JPS59174620A - Thermosetting resin for dispersing pigment - Google Patents

Abstract

PURPOSE:To provide the titled resin having improved compatibility and pigment ispersibility, and composed of a copolymer of specific amounts of OH-containing, glycidyl-containing and alkyl-containing ethylenic monomers, a lactone compound and an aromatic compound reactive with glycidyl group. CONSTITUTION:The objective resin is prepared by copolymerizing (A) 5-30wt% of an OH-containing ethylenic unsaturated monomer (e.g. 2-hydroxyethyl methacrylate), (B) 2-20wt% of a glycidyl-containing ethylenic unsaturated monomer (e.g. glycidyl methacrylate), (C) 5-50wt% of an ethylenic unsaturated monomer containing a 4-22C straight, branched or cyclic alkyl group (e.g. lauryl methacrylate), (D) 0-30wt% of other ethylenic unsaturated monomer (e.g. methyl methacrylate), (E) 10-70wt% of a lactone compound (e.g. epsilon-caprolactone) and (F) 1-20wt% of an aromatic compound reactive with glycidyl group (e.g. p-nitrobenzoic acid).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin for dispersing pigments. Compatibility and pigments containing copolymers of polymers, ethylenically unsaturated monomers containing alkyl groups, other ethylenically unsaturated monomers, lactone compounds and aromatic compounds that can react with glycidyl groups. The present invention relates to a thermosetting resin for dispersing pigments with significantly improved dispersibility.

Typically, the pigments used in paints are first processed in a ball mill or other type commonly used in the paint industry, using a portion of the total binder that makes up the paint, along with suitable solvents, diluents, or other additives. Dispersed in a mill.

and the dispersion thus obtained (milbase)
is mixed with the remainder of the binder and any other required ingredients to form a paint. For example, in the case of a paint based on an alkyd resin, a portion of the alkyd resin is first dispersed by ball milling in the presence of a hydrocarbon solvent. The dispersion is then diluted with the remainder of the alkyd resin and other ingredients.

In this case, it is important that the pigment is sufficiently dispersed throughout the film in order to provide the coating with optimum opacity and hue. Therefore, when producing a paint, it is desirable for the pigment to be well dispersed in the paint and to be stable during storage, so that the opacity and hue of the paint film can be satisfied.

In many cases, the desired shade is obtained by first mixing a millbase mixture with a binder to form a paint, and then adding a small amount of a colored millbase containing the same or similar binder. Adjusting the final color tone of the paint.

Incidentally, in the paint industry, a wide range of different binders are normally used depending on the object to be coated, coating conditions, etc. Therefore, when producing paints as described above, even if the coloring from the pigment mixture is the same, if the objects to be coated, coating conditions, etc. are different, each pigment or pigment mixture may be mixed separately at the millpaste stage. To,
It was necessary to disperse it with a suitable binder.

Also, when adding a small amount of mill paste to adjust the color of the final paint, if the pigment dispersion resin contained in the mill base is not compatible with the binder of the spray used, Pigments will aggregate, making it impossible to obtain the desired color tone, so even if the desired color tone is the same, depending on the object to be coated, coating conditions, etc., good compatibility with the binder of the paint used may vary. It was necessary to separately prepare a resin for pigment dispersion and perform pigment dispersion.

It should be noted that a graft copolymer in which a highly polar group such as a nitro group or an amino group is arranged near the main chain and a long aliphatic chain in the side chain exhibits good pigment dispersibility as a resin for pigment dispersion. is known, but its compatibility with other resins was insufficient.

As a result of intensive research into methods for overcoming the above-mentioned problems, the present inventors found that specific amounts of hydroxyl group-containing ethylenically unsaturated monomers, glycidyl group-containing ethylenically unsaturated monomers, and alkyl group-containing ethylenically unsaturated monomers were used. A copolymer consisting of an ethylenically unsaturated monomer, other ethylenically unsaturated monomers, a lactone compound, and an aromatic compound that can react with glycidyl groups is compatible with a wide range of binders and has pigment dispersibility. The inventors discovered that the pigment has excellent properties and can be dispersed at a high pigment concentration in the dispersing resin, leading to the completion of the present invention.

That is, the present invention uses hydroxyl group-containing ethylenically unsaturated monomers in an amount of 5 to 30% by weight, glycidyl group-containing ethylenically unsaturated monomers in an amount of 2 to 20% by weight, and linear or branched carbon atoms having 4 to 22 carbon atoms. Reacts with 5-50% by weight of an ethylenically unsaturated monomer containing a chain or cyclic alkyl group, 0-30% by weight of the #1 ethylenically unsaturated monomer, 10-70% by weight of a lactone compound, and a glycidyl group. Aromatic compounds 1-2 that can be
The present invention relates to a thermosetting resin for dispersing pigments containing 0% by weight of a lactone-modified copolymer.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer used in the present invention include 2- and droxyethyl methacrylate, 2-hydro-cyinopropyl methacrylate, 2-hydroxyethyl acrylate), 2-1
Examples include droxyingrovir acrylate.

These hydroxyl group-containing ethylenically unsaturated monomers should be used in the lactone-modified copolymer in an amount of 5 to 30 parts by weight; if less than 5 parts by weight,
The water resistance and solvent resistance of the final cured coating film decreased by 30% by weight.
If it exceeds 20%, the solubility of the lactone-modified copolymer decreases, and the water resistance of the final cured coating film decreases.

Examples of the glycidyl group-containing ethylenically unsaturated monomer used in the present invention include glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether.

These glycidyl group-containing ethylenically unsaturated monomers are
It is used so that it accounts for 2 to 20% by weight in the 2-chton modified copolymer, and if 2% by weight is ungrooved, the desired pigment dispersibility cannot be obtained, and if it exceeds 20% by weight,
Not only does it have poor compatibility with other binders, but it also gels when mixed with resins with high acid values.

