JPH02102222A - Preparation of dispersion of crosslinked fine polymer particle - Google Patents

Abstract

PURPOSE:To prepare a stable non-aq. dispersion of gel particles of a polymer insoluble in a specified org. liquid by copolymerizing a plurality of radical- polymerizable unsatd. monomer in this liquid in the presence of a specified alkyd resin. CONSTITUTION:A dispersion of fine crosslinked polymer particles insoluble in an org. liquid contg. at least 30wt.% arom. solvent is prepd. by copolymerizing radical polymerizable unsatd. monomers contg. at least each 0.5wt.% at least two vinyl monomers each contg. a supplemental functional group capable of reacting and binding with each other or a polyvinyl monomer in the presence of an alkyd resin having at least 0.1 polymerizable double bond on average in its molecule and the rate of fatty acid modification of 25wt.% or less in said org. liquid. A coating film formed from a paint contg. the non-aq. dispersion of the resin soln. obtd. by this method can satisfy simultaneously both hardness and processability. In addition because the coating viscosity becomes lower when this dispersion of the resin soln. in used, excellent coating workability can be obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a stable non-aqueous dispersion of a vinyl polymer, and more specifically, to a method for producing a stable non-aqueous dispersion of a vinyl polymer, and more specifically, a method for producing a non-aqueous dispersion of a vinyl polymer containing an aromatic ring in the molecule and a fatty acid modified amount of 25% by weight. % or less, or an alkyd resin that does not contain any fatty acids (hereinafter, this resin is referred to as an oil-free alkyd resin), and in the presence of the resin, a radically polymerizable unsaturated monomer is used as a dispersion stabilizer. The present invention relates to a method for producing a stable non-aqueous dispersible resin liquid of gel particles of a polymer insoluble in the organic liquid by polymerizing a polymer.

(Problems to be Solved by the Prior Art and the Invention) Alkyd resins have excellent processability, and are therefore widely used today as paint resins for processed steel plates, building materials, industrial machinery, and the like.

However, alkyd resins with a fatty acid modification amount of more than 25% by weight have poor scratch resistance, erosion resistance, stain resistance, etc. because the fatty acids and oil components act as plasticizers.
It does not have sufficient performance for that purpose. In order to improve this drawback, attempts have been made to use alkyd resins with a resin acid modification amount of 25% by weight or less, or to increase hardness, but on the other hand, these have resulted in brittleness and reduced workability. That is, until now it has not been possible to simultaneously satisfy both workability and hardness in alkyd resins. It is also possible to satisfy both workability and hardness by increasing the molecular weight, but in that case, painting workability will be impaired.

In order to improve processability, a dispersion type resin, that is, a resin liquid in which vinyl unsaturated monomer particles are dispersed in an organic liquid using an alkyd resin as a dispersion stabilizer (hereinafter referred to as a non-aqueous dispersion resin) However, since the alkyd resin used as a conventional NAD dispersion stabilizer usually has a fatty acid modification amount of more than 25% by weight, The drawbacks of the resin remain a problem. Although NAD is sometimes used alone, it is generally used in a blend with other alkyd resins. However, alkyd resins have poor compatibility unless they have approximately the same oil length, so NA using alkyd resins with a fatty acid modification amount of 25% by weight or more as a dispersion stabilizer
D can be blended only with alkyd resins having a fatty acid modification amount of 25% or more by weight. Therefore, there is a problem that conventional NAD or its blend with an alkyd resin cannot provide sufficient hardness.

(Means for Solving the Problems) As a result of the inventors' earnest efforts to solve the above-mentioned technical problems, it is possible to blend the alkyd resin with an alkyd resin having a fatty acid modification amount of 25% by weight or less. By using NAD, that is, an alkyd resin with a fatty acid modification amount of 25% by weight or less as a dispersion stabilizer, and using a resin liquid in which gel particles of a polymer of vinyl unsaturated monomers are stably dispersed, the above purpose can be achieved. They have discovered what they can achieve and have completed the present invention.

Thus, according to the present invention, in an organic liquid containing at least 30 wt. At least 0.5% by weight of each of at least two vinyl monomers or multivinyl monomers each having complementary functional groups capable of reacting and bonding with each other in the presence of an alkyd resin of up to 0.5% by weight There is provided a method for producing a dispersion of polymer crosslinked fine particles insoluble in the organic liquid, which comprises copolymerizing a radically polymerizable unsaturated monomer containing % by weight of the organic liquid.

The continuous phase of the coating film formed from the coating material containing the non-aqueous dispersible resin liquid obtained by the method of the present invention as a main component is mainly composed of an alkyd resin or oil-free alkyd resin having a fatty acid modification amount of 25% by weight or less, which is a dispersion stabilizer. Made of resin. Therefore, by containing a certain amount or more of aromatic dicarboxylic acid or tricarboxylic acid, which is the acid component, the hardness of the coating film is improved, and the action of the polymer gel particle part of the non-aqueous dispersible resin liquid allows processing and modification. Since the internal stress of the coating film that occurs when the force is applied can be alleviated, a coating film that simultaneously satisfies the required hardness and workability can be obtained.

Furthermore, the polymer portion of the dispersion provided by the present invention is
Even when using aromatic solvents that have strong solubility for gel particles, swelling and dissolution of the particles can be prevented. moreover,
Conventional alkyd resins and oil-free alkyd resins with improved coating film hardness have drawbacks such as reduced coating workability due to high coating viscosity. When a non-dispersible resin liquid is used, coating workability is also excellent because the coating viscosity is low.

The present invention will be explained in more detail below.

An important feature of the present invention is that as a dispersion stabilizer for the polymer crosslinked fine particle dispersion, on average at least 0.1 in the molecule;
Preferably 0.3 to 5.0, more preferably 1.0
An alkyd resin (short-oil alkyd resin or oil-based alkyd resin) having ~3.0 polymerizable double bonds and having a fatty acid modification amount of 25% by weight or less, preferably 20% by weight or less, and more preferably 17% by weight or less. The point is that it uses resin).

Such alkyd resins use an aromatic di- or tricarboxylic acid as an essential acid component, together with other polybasic acids and polyhydric alcohols, and if necessary, saturated or unsaturated fatty acids, in combination with alkyd resins known per se. It can be produced in the same manner as in the production method, for example, by carrying out a condensation reaction in the presence of an esterification catalyst at a temperature of about 150 to about 250°C for about 3 to about 10 hours.

Examples of aromatic di- or tricarboxylic acids used as an essential component in the production of the alkyd resin include phthalic acid or its anhydride, isophthalic acid, terephthalic acid, dimethylterephthalic acid, trimetholitic acid, trimesic acid, and 2-methyltricarboxylic acid. Examples include mellitic acid,
These can be used alone or in a mixture of two or more.

These aromatic di- or tricarboxylic acids are useful components for improving the hardness, stain resistance, weather resistance, erosion resistance, and chipping resistance of coating films, and are generally based on the total amount of raw materials for producing alkyd resins. at least 10% by weight, preferably 20-70% by weight, more preferably 3% by weight.
Amounts ranging from 0 to 60% by weight can be used.

