JPH0151504B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating resin composition with excellent pigment dispersibility. More specifically, a novel resin composition comprising a copolymer obtained by polymerizing a double bond-containing addition reaction product, an unsaturated oil-free alkyd, and a copolymerizable polymerizable monomer with a crosslinking component. Pertaining to things. A coating composition that combines a vinyl copolymer and a crosslinking component is characterized in that when the vinyl copolymer mainly consists of styrene and methyl methacrylate, the resulting coating film has good weather resistance, quick drying properties, durability, and resistance to yellowing. , has excellent performance in terms of solvent resistance and physical properties, and has excellent performance in terms of solvent resistance and physical properties.
It is already widely used for finishing aluminum sash, wood, plastic, slate, etc. However, due to its molecular structure, vinyl copolymers are generally less compatible with pigments than alkyd resins (hereinafter abbreviated as alkyd).
This causes color separation during coating and pigment separation during storage, and therefore, from a practical standpoint, improvements in pigment dispersibility have been required. In order to improve the pigment dispersibility, for example, (a) an unsaturated dicarboxylic acid diester obtained by the reaction of an unsaturated dicarboxylic acid with a glycidyl ester of a tertiary aliphatic carboxylic acid, (b) an unsaturated oil Attempts have already been made to use free alkyds and (c) copolymers with polymerizable monomers. (Japanese Patent Publication No. 53-766) To further explain this, the unsaturated dicarboxylic acid diester of component (a) is It can be obtained as follows. In addition, as another method for improving the above-mentioned drawbacks, an oil- or fatty acid-containing unsaturated polyester,
It has also been proposed to use it in combination with an unsaturated trialkoxysilane monomer. (Japanese Unexamined Patent Publication No. 53-61694) However, even in the resin composition characterized by using an unsaturated dicarboxylic acid diester or an unsaturated trialkoxysilane monomer as described above, it is difficult to obtain a coating film performance sufficient for practical use. Pigment dispersibility could not be obtained. The present invention has been made to improve the drawbacks of the prior art as described above. That is, the present invention aims to provide a coating resin composition that has excellent pigment dispersibility and excellent coating film performance. That is, the present invention provides a product obtained as a result of the reaction of A (i) a glycidyl ester of a tertiary aliphatic carboxylic acid, (ii) an unsaturated polyhydric carboxylic acid anhydride, and (iii) a hydroxyl group-containing saturated compound. 5 to 95% by weight of an addition reaction product having one double bond in the molecule [However, the ratio of each of the above compounds is (i) epoxy group: (ii) acid anhydride group: (iii) Hydroxy group =
The molar ratio is 0.8-1.2:1.0:0.8-1.2. ] (B) A mixture consisting of 95 to 5% by weight of unsaturated oil-free alkyd...5 to 45% by weight B At least one type of copolymerizable polymerizable monomer...95 to 55% by weight The present invention relates to a coating resin composition with excellent pigment dispersibility, which is obtained by further blending a crosslinking agent component with the copolymer obtained by the reaction described above. One of the characteristics of the present invention is that 1
The purpose is to use an addition reaction product (a) containing double bonds. The reaction product (a) is synthesized by the following one-step reaction or two-step reaction. One step reaction two-step reaction The production of the addition reaction product (a) containing one double bond in the molecule is carried out in an atmosphere of an inert gas such as carbon dioxide or nitrogen gas, or in an atmosphere of air if coloring is not a problem. Perform under atmosphere. The reaction temperature is 180°C or lower. preferably 90
