JPH0768317B2 - Method for producing graft-modified alkyd resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel and useful method for producing a graft-modified resin. More specifically, the present invention substantially comprises
It can be used without adding a pigment dispersant, in particular, it is extremely excellent in dispersion stability, mainly,
The present invention relates to a method for producing a graft-modified resin which is highly practical for paints.

(Prior Art) So far, there is no such thing that the pigment dispersibility is perfect with the coating resin itself.

Therefore, at present, in order to improve the pigment dispersibility, a method of adding a surfactant, a silicone compound or the like as a pigment dispersant is adopted.

By the way, paints using an alkyd resin as a vehicle are generally superior to other types of paints such as acrylic resins in dispersibility in organic pigments, carbon black, etc. However, in general,
The pigment dispersibility is still insufficient, and moreover,
The current situation is that satisfactory results have not been obtained in terms of color separation during color mixing.

(Problems to be Solved by the Invention)
As a result of diligent research to improve the defects such as color separation during color mixing, when alkyd resin is graft-copolymerized with a nitrogen atom-containing vinyl monomer, the alkyd resin itself can be added without adding a surfactant or a pigment dispersant such as a silicone compound. The inventors have found that the pigment dispersibility and color separation at the time of color mixing are drastically improved, and have completed the present invention.

(Means for Solving the Problems) That is, the present invention provides a graft-modified alkyd resin, which comprises graft-copolymerizing a nitrogen atom-containing vinyl monomer to an alkyd resin within a range of 0.01 to 5.0% by weight. It is intended to provide a manufacturing method.

To outline the present invention, the present invention is based on the solid content of the alkyd resin, 0.01 to 5.0% by weight.
Within the range, the present invention relates to a method for producing a graft-modified alkyd resin having excellent pigment dispersibility, which comprises graft-copolymerizing a nitrogen atom-containing vinyl monomer.

Hereinafter, the configuration of the present invention will be described in detail.

The alkyd resin component which is the graft base used in the present invention may be any one as long as it has an unsaturated point that is graft-copolymerized with the nitrogen atom-containing vinyl monomer component described below, and is not particularly limited. Absent.

That is, the alkyd resin component as a graft base used in the present invention is a short oil alkyd resin, a medium oil alkyd resin,
Long oil alkyd resin, phenol resin modified alkyd resin,
All alkyd resins such as epoxy modified alkyd resin and oil-free alkyd resin are targeted.

As the raw material used for producing such an alkyd resin, fats and oils and fatty acid fatty acids, mono- or polybasic acids, polyhydric alcohols, modifiers and the like are usually used.

For example, as fats and oils and fatty acids, linseed oil, soybean oil, tung oil, rice bran oil, palm oil, palm oil, safflower oil, fishing oil, hydrogenated fishing oil, castor oil, dehydrated castor oil and the like, dehydrated castor oil When polymerized oils such as oil, linseed oil, tung oil and alkyd resins are produced by the fatty acid method, the fatty acids of the above-mentioned fats or oils or tall oil fatty acids are used.

As monobasic or polybasic acids, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, head acid, trimellitic acid, pyromellitic acid, succinic anhydride, succinic acid, oxalic acid, adipic acid, sebacic acid, benzoic acid Acids, para-tertiary butyl benzoic acid, para-hydrobenzoic acid, rosins, hydrogenated products thereof, monovalent carboxylic acids such as methyl esters and polycarboxylic acids are used.

Also, as polyhydric alcohols, ethylene glycol,
Propylene glycol, neopentyl glycol, 1,6-
Hexanediol, 1.3-butylene glycol, hydrogenated bisphenol A, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, polyhydric alcohols such as 1.4-cyclohexanedimethanol, and their alkylene oxide adducts, cardura E or bisphenol. A system, an alicyclic system, a phenol system epoxy adduct, etc. can be used in an arbitrary arbitrary ratio.

The alkyd resin component used in the present invention preferably has an unsaturation point derived from fats and oils and the like used for a graft reaction with a nitrogen atom-containing vinyl monomer component described later.

