiene, lower alkyl substituted cyclopentadiene such as methyl substituted and ethyl substituted cyclopentadiene, and lower Teils-Alder additions such as dimers, trimers, and codimers thereof. and mixtures thereof, and the comonomers include ethylene,
Propylene, butene, pentene, styrene, α-
Monoolefins such as methylstyrene, conjugated dienes such as 1.3-butadiene, isobrene, and 1.3-pentadiene, vinyl monomers with polar groups such as vinyl acetate, vinyl propionate, acrylic esters, methacrylic esters, acrylonitrile, acrolein, and allyl alcohol. Examples include molecules. Such cyclopentadiene polymers are produced by thermally polymerizing a cyclopentadiene monomer or a mixture of the monomer and a comonomer in the presence or absence of an inert solvent such as benzene, toluene, xylene, etc. method (for example, Japanese Patent Application Laid-Open No. 53-98383),
It can be obtained by a known method such as cationic polymerization. The ratio of component () to component () constituting component (A) is usually within a range such that component (A) accounts for 20 to 70% by weight, preferably 25 to 65% by weight of the total amount of both components. If the amount is small, the effect of improving drying properties will be small, whereas if the amount is large, flexibility, corrosion resistance,
Weather resistance etc. decrease. The conditions for mixing or reacting both components are not particularly limited, and the reaction may be carried out according to a conventional method. For example, a method of mixing both components in the presence of a solvent, a method of heating the reaction at 220 to 300°C for 2 to 20 hours in an atmosphere of a gas inert to the reaction such as nitrogen or carbon dioxide gas, etc. are used. A transparent, light-colored oily or semisolid mixture or reaction product can be obtained by this method. At this time, the viscosity of component (A) can be adjusted as appropriate by appropriately selecting component () to be used, the type of component (), reaction temperature, reaction time, and other cooking conditions. In the present invention, the component (A) thus obtained can be used after being further modified with a phenol resin () if necessary. The component () to be used may be any component used in the field of oil-based varnishes and oil-based paints. CKM-1282, rosin-modified phenolic resins such as Hytanol 30P (manufactured by Hitachi Chemical Co., Ltd.),
Heat-reactive alkylphenol resin such as 1634 (manufactured by Showa Union Gosei Co., Ltd.), CKM-2103,
Examples include non-thermally reactive alkylphenol resins such as 2400 (manufactured by Showa Union Gosei Co., Ltd.). The proportion of component () to be used is appropriately selected depending on the required performance, but it is usually 60 parts by weight or less, preferably 3 parts by weight, per 100 parts by weight of the other two components.
~50 parts by weight; if the proportion used is small, the effect of improving dryness, water resistance, and corrosion resistance will be small; if the proportion is too large, flexibility, weather resistance, etc. will be reduced. Modification by component () is described in () and () above.
This is carried out by mixing the component () into a mixture of components or a heated reaction product, or by further heating the reaction. The mixing of the two is usually carried out in the presence of a solvent, and the reaction between the two is carried out under an atmosphere of a gas inert to the reaction, such as nitrogen or carbon dioxide, at a temperature of 150 to
The reaction is carried out by heating at 300°C for 1 to 20 hours. It is also possible to adopt a method in which the three components (), component (), and component () are mixed simultaneously, or a method in which the three components are reacted all at once in a preparation system. In the present invention, a petrolatum oxide rust preventive agent (B) is used as a second component together with the component (A) thus obtained. The component (B) may be any one that is used as a rust preventive agent in the fields of rust preventive oils, plastic processing oils, lubricating oils, etc. Specific examples thereof include OX-0650B, OX-0153, etc. Petrolatum oxide, such as (manufactured by Nippon Seirosha),
OX-0851, OX-0550, OX-0750B, OX-
Petrolatum oxide metal salts such as 0850B (manufactured by Nippon Seirosha Co., Ltd.) and AD-10 (manufactured by Toyo Yakugakusha Co., Ltd.) are exemplified. Among them, petrolatum oxide metal salts are preferred. The proportion of component (B) to be used is 10 parts by weight or less, preferably 2 to 7 parts by weight, per 100 parts by weight of component (A), and if the proportion is small, the effect of preventing wrinkles and flickering and the drying properties will be reduced. If the improvement effect is not sufficient or is too large, drying properties, water resistance, etc. tend to decrease. In the present invention, an oily or semisolid vehicle component is formed by mixing components (A) and (B). The conditions for mixing the two are not particularly limited, and the mixing can be carried out according to a conventional method.
For example, this is carried out by mixing at room temperature or under heating in an atmosphere of a gas inert to the reaction, such as nitrogen or carbon dioxide. The vehicle component thus obtained can be diluted with a solvent as necessary and further added with a desiccant to form an oil-based varnish. In particular, when an oily component () is used as a modifier, a high-solids oil-based varnish can be obtained because the produced component (A) has a low viscosity. In addition, titanium white, iron oxide,
Various enamels can be made by adding pigments such as zinc white and aluminum powder, paint compounding agents such as fillers, pigment dispersants, and drying agents. Additionally, substances that are normally used as vehicle components for oil-based paints (for example, natural drying oils, processed oils thereof, alkyd resins, etc.) may be blended and used within a range that does not essentially impair the effects of the present invention. It can also be used as a modifier for other vehicle components. The composition of the present invention thus obtained is used in the general field of use of oil-based varnishes and oil-based paints, and is particularly suitable for temporary rust prevention of metal materials, particularly steel pipes. The present invention will be explained in more detail with reference to Examples below. Note that all parts and percentages in the examples are based on weight. Example 1 70 parts of linseed oil and 30 parts of cyclopentadiene oil (obtained by thermal copolymerization of an equal mixture of dicyclopentadiene and 1.3-pentadiene) having a viscosity of 6,000 centipoise at 25°C were placed in a nitrogen atmosphere.
Film-forming component (A) was synthesized by reacting at 280°C for 2 hours. For 100 parts of component (A), component (B) is added as a petrolatum oxide rust preventive agent (OX-
0750B (manufactured by Nippon Seiro Co., Ltd., oxidation point: 100°C) in the proportions shown in Table 1, 100 parts of the mixture was diluted with 17 parts of mineral turpentine, and cobalt naphthenate was added as a dryer per 100 parts of component (A). (5
%) and 3.4 parts of lead naphthenate (15%) were added to prepare an oil-based varnish. Next, this varnish was applied to an untreated cold-rolled steel plate to a dry film thickness of 50 μm, and after drying for 7 days, clear coating film evaluation was performed. The results are shown in Table 1.