A range of ~135°C is suitable. In the case of synthesis by the one-step reaction, the progress of the reaction can be confirmed by measuring the acid value. However, in the present invention, the acid value is set to 40 or less, preferably 20 or less. If the acid value exceeds 40, unreacted substances will remain and this will cause a decrease in the performance of the final coating film, which is not preferable. In addition, in the first step of the two-step reaction, the acid anhydride group of the acid anhydride

When [Formula] is reacted with a hydroxyl group-containing saturated compound, the reaction is carried out at 140°C or lower. That is, a ring-opening reaction of an acid anhydride group and an addition reaction (half-esterification) of a hydroxyl group are performed under conditions in which the formation of water is not observed, to obtain an esterified product containing a terminal carboxyl group. Then, in the second reaction, the esterified product is reacted with a glycidyl ester of a tertiary fatty acid carboxylic acid to obtain a double bond-containing addition reaction product. The end point of the first and second stage reactions can be determined by confirming the disappearance of the acid anhydride group in the first stage. However, since it is generally difficult to confirm by chemical analysis, it is desirable to use an infrared spectrophotometer. In the method using the infrared spectrophotometer, absorption due to acid anhydride groups appears sharply at around 1770 cm ^-1 and around 1850 cm ^-1 although it differs somewhat depending on the type of acid anhydride. Therefore, the progress of the first stage reaction can be determined by tracing these two absorptions, and can be quickly confirmed using this method. Next, the second stage reaction is carried out in the same temperature range as the first stage reaction. The end point of the reaction is when the acid value becomes 40 or less. Water may be produced in the one-stage or two-stage reaction. However, reactions under reaction conditions that produce water should be avoided in the present invention. This is because when water is produced, the acid anhydride and water react to open the acid anhydride group, thereby inhibiting the addition reaction of the hydroxyl group-containing saturated compound. The glycidyl ester of tertiary aliphatic carboxylic acid used to obtain the addition reaction product (a) containing one double bond in the molecule of the present invention includes, for example, Cardiura E [Ciel Co., Ltd. product] Name: Glycidyl ester of versatic acid], glycidyl ester of neopentanoic acid, glycidyl ester of neodecanoic acid, glycidyl ester of neotridecanoic acid, and the like. These may be used alone or as a mixture of two or more. Further, as the anhydride of unsaturated polyhydric carboxylic acid, any anhydride containing a double bond and an acid anhydride group in the molecule, such as maleic anhydride, can be used. Furthermore, as a hydroxyl group-containing saturated compound,
For example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, amyl alcohol, hexyl alcohol, 2-ethylbutyl alcohol, cyclohexanol, 2-ethylhexyl alcohol, benzyl alcohol, which has one hydroxyl group in the molecule. , propylene alcohol, monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and the like. In addition, part or all of the compound having one hydroxyl group in the molecule may be substituted with a polyvalent hydroxyl compound such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
It can also be substituted with 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, etc. The hydroxyl group-containing saturated compounds can be used alone or in mixtures. In the reaction to obtain the addition reaction product (a) containing one double bond in the molecule in the present invention, both the one-step reaction and the two-step reaction can be carried out without a catalyst. The following reaction catalysts may be used as necessary. For example, secondary and tertiary amines or their inorganic or organic acid salts such as dimethylamine hydrochloride, triethylamine, benzyldimethylamine 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl) Examples include metal salts of octylic naphthenate and linoleic acid such as sodium phthalate, zirconium naphthenate, chromium naphthenate, lithium naphthenate, zinc octylate, and chromium linoleate.