In addition, in the present invention, the unsaturated point to be used for the graft reaction may be secured in the alkyd resin component as follows.

(I) An unsaturated dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid is previously used as a raw material for the production of an alkyd resin to cause a condensation reaction, or the hydroxyl group of the alkyd resin is reacted with an anhydrous dicarboxylic acid to form an unsaturated group. How to introduce.

This method is the most preferable from the viewpoint of the pigment dispersibility which is the object of the present invention, and the amount of the unsaturated dicarboxylic acid used at that time is 0.01 to 5% by weight, particularly preferably 0.05 to 3% by weight. If it is less than 0.01% by weight, the effect cannot be expected, and if it is 5% by weight or more, it becomes a resin of extremely high viscosity, which causes a problem in stability as a paint.

(Ii) General formula (R _1: a hydrogen atom or a methylol group, R _2: an alkyl group of C ₁ -C ₅₎ a method of the vinyl monomer containing an isocyanate group represented by is added to the residual hydroxyl group in the alkyd resin.

(Iii) A method of adding glycidyl (meth) acrylate to the remaining carboxy groups of the alkyd resin.

The above is a typical example of introducing an unsaturated group into an alkyd resin, which makes it possible for the alkyd resin component to be graft-copolymerized with a nitrogen atom-containing vinyl monomer described below, but the present invention introduces an unsaturated group. It goes without saying that the method is not limited to those described above.

Next, the nitrogen atom-containing vinyl monomer component to be graft-reacted with the alkyd resin component, which is an essential condition of the present invention, will be described. Examples of the nitrogen atom-containing vinyl monomer component include N, N-dialkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylamide, (meth) acrylamide, N
-Methylol (meth) acrylamide, N, N-dialkyl (meth) acrylamide, diacetone (meth) acrylamide, acryloyl, N-vinylmorpholine, N-
Alkoxymethyl (meth) acrylamide, N-vinylpyrrolidone, acrylonitrile, N, N-dialkylaminoalkylmaleimide, vinylimidazole and the like, and derivatives thereof are used. The amount used is 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the amount is less than 0.01% by weight, the effect cannot be expected, and if the amount is more than 5% by weight, the stability of the coating composition becomes problematic.

The grafting reaction of the nitrogen atom-containing vinyl monomer to the alkyd resin may be carried out according to a usual grafting reaction. Most simply, the graft reaction may be carried out in the presence of an alkyd resin having an unsaturated group which is involved in the graft reaction, and in the presence or absence of the radical polymerization initiator, the vinyl monomer containing a nitrogen atom.

In the present invention, at the time of graft copolymerization, other vinyl-based monomers can be used in addition to the nitrogen-containing vinyl monomer component. For example, styrene and its derivatives such as styrene and P-tert-butyl styrene; alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; acids such as acrylic acid and methacrylic acid. Monomers; hydroxy (meth) acrylates such as 2-hydroxy (meth) acrylate can be used in combination.

The amount of such a monomer used is 5.0% by weight or less, preferably 3.0% by weight or less. Use of 5% by weight or more is not preferable because the compatibility with other resins deteriorates.

Further, in the graft copolymerization of the present invention, use of a polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, tertiary butyl perbenzoate, tertiary butyl hydroxide, ditertiary butyl hydroxide, cumene hydroxide. Can be done.

The graft copolymerization reaction can be carried out without diluting the alkyd resin with an organic solvent, but generally, the graft copolymerization reaction is carried out in a solution diluted with an organic solvent. The organic solvent used is xylene, toluene,
Aromatic compounds such as Swazol 1000 and Swazol 1500 (manufactured by Cosmo Oil Co., Ltd.); ester compounds such as ethyl acetate, butyl acetate and cellosolve acetate; ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone; 1-butanol, Alcohol type such as 2-butanol Cellosoble; Mineral spirit, Swazol 31
As described in 0, aromatic, aliphatic, and alicyclic mixed systems can be used alone or in combination.

