JPS6123652A - Preparation of coating resin - Google Patents

Abstract

PURPOSE:To prepare the titled resin which allows excellent pigment dispersion, is free of the amine odor, and has excellent weatherability and colorability, by the copolymerzation of a composition mainly consisting of a vinyl monomer containing amide bonds and a polyester resin containing unsaturated bonds. CONSTITUTION:0.05-10wt% vinyl monomer (A) containing amide bonds of formula I (where R1 and R2 each are H or CH3; R3 is H, a 1-12C alkyl or a group of formula II) [e.g. (meth)acrylamide], 0-5wt% vinyl monomer (B) containing phosphorus atoms {e.g. dibutyl[2-(meth)acryloyloxyethyl] phosphate}, 0.1-40wt% polyester resin (C) containing unsaturated bonds, and 45-99.85wt% other vinyl monomer (D) copolymerizable with A-C (e.g. styrene) are copolymerized in the presence of a radical generator to give a coating resin which has a ratio of the weight average molecular weight Mw to the number-average molecular weight Mn, Mw/Mn, of 2-25 and allows excellent pigment dispersion.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a new and useful method for producing a coating resin. More specifically, it mainly consists of a combination of a vinyl monomer having a specific functional group, especially an amide bond, and an unsaturated bond-containing polyester resin. In particular, it relates to a method for producing paint resins with excellent pigment dispersibility. [Conventional technology and problems to be solved] Copolymers obtained by copolymerizing vinyl monomers such as acrylic resins and vinyl acetate/acrylic resins are
JI! Although it has excellent membrane performance, it does not have good pigment dispersibility. In addition to the long time required for kneading, the pigments may separate during storage, and other troubles may occur, such as uneven coloring during toning, or difficulty in matching colors or differences in color.
These are fatal defects of the resin paint. In order to overcome these deficiencies, attempts have been made to add pigment dispersion improvers such as surfactants, silicon compounds, or organic acid metal salts during the preparation of paints; The current situation is that the level of damage remains at such a low level that it is difficult to reach the target level. In addition, various proposals have been made to improve the number dispersibility of vinyl copolymers by modifying them with polyester resins, but the dispersibility of pigments with large oil absorption such as carbon black and organic pigments and the number It is difficult to say that the dispersibility is sufficiently expanded when toning a certain mixed color using the primary colors, and therefore, when trying to improve the dispersibility by increasing the modification t, weather resistance, Yellowing and gasoline resistant. Leveling performance and spray workability will deteriorate. Furthermore, when modifying the vinyl copolymer with polyester resin, a small amount of dialkylaminoalkyl (meth)
Although other methods for improving pigment dispersibility have been proposed, such as using acrylate as an essential component or using dialkylaminoalkyl (meth)acrylate in combination with a vinyl monomer containing a phosphoric acid ester bond ( JP-A-54-62294, JP-A-57-
202354), although it is true that a resin of a higher level can be obtained using this method, the dialkylaminoalkyl (meth)acrylate tends to cause a yellowish coloration during the preparation of the resin, and the resulting resin solution has an amine odor. In addition, due to poor UV resistance, the paint film tends to yellow when exposed to UV rays, and when polyincyanate is used as a crosslinking agent component, the pot of the compounded paint There are disadvantages such as a shortened lifespan. [Means for Solving the Problems] However, as a result of intensive studies to solve the various problems in the prior art as described above, the present inventors have developed a method for producing paint resins that meets the intended purpose. Having made this discovery, we have completed the present invention. That is, 1 the present invention is an amide bond-containing vinyl monomer represented by the general formula (0 mL of
．． 05-10% by weight, phosphorus atom-containing vinyl monomer (b
0 to 5% by weight of unsaturated bond-containing polyester tree Ul
0.1-40]ii-% of del, and these (al
- (Other vinyl monomers copolymerizable with each comonomer belonging to the e1 group (45 to pq of dl, s5Mflk%).Copolymerization in the presence of a radical generator, and the number of The ratio of the weight average molecular weight (Mw) to the average molecular Ik (Mn): Mw/'Mn is in the range of 2 to 25.Provides a method for producing a resin for coating material having particularly excellent pigment dispersibility. Here, typical amide bond-containing vinyl monomers (vessels) as shown by the above CI) formula include (meth)acrylamide, dimethyl (meth)acrylamide, and N-tart-butyl ( Examples include meth)acrylamide, N-octyl(meth)acrylamide, and diacetone(meth)acrylamide, which may be used alone or in combination of two or more. The effect given is as mentioned above in Japanese Patent Application Laid-Open No. 54-62294.
It is as excellent as the sialgylaminoalkyl (meth)acrylates in the invention described in No. 2003 or JP-A-57-202354, and it is also superior to this dialkylaminoargyl (meth)acrylate. The amount of the monomer (ILl is excellent in terms of weather resistance, ultraviolet absorption resistance, amine odor, resin coloring, etc. and the upper knob) is 0.05~
10! % by weight, preferably within the range of 0.1 to 5% by weight. If the amount used is less than 0.05% by weight, it is difficult to achieve the effect of use, and on the other hand, if it is used in a large amount exceeding 10Mt%, the effect of use increases, but depending on the Putu' (for example, partially gelled product)
Both are unfavorable because they tend to generate. Next, the aforementioned phosphorus atom-containing vinyl monomer (typical examples of bl include dialkyl [(meth)acryloyloxyalkyl] phosphates or (meth)acryloyloxyalkyl acid phosphates represented by the general formula: or [ However, R1, R4 and RII in the formula are as described above. Examples include dialkyl [(meth)acryloyloxyalkyl]phosphites or (meth)acryloyloxyalkyl acid phosphites represented by Furthermore, alkylene oxide adducts of each of the above-mentioned (meth)acryloyloxyalkyl acid phosphates or acid phosphites; Examples include esterified products with these acidic esters; or 3-chloro-2-acid phosphoxypropyl (meth)acrylate, among which dibutyl [2-(meth)acryloyloxyethyl phosphite, diphenyl [ 2-(meth)acryloyloxyethyl phosphate), 2-(meth)acryloyloxyethyl acid phosphate, 2-(meth)acryloyloxyethyl acid phosphate, 2
-(meth)acryloyloxyethyl phosphite, 2
Particularly preferred are -(meth)acryloyloxyglobyl acid phosphite, glycidyl (meth)acrylate Φ phosphoric acid adduct, or 3-chloro-2-acidophosphoxyglobyl (meth)acrylate. The amount of the phosphorus atom-containing vinyl monomer (bl) used is suitably within the range of 0 to 5% by weight. Thus, in the present invention, the monomer (bl
Even if it is not used at all, it can be graft-modified using the unsaturated bond-containing polyester resin (alt-) so that the paint resin F/6 ratio, which is the target product of the method of the present invention, is within the range of 2 to 25. If it is possible to improve the pigment dispersibility, which is one of the objects of the present invention, it is still possible to improve the pigment dispersibility, which is one of the objectives of the present invention, but it is still necessary to increase the pigment concentration for pigments such as azo, quinacridone, or phthalocyanine pigments. When turning paint into a paint under somewhat harsh conditions, such as when the paint is exposed, there are cases where the dispersibility is still insufficient.