Also, Lewis acids and their organic adducts such as boron trifluoride, boron trifluoride monoethylamine, metal halides such as lithium chloride, lithium bromide, tin chloride, etc., or metal hydroxides such as sodium hydroxide. , lithium hydroxide, etc., hydrogen halides such as hydrobromic acid, and alkyl titanates such as butyl titanate. Furthermore, sulfonic acids and sulfonium salts such as valatoluenesulfonic acid, triphenylsulfonium chloride, etc., phosphonic acids and phosphonium salts such as benzenephosphonic acid, triphenylmethylphosphonium, iodide, etc., and quaternary ammonium salts. is trimethylbenzyl ammonium chloride, etc. Also, imidazoles or their inorganic or organic adducts, such as 2-methyl-4-imidazole, 2-naphthyl-4,5-diphenylimidazole, and adducts such as 2- Examples include a cyanoethylene type obtained by reacting methylimidazole and acrylonitrile, an adduct of 2-methylimidazole and trimellitic acid, and others such as triphenylphosphine and triphenylantimony. These may be used alone or in mixtures. When using such a reaction catalyst, the reactants
The amount used is about 0.01 to 10 parts by weight of catalyst per 100 parts by weight. It is desirable to use about 0.1 to 3.0 parts by weight. In the one-step reaction (i) in the present invention, an epoxy group of a glycidyl ester of a tertiary aliphatic carboxylic acid is attached in parallel to a carboxyl group generated by a ring-opening reaction between an acid anhydride and a hydroxyl group-containing saturated compound. Follow the process of reacting. Therefore, the ring-opening reaction of the acid anhydride group proceeds with a hydroxyl group-containing saturated compound and also with a secondary alcohol produced by the reaction between an epoxy group and a carboxyl group. Therefore, in the case of a one-step reaction, in order to completely ring-open the acid anhydride group, one acid anhydride group
The proportion of hydroxyl groups per mole ranges from 0.8 to 1.2 moles, preferably from 0.9 to 1.1 moles. If the amount of hydroxyl groups is less than 0.8 mole, it is necessary that there is a possibility that acid anhydride groups remain, which may increase the viscosity of the system or deteriorate the performance of the final product during the reaction between component A and component B. Undesirable. Also, if the epoxy group of the glycidyl ester of a tertiary aliphatic carboxylic acid is less than 0.8 mole, the number of remaining carboxyl groups will increase, and conversely, if the epoxy group exceeds 1 or 2 moles, the glycidyl ester will remain and eventually Also, pigment dispersibility and water resistance of the final coating film are deteriorated, so it is not preferable. In addition, when using a two-step reaction to obtain the addition reaction product (a), in order to improve the ring-opening reaction rate of the acid anhydride group, 1.0 mol or more of hydroxyl group is used per 1.0 mol of the acid anhydride group. It is preferable. Next, the unsaturated oil-free alkyd (b) used in the present invention is obtained from a polyhydric alcohol and a polyhydric carboxylic acid or its anhydride by a known esterification reaction. The polyhydric alcohol and polyhydric carboxylic acid are preferably combined so that the hydroxyl value of the unsaturated oil-free alkyd is 50 to 200 (solid content). The unsaturated oil-free alkyd in the present invention contains an unsaturated dicarboxylic acid in its raw material composition in order to exhibit excellent performance by copolymerizing with a double bond-containing addition reaction product and a polymerizable monomer. There is a need. The unsaturated dicarboxylic acid ranges from 0.3 to 10% by weight, preferably from 0.5 to 5.0% by weight. The reaction temperature during the production of unsaturated oil-free alkyd is set at 150 to 280°C, and the reaction is carried out while the produced water is successively removed. The end point of the reaction is determined by measuring the amount of water produced by the esterification reaction or the acid value. From the viewpoint of coating film performance, the acid value at the end of the reaction is preferably 50 or less. Examples of the polyhydric alcohol used in the production of the unsaturated oil-free alkyd include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol 1,3, butanediol 1,4, and butanediol 2. ,3, pentanediol-1,5, hexanediol-1,6,
Neopentyl glycol, 2,2,4-trimethylpentanediol-1,3, hydrogenated bisphenol A, 2,2-di(4-hydroxypropoxyphenyl)propane, glycerin, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3 hexanediol, trimethylolpropane, cyclohexanedimethanol-1,4,2,2,4-tetramethylcyclobutanediol-1,3,1,4-bis(2-oxyethoxy)benzene, 2,2,4,4-tetramethylcyclobutanediol-1,3, etc., and these are used alone or as a mixture. Saturated or unsaturated polycarboxylic acids or their acid anhydrides used in the production of unsaturated oil-free alkyds include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, and phthalic anhydride. , isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, hettic acid, 3,6-endomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Examples include methylnadic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, anthracene-maleic anhydride adduct, rosin-maleic anhydride adduct, and these may be used alone or as a mixture. Although the reaction of the unsaturated oil-free alkyd in the present invention can proceed without a catalyst, it is also possible to use a known reaction catalyst as necessary to shorten the industrial time. For example, tetrabutyl zirconate, zirconium naphthenate, tetrabutyl titanate, tetraoctyl titanate, stannous oxalate-sodium acetate mixture, stannous oxalate-sodium acetate-zinc acetate mixture,
Examples include tetraphenyltin, and the amount used is approximately 0.001 to 1.0 parts by weight per 100 parts by weight of the total formulation.
