JPS62109864A - Air-setting varnish - Google Patents

Abstract

PURPOSE:To provide the titled varnish suitable as a paint for building interior, curable in air at normal temperature and giving a coating film having excellent dryability, by compounding a specific addition polymer having carboxyl group and ester bond at the side chain with an organic solvent. CONSTITUTION:The objective varnish is composed of (A) an addition polymer having carboxyl groups and ester bonds on a number of side chains in a molecule and produced by reacting (i) a copolymer of 1mol of an alpha,beta-unsaturated polybasic acid anhydride (preferably maleic anhydride) and 1-20mol, preferably 1.5-15mol of a vinyl monomer free from hydroxyl group (preferably styrene, vinyltoluene, etc.) with (ii) an alkylene glycol monoester of a drying oil fatty acid having one hydroxyl group in a molecule (e.g. dehydrated castor oil fatty acid, etc.), thereby adding the hydroxyl group of the component (ii) to the acid anhydride group of the component (i) and (B) an organic solvent (e.g. benzene, alcohol, etc.).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an air-curable phenol suitable for applications such as painting, coating, and lining, and is particularly convenient for use when dissolved in a water-organic quenching agent. The present invention relates to an air-curing phenol suitable as a paint for the interior of buildings.

[Conventional technology]

Oil-based paints based on drying oils have been used for a long time as compositions that form air-curable films at room temperature.

In addition, dry oil-modified alkyd resins imparted with air-curing properties are also widely used as paints, coating agents, and lining agents.

However, a phenol that is air-curable at room temperature, has a fast curing speed, has excellent drying properties, and has sufficient water resistance has not yet been obtained.

[Problem that the invention seeks to solve]

In view of the above-mentioned circumstances, the present inventors conducted intensive research on a new polymer having air-curing properties, and found that an acid anhydride group is incorporated into the polymer chain and this acid anhydride group exhibits air-curing properties. The addition polymer of the present invention having an ester bond in the inner chain of the molecule was produced by bonding the hydroxyl groups in the alkylene glycol monoester of a drying oil fatty acid such as the above by ring-opening esterification.

The object of the present invention is to obtain a film exhibiting excellent air drying properties even at room temperature by blending this addition polymer with an organic solvent.

[Means for solving problems]

That is, the present invention comprises (A) (1) a copolymer of 1 mole of α,β-unsaturated polybasic acid anhydride and 1 to 20 moles of a vinyl monomer having no hydroxyl group, and (2) 1 mole in the molecule. A monoester of an alkylene glycol of a drying oil fatty acid having 3 hydroxyl groups is added to the acid anhydride group in the copolymer with the hydroxyl group in the monoester. An air-curable varnish comprising: (B) an addition polymer having an ester bond; and (B) an organic solvent.

[Function] The monomer components of the copolymer used in the addition polymer, which is the main component of the air-curable varnish of the present invention, include α, β
-Unsaturated polybasic acid anhydrides and vinyl monomers without hydroxyl groups are used. Examples of the α,β-unsaturated polybasic acid anhydride include radically polymerizable maleic anhydride and itaconic anhydride, with maleic anhydride being particularly preferred.
used.

Examples of vinyl t-mers without hydroxyl groups include ethylene, vinyl acetate, gummy vinyl pionate, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, ethyl acrylate, butyl Acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, acrylonitrile, styrene,
Examples include chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, acrylamide, acrylic acid, and methacrylic acid. Among them, styrene, vinyltoluene, methyl methacrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (
Meta)ac')V-t and the like are particularly preferably used.

If a vinyl monomer having a hydroxyl group in the molecule, such as 2-hydroxyethyl acrylate, is used, it is not preferable because a crosslinking reaction occurs within or between the molecules of the copolymer, resulting in formation of hydroxyl groups.

The reaction ratio of the α,β-unsaturated polybasic acid anhydride and the vinyl monomer is 1:1 to 20 (molar ratio), preferably 1:1 to 20 (molar ratio).
:1.5 to 15 (molar ratio).

If the reaction ratio of the vinyl monomer is less than 1, it becomes difficult to produce a copolymer. Although it is possible to increase the bonding ratio of the air-curable unsaturated alcohol, the resulting film tends to become brittle.