In addition, as other polybasic acids that can be used in combination, polybasic acids that are commonly used as acid components in the production of alkyd resins can be similarly used, such as adipic acid, maleic acid or its anhydride, azelaic acid, succinic acid, etc. Acids or their anhydrides, aliphatic dicarboxylic acids such as fumaric acid and sebacic acid;
Examples include alicyclic polybasic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene hexahydrophthalic acid, and hexahydroterephthalic acid; pyromellitic acid or its anhydride; each of these may be used alone or in combination. The above can be used in combination.

On the other hand, polyhydric alcohols that can be used include trihydric or higher alcohols, such as glycerin, trimethylolpropane, trimethylolethane, and (2).

Examples of dihydric alcohols include 2,6-hexanediol and pentaerythritol. Examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol,
2-butanediol, trimethylene glycol, l, 5
-bentanediol, 2,4-bentanediol, 2.
3-dimethyltrimethylene glycol, tetramethylene glycol, l,4-bentanediol, 3-methyl-
Examples include 4,5-bentanediol, 1,4-hexanediol, 2,5-hexanediol, 1,5-hexanediol, 1,6-hexanediol, and the like. These polyhydric alcohols can be used alone or in a mixture of two or more. Furthermore, monoepoxy compounds such as Cardura E (product of Shell Chemical Co., Ltd.) can also be used as the dihydric alcohol.

In addition, saturated or unsaturated fatty acids that can be used in the production of short-oil alkyd resins include saturated or unsaturated fatty acids having 6 to 18 carbon atoms or their glycerides, benzoic acid, methylbenzoic acid, p-L- Examples include butylbenzoic acid.

It also contains various natural oils or their fatty acids, such as coconut oil, cottonseed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, etc., or from which they are derived. Fatty acids can also be used. Furthermore, when a monoepoxy compound such as Cardura E is used as a dihydric alcohol, if the monoepoxy compound contains a fatty acid residue having 6 to 18 carbon atoms, the fatty acid can also be used here. It is considered to be a type of saturated or unsaturated fatty acid.

These fatty acids are used so that the amount of fatty acid modification in the short oily alkyd resin obtained falls within the above-mentioned range, that is, 25% by weight or less, preferably 20% by weight or less, and more preferably 17% by weight.
It can be used in amounts such that:

Of course, when producing oil-free alkyd resin,
It is not necessary to use such fatty acids.

The condensation reaction between the acid component and the alcohol component is usually carried out in the presence of an esterification catalyst, and known acid catalysts, base catalysts and metal catalysts can be used as such catalysts. Examples of acid catalysts include sulfuric acid, phosphoric acid, para-toluenesulfonic acid, trichloroacetic acid, trifluoromethanesulfonic acid, motuptil phosphate, dibutyl phosphate, boron trisulfide, etc., and base catalysts include:
For example, monoethanolamine, jetanolamine,
Examples of metal catalysts include dibutyltin oxide, monobutyltin hydroxide, tetrabutylzirconate, tetrabutyltitanate, stannous chloride, zinc oleate, silver oleate, zinc acetate, and the like. can be mentioned. Among these catalysts, monobutyltin hydroxide is particularly preferred because it greatly accelerates the reaction and has little adverse effect when incorporated into a paint. Further, para-toluenesulfonic acid can also be a particularly preferred reaction medium since it has curing catalytic ability when a curing catalyst is required in the paint formulation.

When the alkyd resin prepared as described above is used as a dispersion stabilizer resin according to the invention, it is advantageous that at least a portion of the alkyd resin has polymerizable double bonds in the molecule. The introduction of a polymerizable double bond into the alkyd resin is usually carried out by reacting a carboxyl group that may exist in the alkyd resin with an unsaturated monomer containing a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. can be done. In addition, the introduction of polymeric double bonds can be achieved by adding an equimolar adduct of an isocyanate group-containing unsaturated monomer, such as hydroxyalkyl acrylate or hydroxyalkyl methacrylate, to a diisocyanate compound to a hydroxyl group that may exist in the alkyd resin. It can also be carried out by reacting according to a method. Such a reaction can be carried out by a method known per se, and it goes without saying that the reaction conditions may be modified depending on the catalyst used and the type of unsaturated monomer. By the above reaction, as mentioned above, the alkyd resin has an average of at least 0.1, preferably 0.3 to 5.0, and more preferably 1.0 to 3.0 molecules per molecule. Polymer double bonds can be introduced.

The alkyd resins described above for use as dispersion stabilizer resins in accordance with the present invention generally have a weight average molecular weight of from about 5.000 to about 2.
00.000, preferably about 10,000 to about 50.0
It can have a molecular weight within the range of 0.00. If the molecular weight is less than about 5,000, the stabilization of the polymer particles will be insufficient, while if the molecular weight exceeds 200,000, the viscosity will be extremely high and handling will tend to become difficult.

The present invention uses the above-mentioned alkyd resin as a dispersion stabilizer and polymerizes a radically polymerizable unsaturated monomer in the presence of the alkyd resin to obtain stable gel-like polymer dispersed particles.

The polymerization is carried out in an organic liquid that does not dissolve the resulting dispersed polymer particles but is a good solvent for the alkyd resin. The organic liquid used contains at least 30% by weight of an aromatic solvent as an essential component.

Examples of the aromatic solvent include benzene, toluene, xylene, ethylbenzene, and aromatic petroleum naphtha (e.g., Swasol 200, Swasol 31, manufactured by Cosmo Oil Co., Ltd.).
0, 1500, 1800) can be used alone or in combination of two or more.

Such aromatic solvents can be used in combination with other organic liquids, if necessary. Examples of other organic liquids that can be mixed include aliphatic hydrocarbons such as hexane, heptane, and octane; alcoholic solvents such as isozurobil alcohol, n-butyl alcohol, l-butyl alcohol, and octyl alcohol; cellosolve, butyl cellosolve, Ether solvents such as diethylene glycol monobutyl ether; methyl isobutyl ketone, diisobutyl ketone, ethyl alketone, methyl hexyl ketone,
Ketone solvents such as ethyl butyl ketone: ethyl acetate,
Examples include ester solvents such as isobutyl acetate, acyl acetate, and 2-ethylhexyl acetate, which can be used singly or in combination with the aromatic hydrocarbon described above. If the aromatic solvent content is less than 30%, the solubility of the alkyd resin will be insufficient, so preferably the organic liquid contains 50 to 100% of the aromatic solvent.
It is desirable that the content be 70 to 100% by weight, more preferably 70 to 100% by weight.

The radically polymerizable unsaturated monomers polymerized according to the present invention in such an organic liquid are: (1) at least two vinyl monomers each having complementary functional groups capable of reacting with each other and bonding; or (2) a monomer mixture containing at least 0.5% by weight of a multi-vinyl monomer.

Examples of combinations of complementary functional groups that can react with each other and bond in the monomer mixture of the former (ii) include (i) epoxy group/carboxyl group (U) hydroxyl group/isocyanate group (iii)
) Epoxy group/amino group (iv) Combinations such as isocyanate group/amino group may be mentioned. Specific examples of combinations of two or more vinyl monomers each having complementary functional groups capable of reacting and bonding with each other include the following.