【table】

[Table] This result shows that film performance such as drying properties, wrinkles, and repellency is improved by adding a petrolatum oxide rust preventive agent. Example 2 In place of the cyclopentadiene oil used in Example 1, a cyclopentadiene resin with a softening point of 125°C (70% dicyclopentadiene and 1.3-pentadiene) was used.
An experiment was carried out in the same manner as in Example 1, except that a 30% mixture (obtained by thermal copolymerization) was used. The results are shown in Table 2.

[Table] From the results, it can be seen that the same results as in Example 1 are obtained even when a cyclopentadiene resin is used. Example 3 100 parts of a reaction product of cyclopentadiene oil and linseed oil prepared in the same manner as in Example 1 and an oil-soluble non-thermally reactive phenol resin (softening point 144°C,
20 parts of CKM-2400 (manufactured by Showa Union Gosei Co., Ltd.) were mixed at 150°C for 2 hours under a nitrogen atmosphere to obtain an oily product having a viscosity of 2500 centipoise at 25°C.
Next, an experiment was conducted according to Example 1 using this oily product as component (A). The results are shown in Table 3.

[Table] From this result, it can be seen that a similar improvement effect is exhibited even when a phenolic resin is included in the film-forming component.

Claims (1)

[Scope of Claims] 1. An oil-based coating characterized by containing a natural drying oil film-forming component (A) modified with a cyclopentadiene polymer and a petrolatum oxide rust preventive agent (B) as vehicle components. Composition. 2. The composition according to claim 1, wherein the film-forming component (A) is further modified with a phenolic resin. 3. The composition according to claim 1 or 2, wherein the oil-based coating composition is used for temporary rust prevention of metal materials.