Non-aqueous dispersion resin composition and coating material

Abstract

To provide a nonaqueous dispersion resin composition capable of forming a coating material excellent in weather resistance and pigment dispersibility, and a coating material containing the nonaqueous dispersion resin composition.SOLUTION: The nonaqueous dispersion resin composition contains an organic solvent containing a hydrocarbon solvent, and a nonaqueous dispersion resin having a core and a shell covering the core. The core is a polymer of the core polymerization component. The polymer of the core polymerization component is substantially insoluble in an organic solvent. The shell is a polymer of the shell polymerization component. The polymer of the shell polymerization component is soluble in an organic solvent. The shell has an acid number of at least 0. 5mgKOH / g and no greater than 4. 0mgKOH / g. Acid values of the non-aqueous dispersion-type resins are 0. 5mgKOH / g or more and 6. 0mgKOH / g or less. The amine value of the non-aqueous dispersion-type resins is 0. 2mgKOH / g or more and 4. 0mgKOH / g or less. The non-aqueous dispersion resin composition has a hindered amino group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a non-aqueous dispersion type resin composition and a coating material, and more particularly to a non-aqueous dispersion type resin composition and a coating material containing the non-aqueous dispersion type resin composition. [Background technology]

[0002] Conventionally, paints contain pigments, base resins (synthetic resins), dispersants, etc., and those using non-aqueous dispersion-type resins as the base resin are known.

[0003] As such a non-aqueous dispersion type resin, for example, a non-aqueous dispersion type resin composition (acid value 0.4 mgKOH / g) has been proposed, which is obtained by polymerizing a monomer mixture containing 2-ethylhexyl acrylate, isobutyl methacrylate, and methacrylic acid to obtain a resin solution containing copolymer (B) (acid value 0.3 mgKOH / g), then blending a monomer mixture containing methyl methacrylate, ethyl acrylate, and methacrylic acid with the resin solution, and polymerizing this. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 06-234951 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, weather resistance is required for paints depending on their purpose and use, and therefore, from the viewpoint of improving weather resistance, the incorporation of hindered amine light stabilizers into paints has been considered.

[0006] However, when a hindered amine light stabilizer is blended into a paint containing a non-aqueous dispersion type resin as a base resin, the paint tends to have a problem of reduced pigment dispersibility. Furthermore, when the pigment dispersibility is reduced in this way, the paint tends to have a problem of uneven color in the paint film after the paint is applied to a substrate to form a paint film.

[0007] The present invention provides a non-aqueous dispersion type resin composition capable of forming a coating material having excellent weather resistance and excellent pigment dispersibility, and a coating material containing the non-aqueous dispersion type resin composition. [Means for solving the problem]

[0008] The present invention [1] is a non-aqueous dispersion resin composition comprising an organic solvent containing a hydrocarbon solvent, and a non-aqueous dispersion resin having a core and a shell covering the core, wherein the core is a polymer of a core polymerization component, and the polymer of the core polymerization component is substantially insoluble in the organic solvent, the shell is a polymer of a shell polymerization component, and the polymer of the shell polymerization component is soluble in the organic solvent, the acid value of the shell is from 0.5 mg KOH / g to 4.0 mg KOH / g, the acid value of the non-aqueous dispersion resin is from 0.5 mg KOH / g to 6.0 mg KOH / g, and the amine value of the non-aqueous dispersion resin is from 0.2 mg KOH / g to 4.0 mg KOH / g, and the non-aqueous dispersion resin composition has a hindered amino group.

[0009] The present invention [2] includes the non-aqueous dispersion type resin composition according to the above [1], wherein the core polymer is an alkyd-modified acrylic resin.

[0010] The present invention [3] includes the non-aqueous dispersion type resin composition according to the above [1] or [2], wherein the non-aqueous dispersion type resin composition contains a hindered amine light stabilizer, and the ratio of the acid value of the shell to the amine value of the hindered amine light stabilizer is 0.3 or more and 20.0 or less.

[0011] The present invention [4] is characterized in that the solubility parameter of the shell is 7.70 (cal / cm 3 ) 1 / 2 More than 7.90(cal / cm 3 ) 1 / 2 and the solubility parameter of the core is 7.90 (cal / cm 3 ) 1 / 2 More than 8.25(cal / cm 3 ) 1 / 2 The non-aqueous dispersion type resin composition according to any one of the above [1] to [3] is included.

[0012] The present invention [5] includes the non-aqueous dispersion type resin composition according to any one of the above [1] to [4], in which the shell polymerization component contains styrene.

[0013] The present invention [6] includes a coating material containing the non-aqueous dispersion type resin composition according to any one of the above [1] to [5] and a pigment. [Effects of the Invention]

[0014] The non-aqueous dispersion type resin composition of the present invention has a hindered amino group, which can improve the weather resistance of the non-aqueous dispersion type resin composition, a paint containing this non-aqueous dispersion type resin composition, and ultimately a coating film formed using this paint.

[0015] In addition, in the non-aqueous dispersion type resin composition, the acid value of the shell is 0.5 mgKOH / g or more and 4.0 mgKOH / g or less, the acid value of the non-aqueous dispersion type resin is 0.5 mgKOH / g or more and 6.0 mgKOH / g or less, and the amine value of the non-aqueous dispersion type resin is 0.2 mgKOH / g or more and 4.0 mgKOH / g or less. Therefore, even when the non-aqueous dispersion type resin composition has a hindered amino group, the non-aqueous dispersion type resin composition has excellent pigment dispersibility in a paint containing this non-aqueous dispersion type resin composition.