Parts by weight are used. Furthermore, the copolymerizable polymerizable monomer used in the composition of the present invention includes a monomer having a functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or a monomer having a functional group. At least one type of monomer. The polymerizable monomers used in the present invention include 0.3 to 35% by weight of a monoethylenically unsaturated monomer having a hydroxyl group, and 0.3 to 35% by weight of a monoethylenically unsaturated monomer having a carboxyl group in terms of pigment dispersibility, curing speed, degree of curing, etc. Saturated monomer 0.1-5.0% by weight,
Preferably, the remainder is a mixture (total 100% by weight) of other copolymerizable polymerizable monomers. Examples of the polymerizable monomer include styrene, methylstyrene, chlorstyrene, tertiarybutylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl. (meth)acrylate, β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monoester of (meth)acrylic acid of glycerin trimethylolpropane, glycidyl (meth)acrylate Acrylate, N-butoxymethyl (meth)
Acrylamide, N-tertiarybutyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diacetone acrylamide, vinylpyrrolidone, N-methylolacrylamide, acrylamide, (meth)acrylic acid, crotonic acid, vinyl acetate, ( Examples include meth)acrylonitrile, ethylene glycol mono(meth)acrylate, and derivatives thereof. In the present invention, the components (a) and (b) are 5 to 5.
It is necessary to use it in a proportion of 95/95 to 5% by weight, preferably 10 to 90/90 to 10% by weight. The limits of these weight ranges are determined from the viewpoint of pigment dispersibility. That is, if the content of any component is less than 5% by weight, the pigment dispersibility of the composition tends to decrease. Further, component (A) and component (B) are used in a ratio of 5 to 45/95 to 55% by weight, preferably 10 to 35/90 to 65% by weight. Component (A) is less than 5% by weight or 45% by weight
If it exceeds % by weight, the balance between compatibility with the crosslinking agent, gasoline resistance, water resistance, gloss, weather resistance, flexibility, hardness, etc. of the coating film, pigment dispersibility of the composition, painting workability, etc. will be affected. I don't like it because it will crumble. The copolymer obtained by copolymerizing components (A) and (B) in the present invention preferably has a hydroxyl value (solid content) in the range of 10 to 150. This range is preferable in terms of reactivity with the crosslinking agent and coating film performance. The hydroxyl value can be adjusted, for example, during the reaction of component (A), or by selection of raw materials for component (B), or (B).
