JPS58191766A - Oily composition for coating - Google Patents

Abstract

PURPOSE:The titled composition that contains a mixture of an acid-modified cyclopentadiene resin and a naturally occurring and processed oil as the vehicle, thus showing high weather resistance, drying properties, water resistance and corrosion resistance. CONSTITUTION:For example, (A) 15-85wt% of a processed product of naturally occurring oil is mixed with (B) 85-15wt% of an acid-modified cyclopentadiene resin of 0.5-40, preferably 3-30 acid value and 60-150 deg.C, preferably 80-140 deg.C softening point, which is obtained by adding (i) an unsaturated carboxylic acid such as maleic anhydride to (ii) cyclopentadiene monomer and (iii) a nonpolar vinyl monomer such as conjugate diolefin, to give the objective composition. EFFECT:Pigments such as titanium white, pigment dispersant, drying agent and other additives for paint are added to the composition to give an enamel.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oil-based coating composition with improved film properties, and more specifically, a mixture of an acid-modified cyclopentadiene resin and a natural processing oil as a vehicle component. The present invention relates to an oil-based coating composition containing excellent properties such as weather resistance, drying properties, water resistance, and corrosion resistance.

Traditionally, processed oils obtained by boiling or making stands from natural drying oils or semi-drying oils have been widely used in the fields of oil-based festivals and oil-based paints, but these are not necessarily sufficient in terms of drying properties, weather resistance, etc. Therefore, methods of mixing various cyclopentadiene resins have been attempted in order to improve this drawback.However, as the cyclopentadiene resin, a resin II having a polar group (for example, vinyl acetate copolymer) is used In this case, although they are well compatible, the effect of improving drying properties and weather resistance is not sufficient, and non-polar wood @
(For example, linear diene copolymers) are generally poor in compatibility with processing oils, so there are restrictions on their use (%
@1856-34'163) Even if they were compatible, they were not necessarily sufficient in terms of weather resistance and drying properties at low temperatures.

Therefore, the present inventors conducted extensive studies to improve the drawbacks that occur when using cyclopentadiene resins, and as a result, we found that cyclopentane resins with valve stem properties, Jiil.
It was discovered that when using an acid-modified product with an acid value within a certain range of 4I, it has good compatibility with processing oil and also has excellent weather resistance, drying properties, water resistance, and corrosion resistance, and the present invention was completed. I've come to the point.

Thus, according to the present invention, there is provided an oil-based coating composition containing (A) a mixture of a natural oil-based processed oil and an acid-modified cyclobencdiene resin as a vehicle component. The cyclopentadiene resin has an acid value of 0.5 to 40, preferably obtained by adding an unsaturated carboxylic acid to a cyclobencdiene resin having no polar group or using an unsaturated carboxylic acid as a comonomer. is 3-30. Softening point 60-15
0°C, preferably 80 to 140°C.

In this case, if the acid value is too low, weather resistance, corrosion resistance, drying properties at low temperatures, compatibility, etc. will not be sufficient; conversely, if the acid value is too high, weather resistance, drying properties, water resistance, etc. Separation occurs in terms of corrosion resistance, etc. If the softening point is too low, the effect of improving drying properties will not be sufficient, and if the softening point is too high, the compatibility with processing oil will decrease.

The resin may be manufactured according to a conventional method, for example, a single lid mixture is heated at 250 to 300°C in the presence or absence of a solvent.
The monomer composition used is usually 100 to 35% by weight of cyclopentadiene monomers, preferably 90% by weight.
-45% by weight, non-polar vinyl monomers 0-65% by weight, preferably lO -55% by weight and unsaturated carbon d0.0
5 to 10 weight percent, preferably 0.5 to 7 weight percent, is rice cake,
As the content of the cyclopentadiene monomer increases, the molecular cap and softening point of the resin tend to increase, and the compatibility with processing oil tends to decrease. clopentadiene, lower alkyl-substituted cyclopentadiene such as methyl-substituted and ethyl-substituted cyclopentadiene, and lower Dils-Alder adducts thereof such as dimers, trimers, co-dimers, and mixtures thereof; Preferred non-polar vinyl monomers are unsaturated hydrocarbons having at least one carbon-carbon double bond, such as ethyl/, propylene, buty/, and benzene. /, monoolefins such as hexene, conjugated diolefins such as L3-butadiene, isoprene, L3-pentadiene, etc., and aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, etc. However, conjugated diolefins are especially prized.

The unsaturated carboxylic acid used as the 30th monomer may be any as long as it can impart Psliiii to the resin, specific examples of which include maleic acid, maleic anhydride,
Examples include chloromaleic anhydride, itaconic anhydride, citraconic anhydride, anhydride, domethylenetetrahydrophthalic acid, and acrylic acid, among which maleic anhydride is highly prized in terms of economy, reactivity, and quality. be done.

Such unsaturated carboxylic acids may be copolymerized during resin synthesis, but the general method is to synthesize the resin in advance and then add it according to a conventional method. Alternatively, the volume MW can be obtained by reacting at 50 to 300°C for 0.5 to 10 hours in the absence of K.