[0016] The coating material of the present invention contains the non-aqueous dispersion type resin composition of the present invention, and therefore has excellent weather resistance and pigment dispersibility. DETAILED DESCRIPTION OF THE INVENTION

[0017] 1.Non-aqueous dispersion type resin composition In the present invention, the non-aqueous dispersion type resin composition contains an organic solvent and a non-aqueous dispersion type resin. The non-aqueous dispersion type resin composition also has a hindered amino group. Specifically, the non-aqueous dispersion type resin composition contains a hindered amine-based light stabilizer (described later) and has a hindered amino group derived from the hindered amine-based light stabilizer (described later), and / or the shell polymerization component (described later) contains a hindered amino group-containing (meth)acrylate and the non-aqueous dispersion type resin composition has a hindered amino group derived from the hindered amino group-containing (meth)acrylate.

[0018] In the following description, a case will be described in detail in which the non-aqueous dispersion type resin composition contains a hindered amine-based light stabilizer and has a hindered amino group derived from the hindered amine-based light stabilizer.

[0019] In this embodiment, the non-aqueous dispersion type resin composition contains an organic solvent, a non-aqueous dispersion type resin, and a hindered amine-based light stabilizer.

[0020] <Organic solvents> The organic solvent includes a hydrocarbon solvent.

[0021] Considering the environment and the health of painters, it is preferable to use a weak hydrocarbon solvent. A weak solvent is an aliphatic hydrocarbon solvent that may contain a high-boiling aromatic hydrocarbon solvent, such as turpentine or mineral spirits, which have a high flash point, high boiling point, and low toxicity. Examples of mixed solvents of aliphatic hydrocarbon solvents include mineral spirits, white spirit, mineral turpentine, isoparaffin, solvent kerosene, aromatic naphtha, VM&P naphtha, and solvent naphtha. Other examples of single-component aliphatic hydrocarbon solvents include n-butane, n-hexane, n-heptane, n-octane, isononane, n-decane, n-dodecane, cyclopentane, cyclohexane, and cyclobutane.

[0022] The hydrocarbon solvents can be used alone or in combination of two or more kinds.

[0023] The organic solvent may contain other solvents as needed. Examples of other solvents include ester solvents, ketone solvents, and alcohol solvents. The other solvents may be used alone or in combination of two or more.

[0024] The content of the hydrocarbon solvent relative to the organic solvent is, for example, 80 mass % or more, preferably 90 mass % or more, or more preferably 100 mass %.

[0025] The organic solvent preferably does not substantially contain other solvents. Specifically, the content of other solvents relative to the organic solvent is, for example, 20% by mass or less, preferably 10% by mass or less, and more preferably 0% by mass.

[0026] <Non-aqueous dispersion resin> A non-aqueous dispersion resin (NAD resin) has a core as a core material and a shell that covers the core. In other words, a non-aqueous dispersion resin is a core-shell particle, and by having such a structure, the particle exhibits the function of dispersing in an organic solvent.

[0027] (shell) The shell functions as a coating portion that coats the core material located at the center of the non-aqueous dispersion type resin as core-shell particles and enables the non-aqueous dispersion type resin to be dispersed in an organic solvent.

[0028] The shell is formed by polymerizing a shell polymerization component and is a polymer that is substantially soluble in an organic solvent, i.e., the shell contains a polymer of the shell polymerization component (hereinafter sometimes referred to as a shell polymer).

[0029] The shell polymerizable component is a vinyl group-containing monomer including a (meth)acrylic acid alkyl ester and an acidic group-containing vinyl monomer, and the shell polymer obtained by polymerizing such shell polymerizable components can be said to be composed of an acrylic resin. Note that (meth)acrylic is defined as acrylic and / or methacrylic (the same applies hereinafter).

[0030] Examples of (meth)acrylic acid alkyl esters include C1-18 alkyl esters of (meth)acrylic acid. Examples of C1-18 alkyl esters of (meth)acrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Preferred examples of (meth)acrylic acid alkyl esters include C4-8 alkyl esters of (meth)acrylic acid. More preferred examples of the (meth)acrylic acid alkyl ester include isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Still more preferred examples of the (meth)acrylic acid alkyl ester include isobutyl methacrylate and 2-ethylhexyl (meth)acrylate.

[0031] The (meth)acrylic acid alkyl esters can be used alone or in combination of two or more. Preferably, a C4 alkyl ester of (meth)acrylic acid and a C5-8 alkyl ester of (meth)acrylic acid are used in combination. More preferably, in the core polymerization component described below, a C1-3 alkyl ester of (meth)acrylic acid and a C4 alkyl ester of (meth)acrylic acid are used in combination, and in the shell polymerization component, a C4 alkyl ester of (meth)acrylic acid and a C5-8 alkyl ester of (meth)acrylic acid are used in combination.

[0032] The content of the (meth)acrylic acid alkyl ester relative to the shell polymerization component is, for example, 60% by mass to 85% by mass, or preferably 70% by mass to 80% by mass.