The graft-modified alkyd resin of the present invention thus obtained can also be used as a lacquer coating in combination with other vinyl resin or nitrocellulose, and can be used as a crosslinking agent component such as polyisocyanate, amino resin and epoxy resin. It can be contained and used as a curable paint.

Furthermore, in the case of a graft-modified alkyd resin that uses a drying oil or a semi-drying oil, add a dryer (cobalt-based, zirconium-based, lead-based, manganese-based organic metal salt) and use it as an air-curable paint. Can be done.

It goes without saying that the above-mentioned graft-modified alkyd resin of the present invention can also be used by adding a curing accelerator which is effective for the known or commonly used additive for paints or the above-mentioned crosslinking agent component.

(Examples) Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples without departing from the technical idea thereof. In addition, unless otherwise specified, the ratio of each component used is based on weight.

<Production Example 1> 370 parts of rice bran fatty acid and 425% phthalic anhydride were placed in a four-necked flask equipped with a stir bar, thermometer, cooling tube, nitrogen introducing tube and heating device.
Parts, 100 parts of pentaerythritol, 150 parts of glycerin, 50 parts of ethylene glycol are heated to 180 ° C. in a nitrogen atmosphere, and 2
After holding for an hour, the temperature was raised to 230 ° C. over 1.5 hours and kept as it was. The reaction was allowed to proceed until the acid value became 5 to 7, and 660.0 parts of xylene was added after completion of the reaction.

The resin solution thus obtained had a nonvolatile content of 60.0%, a viscosity (Gardner 25 ° C.) of Z _{3 to} Z ₄ , and an acid value of 4.0. Less than,
This is called (resin solution A).

<Production Example 2> (Resin solution A) of <Production Example 1> in a four-necked flask equipped with a stirring rod, a thermometer, a cooling tube, a nitrogen introducing tube and a heating device.
1000 parts, dimethylaminoethyl methacrylate 5.0 parts,
Xylene 5.0 parts, ditertiary butyl peroxide
After adding 5.0 parts and stirring well, the temperature was raised to 135 ° C. and the temperature was maintained for 4 hours to carry out a graft copolymerization reaction. After the reaction
Upon cooling, a resin solution was obtained.

The resin solution thus obtained had a nonvolatile content of 60.0%, a viscosity (Gardner 25 ° C.) Z ₃ , and an acid value of 3.9. Hereinafter, this is referred to as (resin solution B).

<Production Example 3> 1000 parts (resin solution A) and 5 parts of styrene were placed in a four-necked flask equipped with a stirring rod, a thermometer, a cooling tube, a nitrogen introducing tube and a heating device.
Parts, normal butyl methacrylate 5 parts, fumaric acid 5
Part, N, N dimethylaminopropyl methacrylamide 3.0
Parts, 5.0 parts of di-tert-butyl peroxide and 12 parts of xylene were added and well stirred, then the temperature was raised to 135 ° C. and the temperature was maintained for 5 hours to carry out a graft copolymerization reaction. After completion of the reaction, the mixture was cooled to obtain a resin solution.

The resin solution thus obtained had a nonvolatile content of 60%, a viscosity (Gardner 25 ° C.) Z ₃ -Z ₄ , and an acid value of 6.0. Hereinafter, this is referred to as (resin solution C).

<Production Example 4> 250 parts of isophthalic acid and 380 adipic acid were placed in a four-necked flask equipped with a stir bar, thermometer, cooling tube, nitrogen introducing tube and heating device.
Parts, 150 parts of trimethylolpropane, 170 parts of neopentyl glycol, and 200 parts of 1.6 hexanediol were added, and the temperature was raised to 160 ° C. in a nitrogen atmosphere, further raised to 220 ° C. over 4 hours, and kept as it was. In this way, the acid value is 8-10
The reaction was allowed to proceed until the temperature reached, and after completion of the reaction, the mixture was cooled to 180 ° C. and 830 parts of xylene and 150 parts of cellosolve acetate were added.

The resin solution thus obtained had a nonvolatile content of 50%, a viscosity (Gardner 250 ° C.) X, and an acid value of 4.0. Hereinafter, this is referred to as (resin solution D).

