JPS58213059A - Room temperature setting, high-solid paint composition - Google Patents

Abstract

PURPOSE:To provide a room temperature setting, high-solid paint having improved dryness, film physical properties and coating workability, consisting of a non-aqueous polymer dispersion, obtd. by dispersion-polymerizing an unsaturated vinyl monomer in the presence of a modified alkyd resin, and a fatty acid- modified alkyd resin. CONSTITUTION:A non-aqueous polymer dispersion (A) obtd. by dispersion-polymerizing an unsaturated vibyl monomer in the presence of an alkyd resin modified with a drying (semidrying) oil having an oil length of 20-70 and/or a drying (semidrying) oil fatty acid in an org. solvent in which the monomer is soluble, but the produced polymer is insoluble, is mixed with an alkyd resin (B) modified with a drying (or semidrying) oil having an oil length of 15-75 and/or drying (semidrying) oil fatty acid in a weight ratio of A/B of 5/95-50/50 on a solid basis, the difference in oil length between components A and B being less than 10.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high solids coating composition that dries at room temperature, and more specifically, a non-aqueous polymer dispersion containing a semi-drying oil and/or a semi-drying oil fatty acid-modified alkyd resin as a fractional stabilizer;
The present invention relates to a room temperature tφ type high solids coating composition which is made by blending a semi-drying oil and/or a semi-drying oil and a fatty acid-modified alkyd resin.

Conventionally, it has been widely used and has a drying oil-modified alkyd resin as its main component. However, in recent years, there has been a demand for reducing the amount of organic solvents in paints from the standpoint of resource conservation and prevention of air pollution, that is, high solids paints. It is desired to further improve performance such as workability depending on the application.

However, in the past, various means have been used to make paints high solids and to improve paint performance. gAJJ
Although it is possible to make paints more solid by lowering the molecular weight of the alkyd resin, this method has the disadvantage that the physical properties and drying properties of the paint film deteriorate. It is also possible to improve the performance of alkyd resin paints, such as their drying properties and painting workability, by appropriately adjusting the composition, oil length, molecular weight, etc. of the alkyd resin, but there are naturally limits to its effectiveness, and it is difficult to achieve the desired performance. It has been difficult to obtain a room-temperature-drying high-solids alkyd resin paint with well-balanced properties.

Therefore, the present inventors have conducted extensive research in order to improve the solidity of conventional room temperature drying alkyd resin paints and to improve the performance of the paints, including their drying properties, film properties, and painting workability. By blending a non-aqueous polymer dispersion obtained by dispersion polymerizing an unsaturated vinyl monomer with a semi-drying oil and/or a semi-drying oil fatty acid-modified alkyd resin as a dispersion stabilizer into an oil-modified alkyd resin. The inventors have discovered that the viscosity of the latter alkyd resin is significantly reduced, which makes it possible to lower the viscosity of the resulting paint, and further improves performance such as drying properties and physical properties of the coating film, leading to the completion of the present invention. .

Thus, according to the invention: (i) a dry (or semi-dry) oil with an oil length of 20 to 70 and/or
or dispersion polymerization of unsaturated vinyl monomers in the presence of a dry (or semi-dry) oil-fatty acid-modified alkyd resin in an organic liquid in which the monomers are soluble but the polymer formed is insoluble. and (2) a drying (semi-drying) oil and/or drying oil having an oil length of 15 to 75 and a difference of less than 10 from the oil length of the alkyd resin used in component (2). (still semi-dry) oil fatty acid modified alkyd resin, solid content weight ratio (At/(B=5/95~5015)
Provided is a high solids paint composition that retains its shape at room temperature and is characterized by being mixed at a temperature of 0°.