[0033] The acidic group-containing vinyl monomer is a monomer (vinyl group-containing monomer) that has an acidic group (acid group) and can undergo radical polymerization (vinyl polymerization) with a (meth)acrylic acid alkyl ester.

[0034] Examples of the acidic group-containing vinyl monomer include a carboxyl group-containing vinyl monomer, a sulfonic acid group-containing vinyl monomer, and a phosphoric acid group-containing vinyl monomer.

[0035] Examples of the carboxyl group-containing vinyl monomer include monocarboxylic acids having a vinyl group, dicarboxylic acids having a vinyl group, and salts thereof. Examples of the monocarboxylic acids having a vinyl group include (meth)acrylic acid and ω-carboxy-polycaprolactone monoacrylate. Examples of the dicarboxylic acids having a vinyl group include itaconic acid, maleic acid, fumaric acid, itaconic anhydride, maleic anhydride, and fumaric anhydride. A preferred example of the carboxyl group-containing vinyl monomer is a monocarboxylic acid having a vinyl group. A more preferred example of the carboxyl group-containing vinyl monomer is methacrylic acid.

[0036] Examples of sulfonic acid group-containing vinyl monomers include sulfonic acids having a vinyl group, such as allyl sulfonic acid, methallyl sulfonic acid, and acrylamido t-butyl sulfonic acid.

[0037] An example of the phosphate group-containing vinyl monomer is 2-methacryloyloxyethyl acid phosphate.

[0038] As the acidic group-containing vinyl monomer, a carboxy group-containing vinyl monomer is preferably used.

[0039] The acidic group-containing vinyl monomers can be used alone or in combination of two or more kinds.

[0040] The content of the acidic group-containing vinyl monomer relative to the shell polymerization component is, for example, 0.03 to 0.60% by mass, preferably 0.10 to 0.50% by mass, and more preferably 0.15 to 0.30% by mass.

[0041] If the content of the acidic group-containing vinyl monomer is within the above range, the acid value of the shell (described later) and the acid value of the non-aqueous dispersion-type resin (described later) can be adjusted relatively easily to within a predetermined range.

[0042] The shell polymerization component may optionally contain an amino group-containing vinyl monomer in addition to the (meth)acrylic acid alkyl ester and the acid group-containing vinyl monomer.

[0043] The amino group-containing vinyl monomer is a monomer (vinyl group-containing monomer) that has an amino group and can undergo radical polymerization (vinyl polymerization) with a (meth)acrylic acid alkyl ester and an acid group-containing vinyl monomer.

[0044] Examples of amino group-containing vinyl monomers include 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, and 2-(N,N-diethylamino)ethyl (meth)acrylate. Preferred examples of amino group-containing vinyl monomers include 2-(N,N-dimethylamino)ethyl (meth)acrylate. More preferred examples of amino group-containing vinyl monomers include 2-(N,N-dimethylamino)ethyl methacrylate.

[0045] The amino group-containing vinyl monomers can be used alone or in combination of two or more kinds.

[0046] The content of the amino group-containing vinyl monomer relative to the shell polymerization component is, for example, 0.4 mass % or less, preferably 0.3 mass % or less, more preferably 0.1 mass % or less, and still more preferably 0 mass %.

[0047] That is, more preferably, the shell polymerization component does not contain an amino group-containing vinyl monomer. In other words, more preferably, the amine value (described later) of the non-aqueous dispersion-type resin can be relatively easily adjusted to a predetermined range by adjusting only the content ratio of the amino group-containing vinyl monomer in the core polymerization component.

[0048] When the content of the amino group-containing vinyl monomer is within the above range, the amine value (described later) of the non-aqueous dispersion-type resin can be adjusted relatively easily to a predetermined range.

[0049] The shell polymerization component may optionally contain, in addition to the (meth)acrylic acid alkyl ester, acidic group-containing vinyl monomer, and amino group-containing vinyl monomer, a copolymerizable monomer capable of undergoing radical polymerization (vinyl polymerization) with these.

[0050] Examples of the copolymerizable monomer include hydroxyl group-containing vinyl monomers, aromatic vinyl monomers, and cyano group-containing vinyl monomers.

[0051] Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. A preferred example of the hydroxyl group-containing vinyl monomer is 2-hydroxyethyl (meth)acrylate. A more preferred example of the hydroxyl group-containing vinyl monomer is 2-hydroxyethyl acrylate.

[0052] The content of the hydroxyl group-containing vinyl monomer relative to the shell polymerization component is, for example, 4.8 to 8.0 mass %, preferably 5.0 to 7.0 mass %, and more preferably 6.0 to 6.5 mass %.

[0053] Examples of aromatic vinyl monomers include styrene and α-methylstyrene. Styrene is a preferred aromatic vinyl monomer. That is, the shell polymerization component preferably contains styrene. When the shell polymerization component contains styrene, the water resistance and heat resistance of the non-aqueous dispersion-type resin composition, the coating material containing this non-aqueous dispersion-type resin composition, and ultimately the coating film formed using this coating material can be improved.

[0054] The content of the aromatic vinyl monomer relative to the shell polymerization component is, for example, 1.0 to 30.0 mass%, preferably 1.5 to 22.0 mass%, and more preferably 2.0 to 18.0 mass%.