Examples of (i) include combinations of epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, and carboxyl group-containing monomers such as acrylic acid and methacrylic acid; examples of (■) include hydroxyethyl Combination of a hydroxyl group-containing monomer such as acrylate or hydroxyethyl methacrylate and an incyanate group-containing monomer such as incyanate ethyl acrylate, isocyanate ethyl methacrylate, or inphorone diisocyanate/hydroxyethyl acrylate or hydroxyethyl methacrylate equivalence adduct 1 An example of (i) is a combination of the epoxy group-containing monomer and an aminoalkyl acrylate or aminoalkyl methacrylate monomer; an example of (iv) is a combination of the isocyanate group-containing monomer and the acrylic acid monomer; combinations with aminoalkyl acids or aminoalkyl methacrylate monomers; etc.

At least two types of vinyl monomers having complementary functional groups as described above each contain at least 0% of the vinyl monomers in the monomer mixture.
．． It may be present in a concentration of 5% by weight or more, preferably in the range 0.5-20% by weight.

Further, the multi-vinyl monomer (①) is a compound having at least 2 to 4 polymer double bonds in one molecule, such as divinylbenzene, ethylene glycol di(meth)
Acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, l
, 3-butanediol di(meth)acrylate, 1.4
-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate% 16-hexanethiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) acrylate, glycerol di(meth)acrylate, glycerol methacrylate, etc., and these can be used alone or in a mixture of two or more. Such multivinyl monomers are also present in the monomer mixture at least 0.5% by weight, preferably from 0.5 to 1
O may be present in concentrations within the range of % by weight. These vinyl monomers are components for crosslinking the prepared dispersed fine particles, and the use and type or combination of monomers can be arbitrarily selected depending on the desired performance. Particularly preferred are vinyl monomers and multivinyl monomers having a combination of complementary functional groups described in (i) above.

In order to obtain gel-dispersed particles by polymerizing a radically polymerizable unsaturated monomer in the presence of the above-mentioned dispersion stabilizer resin and an organic solution, glycidyl (meth)acrylate is added to the radical polymerizable unsaturated monomer. and (meth)acrylic acid, respectively.
The content may be 5% by weight or more, preferably 0.5 to 20% by weight. When the content is less than 0.5%, sufficient gel-dispersed particles cannot be obtained, and the storage stability of the dispersed resin liquid deteriorates, and the physical properties and hardness of the coating film deteriorate. On the other hand, the content is 2
If it is more than 0%, the entire resin liquid system may be crosslinked or thickened during the production of dispersed particles, which is not preferable.

When obtaining the above-mentioned gel-dispersed particles, it is preferable to use a basic catalyst such as a tertiary amine.

The vinyl monomer or multi-vinyl monomer having the above-mentioned combination of complementary functional groups can be used in combination with other radically polymerizable unsaturated monomers.

Representative examples of other radically polymerizable unsaturated monomers that can be used are as follows.

(a) Esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
C3-18 alkyl esters of acrylic acid or methacrylic acid such as propyl methacrylate, inglovir methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; acrylic acid or methacrylic acid such as allyl acrylate-1, allyl methacrylate, etc. 02-8 alkenyl esters of acids; 02-. Hydroxyalkyl ester: 03-18 alkenyloxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.

(b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene,
Vinylpyridine.

(C) Others: acrylonitrile, methacrylaterile, methyl isopropenyl ketone; vinyl acetate, peobamomonomer (Shell Chemical Products), vinylpropione-1.
vinyl vivarate etc.

The monomer mixture described above is polymerized using a radical polymerization initiator. Examples of usable radical polymerization initiators include 2,2-azoisobutyronitrile,
Examples include azo initiators such as 2'-azobis(2,4-dimethylvaleronitrile); peroxide initiators such as benzoyl peroxide, lauryl peroxide, and Lert-butyl peroctoate; The agent is generally 0.2 parts by weight per 100 parts by weight of monomers subjected to polymerization.
~IO parts by weight, preferably 0.5 to 5 parts by weight.

Furthermore, the amount of the alkyd resin used as a dispersion stabilizer during the polymerization can be varied over a wide range depending on the type of the polymer, but generally the total amount of the polymer to be polymerized and the alkyd resin is 10 based on
A suitable range is from 30 to 70% by weight, preferably from 30 to 70% by weight.

Furthermore, the total concentration of monomer and alkyd resin in the organic solution is generally 30-70% by weight, preferably 40% by weight.
~60% by weight.

As the dispersion polymerization method, a radical polymerization method known per se can be used, and the reaction temperature during polymerization is generally appropriate within the range of about 50 to about 150 ° C.
Polymerization can usually be completed in about 1 to 15 hours at such temperatures. In this way, a polymer fine particle dispersion crosslinked inside the dispersed fine particles is obtained, and the polymer crosslinked fine particle dispersion is used as it is or mixed with an oil-free alkyd resin, a short oil alkyd resin, etc., and is generally mixed with a colorant. , a curing agent, etc. can be blended and used as a coating composition. Examples of the coloring agent include dyes, organic pigments, and inorganic pigments, and examples of the curing agent include crosslinking agents such as amino resins, epoxy resins, and polyisocyanes.

(Examples) The present invention will now be described in more detail with reference to Examples. In the examples, parts and percentages are by weight.

Production example> Synthesis of dispersion stabilizer A In a flask equipped with a thermometer, a stirrer and a water separator, 513.2 parts of phthalic anhydride Neopentyl glycol 214,2 //Ethylene glycol 50.6 //Trimethylol Propane 167.0//Coconut oil fatty acid 128.57/Monobutyltin hydroxide 1. The contents were stirred and heated to 230°C for 4 hours. After further heating at 230°C for 2 hours, 5% xylene was added to the total charge to promote the removal of condensed water, which is a by-product of the esterification reaction, and the temperature was maintained at 230°C to increase the acid value. Heating was continued until the temperature reached 5. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained alkyd resin varnish with a fatty acid modification amount of 12.8% is X, and the weight average molecular weight of the resin is 170.
It was 00. Then, 50 l:l (mole ratio) adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the above varnish.
．． 0 part and 0.1 part of 4-tert-butylcatechol were added and reacted at 100°C for 3 hours to introduce copolymer double bonds into the molecular chains of the dispersion stabilizer.

Synthesis of Dispersion Stabilizer B In a flask equipped with a thermometer, a stirrer and a water disperser, 473.4 parts of talic anhydride 473.4 parts Adipic acid 133.4 // Neopentyl glycol 239.9 // Ethylene glycol 56.7 /trimethylolpropane 187.1//monobutyltin hydroxide 1, Q tt were charged, and the contents were heated to 230°C for 4 hours while stirring. After further heating at 230°C for 2 hours, 5% xylene was added to the total charge to promote the removal of condensed water by-produced in the esterification reaction, and the temperature was maintained at 230°C until the acid value reached 5. Heating continued until it heated up. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained oil-free alkyd resin varnish was Z, and the weight average molecular weight of the resin was 15,000.

Next, 50.0 parts of an adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method at a molar ratio of 1 to 1 was added to the entire amount of the varnish.
Add 0.1 part of tetr-butylcatechol and heat to 100°C.
The mixture was reacted for 3 hours to introduce copolymer double bonds into the molecular chains of the dispersion stabilizer.