In order to further increase the level of dispersibility, it is preferable to use the phosphorus atom-containing vinyl monomer (bl'ii).In addition, by using the monomer (bl'ii), it is possible to improve adhesion, corrosion resistance, hardenability, etc. If the amount of the monomer (Cl) used exceeds 5% by weight, the stability of the paint, especially the storage stability of the paint when a crosslinking agent component is used, that is, the pot life Otherwise, it is not preferable because it tends to cause some problems in resin appearance, resin viscosity, etc. In addition, as the above-mentioned unsaturated bond-rich polyester resin Kcl, so-called alkyd resin modified with oil or fatty acid, or Among the so-called oil-free alkyds that have not been modified with these materials, those containing ethylenically unsaturated bonds that are copolymerizable with vinyl monomers are suitable, and polyester resins containing such unsaturated bonds are suitable. Typical examples include JP Publication No. 44-7134, No. 45-22011, No. 46-20502, and JP-A No. 48-1972.
-78235 and 50-58123, etc., raw material components having copolymerizable unsaturated bonds are essential, and these unsaturated bonds are created in the resin skeleton by reacting with other raw material components. It is said that it was held in the possession of the government, or that the
As described in Japanese Patent No. 225, etc., once a saturated polyester having no copolymerizable unsaturated bonds is obtained, functional groups such as hydroxyl groups and/or carboxyl groups (polar A compound having a functional group (polar group) that is reactive with the epoxy group (polar group) and a copolymerizable unsaturated bond (vinyl group), for example, a compound having an epoxy group and a vinyl group such as glycidyl (meth)acrylate. A monomer having an alkoxysilanol group and a vinyl group such as silane, vinylmethoxysilane or (meth)acryloyloxyethyltrimethoxysilane 1 A monomer having an acid anhydride group and a vinyl group such as maleic anhydride, or 2-hydroxy ( A monomer having an incyanate group and a vinyl group, such as an equimolar adduct of meth)acrylate-hexamethylene diisocyanate, is added to a saturated polyester to similarly have unsaturated bonds in the resin skeleton. The mel in the unsaturated bond-containing polyester is mainly used to adjust the My/R ratio, and the above-mentioned amide group-containing vinyl monomer (along with ml is an essential component for improving pigment dispersibility). However, the monomer (cl) includes saturated fatty acids such as octylic acid, lauryl acid, stearic acid or "persatic acid" (synthetic branched fatty acids manufactured by Shell in the Netherlands); oleic acid, linoleic acid, liluic acid, Unsaturated fatty acids such as eleostearic acid and ricinoleic acid; "PAMOLYN"
200 or 300J (synthetic drying oil fatty acid manufactured by Vercules, USA). Chinese tung oil (fatty acid), linseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid)
(semi-)drying oils (fatty acids), such as soybean oil (fatty acids), olive oil (fatty acids), safflower oil (fatty acids), castor oil (fatty acids) or rice bran oil (fatty acids); or hydrogenated coconut oil (fatty acids); Coconut oil (fatty acid) or non-drying oil (fatty acid) such as balm oil (fatty acid) can be used to produce ethylene with or without the use of 1m or a mixture of two or more of various oils or fatty acids. glycol,
Propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,2. <One or more polyhydric alcohols such as S-hexanetriol, pentaerythritol or nrubitol, and benzoic acid, p-t@rt-butylbenzoic acid, (anhydrous) phthal'r 11% hexahydro (anhydrous) Futar! I,
Te) Lahydro (anhydrous) Tsutarumi 2. Hexachlorophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, Himic acid [endomethylenetetrahydrophthalic anhydride manufactured by Hitachi Chemical @], (anhydrous) moss <WIl, (anhydrous) maleic acid, Humar'WR, (
anhydrous) with one or more polyhydric carboxylic acids such as itaconic acid, adipic acid, sepatic acid or oxalic acid, and if necessary, "Cardura E-1".
Monoepoxy compounds such as 04 (manufactured by Shell, Netherlands; glycidyl esters of fatty acids). "Evicron 200 or Iguha 400J (epoxy resin manufactured by Dainippon Ink and Chemicals)" or "Epicoat 828"
or polyepoxy compounds such as 1001J (epoxy resin manufactured by Shell, Netherlands) or diincyanates such as tolylene diisocyanate, hexamethylene diisocyanate, inholone diisocyanate or 4,4'-methylenebis(cyclohexyl isocyanate). , polyisocyanates (incyanate prepolymers) obtained by the addition reaction of these diisocyanates with polyhydric alcohols such as dyes and water, or incyanur obtained by (co)polymerization of diincyanates with each other. Typical examples include those obtained by replacing a part of the polyhydric alcohol or carboxylic acid mentioned above with one type of polyisocyanate having a ring or a ring-containing polyisocyanate or a ring-containing polyisocyanate of 2 m or more, and reacting it in a conventional manner. Polyester resins (so-called alkyd resins) that have no copolymerizable unsaturated bonds in the resin skeleton or are modified with saturated fatty acids or non-drying oils (fatty acids), semi-drying oils or A type of polyester resin that has not been modified with these fatty acids (so-called oil-free alkyd resin) contains % copolymerizable unsaturated bonds that serve as grafting points for vinyl monomers (anhydrous) and unsaturated polycarbonate such as maleic acid or fumaric acid When an acid is used to contain the polyester, or when a vinyl monomer having a functional group (polar group) is added to a saturated polyester as described above to introduce a copolymerizable unsaturated bond. The amount of the compound used as a source of copolymerizable unsaturated bonds is 1.