<Production Example 5> (Resin solution D) of <Production Example 4> described above in a four-necked flask equipped with a stirring rod, a thermometer, a cooling tube, a nitrogen introducing tube and a heating device.
1000 parts, glycidyl methacrylate 2.0 parts, styrene 1
0 parts, 5 parts of methylmethacrylate, 3.0 parts of N, N-dimethylaminoethylmaleimide, 12.0 parts of xylene, 5.0 parts of ditertiarybutylmethacrylate were added and stirred well, then heated to 135 ° C and kept for 5 hours. Graft copolymerization was performed. After the reaction, it was cooled to obtain a resin solution.

The resin solution thus obtained had a nonvolatile content of 50.0%, a viscosity Z and an acid value of 3.2. Hereinafter, this is referred to as (resin solution E).

<Production Example 6> In a four-necked flask equipped with a stir bar, a thermometer, a nitrogen introduction tube, a cooling tube and a heating device, the above (resin solution D) 1000 parts, isocyanate ethyl methacrylate 5.0 parts, dimethylaminoethyl methacrylate 2.5 parts, jitter 5.0 parts of sharybutyl peroxide and 8 parts of xylene were added, and after well stirring, the temperature was raised to 135 ° C. and the temperature was maintained for 5 hours to carry out a graft copolymerization reaction. After the reaction, it was cooled to obtain a resin solution.

The resin solution thus obtained had a nonvolatile content of 50.0% and a viscosity of
It had Z ₁ and an acid value of 3.0. Hereinafter, this is referred to as (resin solution F).

<Production Example 7> In a four-necked flask equipped with a stir bar, a thermometer, a nitrogen introducing tube, a cooling tube and a heating device, the above (resin solution D) 1000 parts, maleic anhydride 2.0 parts, dimethylaminoethyl methacrylate were used.
Add 2.5 parts, styrene 4.5 parts, xylene 6 parts, ditertiary butyl peroxide 3.0 parts and stir well, then 135 ℃
The temperature was raised to, and the temperature was maintained for 5 hours to carry out a graft copolymerization reaction. After the reaction, the mixture was cooled to obtain a resin solution.

The resin solution thus obtained has a nonvolatile content of 50%, a viscosity of Y,
The acid value was 4.2. Hereinafter, this is referred to as (resin solution G).

<Production Example 8> 400 parts of coconut oil and 8 parts of trimethylpropane in a four-necked flask equipped with a stirring rod, a thermometer, a cooling tube, a nitrogen introducing tube and a heating device.
Add 0 parts and 0.2 parts lithium hydroxide to 220 ℃ in a nitrogen atmosphere.
The temperature was raised to and held for 1 hour. After cooling to 180 ℃, add 190 parts of isophthalic acid, 180 parts of phthalic anhydride, 100 parts of trimethylolpropane, 100 parts of pentaerythritol, and 15 parts of fumaric acid. The reaction proceeded until. After completion of the reaction, the mixture was cooled to 180 ° C and 650 parts of xylene was added.

The resin solution thus obtained had a nonvolatile content of 60.0%, a viscosity (Gardner 25 ° C.) T, and an acid value of 4.0. Hereinafter, this is referred to as (resin solution H).

<Production Example 9> 1000 parts of (resin solution H), 3.5 parts of styrene, 2.5 parts of dimethylaminoethyl methacrylate were placed in a four-necked flask equipped with a stir bar, a thermometer, a nitrogen introducing tube, a cooling tube and a heating device.
After 3.0 parts of dibutyl butyl peroxide was added and stirred well, the temperature was raised to 135 ° C. and the temperature was maintained for 5 hours to carry out a graft copolymerization reaction. After the reaction, it was cooled to obtain a resin solution.

The resin solution thus obtained had a nonvolatile content of 50%, a viscosity (Gardner 25 ° C.) W and an acid value of 3.2. Hereinafter, this is referred to as (resin solution I).