The linear, branched, or cyclic alkyl group-containing ethylenically unsaturated monomers having 4 to 22 carbon atoms (hereinafter simply referred to as alkyl group-containing ethylenically unsaturated monomers) used in the present invention include, for example: Butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, 2uryl methacrylate, stearyl methacrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate etc.

These alkyl group-containing ethylenically unsaturated monomers are used in the lactone-modified copolymer in an amount of 5 to 50% by weight. Dispersibility decreases, and if it exceeds 50% by weight, compatibility with other binders decreases.

Examples of the slightly ethylenically unsaturated monomer used in the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, inpropyl acrylate, acrylonitrile, styrene, vinyl Examples include toluene, acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid.

These ethylenically unsaturated monomers are used in the lactone-modified copolymer as needed in an amount not to exceed 30% by weight, and if it exceeds 30% by weight, compatibility with other binders may occur. Solubility and pigment dispersibility are reduced.

Examples of the lactone compound used in the present invention include β-gproolactone, γ-butyrolactone, bivalolactone, r-valerolactone, δ-valerolactone, and 6-caprolactone.

These lactone compounds are present in lactone-modified copolymers.
The button is used so that the amount is 10 to 70% by weight, but if it is less than 10% by weight, the desired compatibility cannot be obtained, and if it exceeds 70% by weight, the resulting lactone-modified copolymer will crystallize. .

Examples of the aromatic compound that can react with the glycidyl group used in the present invention include benzoic acid and derivatives containing p-nitrobenzoic acid, p-nitrobenzoic acid, and p-nitrobenzoic acid.
-Ami7 benzoic acid is useful.

Substituents NR, -8o, -Coo, -CN.

3 -N=C=O1-N=C=S, -COCノ, 8, Lee-C=NOH, SO2NH2, -CF3, -CCノ3
, -CHCno2, -C) (2C), -8OaH, -C
OOHl-COOR,OR.

-F, -CJ, -Br, -I, -NHCOR.

-OR, -8R, -NR2, -NHR.

NR2 The aromatic compound that can react with these glycidyl groups is used in an amount of 1 to 20% by weight in the lactone-modified copolymer, but if it is less than 1 weight φ, the desired pigment dispersibility may not be obtained. However, if it exceeds 20% by weight, the resulting lactone-modified copolymer will be colored dark brown, making it difficult to obtain the desired hue when dispersing the pigment, as well as making it less compatible with the binder. Sexuality decreases.

The lactone-modified copolymer in the present invention can be obtained by various methods.

For example, in the first method, a hydroxyl group-containing ethylenically unsaturated monomer, a glycidyl group-containing ethylenically unsaturated monomer, an alkyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers are used. , conventional solution polymerization methods, e.g. inert solvents (e.g. mineral spirits,
Polymerization initiators (7IC, such as peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, etc.) in toluene, xylene, ethyl acetate, butyl acetate, cellosolve acetate, methyl isobutyl ketone, etc. or an azo compound such as azobisisobutyronitrile, azobisisovaleronitrile, etc.) at 80 to 160°C for 3 to 8 hours to obtain a copolymer. Then, a lactone compound is added to the hydroxyl groups of the obtained copolymer at 100 to 160°C for 1 to 15 hours, preferably at 130 to 150°C, in the presence of a catalyst such as an organometallic compound such as dibutyltin dilaurate or tetrabutyl titanate. Graft ring-opening polymerization is carried out for 2 to 10 hours. The glycidyl groups of the copolymer are then treated with an aromatic compound capable of reacting with the glycidyl groups and a tertiary amine (e.g., dimethyldodecylamine, tributylamine, benzyldimethylamine, dimethylethanolamine, monomethyljetanolamine, dimethyllaurylamine). There is a method of obtaining a lactone-modified copolymer by reacting at 90 to 150°C for 2 to 10 hours in the presence of a lactone-modified copolymer.

As a second method, a lactone compound is grafted onto the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer as described above to form a ring-opened heavy unsaturated monomer, an alkyl group-containing ethylenically unsaturated monomer. and other ethylenically unsaturated monomers by the solution polymerization method described above, and then the glycidyl groups of the obtained copolymer are combined with an aromatic compound capable of reacting with the glycidyl groups and the above-mentioned There is a method of obtaining a lactone-modified copolymer by reacting with a similar temperature.

As a third method, ethylene containing an aromatic group obtained by reacting the glycidyl group of the glycidyl group-containing ethylenically unsaturated monomer with an aromatic compound capable of reacting with the glycidyl group as described above is used. copolymerization of a hydroxyl group-containing ethylenically unsaturated monomer, an alkyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers by the solution polymerization method described above. After that, the hydroxyl group of the nine copolymer obtained is
There is a method of obtaining a lacto/modified copolymer by subjecting a lactone compound to graft ring-opening polymerization as described above.

As a fourth method, an ethylenically unsaturated monomer containing a polylacty group obtained by graft ring-opening polymerization of a lactone compound to the hydroxyl group of a hydroxyl group-containing ethylenically unsaturated monomer as described above. An ethylenically unsaturated monomer containing an aromatic group obtained by reacting the glycidyl group of the glycidyl group-containing ethylenically unsaturated monomer with an aromatic compound that has reacted with the glycidyl group as described above. There is a method of obtaining a polymer, an alkyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers by the solution polymerization method described above. According to the third and fourth methods, if other ethylenically unsaturated monomer polymers (for example, acrylic acid, methacrylic acid, acids, etc.) are used, carboxyl groups can be added to the lactone-modified copolymer. can be contained.

Since it has a structure in which aliphatic polyester groups are grafted onto the main chain of lyl resin, it can be considered to have the same solubility parameters as the lactone-modified copolyester resin, and can be used with a wide range of resins. In addition, a highly polar nitro group or amine 7 group is arranged near the acrylic resin main chain, while a low polar aliphatic polyester group is contained as a graft group, and a low polar aliphatic alkyl group is Contains □, so to speak.
Because it has a bipolar structure, it has excellent pigment dispersibility.