At the time of the subsequent graft copolymerization, the mixture became cloudy and thickened. Alternatively, considering the risk of gelation, it is preferably selected within a range of 0.1 to 10% by weight, particularly 0.5 to 5% by weight. When such unsaturated fatty acids are obtained only from unsaturated fatty acids or (semi-)drying oils (fatty acids), 5
It is preferable to use it in a range of 15 to 70% by weight, in particular 15 to 70% by weight, in view of the risk of cloudiness, thickening or gelation. Furthermore, in the case of using both of the above-mentioned methods together, it goes without saying that the optimum conditions may be selected according to the respective usage ranges. Then, the unsaturated bond-containing polyester tree Jffde
When using +, it is difficult to improve pigment dispersibility when it is less than 11% by weight, and conversely, when it exceeds 40% by weight, pigment dispersibility improves, but hardness, weather resistance,
It is unfavorable in terms of yellowing, solvent resistance, stain resistance, etc. Therefore, 0.5 to 3 of 01 to 40% by weight 1
It is preferably within the range of 0%. Further, as mentioned above, the seeding ratio of the copolymer resin obtained by the method of the present invention is adjusted by copolymerizing the unsaturated polyester resin (Cl), and this ratio is When the ratio is less than 2, the pigment dispersibility cannot be improved at all, and conversely, when this ratio exceeds 25, the pigment dispersibility is not improved to a certain extent, and it is more likely that the coating workability and dilutability will be improved. Both of these are undesirable since they tend to cause problems in terms of non-volatile content and pot life during coating. Therefore, the M←46 ratio is within the range of 2 to 25, more preferably 3 to 20. However, in order to keep it within this range, the ratio of the relatively high molecular weight part to the relatively low molecular weight part (the relative amount and the absolute amount of each are major factors) Therefore, the important point is how to create these two subcomponents.In order to do so, it is important to consider the degree of reactivity in the reaction process that mainly produces high molecular weight parts and the reaction process that mainly produces low molecular weight parts. In general, in order to obtain a tree Kel mainly in the high molecular weight range, it is achieved by carrying out the reaction at a low initiator concentration and a high monomer concentration; In carrying out the method of the present invention, it is possible to obtain a molecular weight range tree by conducting the reaction under conditions opposite to the above, with a low monomer concentration and a high initiator concentration. Therefore, these reaction conditions can be adjusted to the desired MW/
It is sufficient to select five combinations as appropriate depending on the fn ratio. Furthermore, other copolymerizable vinyl monomers (
The appropriate amount of di to be used is within the range of 45 to 9985% by weight.Representative examples of the vinyl monomer (dl) include the following: +11 Styrene, α-methylstyrene sPta
Aromatic vinyl monomers such as vinyltoluene, (11) methyl (meth)acrylate, ethyl (methane acrylate), n-70 pyl (meth)acrylate,
1so-propyl (meth)acrylate, n-butyl (meth)acrylate, 1so-butyl (meth)acrylate, t@rt-butyl (meth)acrylate, 2-
Ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dipromoglovir (
(meth)acrylates such as meth)acrylate, tribromophenyl (meth)acrylate or alkoxyalkyl (meth)acrylate; unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid;
Diesters with alcohol: Vinyl esters such as vinegar-vinyl, vinyl benzoate or “Beoba” (vinyl ester manufactured by Shell, Netherlands); “Visco” 8
F, 8FM, 3F4 or 3FMJ (fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical ■), perfluorocyclohexyl (methane acrylate, diperfluorocyclohexyl fumare) 1 fcId N -1@o-
Provil perfluorooctane sulfonamidoethyl (
(bar)fluoroalkyl group-containing vinyl esters, vinyl ethers, (meth)acrylates, etc.
Fluorine-containing compounds such as acrylates or unsaturated polycarboxylic acid esters; or containing functional groups (polar groups) such as olefins such as (meth)acrylonitrile, vinyl chloride, vinylidene chloride, vinyl butoxide, or vinylidene butoxide. vinyl monomers, 0++1 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-
Hydroxypropyl (methanoacrylate, 2-hydroxybutyl

[Methacoacrylate, 3-hydroxybutyl (meth)acrylate, 4-human tetraxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl 7maleate% 7-hydroxyethyl hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as rumonoptyl malate or polyethylene glycol mono(meth)acrylate; [meth)acrylic acid;
unsaturated mono- or dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, as well as α,β-ethylenically unsaturated acids such as monoesters of these unsaturated dicarboxylic acids and m alcohols; Saturated carboxylic acids, hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as deficiencies, maleic acid, succinic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid Acid - ``Himikjo'', tetrachlorophthalic acid or dobu V = 'b5 licorice like succinic acid''
yj (anhydride of 7 acids and 0 (adduct), in addition to F Cardura E-10J, -? or a compound obtained by adding a monoepoxy compound such as propylene oxide; a methylol group-containing compound such as N-methylolated acrylamide; or a hydroxyl group-containing vinyl monomer such as hydroxyethyl vinyl ether; Qvl (meth)acrylic acid as described above. α, β-ethylenically unsaturated mono- or dicarboxylic acids such as , crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid, and monoesters of these dicarboxylic acids with m alcohols. , β-unsaturated carboxylic acids; or adducts of various α,β-unsaturated carboxylic acid hydroxyalkyl esters as listed above and anhydrides of polycarboxylic acids as listed above; -, (Vl Glycidyl (meth)acrylates listed above, (
β-methyl)glycidyl(meth)acrylate or (
meth)allyl glycidyl ether; or mono-2-
(Molecular adducts of the above-mentioned hydroxyl group-containing vinyl monomers, such as methane acryloyloxymonoethyl phthalate, and the above-mentioned polycarboxylic acid anhydrides, and various unsaturated substances such as the above-mentioned α, β-ethylenically unsaturated carboxylic acids) To the carboxylic acid, [Epicron 200, 4001441.850 or 1050J (1?ff output), U epir-) 828
．． 1001 or 1004J (mentioned above), Araldite 6o71 Mogha (SO84J (epoxy resin manufactured by Ciba Geigy, West Germany), r Chissonox 221