Furthermore, if the molar ratio of the vinyl monomer is greater than 20, the bonding ratio of the air-curable unsaturated alcohol becomes too small, making it difficult to improve the water resistance and solvent resistance of the resulting film. So I don't like it.

The copolymerization reaction is carried out according to normal rough polymerization reaction operations. At this time, a molecular weight modifier such as alkyl meryl glycan can also be used in combination.

In the present invention, a monoester of an alkylene glycol of a drying oil fatty acid having one hydroxyl group in the molecule is used as the component added to the acid anhydride group in the copolymer.

As the drying oil fatty acid, various drying oil fatty acids such as linseed oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid, etc. can be used, and these include (poly)alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, noclobylene glycol, t+) f robylene glycol l.

3.1.4 Butanediol 1.6 It can be used in the present invention as a monoester of lower alkylene glycols such as hexane and nol.

Esterification of drying oil fatty acids with alkylene glycol can be easily carried out by heating a mixture of the two to around 200° C. and volatilizing the water produced by the esterification. In this case, a noester is produced together with a monoester, which can be used as the monoester of the present invention without special separation, but the alkylene glycol as a raw material should be separated and removed.

It is also well known that these monoesters can be synthesized from drying oil fatty acids and alkylene oxides.

The reaction ratio between the copolymer and the monoester is 0,3~
The ratio may be 1:1.5, and an alkaline component that does not participate in the addition reaction may be present. When carrying out the addition reaction, it is effective to use an acidic catalyst or a basic catalyst such as a tertiary amine. It is desirable to add a catalyst for this purpose. Particularly effective as a catalyst is cobalt acetylacetone, which has a concentration of 1 to 11,000 pps, preferably 10' in terms of cobalt metal.
It is desirable to blend it in an amount of ~500 ppm. Since the dry curing of the film proceeds from the surface that comes into contact with air, even if one or more of the above components are added, the curing of the entire film will not become proportionally faster, so the amount of the film in the above range is suitable.

Organic solvents used in the present invention include hydrocarbons such as petroleum ether, benzene, toluene, xylene, and decalin, chlorinated hydrocarbons such as chloroform, alcohols such as isoproalcohol, esters such as ethyl acetate, and acetone. , methyl ethyl ketone, ethyl ether, ethylene glycol, monomethyl ether and the like. These organic solvents are added during or after the reaction.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.

Synthesis example (1) Esterification of drying oil fatty acid Dehydrated castor oil fatty acid (manufactured by Ito Oil Co., Ltd., acid value 201.8) 2
80g and 60g of ethylene glycol from 190℃ to 22
The reaction was carried out while raising the temperature to 0'C for 5 hours, and about 5.5 ml of volatile water was removed.

Next, 50 ml of water was added to the reaction solution kept at 60 to 80°C, and the lower aqueous phase was removed. This operation was performed four times.

Unreacted ethylene glycol was extracted and removed into the aqueous phase.

Next, the reaction solution was heated to 200°C again to remove the volatilized water, and an esterified product containing 78% monoester alcohol (raw material A) was obtained.
I got it.

(11) Production of fatty acid adducts of allyl glycityl ether 280 g of dehydrated castor oil fat (example (1)), 115 g of allyl glycytyl ether, and 2 triphenylphosphine
0g was added and heated at 170℃ for 15 hours to obtain an additive with an acid value of 8 (
Raw material B) was obtained.

G11) Production of copolymer (1) In a 3-ton stirring flask equipped with a cooling condenser, 600 g of styrene monomer, 112 g of methyl methacrylate, 81 g of maleic anhydride, 7009 g of methyl ethyl ketone. Azobisin butyronitrile J, G9, and 7 g of lauryl mercaptan were charged and the reaction was started while maintaining the temperature at 78 to 80°C. Over a reaction time of 10 hours, a total of 81 P of a solution of 200 g of maleic anhydride in methyl ethyl ketone was added in portions. At the same time, a total of 2.1 g of azobisisobutyronitrile was added in portions.

After concentrating the polymerization solution using a rotary evaporator, the solid polymer was air-dried to obtain a weight of 752 g.

A copolymer (raw material C) containing 22 mol of maleic anhydride was obtained.

(Preparation of ψ copolymer (II) In a 3-ton stirring flask with a cooling condenser, 550 g of styrene monomer, 709.2 ethylhexyl acrylate 100.! i' of vinyl acetate, 60.9.
700 g of methyl ethyl ketone, 1.6 g of azobisin butyronitrile.