When dispersing pigments in a solvent with low polarity, the nitro groups or amine groups of the pigment dispersion resin are arranged on the surface of the pigment, and the higher aliphatic alkyl groups with low polarity extend into the solvent. However, since the lactone-modified copolymer of the present invention contains an aliphatic polyester group with low polarity as a graft group, the stabilizing effect of the dispersed pigment is even more It is elevated.

Therefore, the thermosetting resin for pigment dispersion of the present invention can be used with a wide range of binders, has excellent pigment dispersibility, and can disperse pigments at a high pigment concentration with respect to the dispersion resin. The amount of pigment dispersion resin added can be minimized during manufacturing and a common millpase can be provided for a wide range of thermosetting paints if the desired shade is the same. .

Thus, by producing MilPace using the pigment dispersion resin of the present invention, ordinary thermosetting paints such as paints for automobile steel plates, paints for automobile glass, paints for precoated metals, paints for electrical equipment products, etc. By substantially reducing the number of millpastes in the production of paints, the production of a series of paints can be streamlined.

In the production of the thermosetting paint as described above, the binder to be mixed with the millpaste obtained using the thermosetting resin for pigment dispersion of the present invention may be a base material such as a thermosetting acrylic resin, a polyester resin, Examples include alkyd resins, epoxy resins, epoxy ester resins, polyester polyurethane resins, thermosetting fluororesins, thermosetting silicone resins, etc. As curing agents, examples include melamine resins, urea resins, benzoguanamine resins, polyisocyanate compounds, and blocked Examples include polyisocyanate compounds, phenolic resins, toluene resins, and xylene resins. In addition, if necessary, cellulose resin,
Seven is created by mixing phenoxy resin, vinyl chloride resin, thermoplastic fluororesin, etc.

In addition, solvents used when dispersing pigments or producing paints using the thermosetting resin for pigment dispersion of the present invention include:
Solvents that are usually used in the paint industry include aromatic hydrocarbons, aliphatic hydrocarbons, esters, ketones, alcohols, etc., with aromatic hydrocarbons and esters being particularly preferred.

In addition, examples of pigments used when manufacturing millpaste using the thermosetting resin for pigment dispersion of the present invention include iron oxide (black, yellow, brown, etc., transparent ones), lead chromate, basic Lead silicate, strontium chromate, chromium green, chromium oxide green, red lead,
Cobalt blue, graphite, carbon blank, rutile titanium dioxide, anatase titanium dioxide, zinc oxide, basic lead carbonate, basic lead sulfate, zinc sulfide, zirconium oxide, metallic aluminum, metallic lead, Kinzo zinc, benzidine yellow, Hansa yellow , Quinoline Yellow Lake, Chromophthal Yellow, 7 Talocyanine Blue, Fast Sky Blue, Phthalocyanine Green, Lake Red, Rhodamine Lake, Methyl Violet Lake, Alizarin Lake, Anse 9 Quince, Thioindigo Bordeaux, Perylene Red, Quinacridone Red, Dioxazine Violet Hikodo is an example.

Pigment dispersion using the thermosetting resin for pigment dispersion of the present invention can be carried out using conventional equipment used for producing millpaste, such as a sand mill, three-roll mill, kneader, and the like. In that case, additives commonly used in paints, such as dispersion stabilizers, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, etc., can be added as necessary.

The thermosetting paint obtained using the thermosetting resin for pigment dispersion of the present invention can be applied to the object to be coated using a conventional coating method such as air spray coating, airless spray coating, electrostatic coating, dipping coating, or roll coating. After painting with etc., 80-23
By heating and drying at 0°C for 0.5 to 60 minutes,
A good coating film can be obtained.

Next, the present invention will be explained in more detail by giving Examples and Comparative Examples. In the examples, parts are parts by weight and % by weight.

Example 1 (1) 2-chthonic modified copolymer: 2-hydroxyethylmethac 20. O0 part lylate glycidyl methacrylate) 7.507 Premer S LMA (made by Japan Oil Co., Ltd., methacrylic acid ester of a synthetic alcohol mixture having 12 to 13 carbon atoms) t-butylperoxybenzo 0.92 #ate (Japan Perbutyl 2, manufactured by Oil & Fat ■) A monomer mixture with the above composition was mixed with a mixed solvent (1126 parts of xylene, 7.6 parts of butyl acetate) kept at 140°C under stirring.
3 parts) at a constant rate over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then, dilute with 448 parts of xylene and 224 parts of butyl acetate to obtain a copolymer solution with a nonvolatile content of 60%.

76.30 parts of the obtained diluted copolymer solution, 4830 parts of ε-caprolactone (Plaxel M manufactured by Daicel Chemical Industries, Ltd.), 0.0 parts of a 10-thixylene solution of dibutyltin dilaurate,
After stirring a mixture of 9.56 parts (24 parts and cellosolve acetate) at 150°C for 6 hours, when the nonvolatile content of the resin/resin solution reached 70%, 5.90 parts of p-nitrobenzoic acid and benzyl dimethyl After adding 0.25 parts of amine and 59.45 parts of xylene and stirring at 145°C for 4 hours, the reaction was terminated when the resin acid value became 0.5 or less, and a lacto/modified copolymer with a nonvolatile content of 50 Obtain the combined solution a.

(2) Mill base: 9.09 parts of the above bichtonic modified copolymer (solution a) cellosolve acetate) 13.64# rutile titanium dioxide (manufactured by Teikoku 6 & 18 p Kako ■, Tica oxide titanium JR-602) Mixture of the above composition After premixing with DiSilver,
Dispersed in a sand mill. Then, while stirring, repeat the above (
4.55 parts of the modified copolymer solution of 1) and 4.54 parts of cellosolve acetate were added to obtain white millbase a.