Addition of various polyepoxy compounds having at least two epoxy groups in one molecule such as J (an epoxy compound manufactured by Chisso ■) or Denacol EX-611J (an epoxy compound manufactured by Nagase Sangyo ■) in an equimolar ratio. Epoxy group-containing vinyl monomers obtained by the reaction, and silyl group-containing vinyl monomers such as (VD vinyl ethoxysilane or r-methacryloyloxyglobyltrimethoxysilane). Other vinyl monomers (dl are the above-mentioned amide bond-containing vinyl monomers (!L), phosphorus atom-containing vinyl monomers (bl), and unsaturated bond-containing polyester resins (cl) and copolymerization and From the physical properties of paints or coatings such as properties, workability, gloss, flexibility, hardness, weather resistance, drying properties, solvent resistance, abrasion resistance, compatibility, dilutability, or glass transition temperature, As mentioned above, it may be determined as appropriate within the range of 45 to 9985% by weight.However, only the carboxyl group-containing vinyl monomer may have an influence on properties such as resin viscosity, water resistance, or alkali resistance, or may be used on amino resins or The balance between storage stability and curability when using a crosslinking agent component such as polyincyanates, where the presence of carboxyl groups affects the storage stability of the paint system when it is made into a paint. Considering this, the appropriate amount of the carboxyl group-containing vinyl monomer to be used is within the range of 11 to 10% by weight, more preferably 0.5 to 5% by weight. Alternatively, when an aromatic vinyl monomer such as vinyltoluene is used, and the resulting coating film is required to have weather resistance or yellowing resistance, the amount of the aromatic vinyl monomer used is 50% It should be kept at less than 40% by weight, preferably less than 40% by weight.The method of the present invention can be carried out by making full use of known and commonly used graft copolymerization reaction methods using each of the comonomers listed above. Often, at that time, azobisin butyronitrile (AI
BN), benzoyl peroxide (BPO), tert
-Butyl perbenzoate (TBPB), tart-
Butyl hydroperoxide, di-t@rt-butyl peroxide (DIBpo)'! One or more radical generators such as cumene hydroperoxide (cup) are used. In addition, when carrying out the method of the present invention, toluene, xylene,
Aromatic hydrocarbons such as 00J [Maruzen Oil ■ products]; n
- aliphatic or cycloaliphatic hydrocarbons such as hexane, heptane, octane, mineral spirits, methylcyclohexane, ethylcyclohexane, Φsan, Tahar rLAWsJ (product of Shell, Netherlands); methanol, ethanol,
Alcohols such as 1ao-glopanol, butanol, igo-butanol, ethyl cellosolve or butyl cellosolve; ethyl acetate, butyl acetate, vinegar H-1aa
- esters such as butyl, selonlupe acetate or 5-methoxybutyl acetate; or acetone,
Solvents such as ketones such as methyl ethyl ketone, methyl-1so-butyl ketone, or cyclohexanone can be used; however, when polyincyanates are used as the crosslinking agent component, alcohol-based solvents cannot be used. Of course. In this way, the paint resin obtained by the method of the present invention can be mixed with a desired crosslinking agent component and used as a crosslinked paint, or it can be used as a so-called lacquer type paint without using any crosslinking agent component. It can also be used as a paint. Examples of materials that can be used as such crosslinking agent components include polyincyanates, amino resins, epoxy W,
All known and commonly used crosslinking agents such as phenolic resins and metal chelate compounds can be used, and these crosslinking agents can be used alone or as a mixture of two or more in conventional amounts. If desired, the coating resin obtained by the method of the present invention may include nitrified cotton, cellulose compounds such as trocellulose (NO) or nitrocellulose acetate butyrate (CAD), alkyd resins, polyester resins, silicone resins, or other acrylic resins or chlorinated polyolefins, or plasticizers, pigment dispersants, leveling agents,
Various known and commonly used coating additives such as ultraviolet absorbers, antioxidants, and curing accelerators can also be blended in conventional amounts. [Applications of the present invention] The paint thus obtained can be applied by known and commonly used methods such as spray painting, roll painting, brush painting, etc. However, the paint resin produced by the method of the present invention can be applied to automobiles, automobiles, etc. For repairs, for large vehicles, for building exteriors, for bridges,
It can be applied to floors, plastics, paper, alternate layers, home appliances, inorganic materials, plants, etc., depending on the type of crosslinking agent and curing conditions, or without using a crosslinking agent. It can be deployed in a wide range of application fields. It goes without saying that the modified vinyl copolymer obtained by the method of the present invention can be used for clear paints that do not use pigments, or for enamel paints that use pigments. [Example] Next, the present invention will be specifically explained using reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, parts and percentages are all based on weight unless otherwise specified. shall be. Reference example 1 [Unsaturated bond-functionalized polyester resin (el
Preparation example] In a four-way flask equipped with a stirrer, a thermometer, a reaction product water removal device, and a nitrogen gas inlet tube, 382 parts of dehydrated castor oil fatty acid, 5 parts of maleic anhydride, and 64 parts of phthalic anhydride were added.
9 parts, 134 parts of neopentyl glycol, 98 parts of trimethylolpropane, 100 parts of pentaerythritol
1 part and 0.005 part of an antifoaming agent were charged, the temperature was raised to 180°C, maintained at the same temperature for 2 hours, and heated to 22°C over 3 hours.
The temperature was raised to 0°C, maintained at the same temperature under a nitrogen atmosphere until the acid value became 9 or less, and then cooled.
) is about 50%, and NY is 5%.
Gardner viscosity (G, V
A solution of a dehydrated castor oil-modified unsaturated polyester resin having LM, an acid value (Av) of 5.0, a hydroxyl value (OHM) of 45f, and a copper oil length of 40% was obtained. Hereinafter, this will be abbreviated as resin (c-1). Rust example 2 (same as above) 92 parts of soybean oil fatty acid, 100 parts of safflower oil fatty acid, 464 parts of phthalic anhydride, 212 parts of neopentyl glycol, 102 parts of trimethylolpropane, 100 parts of pentaerythritol and antifoaming. In the same manner as in Reference Example 1, except that 0.005 part of the agent was used as the raw material for preparation,
NY is 5 parts 0%, G, Vim, O, AV is 4.0,
O) A solution of an unsaturated polyester tree Mel modified with soybean oil fatty acid and safflower oil fatty acid with a LM of 70 and an oil length of 40% was obtained. Hereinafter, this resin (e-2
). Reference example 3 (same as above) 513 parts of isophthalic acid, 19 parts of maleic anhydride, 106 parts of adipic acid, 391 parts of neopentyl glycol
81 parts of trimethylolpropane, 30 parts of pentaerythritol, and 0.005 parts of an antifoaming agent were used as raw materials, and toluene/ethyl acetate = 5 parts as a diluting solvent.
0750 (weight ratio) was used in the same manner as in Reference Example 1, except that NY was 50.0%,
G, Vlg, is N, AV is 4.2, and OUV is 6
A solution of unsaturated bond-containing polyester 7 (mM C) was obtained. Hereinafter, this will be abbreviated as resin (c-3). Reference Example 4 (Same as above) In a flask similar to Reference Example 1, 200 parts of phthalic anhydride, 208 parts of adipic acid, and 4 parts of neopentyl glycol were added.