Synthesis of Dispersion Stabilizer C In a flask equipped with a thermometer, a stirrer, and a water disperser, 680.8 parts of isophthalic acid, 231.5 parts of neopentyl glycol, 54.7 parts of ethylene glycol, 180.6 parts of trimethylolpropane, were added. 1.0 of monobutyltin hydroxide was charged, and the contents were heated to 230°C for 4 hours while stirring. Hereinafter, the viscosity of the oil-free alkyd resin varnish obtained by the same method as dispersion stabilizer B was Z-1, and the weight average molecular weight of the resin was 16,000. Then, inphorone diisocyanate synthesized by a known method and 2 were added to the entire amount of the above varnish.
-1311 (molar ratio) of hydroxyethyl acrylate
500 parts of the adduct and 0.1 part of 4-tert-butylcatechol were added and reacted at 100°C for 3 hours to introduce a copolymerizable double bond into the molecular chain of the dispersion stabilizer.

In a flask equipped with a dispersion stabilizer, a thermometer, a stirrer, and a water disperser, 382.4 parts of terephthalic acid, 282.5 parts of adipic acid, 241.9 parts of neopentyl glycol, 57.1 parts of ethylene glycol, Methylolpropane 188.7//monobutyltin hydroxide 1, Q tt were charged, and the contents were heated to 230° C. for 4 hours while stirring. below,
The viscosity of the oil-free alkyd resin varnish obtained by the same method as dispersion stabilizer B was Z, and the weight average molecular weight of the resin was 180,000. Then, in the total amount of the above varnish, isophorone diisocyanate synthesized by a known method and 2
- 50.0 parts of 1:1 (molar ratio) adduct of hydroxyethylethyl acrylate and 0.1 part of 4-tert-butylcatechol were added and reacted at 100°C for 3 hours to stabilize the dispersion of copolymerizable double bonds. The agent was introduced into the molecular chain.

Synthesis of Dispersion Stabilizer E In a flask equipped with a thermometer, stirrer and water disperser, 439.2 parts of 7-talic anhydride Neopentyl glycol 194.7 // Ethylene glycol 69,0 // Trimethylolpropane 101,3 //Coconut oil fatty acid 272.6//Monobutyltin hydroxide 1. A Qtt was charged and the contents were heated to 230°C for 4 hours while stirring.

After further heating at 230°C for 2 hours, 5% xylene was added to the total charge to promote the removal of condensed water, which is a by-product of the esterification reaction, and the temperature was maintained at 230°C to increase the acid value. Heating was continued until the temperature reached 5. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained alkyd resin varnish with a fatty acid modification amount of 27.3% is T, and the weight average molecular weight of the resin is]
It was 3000. Next, 50.0 parts of a 1:1 (molar ratio) adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method and 0.1 part of 4-tert-butylcatechol were added to the entire amount of the above varnish. The reaction was carried out at 100°C for 3 hours to introduce a copolymerizable double bond into the dispersion stabilizer molecular chain.

Example of manufacturing non-water dispersible resin liquid 1 Place xylene in a flask equipped with a thermometer and a stirrer.
104.8 parts heptane 3
6,9 //Dispersion stabilizer Al42.9 (solid content 100
) // was heated to 100°C, and the following monomers, polymerization initiators, and basic catalysts were added dropwise over 3 hours, and the mixture was further aged for 4 hours.

Methyl methacryle-1-60.0 parts Acrylonitrile 20.0//2-
Hydroxyethyl acrylate I O, 0//glycidyl methacrylate 7. O7l acrylic acid
3, Q tt azobisisobutyronitrile 2. Q tt dimethylaminoethanol 1.0 The obtained resin liquid was a dispersion liquid with a non-volatile content of 52% and a viscosity D1 polymer particle particle size (measured by an electron microscope, hereinafter the same) of 0.2-0.3 μm. . Even after standing at 50°C for 3 months, there was no generation of precipitates or coarse particles, and no change in the properties of the varnish.

Production Example of Non-Aqueous Dispersible Resin Liquids 2 to 5 Except for changing the dispersion stabilizer A in the production example of the non-aqueous dispersible resin liquid 1 to dispersion stabilizer B, C, D or E, the other compositions and methods were the same. Non-water-dispersible resin liquids were produced, and non-water-dispersible resin liquids 2 to 5 each having a non-volatile content of 52% were obtained. All of these were dispersions with a particle size of 0.2-0.3 μm, and even after being left standing at 50°C for 3 months, there was no generation of precipitates or coarse particles, and no change in the properties of the varnish.

Example of manufacturing non-aqueous dispersible resin liquid 6 Place a flask equipped with a thermometer and a stirrer.
104.8 parts heptane 3
6.9//Dispersion stabilizer A 142.9 (solid content 100)// was charged and heated to lOOoC, the following monomers and polymerization initiator were added dropwise over 3 hours, and further aged for 4 hours. I did it.

Methyl methacrylate 70 parts Acrylonitrile 20112-Hydroxyethyl acrylate 107 l The resulting resin liquid was a dispersion in which the dispersed particles were not gelled, had a non-volatile content of 52%, and had a viscosity of D1 and a particle size of polymer particles of 0.2-0.3 μm. . If left standing at 50℃ for 3 months, the particle size will decrease to 0.1-
The diameter changed to 0.5 μm, and the formation of a precipitate was observed. Also,
The viscosity had increased to G.

Examples 1 to 7 and Comparative Examples 1 to 2 Oil-free alkyd resins, non-aqueous dispersible resin liquids 1 to 5, and crosslinking agents were blended at the solid proportions shown in Table 1 below, and each test plate (thickness 3,5 mm, phosphorous zinc treatment)
The coating was cured by baking at 140° C. for 30 minutes (cured film thickness: 20 to 25 μm). The results of various tests on the resulting coating film are shown in Table 2 below.

-32- (Note) l) Flexibility: Tested under the conditions of JIS K 5400. The cracking and peeling of the coating film was observed when the diameter of the mandrel was 2 mm and the thickness of the auxiliary plate was 4 mm.

- No damage to the paint film such as cracks or peeling 20 - Cracks or peeling occurred: X 2) Impact resistance: A mild steel plate was used as the material. Using a DuPont impact tester, a 500 g weight was dropped onto the coating film at a center of impact of % inches, and the maximum distance without cracking or peeling was determined. (cm) 3) Erichsen: Measured using an Erichsen tester manufactured by Erichsen (unit: mm).

4) Hardness: Evaluated according to JIS K 5400.

5) Substrate: Tested under the conditions of JIS K 5400.

Peel off the squares with cellophane tape, total number of 100.
Evaluation was made based on the number of squares that remained without being peeled off.

6) Weather resistance; aluminum plate was used as the material. QUV weather meter manufactured by The Q Panel (ultraviolet warfare fluorescent lamp rN)
o, QFS-40, UV-8J wavelength range 320-280
The degree of deterioration of the coating film was observed after a cycle of irradiation (15 minutes) and dew condensation (15 minutes) was repeated for 2000 hours at a temperature of 40 to 70° C. using a micrometer (nm).

7) Magic contamination: Color the painted surface with red marker,
It was left at 6°C for 24 hours. The sample was gently wiped three times with absorbent cotton containing an appropriate amount of ethanol, and the presence or absence of coloration was evaluated.