The obtained white millbase a has good fluidity (viscosity measured by a B-type viscometer (20°C) when the non-volatile content is 75%: 5 voids) and dispersion stability (the pigment does not settle even if 6 is stored for months). (not shown) t- showed.

(8) Series of coatings #+ using millbase: Using the above white millbase a, coatings were produced with the following compositions.

(Paint 1) Above white Milmilbase a 37.20 parts Soybean oil-modified alkyd resin solution 39.30 # (manufactured by Dainippon Ink & Chemicals @, Petsucosol 1307-60-EL, oil length 41 cm, non-volatile content 60 cm) Butylated melamine resin solution 1450 parts (manufactured by Dainippon Ink & Chemicals ■, Super Beckamine J82〇1601 non-volatile content 60%) Cellosolve acetate & 001 xylene
40ON After diluting the paint with the above composition with thinner (xylene/butanol weight ratio: 971) to a coating viscosity (7 ohdkatupuna 4.22 seconds at 20°C), it was applied to a tin plate with an air spray to a dry film thickness of 40μ. It was dried by heating at 140° C. for 30 minutes to obtain a uniform and smooth coating film with a 60 degree specular gloss of 910.

(Paint 2) The above white milbase a, 42+38 parts polyester resin (manufactured by Jujutsu Pai 2 & 677F Elurethane ■, Desmofene 670, low-branched polyester resin, hydroxyl base content = 43, non-volatile content 100%) Selonlupus acetate) 5. 0 parts xylene 4.00 y Add a polyisocyanate compound (Coronate EH, manufactured by Nippon Polyurethane Industry ■) to the paint having the above composition.

Hexamethylene diisocyanate trimer, isocyanate content = 21%) in 50% butyl acetate solution 24, 95
s All processing, paint viscosity (7 ord cup ÷
4.20C't"22 seconds) After diluting the IC, apply it to a tin plate with air spray to a dry film thickness of 4゜μ, heat dry at 80℃ for 30 minutes, and achieve a uniform 60℃ specular gloss of 9L5. A smooth coating film was obtained.

(Paint 3) Above white Milpace A 51.80 parts Silicone polyester 1ltt 3o9oz solution (manufactured by Solar Eclipse Arrow Chemical ■, Alloplat 1713-R60 non-volatile content 60%) Butylated melamine resin solution 12.30tt (manufactured by Hitachi Chemical ■, Melan 22, non-volatile content 60%) Tsurpets 100 (manufactured by Etsuka 4.00 Department ■,
Aromatic solvent) Cyclohexanone 100 After diluting the paint with the above composition with thinner (7/3 weight ratio of the above Tsurpez 100/cyclohexanone) to a coating viscosity (Ford Cup 44. 60 seconds at 20°C), use a bar coater. It was coated on a tin plate to a dry film thickness of 15μ, and then heated at 220℃ for 5
It was heated and dried for 0 seconds to obtain a uniform and smooth coating film with a 60 degree specular gloss of 900.

(Paint 4) Above white millbase & 34.20 parts thermosetting acrylic resin solution 4150p (Hitachi Chemical @
Co., Ltd., Hitaloid 2439A, non-volatile content: 50%) Butylated melamine resin solution 13.30〃 (Previous Paint 1) Cellosolve Acetate) 5.00 parts 9/1) to a coating viscosity (Ford cup +4.22 seconds at 20°C), and then air sprayed onto a tin plate with a dry film thickness of 40 μm.
A uniform and smooth coating film with a 60 degree specular gloss of 910 was obtained by heating and drying at 140° C. for 30 minutes.

Example 2 (1) Lactone-modified copolymer 2-hydroxyethyl methacrylate 1045 parts Lylate glycidyl methacrylate 11.40 #Blemmer S
LMA (manufactured by Nippon Oil Co., Ltd., Example 1, above) t-Butyl peroxybenzo 135 ate (Example 1, above) A monomer mixture having the above composition was heated at 140°C with stirring. A mixed solvent (2255 parts of xylene, 112 parts of butyl acetate) kept at
8 parts) at a constant rate over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then, 6.61 parts of xylene and 3.31 parts of butyl acetate
A copolymer solution with a non-volatile content of 60% was obtained.

A mixture of 11,175 parts of the obtained copolymer solution, 0 parts of ε-caprolactone (Example 1), 0.24 parts of a 10-thixylene solution of dibutyltin dilaurate, and 16.43 parts of selonlupus acetate. 15
After stirring at 0°C for 6 hours, when the nonvolatile content of the resin solution was 60%, p-aminobenzoic acid was 7.35%
parts, benzyldimethylamine 025 parts and xylene 3 parts
After 7.98 parts were added and stirred at 145°C for 4 hours, the reaction was terminated when the resin acid value became 05 or less to obtain a lactone-modified copolymer solution with a nonvolatile content of 50%.

[2) Milpase: White millbase b was obtained by a method similar to that described in Example 1 (however, instead of the lactone-modified copolymer solution a of Example 1, the above lactone-modified copolymer solution was used) ).

The obtained white millbase B had good fluidity (viscosity measured by a B-type viscometer (20°C) when the nonvolatile content was 75% = 5 voids) and dispersion stability (the pigment did not settle even after storage for 6 months). ).

(8) A series of paints using milbase: In paints 1 to 4 of Example 1, the above-mentioned white milbase b was used in place of the white milbase a used in each of them.
Uniform and smooth coating films of Paints 1 to 4 were obtained using the same method as in Example 1 (from blending raw materials to heating and drying).

The 60 degree specular gloss of the resulting coating film was 9 as shown in Table 1 below.