16 parts of trimethylolpropane, 51 parts of trimethylolpropane, and 0.005 parts of an antifoaming agent were charged, and the temperature was raised to 160°C, and when the same temperature was reached, the temperature was further raised to 180°C over 3 hours until this temperature was reached. After holding for 6 hours, the temperature was raised to 220°C over 2 hours and held at this temperature until the acid value became 6 or less. When the predetermined acid value was reached, the temperature was lowered to 60°C, and while maintaining this temperature, 600 parts of butyl acetate and 6 parts of diptyltin dilaurate were added and homogenized.
Gradually add 200 parts of inphorone diisocyanate over 2 hours while being careful not to generate heat, then hold at 60°C until the viscosity becomes constant, then add 10 parts of maleic anhydride. After that, the temperature was raised to 120°C and maintained at this temperature for 1 hour. After that, after cooling the temperature a little, xylene was added so that NY was about 50%, and NY was 50.1%, G, V.
A solution of a polyester resin (ol) with ig, P, AM of 7.5 Te, and oHv of 115 was obtained. Hereinafter, this will be abbreviated as resin (e-4). Reference Example 5 (Same as above) ) In a flask similar to Reference Example 1, 200 parts of coconut oil fatty acid, 484 parts of isophthalic acid, 355i of neopentyl glycol, 56 parts of MU methylolpropane, 30 parts of pentaerythritol, and 0.005 parts of antifoaming agent were added. The temperature was raised to 160°C, and then to 180°C for another 3 hours.
After raising the temperature to 230° C. and maintaining the same temperature for 3 hours, the temperature was further raised to 230° C. over 2 hours. The temperature was maintained at 230°C until the acid value became 10 or less, and when the predetermined acid value was reached, the temperature was lowered to 100°C, and 400 parts of butyl acetate, 10 parts of γ-methacryloyloxyethyltrimethoxysilane, and methyl 0.02 parts of etherified hydroquinone and 0.00 parts of dibutyltin dioctoate
After adding 1 part and keeping it at 100℃, NY is about 50%
Add toluene to make it 498% NY, G,
A solution of a coconut oil fatty acid-modified unsaturated polyester resin (Cl) with Vim, N-0, AV of 4.0, 0), LV of 79, and cut oil length of 20 was obtained. a
-5). Example 1 100 parts of resin (e-1) and 30 parts of toluene were added to a four-eye flask equipped with a thermometer, a stirrer, and an inert gas inlet tube.
0 parts and 400 parts of butyl vinegar and 300 parts of styrene
Department. 200 parts of methyl methacrylate, 10 parts of diacetone acrylamide, 100 parts of n-butyl methacrylate, 180 parts of n-butyl acrylate, 150 parts of 2-hydroxyethyl methacrylate, 8 parts of methacrylic acid and 2-methacryloyl oxyethyl 250 parts of 950 parts of a monomer mixture consisting of 2 parts of acid phosphate, 2 parts of tert-butyl peroctoate, and 2 parts of BPO were charged and the temperature was raised to 110°C, while being careful not to generate heat. 700 parts of the residual monomer mixture, 10 parts of tart-butyl peroctoate, 6 parts of DTBPO, and 17 parts of toluene.
A mixture of 5 parts and 75 parts of butyl acetate was added dropwise over 4 hours, maintained at the same temperature for an additional 4 hours, and then raised to 115°C over 30 minutes.
Hold for a time, NV is 50.1%, G, Vlm. A coating resin solution with no amine odor and having U, AV of 3.0, OHV of 38, Gardner color CG, C,) of 1 or less, and island Vπn of 8.2 was obtained. Example 2 In a flask similar to Example 1, 600 g of resin (e-2) was added.
100 parts of xylene, 5 parts of acrylamide and 100 parts of lso-butyl acetate, 500 parts of methyl methacrylate, 200 parts of n-butyl methacrylate, 85 parts of lll0-butyl meth/')ate, 2-human 200 parts of 695 parts of a monomer mixture consisting of 50 parts of xyethyl methacrylate, 50 parts of 2-hydroxyethyl acrylate and 10 parts of 2-methacryloyloxypropyl acid phosphate, and t@r
2 parts of t-butyl peroctoate and 1 part of BPO were charged, the temperature was raised to 90°C, maintained at this temperature for 1 hour, then raised to 110°C over 1 hour, and kept at this temperature for 3
After holding for 0 minutes, remaining 495 parts of the seven-summer mixture;
A mixture consisting of 3 parts of AIBN, 5 parts of tart-butyl peroctoate, 5 parts of TBPB, and 200 parts of 1so-butyl acetate was added dropwise at 110°C over 4 hours, and after the addition was completed, It was kept at the same temperature for 15 hours, and then 100 parts of "LAWS" and 10 parts of "Tsurupets"
Add 200 copies of "0", 1, NY 5 copies 6%, G, V
is, KaX-Y. A paint tree N with no amine odor was obtained with AV of 18, OHM > (47, G, C1 of 1 or less, and IM of 46 of 19.8. Example 3 Same as used in Example 1 into the flask, resin (e-3)
40 parts of xylene, 200 parts of xylene and 48 parts of butyl acetate
0 parts, 200 parts of styrene, 200 parts% of methyl methacrylate, 100 parts of n-butyl methacrylate, 1
110 parts of 8o-butyl methacrylate, N-tart
-20 parts of butyl acrylic amide, 101 parts of n-butyl acrylate, 224 parts of 2-hydroxyethyl methacrylate, 15 parts of mono(2-hydroxyethyl) monomethacryloyloxyethyl phthalate, 8 parts of methacrylic acid and 2 parts of - 2-part heptamer mixture of acryloyloxyethyl acid phosphate 98
0 parts, 2 parts of tert-butyl peroctoate, and 1 part of BPO were charged, heated to 90°C, kept at this temperature for 1 hour, and then heated to 120°C over 30 minutes. Raise the temperature and hold at this temperature for 30 minutes, then add the remaining 600 parts of the monomer mixture, 1 part of tsrt-butyl peroctoate, 3 parts of AIBN and D
A mixture consisting of 2 parts of TBPO and 300 parts of xylene was dropped at 120°C over 4 hours, and after the completion of the dropwise addition, about 15 parts of xylene remained.