No coloring 20 Coloring: × Procedural amendments stamped) December 5, 1988 Director General of the Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case 1988 Patent Application No. 253834 2, Name of the invention Polymer Manufacturing method for cross-linked fine particle dispersion 3, relationship with the amended person's case Patent applicant name (140) Kansai Paint Co., Ltd. 4, agent 〒
107 Telephone 585-2256 5. Date of amendment order: None Correction Description ■1 Name of the invention Method for producing polymer crosslinked fine particle dispersion 2. Claims ■ Containing at least 30% by weight of aromatic solvent Reacting and bonding with each other in an organic liquid in the presence of an alkyd resin that has an average of at least 0.1 polymerizable double bonds in its molecules and has a fatty acid modification amount of 25% by weight or less. It is characterized by copolymerizing radically polymerizable unsaturated monomers containing at least 0.5% by weight of each of at least two types of vinyl monomers or a multi-vinyl monomer each having complementary functional groups capable of A method for producing a polymer crosslinked fine particle dispersion insoluble in the organic liquid.

3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a stable non-aqueous dispersion of a vinyl polymer, and more specifically, a method for producing a stable non-aqueous dispersion of a vinyl polymer, and more specifically, a fatty acid-modified 1L 25% by weight dispersion containing an aromatic ring in the molecule. The following kerosene-based alkyd resin or alkyd resin that does not contain any fatty acids (hereinafter referred to as oil-free alkyd resin) is used as a dispersion stabilizer, and in the presence of the resin, radically polymerizable unsaturated monomers are The present invention relates to a method for producing a stable non-aqueous dispersible resin liquid of gel particles of a polymer insoluble in the organic liquid.

(Problems to be Solved by the Prior Art and the Invention) Alkyd resins have excellent processability, and are therefore widely used today as paint resins for processed steel plates, building materials, industrial machinery, and the like.

However, alkyd resins with a fatty acid modification amount of more than 25% by weight have poor scratch resistance, erosion resistance, stain resistance, etc. because the fatty acids and oil components act as plasticizers.
It does not have sufficient performance for that purpose. In order to improve this drawback, attempts have been made to use alkyd resins with a resin acid modification amount of 25% by weight or less, or to increase hardness, but on the other hand, these have resulted in brittleness and reduced workability. That is, until now it has not been possible to simultaneously satisfy both workability and hardness in alkyd resins. It is also possible to satisfy both workability and hardness by increasing the molecular weight, but in that case, painting workability will be impaired.

In order to improve processability, a dispersion type resin, that is, a resin liquid in which vinyl unsaturated monomer particles are dispersed in an organic liquid using an alkyd resin as a dispersion stabilizer (hereinafter referred to as a non-aqueous dispersion resin) It is also possible to use a liquid (abbreviated as NAD), but since the alkyd resin used as a dispersion stabilizer for conventional NAD usually has a fatty acid modification amount of more than 25% by weight, this resin as described above may be used. The shortcomings remain as a problem. Although NAD is sometimes used alone, it is generally used in a blend with other alkyd resins. However, alkyd resins have poor compatibility unless the oil length is approximately the same as that of alkyd resins, so the amount of fatty acid modification is 2
NAD with 5% by weight or more of alkyd resin as dispersion stabilizer
can be blended only with alkyd resins having a fatty acid modification amount of 25% or more by weight. Therefore, there is a problem that conventional NAD or its blend with an alkyd resin cannot provide sufficient hardness.

(Means for Solving the Problems) As a result of the inventors' earnest efforts to solve the above-mentioned technical problems, it is possible to blend the alkyd resin with an alkyd resin having a fatty acid modification amount of 25% by weight or less. By using NAD, that is, an alkyd resin with a fatty acid modification amount of 25% by weight or less as a dispersion stabilizer, and using a resin liquid in which gel particles of a polymer of vinyl unsaturated monomers are stably dispersed, the above purpose can be achieved. They have discovered what they can achieve and have completed the present invention.

Thus, according to the present invention, in an organic liquid containing at least 30 wt. At least 0.5% by weight of each of at least two vinyl monomers or multivinyl monomers each having complementary functional groups capable of reacting and bonding with each other in the presence of an alkyd resin of up to 0.5% by weight Provided is a method for producing a crosslinked fine particle dispersion of a polymer insoluble in the organic liquid, which comprises copolymerizing a radically polymerizable unsaturated monomer containing % by weight of the organic liquid.

The continuous phase of the coating film formed from the coating material containing the non-aqueous dispersible resin liquid obtained by the method of the present invention as a main component is mainly composed of an alkyd resin or oil-free alkyd resin having a fatty acid modification amount of 25% by weight or less, which is a dispersion stabilizer. Made of resin. Therefore, by containing a certain amount or more of aromatic dicarboxylic acid or tricarboxylic acid, which is the acid component, the hardness of the coating film is improved, and the action of the polymer gel particle part of the non-aqueous dispersible resin liquid allows processing and modification. Since the internal stress of the coating film that occurs when the force is applied can be alleviated, a coating film that simultaneously satisfies the required hardness and workability can be obtained. Further, the polymer portion of the dispersion provided by the present invention can prevent the particles from swelling and dissolving even when an aromatic solvent having a strong solubility for gel particles is used. Furthermore, conventional alkyd resins and oil 7-ly alkyd resins are
However, when using the non-dispersible resin liquid produced by the method of the present invention, the coating film with improved hardness has drawbacks such as reduced coating workability due to the high coating viscosity. ,
Paint workability is also excellent because the paint viscosity is low.

The present invention will be explained in more detail below.

An important feature of the present invention is that as a dispersion stabilizer for the polymer crosslinked fine particle dispersion, on average at least 0.1 in the molecule;
Preferably 0.3 to 5.0, more preferably 1.0
An alkyd resin (short-oil alkyd resin or oil-free alkyd resin) having ~3.0 polymerizable double bonds and a fatty acid modification amount of 25% by weight or less, preferably 20% by weight or less, and more preferably 17% by weight or less. The point is that it uses resin).

Such alkyd resins use an aromatic di- or tricarboxylic acid as an essential acid component, together with other polybasic acids and polyhydric alcohols, and if necessary, saturated or unsaturated fatty acids, in combination with alkyd resins known per se. It can be produced, for example, by carrying out a condensation reaction in the presence of an esterification catalyst at a temperature of about 150 to about 250° C. for about 3 to about 10 hours.

Examples of aromatic di- or tricarboxylic acids used as an essential component in the production of the alkyd resin include phthalic acid or its anhydride, isophthalic acid, terephthalic acid, dimethylterephthalic acid, trimetholitic acid, trimesic acid, and 2-methyltricarboxylic acid. Examples include mellitic acid,
These can be used alone or in a mixture of two or more.

These aromatic di- or tricarboxylic acids are useful components for improving the hardness, stain resistance, weather resistance, erosion resistance, and chipping resistance of coating films, and are generally based on the total amount of raw materials for producing alkyd resins. at least 10% by weight, preferably 20-70% by weight, more preferably 3% by weight.
Amounts ranging from 0 to 60% by weight can be used.

In addition, as other polybasic acids that can be used in combination, polybasic acids that are commonly used as acid components in the production of alkyd resins can be similarly used, such as adipic acid, maleic acid or its anhydride, azelaic acid, succinic acid, etc. Acid or its anhydride, aliphatic dicarboxylic acid such as 7-malic acid, sebacic acid;
Alicyclic polybasic acids such as lahydrophthalic acid, hexahydrophthalic acid, endomethylene hexahydrophthalic acid, and hexahydroterephthalic acid; examples include pyromellitic acid or its anhydride; Alternatively, two or more kinds can be used in combination.

On the other hand, polyhydric alcohols that can be used include trihydric or higher alcohols, such as glycerin, trimethylolpropane, trimethylolethane, and I.