This can be carried out as appropriate by using a hydroxyl group-containing monomer in the components. A crosslinking agent component is further added to the copolymer. As the crosslinking agent component used in the present invention, any compound that can react with the functional group in the copolymer, such as polyisocyanates, epoxy resins, and amino resins, can be used. Examples of the crosslinking agent components include Desmodyur N, Desmodyur L, Desmodyur 1L, Desmodyur HL (trade name manufactured by Bayer), Takenate D-110N, Takenate D-202 [trade name manufactured by Takeda Pharmaceutical Company Limited], Burnotsuk D -750, Barnotsk
Polyisocyanates such as DN-950 [trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.], or blocked isocyanates obtained by blocking these isocyanates with a known blocking agent; Epicoat
Epoxy resins such as 1001, Epicort 1004 (trade name manufactured by Ciel Corporation), Araldite 6071, Araldite 6084 (trade name manufactured by Ciba Corporation), Epiclon 1050, Epiclon 4050 (trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.):
Other examples include alkoxylated melamine resins, alkoxylated urea resins, and alkoxylated guanamine resins. These crosslinking agent components can be used alone or as a mixture, and the amount used is customary depending on the type of copolymer, the curability of the composition, the performance of the final coating film, etc. Further, depending on the type of crosslinking agent component used, the resin composition can be a one-pack type or a two-pack type resin composition. The composition of the present invention thus obtained has a low viscosity,
In order to use the (a) component of low hue,
A composition having a lower viscosity and a lower hue can be obtained compared to known compositions such as those disclosed in JP-A No. 766 and JP-A-53-61694. Therefore, it is very advantageous when a clear finish is required or when increasing the nonvolatile content of the copolymer. Furthermore, the coating composition of the present invention may contain known coloring pigments, extender pigments, dyes, various paint additives, modifiers, curing accelerators, reinforcing agents, etc., as necessary, within a range suitable for the application. Can be added. The thus obtained coating resin composition of the present invention can be applied by a known coating method such as brush, roller, dipping, or spray coating. The coating film after painting is formed at room temperature, by far infrared rays, or by baking and drying. In the case of baking drying, a temperature of 50 to 200°C for 10 to 60 minutes is appropriate. The coating resin composition of the present invention can be applied not only to all fields in which acrylic resin compositions have conventionally been used, but also to other coating fields. Therefore, it has great industrial value. The details of the present invention will be explained below with reference to Examples. "Part" or "%" means "part by weight" or "% by weight"
It is shown with. Synthesis Example 1 Synthesis of double bond-containing addition reaction product by one-step reaction Maleic anhydride was added to two flasks equipped with a stirrer, condenser, thermometer, and nitrogen gas inlet.
362.8 parts (acid anhydride group)

[Formula] 3.7 moles), 389.4 parts of hexyl alcohol (3.8 moles of hydroxyl groups), and 925 parts of Cardiura E (3.7 moles of epoxy groups) were charged, and the reaction was carried out at 125 to 130°C for 3 hours in a nitrogen gas atmosphere. 1677.2 parts of a bond-containing addition reaction product [A-1] was obtained. The color number of the reaction product is 1 or less, the viscosity (20°C) is 2.9 Stokes,
The acid value was 6.5 and the hydroxyl value was 125. Synthesis Example 2 Synthesis of double bond-containing addition reaction product by two-step reaction In the same flask as in Synthesis Example 1, in the first stage, 362.8 parts of maleic anhydride (3.7 mol of acid anhydride groups) and 389.4 parts of hexyl alcohol (hydroxyl group) were used. 3.8 moles)
After the reaction was carried out at 115 to 120℃ for 3 hours in an atmosphere of nitrogen gas, an infrared spectrophotometer (hereinafter referred to as IR
The reaction rate was 90% when the residual amount of acid anhydride groups around 1770 cm ^-1 and 1850 cm ^-1 was measured.
It was hot. Next, as a second-stage reaction, 925.0 parts of Cardiura E (3.7 moles of epoxy group) was added to the first-stage reactant, and the reaction was carried out at 125 to 130°C for 3 hours in a nitrogen atmosphere to form a double bond-containing addition reaction product. [A-2]
1677. Obtained 2 copies. The color number of the reaction product is 1 or less, and the viscosity (20℃) is
It had a poise of 2.9 stokes, an acid value of 4.0, and a hydroxyl value of 125. Synthesis Example 3 Synthesis of unsaturated oil-free alkyd In a flask using a partial condenser instead of the condenser in Synthesis Example 1, 370.1 parts of neopentyl glycol (7.1 moles of hydroxyl group),
236.2 parts of trimethylolpropane (5.3 moles of hydroxyl group), 442.8 parts of isophthalic acid (5.3 moles of carboxyl group) and 207.7 parts of adipic acid (2.8 moles of carboxyl group) were charged and heated under a nitrogen gas atmosphere.