2.1 g of lauryl mercaptan was charged and the reaction was started while maintaining the temperature at 78 to 80°C. Over a reaction time of 10 hours, a total of 60 g of maleic anhydride was added to methyl ethyl ketone 2
A solution of 009 was added in portions. At the same time, a total of 2.4 g of azobisisobutyronitrile was added in portions.

After concentrating the polymerization solution using a rotary evaporator, the solid polymer was air-dried and weighed 827 g.

A copolymer (raw material D) containing 16 mol of maleic anhydride was obtained.

Example 1゜200mg of copolymer raw material Cl00g prepared in the synthesis example
of acetone and heated to reflux to dissolve.

This solution was kept at 30°C, mixed with 15ml of triethylamine, and then mixed with 15ml of raw material A605+ prepared in the synthesis example.
Mixed for several minutes. When one drop of the layer solution was spread on a glass plate immediately after mixing, it became transparent. The reaction was continued for 5 hours at 30°C. 0 cobalt acetylacetone powder
．． 10g was added and dissolved.

Take 2 ml of this f6rL, apply it on a piece of paper,
A film with a thickness of about 0.05 mm was formed.

Two hours after a part of this film was applied (it was no longer sticky), it was immersed in water at 25°C. It absorbed water and swelled slightly white, but retained its shape.

The film that had been applied for 120 hours had a water absorption rate of 9.5% after being immersed in water at 25° C. for 24 hours, and maintained its transparency.

Example 2 Raw material C and raw material A were reacted in the same manner and proportions as in Example 1, except that cobalt acetylacetone was not added.

The reaction solution was applied to plywood to form a film about 0.05 to 0.07° C.m thick. After 2 hours of air drying at room temperature, it was further dried at 40°C for 2 hours. Then, it was heated in an oven at 80°C for 3 hours. This plywood became slightly cloudy when immersed in water at 25°C, but when air-dried, it almost returned to its state before immersion.

Example 3゜100g of copolymer raw material 14c prepared in the synthesis example was added to 50ml
The mixture was mixed with acetone and heated under reflux to dissolve.

This solution was kept at 50°C, and triethylamine 1.5 m
1, and then 60g of raw material B prepared in the synthesis example was mixed with 2
The mixing reaction was carried out in the same manner as in Example 1 over a period of 0 minutes. Two hours after coating, it was immersed in water at 25° C. for one hour, and although it absorbed water and swelled white over the entire surface, it retained its shape. The film that had been applied for 120 hours had a water absorption rate of 11.3% when immersed in water at 25° C. for 24 hours, and some areas were slightly cloudy.

Example 4 Copolymer raw material DI O (Jg of 1, 5
The mixture was mixed with 0 ml of methyl isobutyl ketone and dissolved under heating under reflux. Keep this 1 volume solution at 30℃ and use triethylamine 1
Mix 0ml and then trimethylolzorono? 30.9 g of horno allyl ether was mixed over 20 minutes. 30℃
The reaction was continued for 6 hours.

At this point, 0.3 g of cobalt acetylacetone was added and dissolved. The resulting solution was applied to a film about 0.05 inch thick on a liner. 24 hours after application, this film was
When immersed in water at ℃ for 24 hours, it had a water absorption rate of 83 and was transparent. The weight reduction rate when immersed in acetone for 2 hours was 37%. When the same test was conducted 120 hours after application, the water absorption rate was 3.5 inches, and the weight loss rate due to acetone was 16 inches.

〔Effect of the invention〕

The air-curing varnish of the present invention has air-curing properties even at room temperature, and the formed film has excellent drying properties. Even after 2 hours), the surface tackiness disappears and water resistance begins to appear.

Therefore, it is particularly useful as a paint for building interiors.

Claims (1)

[Scope of Claims] (A) (1) A copolymer of 1 mole of α,β-unsaturated polybasic acid anhydride and 1 to 20 moles of a vinyl monomer having no hydroxyl group; A monoester of an alkylene glycol of a drying oil fatty acid having 3 hydroxyl groups is added to the hydroxyl group in the monoester to the acid anhydride group in the copolymer. An air-curable varnish consisting of an addition polymer having an ester bond, and (B) an organic solvent.