Examples of dihydric alcohols include 2,6-hexanediol, pentaerythyl, etc., and examples of dihydric alcohols include EVA, ethylene glycol, propylene glycol, 1,4-butanediol, 2,2-bentanediol, and 3-methyl-
1,2-butanediol, trimethylene glycol, l
, 5-bentanediol, 2.4-bentanediol,
2,3-dimethyltrimethylene glycol, tetramethylene glycol, l,4-bentanediol, 3-methyl-4,5-bentanediol, 1,4-hexanediol, 2,5-hexanediol, 1,5-hexane diol, 1,6-hexanediol, and the like.

These polyhydric alcohols can be used alone or in a mixture of two or more. Furthermore, monoepoxy compounds such as Cardura E (product of Shell Chemical Co., Ltd.) can also be used as the dihydric alcohol.

In addition, saturated or unsaturated fatty acids that can be used in the production of short-oil alkyd resins include saturated or unsaturated fatty acids having 6 to 18 carbon atoms or their glycerides, benzoic acid, methylbenzoic acid, p-t- Examples include butylbenzoic acid.

Also, various natural oils or their fatty acids, such as coconut oil, cottonseed oil, rice bran oil, fish oil, tall oil, soybean oil, linseed oil, tung oil, rapeseed oil, castor oil, dehydrated castor oil, etc., or derived from them. Fatty acids can also be used. Furthermore, when a monoepoxy compound such as Cardura E is used as a dihydric alcohol, if the monoepoxy compound contains a fatty acid residue having 6 to 18 carbon atoms, the fatty acid can also be used here. It is considered to be a type of saturated or unsaturated fatty acid.

These fatty acids are used so that the amount of fatty acid modification in the short oily alkyd resin obtained falls within the above-mentioned range, that is, 25% by weight or less, preferably 20% by weight or less, and more preferably 17% by weight.
It can be used in amounts such that:

Of course, when producing oil 7-ly alkyd resin,
It is not necessary to use such fatty acids.

The condensation reaction between the acid component and the alcohol component is usually carried out in the presence of an esterification catalyst, and known acid catalysts, base catalysts and metal catalysts can be used as such catalysts. Examples of acid catalysts include sulfuric acid, phosphoric acid, para-toluenesulfonic acid, trichloroacetic acid, trifluoromethanesulfonic acid, monobutyl phosphate, dibutyl phosphate, and boron trifluoride; examples of base catalysts include:
For example, monoethanolamine, jetanolamine,
Examples of metal catalysts include dibutyltin oxide, monobutyltin hydroxide, tetrabutylzirconate, tetrabutyltitanate, stannous chloride, zinc oleate, silver oleate, zinc acetate, and the like. can be mentioned. Among these catalysts, monobutyltin hydroxide is particularly preferred because it greatly accelerates the reaction and has little adverse effect when incorporated into a paint. Further, para-toluenesulfonic acid can also be a particularly preferred reaction catalyst since it has curing catalytic ability when a curing catalyst is required in the paint formulation.

When the alkyd resin prepared as described above is used as a dispersion stabilizer resin according to the invention, it is advantageous that at least a portion of the alkyd resin has polymerizable double bonds in the molecule. The introduction of a polymerizable double bond into the alkyd resin is usually carried out by reacting a carboxyl group that may exist in the alkyd resin with an unsaturated monomer containing a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. can be done. In addition, the introduction of a polymerizable double bond can be achieved by adding an equimolar adduct of an isocyanate group-containing unsaturated monomer, such as hydroxyalkyl acrylate or hydroxyalkyl methacrylate, to a diisocyanate compound to a hydroxyl group that may exist in the alkyd resin. It can also be carried out by reacting according to a method. Such a reaction can be carried out by a method known per se, and it goes without saying that the reaction conditions may be modified depending on the catalyst used and the type of unsaturated monomer. By the above reaction, as mentioned above, the alkyd resin has an average of at least 0.1, preferably 0.3 to 5.0, more preferably 1.0 to 3.0 molecules per molecule. Polymerizable double bonds can be introduced.

The alkyd resins described above for use as dispersion stabilizer resins in accordance with the present invention generally have a weight average molecular weight of from about 5.000 to about 2.
00.000, preferably about 10.000 to about 50.0
It can have a molecular weight within the range of 0.00. If the molecular weight is less than about 5,000, the stabilization of the polymer particles will be insufficient, while if the molecular weight exceeds 200,000, the viscosity will be extremely high and handling will tend to become difficult.

The present invention uses the above-mentioned alkyd resin as a dispersion stabilizer and polymerizes a radically polymerizable unsaturated monomer in the presence of the alkyd resin to obtain stable gel-like polymer dispersed particles.

The polymerization is carried out in an organic liquid that does not dissolve the resulting dispersed polymer particles but is a good solvent for the alkyd resin. The organic liquid used contains at least 30% by weight of an aromatic solvent as an essential component.

Examples of the aromatic solvent include benzene, toluene, xylene, ethylbenzene, and aromatic petroleum naphtha (e.g., Swasol 200, Swasol 31, manufactured by Cosmo Oil Co., Ltd.).
0, 1500, 1800) can be used alone or in combination of two or more.

Such aromatic solvents can be used in combination with other organic liquids, if necessary. Other compatible organic liquids include, for example, aliphatic hydrocarbons such as hexane, heptane, and octane; alcoholic solvents such as isopropyl alcohol, n-butyl alcohol, i-7' alcohol, and octyl alcohol; cellosolve, butyl cellosolve; , ether solvents such as diethylene glycol monobutyl ether; ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methyl hexyl ketone, and ethyl butyl ketone; esters such as ethyl acetate, isobutyl acetate, acyl acetate, and 2-ethylhexyl acetate Examples include solvents, and these can be used alone or in combination with the aromatic hydrocarbon. If the content of the aromatic solvent is less than 30%, the solubility of the alkyd resin will be insufficient in the organic liquid, so preferably the content of the aromatic solvent is 50% to 1%.
00% by weight, more preferably 70 to 100% by weight.

The radically polymerizable unsaturated monomers polymerized according to the present invention in such an organic liquid are: (1) at least two vinyl monomers each having complementary functional groups capable of reacting with each other and bonding; or (2) a monomer mixture containing at least 0.5% by weight of a multi-vinyl monomer.

Examples of combinations of complementary functional groups that can react and bond with each other in the monomer mixture of the former (2) include (dish) epoxy group/carboxyl group (i) hydroxyl group/isocyanate group (ii)
Epoxy group/amino group (iv) Combinations such as incyanate group/amino group may be mentioned. Specific examples of combinations of two or more vinyl monomers each having complementary functional groups capable of reacting and bonding with each other include the following.

An example of (i) is a combination of an epoxy group-containing monomer such as glycidyl acrylate or glycidyl methacrylate, and a carboxyl group-containing monomer such as acrylic acid or methacrylic acid; A hydroxyl group-containing monomer such as acrylate or hydroxyethyl methacrylate and an incyanate group-containing monomer such as isocyanate ethyl acrylate or incyanate ethyl methacrylate-1 or isophorone diisocyanate/hydroxyethyl acrylate or hydroxyethyl methacrylate equivalent adduct. A combination of: (ii) is an example of a combination of the epoxy group-containing monomer and an aminoalkyl acrylate or aminoalkyl methacrylate monomer; an example of (iv) is a combination of the incyanate group-containing monomer. and the above aminoalkyl acrylate or aminoalkyl methacrylate monomer; etc.