Table 1 Example 3 (1) Bichtonic modified copolymer: Plaxel FM-4 (Dai-7 51.40 parts manufactured by Kagaku Kogyo ■), 2-hydroxyethyl methacrylate and ε-caprolact/and, 2-hydroxyethyl (Modified monomer in which 4 moles of ε-caprolactone are added to 1 mole of hydroxyl group of methacrylate) Glycidyl methacrylate) 5.00 #Blemmer S LMA (Nippon Oil Co., Ltd. 39.70 manufactured by YF ■, carried out above) Example 1) t-Butylperoxybenzo 1.92 #ate (Example 1) A monomer mixture having the above composition was mixed with a mixed solvent (3 and 44 parts of xylene, 19.9 parts of butyl acetate, and kept at 140°C under stirring).
22 parts) at a constant rate over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then, 24.34 parts of xylene and 1z1 of butyl acetate
It was diluted with 8 parts to obtain a copolymer solution with a nonvolatile content of 50%.

A mixture of 19,120 parts of the obtained copolymer solution, 3.90 parts of p-trobenzoic acid, 0.25 parts of benzyldimethylamine, and 165 parts of xylene was stirred at 145°C for 4 hours, and then the resin acid value was 0. The reaction was terminated when the temperature reached 50% or less, and a lactone-modified copolymer solution C with a nonvolatile content of 50% was obtained.

(2) Millbase: A white millbase C was obtained by a method similar to that described in Example 1 (However, in place of the lactone-modified copolymer solution of Example 1, the above lactone-modified copolymer solution C was used. ).

The obtained white millbase C has good fluidity (non-volatile content 7
The viscosity measured by a type B viscosity needle at 5% (20° C. = 5 voids) and dispersion stability (pigment did not settle even after storage for 6 months) were shown.

(8) A series of paints using milbase: The same as in Example 1 except that in Paints 1 to 4 of Example 1, the above white Millbase C was used in place of the white Millbase a used in each. Uniform and smooth coating films of each of Paints 1 to 4 were obtained using a method (from blending raw materials to heating and drying).

The 60 degree specular gloss of the obtained thin coating film was 9 as shown in Table 2 below.

Example 4 (1) Lactone-modified copolymer: ethylenically unsaturated monomer containing an aromatic group (p-
2) Production of benzoic acid-modified monomer: toluene
19.62 parts p-nitrobenzoic acid
4L14#hydro5quinone
0.18 #Benzyldimethylamine 0
20 parts To a mixture having the above composition, 86 parts of glycidyl methacrylate 3B were added at a constant rate of 2 at 90°C while stirring.
After adding over a period of time and stirring at 90°C for 6 hours, the reaction was terminated when the solution acid value became 0.3 or less, and a p-nitrobenzoic acid-modified monomer solution with a nonvolatile content of 80% was prepared. Obtained.

(B) Production of lactone-modified copolymer: A monomer mixture having the following composition was placed in a mixed solvent (4000 parts of xylene, 2000 parts of butyl acetate) kept at 140°C with stirring.
After dropping at a constant rate over 2 hours, the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then, 2110 parts of xylene and 1155 parts of butyl acetate
% to obtain a lactone-modified copolymer solution d with a nonvolatile content of 50%.

Above p-2) Monomer solution of benzoic acid modified with 1675 parts Plaxel FM-4 (manufactured by Daishichi 6200〃L Chemical Industry @, above-mentioned Example 3) Bremmer S LMA (Japan Oil 2310 parts fat ■ (Example 1) Acrylic acid 1.50 IFt-
7'Tylperoxybenzo λ00〃ate (Example 1 above) (2) Milbase: White millbase d was obtained by a method similar to that described in Example 1 (with the exception that the lactone-modified In place of copolymer solution a, the above lactone-modified copolymer solution d
).

The obtained white Millbase d has good fluidity (viscosity measured with a B-type viscometer (20°C) when non-volatile content is 75%: 5 poise) and dispersion stability (pigment does not settle even after storage for 6 months). ).

(8) A series of paints using milbase: Paints 1 to 4 in Example 1 and 11 using white Millbase d were prepared using the same method as in Example 1 (from raw material blending to heat drying). ) to obtain uniform and smooth coating films for each of Paints 1 to 4.

The 60 degree specular gloss of the resulting coating film was as shown in Table 3 below.

Example 5 (1) Lactone-modified copolymer: Plaxel FM-4 (previously -51.40 parts Example 3) Glycidyl methacrylate~) 10.00 #stearyl methacrylate~) 2 s, o o tt
Methyl methacrylate 570 t-Butyl peroxybenzo 1.84 tt ate (Example 1 above) A monomer mixture having the above composition was mixed with a mixed solvent (3684 parts of xylene, 184 parts of butyl acetate) kept at 140°C under stirring.
2 parts) at a constant rate over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete the radical polymerization.

Then, 2333 parts of xylene and 11.6 parts of butyl acetate
The mixture was diluted with 7 parts to obtain a copolymer solution with a nonvolatile content of 50%.

18,420 parts of the obtained copolymer solution, 7.90 parts of p-di)lobenzoic acid, 025 parts of benzyldimethylamine and 765 parts of xylene were added, and after stirring at 145°C for 4 hours, the resin acid value was 0.5. When the reaction is finished, the non-volatile content is 50% of the lactone-modified copolymer solution e.
I got it.

(2) Millbase: A white millbase e was obtained by a method similar to that described in Example 1 (however, in place of the lactone-modified copolymer solution a of Example 1, the above lactone-modified copolymer solution was used) solution e
).

The obtained white millbase e has good fluidity (viscosity measured by a B-type viscometer (20°C) with a nonvolatile content of 75 mm = 5 voids) and dispersion stability (pigment does not settle even after storage for 6 months). Nakatsufc) was shown.

(8) A series of paints using milbase: Paints 1 to 4 of Example 1 were the same as those of Example 1, except that the above-mentioned white milbase e was used instead of the white milbase a used in each of them. Uniform and smooth coating films of Paints 1 to 4 were obtained using the same method (from blending raw materials to heating and drying).