In the present invention, the dry (or semi-drying) oil and/or dry (or semi-drying) oil fatty acid-modified alkyd resin with an oil length of 20 to 70 used as a dispersion stabilizer for the (anhydrous ) Phthalic acid, isophthalic acid, terephthalic acid, dimethyl isophthalic acid, dimethyl terephthalic acid, tetrahydro(m-water) 7-thalic acid, hexahydro-(anhydride) 7-thalic acid, adipic acid, (anhydrous) maleic acid, azelaic acid, (anhydrous) Using a polybasic acid such as succinic acid, and
/l/Call 11-) 1. Teke ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol 1.5-hentanediol, neopentyl alcohol/L/, 1.6-
hexanediol, 2,5-hexanediol, 2,2
．． Polyhydric alcohols such as 4-trimethyl-1,3-bentanediol, dipropylene glycol, trimethylolethane, trimethylolpropane, chrycerin, diglycerin, and pentaerythritol are used, and as modified oils, drying oils to semi-drying oils are used. Animal oils, vegetable oils and their fatty acids leading to oils, such as sesame oil, cottonseed oil, oyster oil,
Oiticica oil, rice bran oil, soybean oil, safflower oil, dehydrated castor oil, linseed oil, tung oil, fish oil, sesame oil fatty acid, edible oil fatty acid, rice bran oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid, It is manufactured using safflower oil fatty acids, dehydrated castor oil fatty acids, linseed oil fatty acids, fish oil fatty acids, etc. The alkyd resin can be produced in accordance with a conventional method known per se.
This is carried out by carrying out a dehydration condensation reaction for 0 hours.

The number average molecular weight of the alkyd resin thus obtained is approximately 1 to 1.
,000 to about 1 (1,000, preferably about 2,000
~5,000. If the molecular weight is smaller than 100 ('l), performance as a dispersion stabilizer cannot be obtained;
If it is larger than 00, gelation may occur during manufacturing. The reason why the oil length of the alkyd resin should be limited to a range of 20 to 70 is that oil lengths outside this range do not function well as a dispersion stabilizer, and in order to obtain a stable fraction, the core subject to compositional constraints. Furthermore, there is a drawback that the compatibility with the intermediate resin is poor, which significantly limits the range of use.

Examples of the unsaturated vinyl monomers used as a dispersion polymer include vinyl aromatic compounds such as styrene and vinyltoluene; methyl methacrylate, ethyl methacrylate, 6-n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate,
C1-12 alkyl esters of acrylic acid or methacrylic acid such as t-butyl acrylate, 2-ethylhexyl acrylate; 2-vitrogine ethyl acrylate;
Hydroxyalkyl esters of acrylic or methacrylic acid with 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; glycidyl acrylate, glycidyl methacrylate; Saturated acids; monomers among them;
For example, acrylonitrile, acrylonitrile, acrylamide, methacrylamide, vinyl acetate, etc. are used, and these monomers can be used alone or in combination of two or more.

Dispersion media used when dispersing and polymerizing unsaturated vinyl monomers using the above-mentioned alkyd resin as a dispersion stabilizer include:
It is an organic liquid in which the monomers are soluble but the polymers formed are substantially insoluble.

Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, especially -7'-ethyl alcohol,
Alcohol solvents such as methyl isobutyl carbinol and isobutyl alcohol; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aromatic solvents such as toluene and xylene; n-pentane, n
- Aliphatic hydrocarbon solvents such as hexane, n-hebutane, n-octane are used. These can be used alone or in combination of two or more.

As the method for producing the non-aqueous polymer dispersion in the present invention, conventionally known methods may be used, such as a stirring device, a heating device and a thermometer, a solvent cooling pipe and a reflux device,
Using a reaction vessel equipped with a monomer dropping device and a pressure reducing device, add the alkyd resin for the dispersion stabilizer □ to a reaction vessel with a solid content of 1.
The mixture is dissolved in an appropriate organic solvent as mentioned above to a concentration of 0 to 70% by weight, heated while stirring, and when the temperature reaches a temperature at which the solvent refluxes, radical polymerization with the unsaturated vinyl monomer begins. It takes about 1 to 6 hours to add the agent, and the mixture is further reacted for about 0.5 to 2 hours. The reaction temperature is usually 50 to 150°C, although it depends on the solvent used.