Hold time, NY, dJ50.8%, G, Vltl
, dfW-X, AM, $50, OHV is 56, G
, C, was 1 or less, and M←4c was 6.1, and a coating resin free from amine odor was obtained. Example 4 In a flask similar to Example 1, 400 g of resin (e-s) was added.
300 parts of styrene, 2 parts of methyl methacrylate
00 parts of ethyl acrylate, 188 parts of ethyl acrylate, 100 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylamide, 9 parts of methacrylic acid and 1 part of 2-methacryloyloxyethyl acid phosphite. 400 parts of xylene, 200 m of xylene, 100 parts of luene,
and 200 parts of butyl acetate, and 200 parts of BPO.
1 part, 0.5 parts of tart-butyl peroctoate and 0.5 parts of AIBN were charged, the temperature was raised to 90°C, maintained at this temperature for 1 hour, and then raised to 120°C over 1 hour. After holding the lever temperature for 30 minutes, 800 parts of the remaining monomer mixture and 200 parts of butyl acetate are added.
and 14 parts of tart-butyl peroctoate, D
A mixture of 5 parts of TBPO and 3 parts of AIBN? : Dropped over 4 hours, kept INK at the same temperature for about 15 hours after dropping, NV was 51.0%, G, Vim,
A coating resin solution with no amine odor was obtained, which had a coefficient of X, AV of '5.8, an OHV of 39, a coefficient of G, C, a coefficient of less than 1, and a coefficient of KMy/Mn of 98. Example 5 In a flask similar to Example 1, 200 g of resin (c-3) was added.
Part zero ε1 305 parts of styrene, 110 parts of n-butyl methacrylate, 25 parts of tart-butyl methacrylate
0 parts of N-1so-probilverfluoro-tetraoctanesulfonamide ethyl methacrylate, 60 parts of 2-ethylhexyl acrylate, 80 parts of 2-hydroxyethyl acrylate, 35 parts of monomethacryloyloxyethyl phthalate and 4 out of 100 parts of a monomer mixture consisting of 10 parts of acetone acrylamide
00 parts, 300 parts of xylene and 20 parts of butyl acetate.
0 part, 1 part of BPO, and 1 part of tsrt-butyl peroctoate were charged, the temperature was raised to 90°C, maintained at this temperature for 1 hour, and then raised to 120°C over 1 hour. After holding at temperature for 30 minutes, subsequently add 700 parts of the remaining monomer mixture, 200 parts of xylene and 200 parts of butyl acetate,
3 parts of IBN, 8 parts of tart-butyl peroctoate
A mixture of 1 part and 2 parts of DTBPO was added dropwise over 4 hours, and the temperature was kept at the same temperature for about 16 hours after the addition was completed.
NY is 51.0%, G, VisJfV -W, AM
is 3.5, and OHv is 30. A coating resin solution with no amine odor and having G and C' of 1 or less and 12.1 was obtained. Example 6 In a flask similar to Example 1, 300 g of resin (c-4) was added.
parts, 600 parts of styrene, and 2 parts of methyl methacrylate.
00 parts, 50 parts of 1so-butyl methacrylate, N-
50 parts of octylacrylamide, “Viscoat 8FJ
5 (65 parts of 1,1so-butyl acrylate, 2-
545 parts of 145 parts of a monomer mixture t consisting of 100 parts of hydroxyethyl acrylate and 30 parts of diptyl (2-methacryloyloxy) phosphate, 5 parts of fumaric acid, 200 parts of xylene and 350 parts of butyl acetate, One part of BPO and one part of tsrt-butyl peroctoate were charged and the temperature was raised to 90°C.
Hold at the same temperature for 1.5 hours, then increase to 30 minutes to 220°C.
and held at the same temperature for 30 minutes, followed by adding the remaining 600 parts of the monomer mixture, 300 parts of xylene, BP
5 parts of O, 15 parts of tart-butyl peroctoate and TBPB (2)! 1 part of the mixture was added dropwise over 6 hours, and the temperature was kept at the same temperature for about 15 hours after the addition was completed. %VVS20.1 'A, G, Vim,
4. ! A solution of a coating resin without amine odor was obtained, with l, OHV of 53, G, C9 of 1 or less, and 4G of 15.2. Example 7 In a flask similar to Example 1, 16 parts of resin (c-5), 100 parts of methyl methacrylate, 100 parts of n-butyl methacrylate, 32 parts of n-butyl acrylate
parts, [75 parts of Cardura B-10J, 50 parts of 2-hydroxyethyl acrylate and 10 parts of diphenyl (2-methacryloyloxyethyl phosphate);
1 part of BPO and 1 part of tsyt-butyl peroctoate and 600 parts of xylene and 30 parts of butyl acetate.
0 parts of methyl methacrylate, heated to 90°C, held at this temperature for 30 minutes, then heated to 120°C over 30 minutes and held at this temperature for 3 parts, then 290 parts of methyl methacrylate, 200 parts of n-butyl methacrylate,
50 parts of 2-hydroxyethyl acrylate, 2 parts of N-dimethylacrylamide, 25 parts of methacrylic acid, 8 parts of acrylic acid, 48 parts of diphenyl (2-methacryloyloxyethyl) phosphate, and glycidyl methacrylate phosphoric acid. A mixture of 2 parts of the isothyl adduct, 200 parts of xylene, 6 parts of TBPB, and 12 parts of tert-butyl peroctoate was added dropwise over 4 hours, and the temperature was maintained at 120°C for 2 hours after the addition was completed. Then BF
, - A mixture of 0.1 part of ethyl etherate and 2 parts of butyl acetate is added and held for about 15 hours to form a mixture of N
V is 495%, G, Via, Y-21A■ is 3.2
, OHv is 40, G, C, is 1 or less, and M→
A coating resin solution with no amine odor and having 4b of 3.2 was obtained. Example 8 NY was 5Q, 1
%, G, Vim, KaW-X, AV is 2.8, OHV
is 56, G, C. was 1 or less, My/Mn was &0, and there was obtained a coating resin solution free from amine odor. Comparative example 1 tlHN (e-1) O100@O'f'iゎDvc,
2-:)'. (using 10.5 parts of methyl methacrylate and 39.5 parts of styrene, 25 parts of toluene and 25 parts of butyl acetate, and 2 parts of 2-methacryloyloxyethyl acid phosphate and 10 parts of diacetone acrylamide) In place of
2 parts of methacrylic acid and 1 part of n-butyl acrylate
NY was 50.0 parts in the same manner as in Example 1 except that 0 parts were used. G, Vig, is T-U, A
V is 2.9, OHV is 38, G, C0 is 1 or less,
A comparative coating resin solution having a symptom 4i of 1.6 was obtained. Comparative Example 2 98 parts of 2-hydroxyethyl methacrylate was used instead of 600 parts of resin (e-2) and 5 parts of acrylamide.
parts, 100 parts of methyl methacrylate, 107 parts of n-butyl methacrylate, 100 parts of LAWSJ, 100 parts of xylene, 100 parts of xylene and 1s of acetic acid.