The 60 degree specular gloss of the resulting coating film was as shown in Table 4 below.

(1) 2 Chtonic modified copolymer: Plaxel FM-4 (above-2580 parts Example 3) Glycidyl methacrylate 15.00 #2-
Ethylhexyl methacrylate 47.40 #rate
1 t-Butylperoxybenzo 1.7 e parts ate (example 1 above)
) A monomer mixture having the above composition was mixed with a mixed solvent (xylene 35.28 parts, butyl acetate 17 parts) kept at 140°C under stirring.
．． 64 parts) at a constant speed over 2 hours,
The mixture was further stirred at 14''o C for 3 hours to complete the radical polymerization.

Then, 2235 parts of xylene and 11,1 parts of butyl acetate
It was diluted with 7 parts to obtain a copolymer solution with a nonvolatile content of 50%.

□ 176.40 parts of the obtained copolymer solution, 11.80 parts of p-dibenzoic acid, 0.25 parts of benzyldimethylamine and 11.55 parts of xylene were added, and after stirring at 145°C for 4 hours, The reaction was terminated when the resin acid value became 0.5 or less, and a lactone-modified copolymer solution f having a nonvolatile content of 50% was obtained.

(2) Millbase: A white millbase f was obtained by a method similar to that described in Example 1 (however, in place of the lactone-modified comonomer solution a of Example 1, the lactone-modified copolymer solution a) using coalescing solution f).

The obtained white mill base f was 1. Good fluidity (viscosity measured by B-ya viscosity needle (20°C) when non-volatile content is 75%: 5
voids) and dispersion stability (pigment did not settle even after storage for 6 months).

(8) Series of paints using Milbase: Example 1L
:D paint 1~! ! In #1, the above-mentioned white millbase f was used in place of the white millbase a used in each of Coating I 4. Coatings 1 to 4 were prepared in the same manner as in Example 1 (from blending raw materials to heating and drying). A uniform and smooth coating film of paint 4 was obtained.

The 60 degree specular gloss L1 of the resulting coating film was as shown in Table 5 below.

Table 5 Example 7 (1) Lactone-modified copolymer nib 2xel FM-4 (previously mentioned - 77.10 parts Example 3) Glycidyl methacrylate 500 Cyclohexyl methacrylate - 14.00 g t-butyl peroxybenzo L92#neat (example 1) A monomer mixture having the above composition was mixed with a mixed solvent (3 & 44 parts of xylene, 1 & 2 parts of butyl acetate, kept at 140°C under stirring).
2 parts) at a constant speed over 2 hours, and then stirred at 140° C. for an additional 3 hours to complete radical polymerization.

Then, 24.35 parts of xylene and 111 parts of butyl acetate
The solution was diluted with 7 parts to obtain a copolymer solution with a non-volatile content of 50 parts.

192.20 parts of the obtained copolymer solution, 190 parts of p-2l'benzoic acid, 0.25 parts of benzyldimethylamine and 165 parts of xylene were added, and after stirring at 145°C for 4 hours, the resin acid value was When the temperature reached 0.05 or less, the reaction was terminated to obtain a 2-chton modified copolymer solution g with a nonvolatile content of 5.0%.

(2) Milpase 2 A white milbase g was obtained in the same manner as described in Example 1 (however, in place of the modified copolymer solution a of Example 1, the above modified copolymer solution g was used). Using).

The obtained white millbase G has good fluidity (viscosity measured with a B-type viscometer (20°C) when the non-volatile content is 75%: 5 voids) and dispersion stability (the pigment does not settle even if stored for months). did not).

(8) A series of paints using a milbase: Same as in Example 1, except that the above-mentioned white milbase g was used instead of the white milbase a used in each of the paints L and 4 of Example 1. Uniform and smooth coating films of each of Paints 1 to 4 were obtained by the method (from blending raw materials to heating and drying).

The 60 degree specular gloss of the resulting coating film was as shown in Table 6.

Table 6 Example 8 (1) Mill base: Lactone-modified copolymer solution of Example 3 C27, 3 parts Seven long acetate 17.6# Quinacridone Red (manufactured by Hoechst 33.3 parts, Hostapalm Red EG) Above After pre-mixing the composition mixture with a disilver,
Dispersed for 24 hours in an attriter. Next, 1 part of the modified copolymer solution C6 and 15.7 parts of cellosolve acetate were added under stirring to obtain a red millbase.

The obtained ° red mill base had good fluidity (viscosity measured with a B-type viscometer (20°C) near poise when non-volatile content was 50%) and dispersion stability (pigment did not settle even after storage for 6 months). )showed that.

(2) Paint using Milbase: A paint was manufactured with the following composition.

Above red millbase 19.7 parts Example 3
White Milpace C32# Soybean oil-modified alkyd resin solution Soybean oil-modified alkyd resin solution 9.8 (Example 1 above) Butylated melamine resin solution 182# (Example 1 above) Cellosolve acetate 5. Of xylene 4.1N Paint with the above composition was coated with the thinner of Example 1 to reduce the viscosity (Ford cup +4
．． After diluting K (at 20℃ for 22 seconds), apply it to a tin plate with air spray to a dry film thickness of 40μ, and heat dry at 140℃ for 30 minutes to obtain a uniform and smooth coating with a 60℃ specular gloss of 94.0. A membrane was obtained.

Example 9 (1) Mill base: Lactone-modified copolymerization of Example 3 24.0 parts Body solution C Cellosolve acetate) 18.5 parts Yellow iron oxide (manufactured by Titan Kogyo ■, 45.0 #Mabiko Yellow Lemon) Above After pre-mixing the composition mixture with a disilver,
Dispersed for 24 hours in an attriter. Next, 0 parts of the above modified copolymer solution C6 and 6.5 parts of celonoldiacetate were added under stirring to obtain a yellow millbase.