At least two types of vinyl monomers having complementary functional groups as described above each contain at least 0% of the vinyl monomers in the monomer mixture.
．． It may be present in a concentration of 5% by weight or more, preferably in the range 0.5-20% by weight.

Further, the multi-vinyl monomer (2) is a compound having at least 2 to 4 polymerizable double bonds in one molecule, such as divinylbenzene, ethylene glycol di(meth)
Acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, l
, 3-butanediol di(meth)acrylate, l, 4
-Butanediol di(meth)acrylate, unskilled pentyl glycol di(meth)acrylate, ■.

Examples include 6-hexanethiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, glycerol methacrylate acrylate, etc. , these can be used alone or in combination of two or more. Such multivinyl monomers may also be present in the monomer mixture at a concentration of at least 0.5% by weight, preferably within the range of 0.5 to IO% by weight. These vinyl monomers are components for crosslinking the dispersed fine particles prepared, and the use and type or combination of monomers, etc. can be arbitrarily selected depending on the desired performance. Suitable examples include vinyl monomers and multivinyl monomers having a combination of complementary functional groups described in (i) above.

In order to obtain gel-dispersed particles by polymerizing a radically polymerizable unsaturated monomer in the presence of the above-mentioned dispersion stabilizer resin and an organic solution, glycidyl (meth)acrylate is added to the radical polymerizable unsaturated monomer. and (meth)acrylic acid, respectively.
The content may be 5% by weight or more, preferably 0.5 to 20% by weight. When the content is less than 0.5%, sufficient gel-dispersed particles cannot be obtained, and the storage stability of the dispersed resin liquid deteriorates, and the physical properties and hardness of the coating film deteriorate. On the other hand, the content is 2
If it is more than 0%, the entire resin liquid system may be crosslinked or thickened during the production of dispersed particles, which is not preferable.

When obtaining the above-mentioned gel-dispersed particles, it is preferable to use a basic catalyst such as a tertiary amine.

The vinyl monomer or multivinyl monomer having the combination of complementary functional groups described above can be used in combination with other radically polymerizable unsaturated monomers.

Representative examples of other radically polymerizable unsaturated monomers that can be used are as follows.

(a) Esters of acrylic acid or methacrylic acid; for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
01-18 alkyl esters of acrylic acid or methacrylic acid such as propyl methacrylate, inglovir methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; 02~. Alkenyl ester; 02-6 hydroxyalkyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; Acrylic acid or methacrylic acid such as allyloxyethyl acrylate, allyloxymethacrylate C1-,8 alkenyloxyalkyl ester.

(b) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene,
Vinylpyridine.

(C) Others: acrylonitrile, methacriminitrile, methyl isopropenyl ketone; vinyl acetate, peobamonomer (Shell Chemical Products), vinyl propionate, vinyl pivalate, etc.

The monomer mixture described above is polymerized using a radical polymerization initiator. Examples of usable radical polymerization initiators include 2,2-azoisobutyronitrile,
Examples include azo initiators such as 2'-azobis(2,4-dimethylvaleronitrile); peroxide initiators such as benzoyl peroxide, lauryl peroxide, and tert-butyl peroctoate; The agent is generally 0.2 parts by weight per 100 parts by weight of monomers subjected to polymerization.
It can be used within the range of ~10 parts by weight, preferably 0-5 to 5 parts by weight.

Furthermore, the amount of the alkyd resin used as a dispersion stabilizer during the polymerization can be varied over a wide range depending on the type of the monomer, but in general, the amount of the alkyd resin used as a dispersion stabilizer is 10 based on the total amount
A suitable range is from 30 to 70% by weight, preferably from 30 to 70% by weight.

Furthermore, the total concentration of monomer and alkyd resin in the organic solution is generally 30-70% by weight, preferably 40% by weight.
~60% by weight.

As the dispersion polymerization method, a radical polymerization method known per se can be used, and the reaction temperature during polymerization is generally within the range of about 50 to about 150 °C,
The reaction can usually be completed in about 1 to 15 hours at the same temperature as the polymerization.

In this way, a polymer fine particle dispersion crosslinked inside the dispersed fine particles is obtained, and the polymer crosslinked fine particle dispersion is used as it is or mixed with an oil-free alkyd resin, a short oil alkyd resin, etc., and is generally mixed with a colorant. , a curing agent, etc. can be blended and used as a coating composition. Examples of the coloring agent include dyes, organic pigments, and inorganic pigments, and examples of the curing agent include crosslinking agents such as amino resins, epoxy resins, and polyisocyanates.

(Examples) The present invention will now be described in more detail with reference to Examples. In the examples, parts and percentages are by weight.

<Production example> Synthesis of dispersion stabilizer A In a flask equipped with a thermometer, a stirrer and a water separator, 513.2 parts of 7-talic anhydride Neopentyl glycol 214, 2 II Ethylene glycol 50.6 // Trimethylol Globan 167.0/coconut oil fatty acid 128.57/monobutyltin hydroxide 1, Q tt were charged, and the contents were heated to 230° C. for 4 hours while stirring.

After further heating at 230°C for 2 hours, 5% xylene was added to the total amount of charge to promote the removal of condensed water by-produced in the esterification reaction, and the temperature was maintained at 230°C.
Heating was continued until the acid value reached 5. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained alkyd resin varnish with a fatty acid modification amount of 12.8% is X, and the weight average molecular weight of the resin is 17.
It was 000. Then, 50 l:l (molar ratio) of an adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the above varnish.
．． 0 parts and 0.1 part of 4-tert-butylcatechol were added and reacted at 100°C for 3 hours to introduce copolymer double bonds into the dispersion stabilizer molecular chains.

Synthesis of Dispersion Stabilizer B In a flask equipped with a thermometer, a stirrer and a water disperser, 473.4 parts of talic anhydride 473.4 parts Adipic acid 133.4 // Neopentyl glycol 239.9 // Ethylene glycol 56.7 /trimethylolpropane 187.1//monobutyltin hydroxide 1, Q tt were charged, and the contents were heated to 23,000 for 4 hours while stirring.

After further heating at 230°C for 2 hours, 5% xylene was added to the total charge to promote the removal of condensed water produced as a by-product in the esterification reaction, and the temperature was maintained at 230°C.
Heating was continued until the acid value reached 5. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained oil 7-ary alkyd resin FES was Z, and the weight average molecular weight of the resin was 15,000. Next, 50.0 parts of a 1:1 (molar ratio) adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method were added to the entire amount of the varnish.
Add 0.1 part of tert-butylcatechol to 100
The reaction was carried out at °C for 3 hours to introduce polymerizable double bonds into the dispersion stabilizer molecular chains.

Synthesis of Dispersion Stabilizer C In a flask equipped with a thermometer, a stirrer, and a water disperser, 680.8 parts of isophthalic acid, 231.5 parts of neopentyl glycol, 54.7 parts of ethylene glycol, 180.6 parts of trimethylolpropane, were added. Monobutyltin hydroxide 1.071 was charged, and the contents were heated to 230°C for 4 hours while stirring. Hereinafter, the viscosity of the oil-free alkyd resin varnish obtained by the same method as dispersion stabilizer B was Z-1, and the weight average molecular weight of the resin was 16,000. Next, 500 parts of an adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate (molar ratio) of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method were added to the entire amount of the above varnish, and 0.1 part of 4-tert-butylcatechol was added to 100 parts. React at °C for 3 hours to introduce polymerizable double bonds into the dispersion stabilizer molecular chain.