The reaction was carried out at 200°C for 2 hours and then at 210°C for 2 hours to obtain an esterified product with an acid value of 30.6. Next, 41.2 parts of fumaric acid (carboxyl group 0.7 mol, raw material composition
3.2%) and reacted at 210°C for 2 hours to obtain an unsaturated oil-free alkyd with an acid value of 14.5 and a hydroxyl value of 158. The alkyd was diluted with triol to a nonvolatile content of 60%, and the viscosity (20
°C) Unsaturated oil-free alkyd solution with 5.0 stoke poison, acid number 8.7, and hydroxyl number 98 [B-
1] was obtained. Example 1 73.5 parts of toluene and 119.0 parts of isobutyl acetate were placed in flask 1 equipped with a stirrer, condenser, thermometer, and dropping device, and after raising the temperature to 110°C, the double bond-containing mixture obtained in Synthesis Example 1 was charged. Addition reaction product [A-1] 42.0 parts, unsaturated oil-free alkyd obtained in Synthesis Example 3 [B-1] 105.0 parts, styrene
A mixture consisting of 85.8 parts of methyl methacrylate, 80.9 parts of isobutyl acrylate, 27.7 parts of β-hydroxyethyl methacrylate, 1.8 parts of methacrylic acid, 80.5 parts of toluene, 35.0 parts of isobutyl acetate, and 12.3 parts of benzoyl peroxide was placed in a flask over 3 hours. The polymerization reaction was carried out while dropping the mixture, and after the completion of the dropping, the reaction was further carried out for 5 hours. The obtained copolymer solution [C-1] had a viscosity (20°C) of 4.3 Stokes, an acid value of 4.7, a hydroxyl value of 39,
The non-volatile content was 51.5%. Example 2 In Example 1, the double bond-containing addition reaction product [A-2] obtained in Synthesis Example 2 was used instead of the double bond-containing addition reaction product [A-1]. A polymerization reaction was carried out in the same manner. The obtained copolymer solution [C-2] has a viscosity (20
°C) 4.0 Stoke poison, acid value 4.6, hydroxyl value 38, and non-volatile content 51.0%. Comparative Example 1 Xylol 119.0 in the same flask as Example 1
After charging 175.0 parts of butyl acetate and raising the temperature to 100℃, add 140.0 parts of styrene, 81.2 parts of β-hydroxylethyl methacrylate, and butyl acrylate.
A mixture consisting of 98.0 parts of methyl methacrylate, 23.8 parts of methyl methacrylate, 7.0 parts of methacrylic acid, 0.7 parts of benzoyl peroxide, and 21.0 parts of xylol was added dropwise into the flask over 3 hours. After the dropwise addition, the polymerization reaction was further carried out at 100℃ for 6 hours, and the xylol was 35.0
part was added to dilute. The obtained copolymer solution [D-1] had a viscosity (20°C) of 5.1 Stokes, an acid value of 6.1, a hydroxyl value of 50, and a non-volatile content of 51.5.
It was %. 97.0 parts of the copolymer solution obtained in Examples 1 and 2 and Comparative Example 1 and carbon black
3.0 parts were mixed and kneaded using three rollers, and the pigment dispersibility after kneading was compared twice and five times. The results are shown in Table 1.

[Table] Example 3 Copolymer solution obtained in Example 1 [C-1] 70
30 parts of titanium oxide was mixed with the mixture and dispersed by roller kneading to obtain a paint. Example 4 Using the copolymer solution [C-2] obtained in Example 2, a paint was obtained in the same manner as in Example 3. Example 5 Copolymer solution obtained in Example 1 [C-1]
A paint was obtained by dispersing 30.0 parts of titanium oxide and 20.0 parts of butylated melamine resin (trade name: Super Betsucomin J-820, manufactured by Dainippon Ink and Chemicals Co., Ltd.) into 50.0 parts by roller kneading. Example 6 Using the copolymer solution [C-2] obtained in Example 2, a paint was obtained in the same manner as in Example 5. Example 7 50.0 parts of the copolymer solution [C-1], epoxy resin solution (70% of Ciel Co., Ltd. trade name Epicote 1001)
A coating material was obtained by dispersing 2.0 parts of xylol solution, 18.0 parts of butylated melamine resin (same as in Example 5), and 30.0 parts of titanium oxide by roller kneading. Example 8 A coating material was obtained in the same manner as in Example 7 using the copolymer solution [C-2]. Example 9 A black pigment (trade name: Laben 14, manufactured by Columbia Carbon) was added to 94.0 parts of the copolymer solution [C-1].