The resulting yellow millbase has good fluidity (non-volatile content 6
The viscosity measured by a B-type viscometer at 0° C. (28 poise at 20° C.) and dispersion stability (the pigment did not settle even after storage for 6 months) were exhibited.

(2) Paint using Milbase: A paint was manufactured with the following composition.

15.3 parts of the above yellow millbase Example 3
White Milpace C3.4 # Soybean oil modified alkyd resin solution 53.2 # (Example 1 above) Butylated melamine resin solution (19.1 parts Example Cellosolve acetate xylene) After diluting the coating viscosity (Ford Cobbna 4.22 seconds at 20°C) with thinner, it was applied to a tin plate with a dry film thickness of 40 plC using air spray.
4 (Ic) for 30 minutes to obtain a uniform and smooth coating film with a 60 degree specular gloss of 94.2.

Example 10 (1) Mill base: 2-chthonic modified copolymerization of Example 3 27.3-part body solution C Cellosolve acetate 17] 6#7 Talocyanine blue (manufactured by Toyo I 33.3# Nki Urazo ■,
Lionor Plue ESP) After pre-mixing the mixture with the above composition in a disilver,
Dispersed for 24 hours in an attritor. Next, 1 part of the above modified copolymer solution C6 and 15.7 parts of cellosolve acetate were added under stirring to obtain a w-color millbase.

The resulting blue millbase has good fluidity (non-volatile content 5
Viscosity measured by a B-type viscometer at 0% (20° C. = 8 voids) φ Dispersion stability (the pigment did not settle even after storage for 6 months).

(2) Paint using Milbase: A paint was manufactured with the following composition.

White millbase C of the above blue millbase Example 3 Soybean oil-modified alkyd resin solution (example 1, above) Butylated melamine resin solution (example 1, above) Cellosolve acetate xylene Coating composition of Example 1 After diluting the coating viscosity (22 seconds at 7 ordkatuguna 4.2G'C) with thinner,
Paint the tin plate with air spray to a dry film thickness of 40μ,
Heat and dry at 40℃ for 30 minutes to achieve a 60 degree specular gloss level of 9.
A uniform and smooth coating film of 3.5 was obtained.

Example 11 (1) Mill base: Lactone-modified copolymerization of Example 3 42.7 part body solution C Cellosolve acetate 21.1# carbon black (manufactured by Mitsubishi Kasei Corporation 13.3 & Co., Ltd., carbon black 240 0B) of the above composition After premixing the mixture with DiSilver,
Dispersed for 24 hours in an attriter. Then, 10.7 parts of the above modified copolymer solution C and cellosolve acetate 1z, 2@ were added under stirring to obtain a black millbase.

The resulting black millbase has good fluidity (non-volatile content <
Viscosity measured by a B-type viscometer at 46 o'clock (20°C) = 5 poise) and dispersion stability (pigment did not settle even after storage for 6 months).

(2) Nine paints using Milbase: A paint was manufactured with the following composition.

The above black mill base 7.8 parts Soybean oil modified alkyd resin solution 61.5# (above Example 1
) Butylated melacine resin solution (Example 21.71-Example 1) - Cellosolve acetate &o #Gysilene 4. o.

After diluting the paint with the above composition with the thinner of Example 1 to a coating viscosity of 70°C (22 seconds at 20°C), it was applied to a tin plate with an air spray to a dry film thickness of 40 μkm.
Heat and dry at 0℃ for 30 minutes to achieve a 60 degree specular gloss of 95.
．． A uniform and smooth coating film of o was obtained.

Comparative Example t (1) Copolymer modified with 2 chthons: 2-Hydroxyethylmethac 20.00 parts Rylatebrene-r-8 parts MA (Nihonmae 18.30 parts manufactured by Nippon Mae Co., Ltd., above-mentioned Example 1) -1) Methyl methacrylate) 13.40#t-butylperoxybenzo 1.03#ate (previously -
Example 1) A monomer mixture having the above composition was mixed with a mixed solvent (23 parts of xylene F, 8 parts of butyl acetate) and kept at 140°C under stirring.
62 parts) at a constant speed over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then 5.06 parts of xylene and 2.53 parts of butyl acetate
A copolymer solution with a non-volatile content of 60% was obtained.

A mixture of 8,617 parts of the obtained copolymer solution, 48.30 parts of ε-capro2chton (example 1 above), 0.24 parts of a 10% xylene solution of dibutyltin dilaurate, and 8.15 parts of thelonoldiacetate was added. After stirring at 150° C. for 6 hours, the reaction was terminated when the nonvolatile content of the resin solution reached 70%. Next, xylene 57.14
A lactone-modified copolymer solution with a nonvolatile content of 50% was obtained.

(2) Mill base: Base modified with the above lactone 9.09-part coalescent solution cellosolve acetate) 13.64 #Rutile titanium dioxide (68, 18 #Example 1) A mixture of the above composition is a fluid It had poor properties, and it was impossible to mix it with a disilver or disperse it with a sand mill.

Comparative Example 2 (2) Copolymer modified with lactone: 2-hydroxyethyl meth 20.00 parts Acrylate Glycidyl methacrylate 7.50 #Prene-q-SLMA (Nihonmae 18.30 # Manufactured by Seishi ■, Example 1 above) Methyl methacrylate 43.30yt-Butylperoxybenzo 1.78 #ate (Example 1 above) A phosphor mixture having the above composition was mixed with a mixed solvent maintained at 140°C under stirring ( 29.70 parts of xylene, 14 parts of butyl acetate
85 parts) at a constant rate over 2 hours, and then stirred at 140° C. in a colander for 3 hours to complete radical polymerization.

Then, 8.71 parts of xylene and 4.36 parts of butyl acetate
A copolymer solution with a non-volatile content of 60% was obtained.