Except that 100 parts of o-butyl was used and the same amount of methacrylic acid was used in place of 10 parts of 2-methacryloyloxyglopyl acid phosphate.
Similarly to Example 2, NY is 50.2. G, Vi
s, is Y-2s AV2>”3.5.0RV2>147
Thus, a comparative I# resin solution for paints with G and C0 of 1 or less and y-4C of 19 was obtained. Comparative Example 3 In place of 40 parts of resin (e-!+), 7 parts of 2-hydroxyethylethyl methacrylate, 13 parts of styrene and 20 parts of xylene were used, and 20 parts of N-tart-butylacrylamide. and 1s instead of 2 parts of 2-acryloyloxyethyl acid phosphate
The same procedure as in Example 6 was carried out except that 20 parts of o-butyl acrylate and 2 parts of acrylic acid were used.
2. OHv is 56, G, C, Ji or less, and symptom-4
A comparative coating resin solution in which 6 was 15 was obtained. Comparative Example 4 In place of 400 copies of 111MEfl (c-4),
Using 107 parts of 2-hydroxyethyl methacrylate, 96 parts of styrene, 100 parts of "Nrupetso 100" and 100 parts of butyl acetate, 2 parts of Kumecutiumide and 1 part of 2-methacryloyloxyethyl acid phosphate were combined. In the same manner as in Example 4, except that 2 parts of methyl acrylate and 1 part of methacrylic acid were used instead, NY was 50.6%, G, Vis, KaV-W, AM
is 3.7. A comparative coating resin solution having an OHM of 39, G, C, and 1 or less and wig waste of 18 was obtained. Comparative Example 5 31 parts of 2-hydroxyethyl methacrylate, 69 parts of styrene and 100 parts of xylene were used instead of 200 parts of resin (e-5), and the same amount of p was used instead of 10 parts of diacetone acrylamide. The procedure was the same as in Example 5 except that n-butyl methacrylate was used, NY was 50.5%, G and Vim were U, AV was 3.3,
A comparative paint resin solution with an OHV of 30T, G, C, and 1.3 was obtained. Comparative Example 6 In place of 300 parts of mM'ft (c-4), 80 parts of 2-hydroxyethyl methacrylate, 7 parts of styrene/
0 parts and 150 parts of xylene, and 50 parts of N-octylacrylamide and 30 parts of dibutyl (2-methacryloyloxyethyl) phosphate were replaced with 80 parts of n-butyl acrylate. Except for this, NY was 50.3% as in Example 6.
@G, Vi g, is v-W, AV is 4.2, O
A comparative coating resin solution was obtained in which HV was 53, G and C0 were 1 or less, and MW/Mn was 17. Comparative Example 7 Instead of 16 parts of resin (c-5), 6 parts of 2-hydroxyethyl methacrylate, 5 parts of methyl methacrylate
In the same manner as in Example 7, NY was 499%, G- Vig, GA, AV Ka3.2
, OHv was 40, G, C, was 1 or less, and 6-chip was 1.3. A comparative paint resin solution was obtained. Comparative Example 8 Same as Example 8 except that 7 parts of 2-hydroxyethyl methacrylate, 13 parts of styrene, and 20 parts of xylene were used instead of 40 parts of mN(c-s). TENY Ka50.3%, G, Vig,
A resin solution for a paint for comparison was obtained, which had F, AV and F of 2.8, OHV of 56, G and C0 of 1 or less, and F of 0V5r7'Mn of 14. Comparative Example 9 NV was 50.6%, Q, V in the same manner as Example 5 except that the same amount of dimethylaminoethyl methacrylate was used instead of diacetone acrylamide.
im, 'l)" sAV is &3, OHM is 30, G,
A comparative coating resin solution having an amine odor and having a Kap Mw/Mn of CJf5-t' of 116 was obtained. Comparative Example 1O Example 7 except that the same amount of diethylaminoethyl methacrylate was used in place of N-dimethylacrylamide.
Similarly, if NV is 5 [10%, G, Vig-ka Z-
Z1, AV is 50, OHV is 40, G-CJ (,5
Thus, a comparative coating resin solution with an amine odor in which Ka6l2>Z6.0 was obtained. Reference Example 6 (Example of Preparation of Unsaturated Dicarboxylic Diester) 116 parts of fumaric acid and 500 parts of Cardura E-10j were charged into the same flask as in Reference Example 1, and the reaction was heated at 130°C for 4 hours under a nitrogen atmosphere. Finally, 616 parts of 7-malate diester of Cardura E-10J was obtained. G and C1 of this product were 5 to 6, AV was 2.5 and OHV was 182. Comparative Example 11 Resin In addition to 40 parts of (c-5), 142 parts of the unsaturated dicarboxylic acid diester obtained in Reference Example 6 was also used, and the monomer charge composition was changed to 200 parts of styrene, methyl methacrylate. 168 parts, 100 parts of n-butyl methacrylate, 110 parts of 1ao-butyl methacrylate, 101 parts of n-butyl acrylate, 164 parts of 2-hydroxyethyl methacrylate, mono(2-hydroxyethyl) monomethacryloyloxyethyl 7 tallate -1 in the same manner as in Example 3, except that 15 parts of methacrylic acid and 10 parts of methacrylic acid were used.
(NY is 50.1%, G, Vig. Ka U-v, AV>D,, 1. ouv Ka56 Te, G,
c. A control resin solution for coating material having a strength of 1 or less and a MW/Mn of 62 was obtained. Application Examples 1 to 8 and Comparative Application Examples 1 to 8 100 parts of each coating resin obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were added with (11 and (2) in Table 1).