[0055] When the content of the aromatic vinyl monomer (preferably styrene) is within the above range, the above effects can be more significantly exhibited in the non-aqueous dispersion type resin composition, the paint containing this non-aqueous dispersion type resin composition, and ultimately in the paint film formed using this paint, and as a result, the weather resistance of the paint film can be improved.

[0056] An example of the cyano group-containing vinyl monomer is (meth)acrylonitrile.

[0057] The copolymerizable monomers can be used alone or in combination of two or more kinds.

[0058] As will be described in detail later, the shell polymer is obtained by polymerizing the above-mentioned shell polymerization components (monomer components).

[0059] From the viewpoint of pigment dispersibility in the non-aqueous dispersion-type resin composition, the shell polymer is preferably modified with an alkyd resin, i.e., the shell polymer is preferably an alkyd-modified acrylic resin, i.e., one containing both an alkyd resin and an acrylic resin (shell polymerization component polymer).

[0060] Although the details will be described later, the alkyd-modified acrylic resin is obtained by polymerizing a shell polymerization component (monomer component) in the presence of an alkyd resin.

[0061] The alkyd resin can be produced according to the method described in JP 2019-006859 A. Specifically, the alkyd resin is produced, for example, by a condensation reaction of a polyhydric alcohol, a polybasic acid, a monobasic acid (if necessary), and an unsaturated fatty acid and / or a fat or oil.

[0062] Examples of polyhydric alcohols include dihydric alcohols, trihydric alcohols, and tetrahydric alcohols.

[0063] Examples of dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and hexanediol.

[0064] Examples of the trihydric alcohol include glycerin and trimethylolpropane, and a preferred example of the trihydric alcohol is glycerin.

[0065] An example of the tetrahydric alcohol is pentaerythritol.

[0066] The polyhydric alcohol preferably includes a trihydric alcohol and a tetrahydric alcohol.

[0067] The polyhydric alcohols can be used alone or in combination of two or more kinds. Preferably, a trihydric alcohol and a tetrahydric alcohol are used in combination as the polyhydric alcohols.

[0068] Examples of polybasic acids include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, succinic anhydride, maleic acid, maleic anhydride, adipic acid, sebacic acid, and tetrahydrophthalic anhydride. Preferred examples of polybasic acids include phthalic anhydride. Polybasic acids can be used alone or in combination of two or more.

[0069] If necessary, a polybasic acid and a monobasic acid can be used in combination.

[0070] Examples of monobasic acids include benzoic acid, t-butylbenzoic acid, hexahydrobenzoic acid, and cinnamic acid. Benzoic acid is preferred as the monobasic acid. The monobasic acids can be used alone or in combination of two or more.

[0071] The unsaturated fatty acid is not particularly limited as long as it has at least one unsaturated carbon bond in the molecule, and examples thereof include known unsaturated fatty acids.

[0072] Examples of unsaturated fatty acids include fish oil fatty acids, dehydrated castor oil fatty acids, safflower oil fatty acids, linseed oil fatty acids, tung oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy seed oil fatty acids, perilla oil fatty acids, hempseed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, hygienic acid fatty acids, oleic acid, linoleic acid, and linolenic acid.Preferably, dehydrated castor oil fatty acids are used.Unsaturated fatty acids can be used alone or in combination of two or more types.

[0073] Examples of fats and oils include fats and oils having unsaturated carbon bonds. Examples of fats and oils include fish oil, dehydrated castor oil, safflower oil, linseed oil, tung oil, soybean oil, sesame oil, poppy seed oil, perilla oil, hemp seed oil, grape kernel oil, corn oil, tall oil, sunflower oil, cottonseed oil, walnut oil, and rubber seed oil. A preferred example of fats and oils is linseed oil. The fats and oils can be used alone or in combination of two or more.

[0074] The unsaturated fatty acids and / or fats and oils can be used alone or in combination of two or more. As the unsaturated fatty acids and / or fats and oils, a combination of unsaturated fatty acids and fats and oils is preferred.

[0075] The mixing ratio of the alkyd resin relative to the total amount of the shell polymerization component (acrylic resin) and the alkyd resin is, for example, 1.0 mass % to 20.0 mass %, preferably 2.0 mass % to 10.0 mass %, and more preferably 3.0 mass % to 5.0 mass %.

[0076] The blending ratio of the alkyd resin relative to the total amount of the shell polymerization component, the alkyd resin, and the core polymerization component is, for example, 0.1 mass % to 10.0 mass %, preferably 0.5 mass % to 7.0 mass %, more preferably 1.0 mass % to 5.0 mass %, even more preferably 1.2 mass % to 3.0 mass %, and particularly preferably 1.4 mass % to 2.0 mass %.

[0077] The acid value based on the entire shell, i.e., the proportion of the acid value based on the alkyd resin in the total amount of the acid value based on the shell polymerization component (acrylic resin) and the acid value based on the alkyd resin, is, for example, 5% to 70%, preferably 10% to 60%, more preferably 15% to 50%, even more preferably 25% to 40%, and particularly preferably 30% to 35%. By setting the proportion of the acid value based on the alkyd resin within the above range, further improvement in pigment dispersibility in paint containing the nonaqueous dispersion-type resin composition can be achieved.