<Production Example 10> 500 parts of linseed oil, 50 parts of benzoic acid, 90 parts of pentaerythritol, and 0.5 parts of lithium hydroxide were added to a four-necked flask equipped with a stirring rod, a thermometer, a nitrogen introduction tube, a cooling tube and a heating device, The temperature was raised to 240 ° C. in a nitrogen atmosphere and kept as it was for 1 hour. Then cool to 180 ℃, and add phthalic anhydride 300
Part, and 100 parts of pentaerythritol were added, the temperature was raised to 230 ° C., the temperature was maintained as it was, and the reaction was allowed to proceed to an acid value of 8.0.
After completion of the reaction, the mixture was cooled to 180 ° C., and 650 parts of Swazol 310 (manufactured by Cosmo Oil Co., Ltd.) was added.

The resin solution thus obtained had a nonvolatile content of 60.0%, a viscosity (Gardner 25 ° C.) V, and an acid value of 4.0. Hereinafter, this is referred to as (resin solution J).

<Production Example 11> In a four-necked flask equipped with a stir bar, a thermometer, a nitrogen introducing tube, a cooling tube and a heating device, 1000 parts of (resin solution J), 2.5 parts of dimethylaminoethyl methacrylate, 3.0 parts of xylene,
After 3.0 parts of dibutyl butyl peroxide was added and stirred well, the temperature was raised to 135 ° C. and the temperature was maintained for 5 hours to carry out a graft copolymerization reaction. After the reaction, it was cooled to obtain a resin solution.

The resin solution thus obtained had a nonvolatile content of 50.0%, a viscosity (Gardner 25 ° C.) W, and an acid value of 3.0. Hereinafter, this is referred to as (resin solution K).

The dispersibility of the pigment was evaluated for the resin solutions obtained in the above production examples. In order to evaluate the pigment dispersibility, first, for each 100 parts of each resin solution, the pigment content (PWC) shown in Table 1
The pigment was added so that 30 parts of xylene and 100 parts of glass beads were added thereto, and the mixture was kneaded with a sand mill for 1 hour. Subsequently, the glass beads were filtered to obtain color bases (Comparative Examples 1 to 4). , Examples 1-7). Then, for Comparative Examples 1 to 3 and Examples 1 to 6, the mixture was diluted with 30 parts of thinner (xylene: 1-butanol = 7: 3). In addition, Comparative Example 4 and Example 7
Was diluted with 30 parts of xylene. With this diluted solution, the miscibility and the presence or absence of pigment aggregation were examined.

Further, this diluted coating material was applied to a tin plate and allowed to stand at room temperature for a whole day and night, and then the gloss of the coating film was compared.

The respective results are collectively shown in Table 1 as primary color dispersibility data.

Further, compared to 70% of resin solids in the diluted paints of Comparative Examples 1 to 3 and Examples 1 to 6, 30% of melamine resin (solids), Super Beckamine G-821-60 (Dainippon Ink and Chemicals) An isobutyl etherified melamine resin manufactured by Co., Ltd.) was added to prepare a curable paint. To 80% of each white paint prepared in this way, 20% of each color paint is added and spray-painted, and then it is flow-coated and then baked at 130 ° C for 20 minutes and spray-painted part and flow-coated part The color difference was determined. The results are summarized in Table 1. Regarding the color difference between the paints of Comparative Example 4 and Example 7, 6% cobalt naphthenate 1.0%, based on the resin solid content in these diluted paints,
A tin plate was coated with 2.0% of lead naphthenate and 0.5% of MEK ketoxime, left for 1 day, and the color difference was evaluated. The results are summarized in Table 1.

[Advantages of the Invention] The graft-modified alkyd resin obtained by graft-copolymerizing a nitrogen atom-containing vinyl monomer with the alkyd resin of the present invention is excellent in kneading and dispersibility with respect to various pigments.
Therefore, the graft-modified alkyd resin of the present invention can form an excellent coating film with little difference in color due to difference in gloss and coating method without using a pigment dispersant.

Claims (1)

[Claims] 1. A process for producing a graft-modified alkyd resin, which comprises graft-copolymerizing a nitrogen atom-containing vinyl monomer to an alkyd resin within a range of 0.01 to 5.0.