The mixing ratio of the alkyd resin and the unsaturated vinyl monomer in the above reaction is usually 10/90 to 70/30 by weight.
It is preferably in the range of 20/80 to 60/40.

In addition, the radical polymerization initiators used include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, and phthyl peroxide.
Peracids such as 2-ethylhexanoate and t-butylperoxybenzoate ([1 series) and azo catalysts such as azobisdimethylvaleronitrile and azobisisobutylnitrile are typically used.

In the present invention, the alkyd resin [F] to be blended with the non-aqueous polymer dispersion (to) has an oil length of 15 to 759 (same as the alkyd resin used as a dispersion stabilizer in component A). The solvent used for this alkyd resin may be appropriately selected from the aliphatic and aromatic solvents used as the dispersion medium of component A. However, in the present invention, blended It is essential that the oil length of the alkyd resin to be used is within the above-mentioned range and has a difference of 10 meters from the oil length of the alkyd resin used in component (a). is less than 10. For example, if the oil length of the component alkyd resin is 50, it means that the oil length of the component alkyd resin to be blended is in the range of more than 40 and less than 60.

If the difference in oil length between the above-mentioned two alkyd resins is 10 or more, the compatibility between the component and the component (g) becomes poor, the high solids ability is insufficient, and the coating film performance such as drying property and physical properties deteriorates. There is a disadvantage that a high solids coating composition with good quality cannot be obtained.

In addition, the mixing ratio of the component with the component (ii) is solid content weight ratio, CAI/(9=5/95 to 50150, preferably 10
- It is 10/90 to 30/70. (If the ratio of At/T is less than 5/95 (lower viscosity of the paint obtained due to a small amount of A component), it is not possible to induce isolytization or sodization; on the other hand, if it is more than 50150, (If component B is too small, Realquito resin will not be able to exhibit its original performance.

A feature of the present invention is that by blending the non-aqueous polymer dispersion (A) with an oil-modified alkyd resin, the blended product can be made to have a low viscosity even if the [F] acid component is a high-viscosity alkyd resin. , high solidity differentiation can be achieved without lowering the molecular weight of the alkyd resin.

For example, as seen in Example 1, a high viscosity alkyd resin (B is a non-aqueous polymer dispersion (B) having a solid content of 50% ( By blending with 2), the viscosity of the blended product decreases significantly when it is crushed, near N.

Due to the viscosity-reducing effect of the non-aqueous polymer dispersion on the alkyd resin as described above, the solid content at the normal coating viscosity of 70 to 75 Ku (Stormer viscometer 25°C) of the alkyd resin paint that dries at room temperature and can be processed is reduced. Approximately 75-80% by weight
It is possible to increase the amount of heat by about 15% by weight or more compared to the conventional one. This means that the viscosity of the nonaqueous polymer dispersion is A
1 or less (solid content 50%) and the viscosity of alkyd resin ■ ~ Z (
This is based on the fact that the solid content is significantly lower than that of solids (50%).

Furthermore, in terms of the performance of the coating composition of the present invention, (even if measures are taken to reduce the molecular weight of the nine component alkyd resins, the non-aqueous polymer dispersion (A) is Since it is made of polymer particles of saturated monomers, the coating film formed from it has excellent drying properties and physical properties, and the high solid content as mentioned above does not adversely affect coating workability. Can be easily prepared to a viscosity that is not paintable.

In the coating composition of the present invention, white pigments such as titanium white, colored pigments such as iron oxide, carbon black, and phthalocyanine punokasumi, extender pigments such as tantalum, sulfur, barium acid, talc, mica, and other pigments used in ordinary paints are used. Additives etc. can be used.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, parts and % show weight parts and weight %.