[0078] The glass transition temperature of the shell (shell polymer) is, for example, 25°C to 50°C, preferably 30°C to 45°C, and more preferably 32°C to 37°C.

[0079] The glass transition temperature can be calculated by the FOX formula (the same applies hereinafter).

[0080] The solubility parameter (SP value) of the shell (shell polymer) is lower than that of the core (core polymer), and from the viewpoint of pigment dispersibility and paint stability (storage stability), for example, 7.70 (cal / cm 3 ) 1 / 2 More than 7.75 (cal / cm 3 ) 1 / 2 More preferably, 7.80 (cal / cm 3 ) 1 / 2 In addition, from the viewpoint of weather resistance, pigment dispersibility, and paint stability (storage stability), for example, 7.90 (cal / cm 3 ) 1 / 2 Preferably, 7.88 (cal / cm 3 ) 1 / 2 Less than or equal to 7.85 (cal / cm 3 ) 1 / 2 The following is the result.

[0081] The solubility parameter is used as a value that represents the polarity of a compound. When two substances are mixed, if the difference in SP value is small, they are likely to be compatible, and if the difference is large, they are incompatible. In the present invention, the value derived by substituting the cohesive energy constant of each Hoy atomic group into the Small calculation formula in the following equation (1) was applied (the same applies hereinafter).

number

[0082] The acid value of the shell (shell polymer) is 0.5 mgKOH / g to 4.0 mgKOH / g, preferably 1.0 mgKOH / g to 3.8 mgKOH / g, more preferably 1.5 mgKOH / g to 3.5 mgKOH / g, even more preferably 1.6 mgKOH / g to 2.5 mgKOH / g, and particularly preferably 1.7 mgKOH / g to 2.0 mgKOH / g.

[0083] Specifically, the acid value of the shell (shell polymer) is 0.5 mgKOH / g or more, preferably 1.0 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, even more preferably 1.6 mgKOH / g or more, particularly preferably 1.7 mgKOH / g or more, and 4.0 mgKOH / g or less, preferably 3.8 mgKOH / g or less, more preferably 3.5 mgKOH / g or less, even more preferably 2.5 mgKOH / g or less, particularly preferably 2.0 mgKOH / g or less.

[0084] When the acid value of the shell (shell polymer) is at least the above lower limit, the pigment dispersibility and paint stability (storage stability) of a paint containing the non-aqueous dispersion-type resin composition can be improved.

[0085] On the other hand, if the acid value of the shell (shell polymer) is less than the above lower limit, the pigment dispersibility and paint stability (storage stability) in a paint containing the non-aqueous dispersion-type resin composition will decrease.

[0086] Furthermore, when the acid value of the shell (shell polymer) is equal to or less than the above upper limit, the pigment dispersibility in a paint containing the non-aqueous dispersion type resin composition can be improved.

[0087] On the other hand, if the acid value of the shell (shell polymer) exceeds the above upper limit, the pigment dispersibility in the paint containing the non-aqueous dispersion-type resin composition decreases.

[0088] The acid value can be measured according to JIS K 0070-1992 (neutralization titration method) based on the solid content of the shell (shell polymer).

[0089] The hydroxyl value of the shell (shell polymer) is, for example, 20 mgKOH / g to 45 mgKOH / g, preferably 30 mgKOH / g to 40 mgKOH / g, and more preferably 31 mgKOH / g to 34 mgKOH / g.

[0090] The hydroxyl value can be measured according to JIS K 0070-1992 (neutralization titration method) based on the solid content of the shell (shell polymer).

[0091] The amine value of the shell (shell polymer) is, for example, 1.5 mgKOH / g or less, preferably 1.0 mgKOH / g or less, more preferably 0.5 mgKOH / g or less, and particularly preferably 0 mgKOH / g.

[0092] When the amine value of the shell (shell polymer) is within the above range, the amine value (described below) of the non-aqueous dispersion-type resin can be adjusted relatively easily to a predetermined range.

[0093] The amine value can be measured according to JIS K-7237-1995 (potentiometric titration method) using the solid content of the shell (shell polymer) as the standard.

[0094] The weight average molecular weight of the shell (shell polymer) is, for example, 10,000 to 200,000, preferably 50,000 to 150,000, more preferably 80,000 to 130,000, and still more preferably 100,000 to 110,000.

[0095] (core) The core functions as a core material located at the center of the non-aqueous dispersion resin as a core-shell particle, and is covered with the shell.

[0096] The core is formed by polymerizing a core polymerization component and is a polymer that is substantially insoluble in an organic solvent, i.e., the core is a polymer of the core polymerization component (hereinafter, sometimes referred to as a core polymer).

[0097] The core polymerization components are vinyl group-containing monomers including (meth)acrylic acid alkyl esters, acidic group-containing vinyl monomers, and amino group-containing vinyl monomers, and the core polymer formed by polymerizing such core polymerization components can be said to be composed of an acrylic resin.

[0098] Examples of (meth)acrylic acid esters include the alkyl (meth)acrylate esters exemplified above for the shell polymerization component. Preferred examples of (meth)acrylic acid esters include alkyl esters of meth)acrylic acid having 1 to 8 carbon atoms. More preferred examples of (meth)acrylic acid esters include alkyl esters of (meth)acrylic acid having 1 to 4 carbon atoms. More preferred examples of (meth)acrylic acid esters include methyl (meth)acrylate, isobutyl (meth)acrylate, and n-butyl (meth)acrylate. Particularly preferred examples of (meth)acrylic acid esters include methyl methacrylate, isobutyl methacrylate, and n-butyl acrylate.