6.0 parts were added and kneaded with a roller to obtain a paint. Example 10 A paint was obtained in the same manner as in Example 9 using the copolymer solution [C-2]. Example 11 7.0 parts of an orange pigment (trade name: Hostapalm Orange GR manufactured by Hoechst) was added to 93.0 parts of the copolymer solution [C-1] and kneaded with a roller to obtain a paint. Example 12 Example 11 using the above copolymer solution [C-2]
Paint was obtained in the same manner. Comparative Example 2 A coating material was obtained in the same manner as in Example 3 using the copolymer solution [D-1]. Comparative Example 3 A coating material was obtained in the same manner as in Example 5 using the copolymer solution [D-1]. Comparative Example 4 A coating material was obtained in the same manner as in Example 7 using the copolymer solution [D-1]. Comparative Example 5 A coating material was obtained in the same manner as in Example 9 using the copolymer solution [D-1]. Comparative Example 6 Example using the copolymer solution [D-1]
A paint was obtained in the same manner as in 11. Examples 3, 4, 9, 10 and comparative examples 2, 5,
The pigment dispersibility of the paint obtained in step 6 was measured, and the results are shown in Table 2. The above pigment dispersibility is paint (white) / paint (black) =
Mix well just before use at a mixing ratio of 9/1 (weight ratio) or paint (white)/paint (orange) = 9/1 (weight ratio), and add polyisocyanate as a crosslinking agent [Bayer's product name Desmodyur N]. -75: Biuret structure of hexamethylene diisocyanate] was added at an equivalent ratio of OH/NCO = 1.0, and after stirring,
Toluol/isobutyl acetate = 60/40 (weight ratio)
Adjust the viscosity of the composition (Food Cup # ⁴ ) to about 20 seconds using mixed thinner, then spray paint or flow coat it on a tin plate, dry at room temperature, and measure the color difference (ΔE) of the paint film. It was determined based on this.

[Table] It is clear from Table 2 that the paint mixtures (Samples Nos. 1 to 8) obtained in the Examples of the present invention were very excellent in pigment dispersibility (ΔE). In the comparative sample, the pigment dispersibility was significantly inferior. Moreover, there is a pigment between the double bond-containing addition reaction products of the present invention obtained by one-step reaction (Samples No. 1, 5) and those obtained by two-step reaction (Samples No. 3, 6). There was no difference in dispersibility. Next, the coating film performance obtained in Examples 3 to 8 and Comparative Examples 2 to 4 was evaluated, and the results are shown in Table 3.

[Table] It is clear from the results in Table 3 above that the coating resin composition of the present invention has significantly improved pigment dispersibility and excellent coating film performance compared to the comparative example composition. It was hot.

Claims (1)

[Claims] 1 A (a) The result of the reaction of (i) a glycidyl ester of a tertiary aliphatic carboxylic acid, (ii) an unsaturated polyhydric carboxylic acid anhydride, and (iii) a hydroxyl group-containing saturated compound 5 to 95% by weight of the resulting addition reaction product having one double bond in the molecule [however, the proportion of each compound is (i) epoxy group:
Acid anhydride group in (ii): hydroxy group in (iii) = 0.8~
1.2:1.0:0.8-1.2 (molar ratio)] (b) A mixture consisting of 95-5% by weight of unsaturated oil-free alkyd...5-45% by weight B. Polymerizable monomer that can be copolymerized A coating resin composition with excellent pigment dispersibility, which is obtained by further blending a crosslinking agent component with a copolymer obtained by reaction with at least one type of...95 to 55% by weight.