Example 1 and Comparative Example 1 N-hebutane 3009. Charge 150 f of n-butyl alcohol and 100 f of xylene, and add soybean oil fatty acid modified alkyd resin (oil length 60 and acid value 5.0) to this.
After adding 1 sor of solid content and dissolving it, reflux the solvent,
Heated at a temperature (80-85°C) t:. Then methyl acrylate) 12Of, methyl methacryle) 80?
, acrylonitrile 80f1 styrene 702, hydroxypropyl methacrylate 60? and acrylic acid 10g
? azobisisobutylnitrile 6,0 to the monomer mixture of
f The completely dissolved solution was prepared in advance in a dropping device, and was dropped into the dispersion stabilizer solution over a period of 3 hours.

One hour after the completion of the dropwise addition, 1 hour of a solution containing 4.02 kg of azobisisobutylnitrile dissolved in 50 fK of xylene was added.
The mixture was added dropwise over a period of time, and the reaction was continued for an additional 2 hours to obtain a non-aqueous polymer dispersion (A-1) with a solid content of 50% and a viscosity of A2.

13 At the same time, add oil length 6 to the above non-aqueous polymer dispersion (A-1).
The soybean oil-modified alkyd resin (B-1) having a phthalic anhydride content of 30%, a solid content of 65%, and a viscosity of Z is blended in the proportions (solid content weight ratio) shown in Table 1 and dried at room temperature according to the present invention.・
F-type high solid paint compositions 1 to 3 and comparative paint 4 were obtained. The viscosity and performance of the coating composition thus obtained are shown in Table 1.

Example 2 and Comparative Example 2 350f of n-heptane and 200f of n-butyl alcohol were charged into a reaction vessel, and the oil length was 60 and the acid value was 1 (1
, 5 linseed oil fatty acid modified alkyd resin (solid content) 1
After adding 20 r to dissolve the mixture, it was heated at the rapid flow temperature of the solvent. Then methyl acrylate 3Of, methyl methacrylate 100f, 7'ZIJ lonitrile 1002,
Styrene 702, Hydroxypropyl methacrylate 7
A solution of 6.6 g of azobisisobutylnitrile dissolved in a monomer mixture of 0 and 10 f of acrylic acid was prepared in advance in a dropping device, and added to the dispersion stabilizer solution.
- Dropped over 3.5 hours. One hour after the dripping finished,
Azobinisobutylnitrile 4.42 to toluene 50f
' was added dropwise over a period of 1 hour, and the reaction was continued for an additional 2 hours to obtain a non-aqueous polymer dispersion (A-2) with a solid content of 50% and a viscosity of A1 to A.

Next, an oil length of 7 was added to the non-aqueous polymer dispersion (A-2).
4. Phthalic anhydride content 8%, solid content 95% and viscosity U
The soybean oil-modified alkyd resin (B-2) was blended in the proportions (solid content to book ratio) shown in Table 1 to produce Tokogata Inui I-type high solids coating compositions 5 to 7 of the present invention and comparative coatings. I got 8. The viscosity and performance of the coating composition thus obtained are shown in Table 1.

In Table 1 above, drying properties are expressed as the time required for curing at 20° C. and 75% RH. In addition, other physical property tests include I
A 50mX 7.5mX 0.8wn polished and degreased mild steel plate was coated to a dry and local film thickness of 30 to 40μ at 20℃, 7
This was done after drying at 5% RH for 7 days.

Patent applicant (140) Kansai Paint Co., Ltd. 17-

Claims (1)

[Claims] 1. (Al) One monomer is soluble in the presence of a dry (or semi-drying) oil with an oil length of 20 to 70 and/or a dry (or semi-drying) oil fatty acid-modified alkyd resin. A non-aqueous polymer dispersion obtained by dispersion polymerizing an unsaturated vinyl monomer in an organic liquid in which the polymer formed is insoluble; and (1) an alkyd having an oil length of 15 to 75 and used in component (A) A dry (or semi-drying) oil and/or a dry (or semi-drying) oil fatty acid-modified alkyd resin having a difference of less than 10 from the oil length of the resin, at a solid content weight ratio of (At/(B=5/95 to 50150)
A high solid paint composition that dries at room temperature.