[0099] The (meth)acrylic acid alkyl esters can be used alone or in combination of two or more. Preferably, a (meth)acrylic acid alkyl ester having 1 to 3 carbon atoms and a (meth)acrylic acid alkyl ester having 4 carbon atoms are used in combination.

[0100] The content of the (meth)acrylic acid alkyl ester relative to the core polymerization component is, for example, 70% by mass to 90% by mass, or preferably 80% by mass to 85% by mass.

[0101] Examples of the acidic group-containing vinyl monomer include the acidic group-containing vinyl monomers exemplified above as the shell polymerization component.Preferably, the acidic group-containing vinyl monomer is a carboxyl group-containing vinyl monomer.More preferably, the acidic group-containing vinyl monomer is (meth)acrylic acid.

[0102] The acidic group-containing vinyl monomers can be used alone or in combination of two or more kinds.

[0103] The content of the acidic group-containing vinyl monomer relative to the core polymerization component is, for example, 0.1 to 1.0 mass %, preferably 0.2 to 0.6 mass %, and more preferably 0.3 to 0.5 mass %.

[0104] When the content of the acidic group-containing vinyl monomer is within the above range, the acid value (described later) of the non-aqueous dispersion-type resin can be adjusted relatively easily to a predetermined range.

[0105] Examples of the amino group-containing vinyl monomer include the amino group-containing vinyl monomers exemplified as the shell polymerization component.

[0106] The amino group-containing vinyl monomer is preferably 2-(N,N-dimethylamino)ethyl (meth)acrylate, and more preferably 2-(N,N-dimethylamino)ethyl methacrylate.

[0107] The amino group-containing vinyl monomers can be used alone or in combination of two or more kinds.

[0108] The content of the amino group-containing vinyl monomer relative to the core polymerization component is, for example, 0.1 mass % to 1.7 mass %, preferably 0.2 mass % to 1.0 mass %, more preferably 0.2 mass % to 0.6 mass %, and even more preferably 0.2 mass % to 0.4 mass %.

[0109] When the content of the amino group-containing vinyl monomer is within the above range, the amine value (described later) of the non-aqueous dispersion-type resin can be adjusted relatively easily to a predetermined range.

[0110] The core polymerizable component may optionally contain the copolymerizable monomers exemplified for the shell polymerizable component.

[0111] Examples of the copolymerizable monomer include the hydroxyl group-containing vinyl monomers exemplified as the shell polymerization component, the aromatic vinyl monomers exemplified as the shell polymerization component, and the cyano group-containing vinyl monomers exemplified as the shell polymerization component.

[0112] The hydroxyl group-containing vinyl monomer is preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl acrylate.

[0113] The content of the hydroxyl group-containing vinyl monomer relative to the core polymerization component is, for example, 7.0 mass% to 13.2 mass%, preferably 7.5 mass% to 11.0 mass%, more preferably 7.7 mass% to 10.0 mass%, and even more preferably 8.0 mass% to 9.0 mass%.

[0114] As the aromatic vinyl monomer, preferably, styrene is used.

[0115] The content of the aromatic vinyl monomer relative to the core polymerization component is, for example, 0.5 to 20.0 mass%, preferably 1.0 to 17.0 mass%, and more preferably 2.0 to 12.0 mass%.

[0116] When the content ratio of the aromatic vinyl monomer is within the above range, the weather resistance of the non-aqueous dispersion type resin composition, the paint containing this non-aqueous dispersion type resin composition, and ultimately the coating film formed using this paint can be further improved.

[0117] As the cyano group-containing vinyl monomer, preferably, acrylonitrile is used.

[0118] The content of the cyano group-containing vinyl monomer relative to the core polymerization component is, for example, 0.05 to 5.0% by mass, or preferably 0.1 to 2.0% by mass.

[0119] The copolymerizable monomers can be used alone or in combination of two or more kinds.

[0120] The content of the copolymerizable monomer relative to the core polymerization component is, for example, 1.0 to 40.0% by mass, or preferably 10.0 to 20.0% by mass.

[0121] As will be described in detail later, the core polymer is obtained by polymerizing a core polymerizable component as a monomer component.

[0122] By appropriately selecting the type of the core polymer component, the core polymer becomes substantially insoluble in organic solvents, and by coating this core polymer with the shell polymer, the non-aqueous dispersion-type resin becomes dispersible in organic solvents.

[0123] The glass transition temperature of the core (core polymer) is, for example, 25°C to 50°C, preferably 30°C to 45°C, and more preferably 36°C to 40°C.