In a flask equipped with a dispersion stabilizer, a thermometer, a stirrer, and a water disperser, 382.4 parts of terephthalic acid, 282.5 parts of adipic acid, 241.9 parts of neopentyl glycol, 57.1 parts of ethylene glycol, Methylolpropane 188.7 // monobutyltin hydroxide 1, Q // were charged, and the contents were heated to 230° C. for 4 hours while stirring. Hereinafter, the viscosity of the oil-free alkyd resin varnish obtained by the same method as dispersion stabilizer B was Z, and the weight average molecular weight of the resin was 18,000. Next, 50.0 parts of a 1:1 (mole ratio) adduct of inphorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method and 0.1 part of 4-tert-butylcatechol were added to the total amount of the above varnish. The reaction was carried out at °C for 3 hours to introduce a polymerizable double bond into the dispersion stabilizer molecular chain.

Synthesis of Dispersion Stabilizer E Phthalic anhydride 439.2 parts Neopentyl glycol 194.7 // Ethylene glycol 69,0 // Trimethylolpropane 101.3/ /Coconut oil fatty acid 272.6//Monobutyltin hydroxide 1. The contents were heated to 230°C for 4 hours while stirring. After further heating at 230°C for 2 hours, 5% xylene was added to the total amount of charge to promote the removal of condensed water produced as a by-product in the esterification reaction, and the temperature was maintained at 230°C.
Heating was continued until the acid value reached 5. When the acid value reached 5, heating was stopped, and the mixture was diluted with xylene so that the heating residue was 70%. The viscosity of the obtained alkyd resin varnish with a fatty acid modification amount of 27.3% is T, and the weight average molecular weight of the resin is 13.
It was 000. Then, 50 l:l (mole ratio) adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate synthesized by a known method was added to the entire amount of the above varnish.
．． 0 part and 0.1 part of 4-tert-butylcatechol were added and reacted at 100°C for 3 hours to introduce a polymerizable double bond into the molecular chain of the dispersion stabilizer.

Example of manufacturing non-water dispersible resin liquid 1 Place xylene in a flask equipped with a thermometer and a stirrer.
104.8 parts heptane 3
6.9//Dispersion stabilizer A142.9 (solid content 100)/
/ was heated to 100°C, and the following monomers, polymerization initiators, and basic catalysts were added dropwise over 3 hours, and the mixture was further aged for 4 hours.

Methyl methacrylate 60.0 parts Acrylonitrile 20.0 // 2-hydroxyethyl acrylate) 10, 0 // Glycidyl methacrylate 7. Qtt acrylic acid
3-Q ttAzobisisobutyronitrile 2.0〃Dimethylaminoethanol 1. Ol/The obtained resin liquid was a dispersion liquid with a nonvolatile content of 52% and a viscosity D1 polymer particle particle size (as measured by an electron microscope, hereinafter the same) of 0.2-0.3 μm. Even after standing at 50°C for 3 months, there was no generation of precipitates or coarse particles, and no change in the properties of the varnish.

Production Example of Non-Aqueous Dispersible Resin Liquids 2 to 5 Except for changing the dispersion stabilizer A in the production example of the non-aqueous dispersible resin liquid 1 to dispersion stabilizer B, C, D or E, the other compositions and methods were the same. Non-water-dispersible resin liquids were produced, and non-water-dispersible resin liquids 2 to 5 each having a non-volatile content of 52% were obtained. All of the dispersions had a particle size of 0.2 to 0.3 μm, and even after being allowed to stand at 50° C. for 3 months, there was no generation of precipitates or coarse particles, and no change in the properties of the varnish.

Example of manufacturing non-aqueous dispersible resin liquid 6 Place xylene in a flask equipped with a thermometer and a stirrer.
104.8 parts heptane 36.9 // dispersion stabilizer p,
142.9 (solid content: 100)// was charged and heated to 100'O, the following monomers and polymerization initiator were added dropwise over 3 hours, and the mixture was further aged for 4 hours.

Methyl methacrylate 70 parts Acrylonitrile 20/12-hydroxyethyl acrylate 1O The obtained resin liquid is a dispersion in which the dispersed particles are not gelled, the non-volatile content is 52%, the viscosity is D1, and the particle size of the polymer particles is 0.2-0.3 μm. Met. 5
If left at 0℃ for 3 months, the particle size will decrease to 0.4-0.5μ.
m, and formation of a precipitate was observed. Also, the viscosity is G
The viscosity had increased.

Examples 1 to 7 and Comparative Examples 1 to 2 Oil 7 Real alkyd resin, non-aqueous dispersible resin liquids 1 to 5, and a crosslinking agent were blended at the solid proportions shown in Table 1 below, and each test plate (thickness 3,5 mm, zinc phosphate treatment)
The coating was cured by baking at 140° C. for 30 minutes (cured film thickness: 20 to 25 μm). The results of various tests on the resulting coating film are shown in Table 2 below.

(Note) ■) Flexibility: Tested under the conditions of JIS K 5400. The cracking and peeling of the coating film was observed when the diameter of the mandrel was 2 mm and the thickness of the auxiliary plate was 4 mm.

- No damage to the paint film such as cracking or peeling: O - Cracking or peeling occurred: × 2) Impact resistance: A mild steel plate was used as the material. Using a DuPont impact tester, a 500 g weight was dropped onto the coating film at a center of impact of % inches, and the maximum distance without cracking or peeling was determined. (cm) 3) Erichsen: Measured using an Erichsen tester manufactured by Erichsen (unit: mm).

4) Hardness: Evaluated according to JIS K 5400.

5) Substrate: The test was conducted under the conditions of JrS K 5400.

Peel off the squares with cellophane tape, total number of 100.
Evaluation was made based on the number of squares that remained without being peeled off.

6) Weather resistance: Aluminum plate was used as the material. QUV weather meter manufactured by The Q Panel (UV 32~Fluorescent lamp rNo., QFS-40, UV-8J wavelength range 3)
20 to 280 nm) at a temperature of 40 to 70 °C with a cycle of irradiation (15 min) and condensation (15 min).
After repeating the test for 0 hours, the degree of deterioration of the coating film was observed.

7) Magic contamination: Color the painted surface with red marker,
It was left at 0°C for 24 hours. The sample was gently wiped three times with absorbent cotton containing an appropriate amount of ethanol, and the presence or absence of coloration was evaluated.

No coloring 20 Colored: × 33~

Claims (1)

[Claims] 1. An alkyd resin having an average of at least 0.1 polymerizable double bond in the molecule and a fatty acid modification amount of 25% by weight or less in an organic liquid containing at least 30% by weight of an aromatic solvent. Radical polymerization containing at least 0.5% by weight of each of at least two vinyl monomers or a multi-vinyl monomer each having complementary functional groups capable of reacting and bonding with each other in the presence of 1. A method for producing a crosslinked fine particle dispersion of a polymer insoluble in an organic liquid, the method comprising copolymerizing a sexually unsaturated monomer.