Other ingredients used in the present invention are natural processing oils conventionally known as vehicle components for oil-based paints or oil-based paints. Specific examples of such processed oils include natural drying or semi-drying oils with an iodine value of 100 or more, such as linseed oil, tung oil, safflower oil, dehydrated castor 7 oil, soybean oil, eno oil, and fish oil. Examples include stand-formed oils and homolized oils, among which those with a viscosity of 50 poise or more at 25°C and a k of 100 to 300 poise are particularly prized.

The ratio of processing oil and acid-modified cyclopentadiene resin used in the Qlik of the present invention is appropriately selected depending on the purpose of use, but usually the processing oil is 15 to 85% by weight, preferably 20 to 7%.
The ratio is about 5% by weight and 85 to 15% by weight of cyclobentadiene/ben fat, preferably 75 to 20% by weight. On this occasion,
As the amount of processing oil increases, the drying properties, weather resistance, water resistance, corrosion resistance, etc. of the film tend to decrease, and as the amount of processing oil decreases, the weather resistance, water resistance, corrosion resistance, etc. decrease.

The mixture thus obtained can be made into an oil-based varnish by itself or by diluting with a diluting solvent under normal pressure and, if desired, can be made into an oil-based varnish, and if desired, it can be made into an oil-based varnish such as titanium white, zinc white, aluminum powder, etc. Various types of enamels can be made by adding paint additives such as paint additives and drying agents, and by blending such oil-based varnishes with substances that are normally used as vehicle components for oil-based paints, such as alkyd resins. It can also be used.

The present invention will be described in more detail with reference to Examples below. In the Examples and Reference Examples, all parts and references are based on weight.

Reference Example 1 70 parts of dicyclopentadiene and 30 parts of 3-pentadiene
250 to 270 parts in an autoclave under nitrogen atmosphere.
After thermal polymerization at ℃ for 4 hours, then distillation at 230℃ to recover unreacted monomers, add maleic anhydride of a specified pupil and react at 230℃ for 2 hours in a nitrogen atmosphere.K
From Table 1, modified cyclopentadiene resins as shown in Table 1 were obtained. 40 g of various cyclopentadiene resins obtained in Table 1 and Reference Example 1,
Linseed oil No. 2 stand oil 60 parts, red iron 40s 1 calcium carbonate 130 parts, zinc white 6 parts and mineral tarpe 7
70 parts were dispersed using a pigment dispersion machine, and then, as a dryer, 0.5 parts of cobalt naphthenate (5%) and 1.59 parts of lead naphthenate (15%) were added to make a paint.
The resulting paint was applied to an untreated rolled steel plate to a dry film thickness of 60 μm, and after drying for one week, the paint film was evaluated.

The results are shown in Table 2.

2nd table I 240″C’ according to JISK-5400
a. Degree of blistering after 96 hours of soaking in water:
No change is O5 Slight swelling (occurs after 70 hours) is O
l Blisters (occurred in 10 hours) are indicated by an X.

This 354 NaCj salt spray, degree of rust after 200 hours: 0.5 to 1+w during rust, 0.
3 or more tones are indicated by an × Weatherometer After 300 hours (occurrence of cracks, shrinkage, and chalking); No change j)),
JP or slight chalking is indicated by 0, large chalking, cracks, or shrinkage are not indicated by △, and cracks or creases are indicated by X.

Half 5 A thermal copolymer of 70 parts of dicyclopentadiene and 30 parts of vinyl acetate (# point: 125°C).

From these results, we found that when no acid is added to the cyclopentadiene resin (experiment number 1-1), the weather resistance and corrosion resistance are poor, and when the acid value is too high (experiment number 1-6), the weather resistance and corrosion resistance are poor. It can be seen that the water resistance and corrosion resistance are poor. In addition, in the case of a resin copolymerized with vinyl acetate (experiment number 1-7), it is found that the water resistance and corrosion resistance are poor.

Example 2 Reference? Modified diclopentadiene resin (D
1 and boiling oil were mixed in the proportions shown in Table 2, and the coating film was evaluated in the same manner as in Example 1 and FffJ. Results are shown in flag 4f - Table 3 Example 3 30 parts of the resin (C) obtained in the reference example and 70 parts of long oil type soybean oil modified alkyd resin (Betsukosol P-470 manufactured by Dainippon Ink & Chemicals) were added. After mixing, 37 parts of red iron, 93 parts of calcium carbonate, 37 parts of Merck, and 19 parts of zinc white were dispersed using a pigment dispersion machine, and then, as a dryer, 1 part of cobalt naphthenate (5 t) and lead naphthenate (15 t) were dispersed. A paint was prepared by adding 0.2 parts of manganese phthenate (5%), 9 parts of naphthi/calcium acid (5%), and the resulting paint was untreated and cold rolled. The coating was applied to a steel plate to a dry film thickness of 30 μm, and after drying for 7 days at room temperature, one-piece evaluation was performed. As a result, a coating film with excellent physical properties such as weather resistance, drying properties, water resistance, and corrosion resistance was obtained. Patent applicant Nippon Zeon Co., Ltd.

Claims (1)

[Claims] An oil-based coating composition comprising a mixture with a tadiene resin as a vehicle component.