[0124] From the viewpoint of pigment dispersibility and coating stability (storage stability), the solubility parameter (SP value) of the core (core polymer) is larger than that of the shell, for example, 7.90 (cal / cm 3 ) 1 / 2 More preferably, 7.90 (cal / cm 3 ) 1 / 2 More preferably, 7.95 (cal / cm 3 ) 1 / 2 More preferably, 7.98 (cal / cm 3 ) 1 / 2 In addition, from the viewpoint of weather resistance, pigment dispersibility, and paint stability (storage stability), for example, 8.25 (cal / cm 3 ) 1 / 2 Preferably, 8.20 (cal / cm 3 ) 1 / 2 Less than or equal to 8.10 (cal / cm 3 ) 1 / 2 More preferably, 8.05 (cal / cm 3 ) 1 / 2 Particularly preferably, 8.00 (cal / cm 3 ) 1 / 2 The following is the result.

[0125] (Production of non-aqueous dispersion resin) The method for producing a non-aqueous dispersion-type resin includes a first step of polymerizing a shell polymerization component to produce a shell polymer, and a second step of blending a core polymerization component in the presence of the shell polymer and polymerizing the core polymerization component to produce a core polymer, thereby producing a non-aqueous dispersion-type resin.

[0126] In the first step, the shell polymerizable components are polymerized to produce a shell polymer.

[0127] Specifically, the shell polymerization component and a polymerization initiator (for example, t-butylperoxyisopropyl monocarbonate) are mixed into an organic solvent to polymerize the shell polymerization component.

[0128] At this time, when the shell polymer is constituted by an acrylic resin modified with an alkyd resin, the alkyd resin is blended into the organic solvent together with the shell polymerization component and the polymerization initiator.

[0129] As for the polymerization conditions, the polymerization temperature is, for example, 80 to 150° C., or preferably 100 to 120° C. The polymerization time is, for example, 1 to 12 hours.

[0130] This produces a solution containing the shell polymer.

[0131] In the solution containing the shell polymer, the solids concentration of the shell polymer is, for example, 20% by mass to 70% by mass, or preferably 40% by mass to 60% by mass.

[0132] In the second step, first, the core polymer is produced by blending the core polymerization components in the presence of the shell polymer and polymerizing the core polymerization components.

[0133] As for the polymerization conditions, the polymerization temperature is, for example, 80 to 150° C., or preferably 100 to 120° C. The polymerization time is, for example, 1 to 12 hours.

[0134] In this case, the shell polymer, which is soluble in organic solvents, coats the core polymer, which is substantially insoluble in organic solvents, thereby stabilizing the core polymer. This production method produces a solution containing a nonaqueous dispersion resin having a core made of the core polymer and a shell made of the shell polymer that coats the core.

[0135] In the solution containing the non-aqueous dispersion type resin, the solid content concentration of the non-aqueous dispersion type resin is, for example, 20% by mass to 70% by mass, or preferably 40% by mass to 60% by mass.

[0136] In the non-aqueous dispersion type resin, the mass ratio of the shell to the core (shell / core) is, for example, 20 / 80 to 80 / 20, preferably 40 / 60 to 60 / 40, or more preferably 42 / 58 to 48 / 52.

[0137] The average particle size of the non-aqueous dispersion resin is, for example, 50 nm to 1500 nm, preferably 100 nm to 800 nm, and more preferably 200 nm to 600 nm.

[0138] The average particle size of the non-aqueous dispersion resin can be measured, for example, using an N4 submicron particle analyzer (manufactured by Coulter) in intensity mode at a temperature of 20°C.

[0139] The acid value of the non-aqueous dispersion resin is 0.5 mgKOH / g to 6.0 mgKOH / g, preferably 0.8 mgKOH / g to 5.5 mgKOH / g, more preferably 1.0 mgKOH / g to 5.0 mgKOH / g, even more preferably 1.5 mgKOH / g to 4.0 mgKOH / g, particularly preferably 2.0 mgKOH / g to 3.0 mgKOH / g, and most preferably 2.2 mgKOH / g to 2.5 mgKOH / g.

[0140] Specifically, the acid value of the non-aqueous dispersion resin is 0.5 mgKOH / g or more, preferably 0.8 mgKOH / g or more, more preferably 1.0 mgKOH / g or more, even more preferably 1.5 mgKOH / g or more, particularly preferably 2.0 mgKOH / g or more, most preferably 2.2 mgKOH / g or more, and is 6.0 mgKOH / g or less, preferably 5.5 mgKOH / g or less, more preferably 5.0 mgKOH / g or less, even more preferably 4.0 mgKOH / g or less, particularly preferably 3.0 mgKOH / g or less, most preferably 2.5 mgKOH / g or less.

[0141] When the acid value of the non-aqueous dispersion type resin is equal to or higher than the above lower limit, the pigment dispersibility in a paint containing the non-aqueous dispersion type resin composition can be improved.

[0142] On the other hand, if the acid value of the non-aqueous dispersion type resin is less than the above lower limit, the pigment dispersibility in the paint containing the non-aqueous dispersion type resin composition will decrease.

[0143] Furthermore, when the acid value of the non-aqueous dispersion type resin is equal to or less than the above upper limit, the pigment dispersibility in a paint containing the non-aqueous dispersion type resin composition can be improved.

[0144] On the other hand, if the acid value of the non-aqueous dispersion type resin exceeds the upper limit, the pigment dispersibility in the paint containing the non-aqueous dispersion type resin composition decreases.

[0145] The acid value can be measured according to JIS K 0070-1992 (neutralization titration method) based on the solid content of the non-aqueous dispersion-type resin.