A predetermined pigment was blended to give the PWC (%) shown in , 40 parts of a mixed solvent of xylene/butyl acetate = 50150 (weight ratio) was blended as a thinner, and 250 parts of glass peas were added. 7)” ＜ /l
/A1-3A15. . 1. I made a 7.1 base crash. Next, we evaluated the dispersibility of various pigments for each enamel base, and the results are shown in (11, +
21. First, the dispersion state was determined by visual inspection of the presence or absence of agglomeration of each enamel base and its degree (degree).Then, the dispersibility of flow coating was determined by adding 5 parts of toluene to 5 parts of each enamel base. The degree of agglomeration of the pigment was visually determined by pouring the mixture onto art paper and visually determining the degree of pigment aggregation. Judging by visual inspection, PL and sedimentation property are color pace/thinner = 50150
(weight ratio) mixtures were prepared separately, and then λ50
The degree of sedimentation of the pigment was visually determined by centrifuging at 0 rpm for 20 minutes. The thinner used for evaluating the sedimentation was a mixed solvent of xylene/butyl acetate = 50150 (weight ratio). there were. The criteria for determining the distributed state are as follows:
・・・・・・・・・No abnormalities ○ ・・・・・・・・・ A little agglomeration ・−・・−
・・・・Kanasi agglomeration × ・−・・−・・・Significant aggregation. The criteria for determining flow-coating dispersibility, gloss, and the presence or absence of thixotropy of the enamel base are as follows. ◎・・・・・・・・・Excellent○・・・・・・・−・Good Δ・・・・・・−・Poor (poor)× ・・・・
・・・・・・Not possible (Significantly inferior) Application Example 9.10 and Comparative Application Example 9.10 To 100 parts of each of the coating resins obtained in Examples 5 and 7 and Comparative Examples 9 and 10, No. Predetermined pigments were blended so that the ffC (%) shown in Table 2 was obtained, 40 parts of a mixed solvent of xylene/butyl acetate = 50150 (weight ratio) was blended as a thinner, and 250 parts of glass peas were added. 1 at Sand Mill
Enamel bases were prepared separately by kneading for 6 hours. Next, application examples 1 to 3 are applied to each enamel base.
The dispersion state and flow coating dispersibility were evaluated in the same manner as in Example 8 and Comparative Application Examples 1 to 8. (However, regarding the evaluation of both of these performances, Application Example 9 is the same as Application Example 5, and Application Example 10 is the same as Application Example 7.) At the same time, the number of colors (coloring degree) of the resin solution, the amine odor presence or absence,"
Clarify the difference between amide group-containing vinyl monomer and dialkylaminoalkyl (meth)acrylate in terms of pot life and ultraviolet resistance (yellowing) when combined with Burnock D-750. The results are summarized in the same table, but the above performance comparison of "Pot Life" ) ] f
Add OH7'NCO to each resin solution in equal amounts, then dilute the total nonvolatile content to 45% with butyl acetate, and then calculate the time (hrs) until tailing, expressed as t-. did. In addition, to compare the performance of "ultraviolet ray resistance", "Burnock DN-950J t-OH/NCO was mixed into the respective resin solutions in equal amounts on a white ceramic plate, and then butyl acetate was added to the total non-volatile content t-OH/NCO. Dilute to 45% and then use a 10 mil applicator (Bonderai) +1
44 treated dull steel plates separately, then air-dried for about 30 minutes, baked at 60℃ for 60 minutes, and then left at room temperature for 10 days.
Each sample thus obtained was expressed as the difference △b1'' between the b value after 100 hours of exposure to the germicidal lamp and the b value before exposure.Here, the larger the Δb value, the more significant the yellowing. Application Examples 11 to 15 Each component was blended into 100 parts of the resin solution obtained in Example 1 with the composition shown in Table 3. PWC = 40
%), kneaded, and further xylene/butyl acetate = 50
Enamel bases were prepared separately by diluting a mixed solvent of 150 (weight ratio) as a thinner with Food Capsule 4 for 12 seconds. However, in Application Example 15, after kneading with only the resin solution and titanium oxide, a predetermined amount of "Burnock DN-950, J" was added and diluted. Next, each enamel base was mixed with Bonderite + 1
44 treated dull steel plates were spray coated separately and cured under the curing conditions shown in the same table to obtain respective cured coatings. Thereafter, various performance comparisons were made on the items shown in the table using conventional methods for each coating film. The results are summarized in the same table. Application Example 16 and Comparative Application Example 11 100 parts of each of the resin solutions obtained in Example 3 and Comparative Example 11 were blended with a predetermined pigment so as to have the PWC (%) shown in Table 4, and mixed with xylene. /butyl acetate=5
0150 (weight ratio) as a thinner
Enamel bases were prepared separately by adding 250 parts of glass peas and kneading them in a sand mill for 1 to 3 hours. Next, application examples 1 to 3 are applied to each enamel base.
8 and Comparative Application Examples 1 to 8, the dispersion state of the primary color system, flow-coating dispersibility, presence or absence of gloss and thixotropy, and the dispersibility of the mixed color system were evaluated. (However, regarding the evaluation of these various performances, Application Example 16 is the same as Application Example 3.) At the same time, OH/N was added to each black enamel paste.
[Burnock DN 950
Regarding both coatings obtained by combining J tJa and painting on a tin plate with a size of 200 x 300 m and curing,
"Jet blackness" was evaluated by visual judgment under daylight from the north window. This jet-black color is said to be the best in books with a bluish tinge, while the reddish one is said to be worse. Here, the evaluation criteria for jet blackness are as follows. ◎・・・・・・・・・・Excellent ○・・・・・・・・・Good △・−・・−・・Possible Effects] As is clear from the results in Tables 1.2 and 4, as well as Table 3, the composition of the present invention has particularly excellent dispersibility, has no amine odor (and has good weather resistance). It is known that the composition has the characteristic effect of being excellent in coloring properties and resin coloring properties. Therefore, the composition of the present invention can be used in a wide range of applications as described above.

Claims (1)

[Claims] In the presence of a radical generator, (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [However, R_1 and R_2 in the formula may be the same or different. A hydrogen atom or a methyl group that may be
R_3 represents a hydrogen atom, an alkyl group of C_1 to C_1_2, or a group of ▲, which has a numerical formula, chemical formula, table, etc. ] 0.05 of the amide bond-containing vinyl monomer shown by
~% by weight, (b) 0 to 5% by weight of the phosphorus atom-containing vinyl monomer, (
c) 0.1 to 40% by weight of the unsaturated bond-containing polyester resin, and (d) 45 to 99.85% by weight of other vinyl monomers copolymerizable with each comonomer of groups (a) to (c) above. and the weight average molecular weight (@Mn@) of the resulting copolymer resin with respect to the number average molecular weight (@Mn@).
A method for producing a paint resin having particularly excellent pigment dispersibility, characterized in that the ratio of @Mw@/@Mn@ is in the range of 2 to 25.