A mixture of 148.50 parts of the obtained copolymer solution, s and oo parts of ε-caprolactone (example 1), 0.24 parts of a 10% xylene solution of digtyltin dilaurate, and 309 parts of cellosolve acetate was added to 145 parts of the copolymer solution. After stirring at ℃ for 6 hours, when the nonvolatile content of the resin solution reached 60%, 5.90 parts of p-=)benzoic acid, 0.25 parts of benzyl dimethylamine and 37.02 parts of xylene were added. After stirring at 145°C for 4 hours, the reaction was terminated when the resin acid value became 0.5 or less, and the nonvolatile content was reduced to 5.
A copolymer solution modified with 0.0% lactone was obtained.

The above modified copolymer solution cellosolve acetate rutile titanium dioxide (example 1) After premixing the mixture with the above composition in a disilver,
Dispersed in a sand mill. Then, 4.55 parts of the above modified copolymer solution and 4.54 parts of cellosolve acetate were added under stirring to obtain a white millbase.

The resulting white millbase lost fluidity when it was allowed to stand for 2 days with a non-volatile content of 75%, so it was vigorously stirred with a Disilver to restore fluidity.

(Paint using grain base) A paint was manufactured with the following composition.

Above white mill base 37.20 parts Soybean oil modified alkyd resin solution 39.301 (Example 1 above)
) Butylated melamine resin solution 14.50# (Example 1 above) Cellosolve acetate 5,00 parts Xylene 4.00# Coating the paint with the above composition with the thinner of Example 1.
．． After diluting K (at 20°C for 22 seconds), a dry film thickness of 40pK was applied to a tinplate plate using air spray, and when the film was heated and dried at 140°C for 30 minutes, the modified copolymer was mixed with soybean oil-modified alyadic resin and butylated melamine. Due to lack of compatibility with resin, pigments aggregate and the 60 degree specular gloss level is 15.
．． 0 uneven and uneven coatings were obtained.

Comparative Example 3 (1) Lactone-modified copolymer: 2-hydroxyethylmethac 10. CjO part linolelate cidyl methacrylate) 2.80# Premar S LMA (Japan oil 5.00 # made by oil ■,
Example 1) t-Butyl peroxybenzo 0.36 #ate (Example 1 described above) A monomer mixture having the above composition was mixed with a mixed solvent (xylene 7 .12 parts, butyl acetate 3.5 parts
6 parts) at a constant speed over 2 hours, and the mixture was further stirred at 140° C. for 3 hours to complete radical polymerization.

Then, 4.51 parts of xylene and 2.25 parts of butyl acetate
A copolymer solution with a nonvolatile content of 50% was obtained.

3 & 60 parts of the obtained copolymer solution, ε-caprolact/
(Example 1 above) A mixture of 80.00 parts, 0.24 parts of dibutyltin dilaurate dissolved in 1096 xylene, and 23.87 parts of cellosolve acetate was heated to 150°C.
After stirring for 0 hours, the non-volatile content of the resin solution is 70%.
2-20 parts of p-nitrobenzoic acid, 0.2 parts of benzyldimethylamine and xylene s7,
After 8 parts were added and stirred at 145°C for 4 hours, the reaction was terminated when the resin acid value became 0.5 or less to obtain a lactone-modified copolymer solution with a nonvolatile content of 50%.

When the resulting lactone-modified copolymer solution was left for one day, crystals precipitated.

Procedural amendment (voluntary) S. 2, 1980 Kazuo Wakasugi, Commissioner of the Patent Office (fP Office Examiner) 1. Indication of the case 1983 Patent Application No. 48353 2. Name of the invention Thermosetting for pigment dispersion Resin 3 Relationship with the case of the person making the amendment Patent applicant 1-10-1-4 Yurakucho, Chiyoda-ku, Tokyo Amended the detailed description of the invention in the detailed description of the invention column of the specification subject to amendment as follows: do.

(1) "Cellosolve acetate xylene" on page 43, lines 4 to 5 of the specification is [cellosolve acetate], 5.0# xylene
4ON” is corrected.

(2) Page 44 of the same book, lines 11 to 18 [White Millbase C of the above blue millbase Example 3 Soybean oil modified alkyd resin solution (the above Example 1) Butylated melamine resin solution (the above mentioned Example 1) 1) Cellosolve acetate xylene” and “120 parts of the above blue millbase White millbase CI? of Example 3, 6# soybean oil modified alkyd resin solution 4
4.7 # (Example 1) Butylated melamine resin solution (Example 1) Cellosolve acetate) 5. Correct as O#xylene 4.0 #j.

(3) "The above modified copolymer solution cellosolve acetate titanium dioxide (example 1)" in lines 1 to 4 of page 50 of the same book was replaced with "the above modified copolymer solution 9.09 Part cellosolve acetate 13.64 #Rutile titanium dioxide (previously -68, l 8 #Example 1)
Correct it with J.

that's all 153-

Claims (1)

[Scope of Claims] E. Hydroxyl group-containing ethylenically unsaturated monomers 5 to 3
0% by weight, glycidyl group-containing ethylenically unsaturated monomer 2
~20% by weight, 5-50% by weight of straight chain, branched or cyclic alkyl group-containing ethylenically unsaturated monomers having 4 to 22 carbon atoms, 0 to 30% by weight of other ethylenically unsaturated monomers , a lactone-modified copolymer comprising 10 to 70% by weight of a lactone compound and 1 to 20% by weight of an aromatic compound capable of reacting with a glycidyl group. 2. The thermosetting resin for pigment dispersion according to claim 1, wherein the aromatic compound capable of reacting with the glycidyl group is p-nitrobenzoic acid. 3. The thermosetting resin for pigment dispersion according to claim 1, wherein the aromatic compound capable of reacting with the glycidyl group is p-aminobenzoic acid.