[0146] The amine value of the non-aqueous dispersion type resin is 0.2 mgKOH / g to 4.0 mgKOH / g, preferably 0.3 mgKOH / g to 3.5 mgKOH / g, and more preferably 1.5 mgKOH / g to 3.0 mgKOH / g.

[0147] Specifically, the amine value of the non-aqueous dispersion resin is 0.2 mgKOH / g or more, preferably 0.3 mgKOH / g or more, more preferably 1.5 mgKOH / g or more, and 4.0 mgKOH / g or less, preferably 3.5 mgKOH / g or less, more preferably 3.0 mgKOH / g or less.

[0148] When the amine value of the non-aqueous dispersion type resin is equal to or greater than the above lower limit, the pigment dispersibility in a paint containing the non-aqueous dispersion type resin composition can be improved.

[0149] On the other hand, if the amine value of the non-aqueous dispersion type resin is less than the above lower limit, the pigment dispersibility in the paint containing the non-aqueous dispersion type resin composition will decrease.

[0150] Furthermore, when the amine value of the non-aqueous dispersion type resin is equal to or less than the above upper limit, the pigment dispersibility in a paint containing the non-aqueous dispersion type resin composition can be improved.

[0151] On the other hand, if the amine value of the non-aqueous dispersion type resin exceeds the upper limit, the pigment dispersibility in the paint containing the non-aqueous dispersion type resin composition decreases.

[0152] The amine value can be measured according to JIS K-7237-1995 (potentiometric titration method) based on the solid content of the non-aqueous dispersion-type resin.

[0153] The hydroxyl value of the non-aqueous dispersion resin is, for example, 10 mgKOH / g to 60 mgKOH / g, preferably 20 mgKOH / g to 50 mgKOH / g, and more preferably 30 mgKOH / g to 40 mgKOH / g.

[0154] The hydroxyl value can be measured in accordance with JIS K 0070-1992 (neutralization titration method) based on the solid content of the non-aqueous dispersion-type resin.

[0155] The weight average molecular weight of the non-aqueous dispersion type resin is, for example, 30,000 to 200,000, preferably 50,000 to 150,000, or more preferably 80,000 to 100,000.

[0156] <Hindered amine light stabilizers> The hindered amine light stabilizer has a hindered amino group represented by the following formula (2). That is, in this embodiment, the hindered amine light stabilizer contained in the non-aqueous dispersion-type resin composition has a hindered amine group, and therefore the non-aqueous dispersion-type resin composition has a hindered amino group. When the non-aqueous dispersion-type resin composition contains this hindered amine light stabilizer, it is contained in a paint containing the non-aqueous dispersion-type resin composition, and this improves the weather resistance of a coating film formed using the paint. [ka]

[0157] In the above formula (2), R 1represents a hydrogen atom, an alkyl group, or an alkoxy group. Examples of alkyl groups include linear alkyl groups having 1 to 12 carbon atoms. Examples of linear alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups. Examples of alkoxy groups include alkoxy groups having 1 to 8 carbon atoms. Examples of alkoxy groups having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, and octyloxy groups. * represents a bond.

[0158] As the hindered amino group, preferably, R 1 However, examples of the hindered amino group include a methyl group.

[0159] The hindered amine light stabilizer is not particularly limited, and examples thereof include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, and bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate. Preferred examples of the hindered amine light stabilizer include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate.

[0160] Commercially available hindered amine light stabilizers can also be used, such as Tinuvin 292 (a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, manufactured by BASF).

[0161] The hindered amine light stabilizers can be used alone or in combination of two or more kinds.

[0162] The content of the hindered amine light stabilizer is, for example, 0.1 parts by mass to 5.0 parts by mass, preferably 0.3 parts by mass to 2.0 parts by mass, more preferably 0.5 parts by mass to 1.5 parts by mass, and even more preferably 0.6 parts by mass to 1.2 parts by mass, relative to 100 parts by mass of the core polymerization component.

[0163] Specifically, the content of the hindered amine light stabilizer relative to 100 parts by mass of the core polymerization component is, from the viewpoints of weather resistance and coating stability (storage stability), for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.6 parts by mass or more, and from the viewpoints of pigment dispersibility and coating stability (storage stability), for example, 5.0 parts by mass or less, preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.2 parts by mass or less.

[0164] The content ratio of the hindered amine light stabilizer relative to 100 parts by mass of the non-aqueous dispersion-type resin is, for example, 0.1 to 1.0 parts by mass, or preferably 0.4 to 0.8 parts by mass.

[0165] The amine value of the hindered amine light stabilizer is, for example, 0.1 mgKOH / g to 2.5 mgKOH / g, preferably 0.4 mgKOH / g to 1.8 mgKOH / g, and more preferably 0.6 mgKOH / g to 1.0 mgKOH / g.

[0166] The ratio of the acid value of the shell to the amine value of the hindered amine light stabilizer (shell acid value / amine value of hindered amine light stabilizer) is, for example, 0.3 to 20.0, preferably 0.5 to 15.0, more preferably 1.0 to 10.0, even more preferably 1.5 to 7.0, particularly preferably 2.0 to 5.0, and most preferably 2.1 to 3.0.

[0167] Specifically, the ratio of the acid value of the shell to the amine value of the hindered amine light stabilizer is, from the viewpoints of pigment dispersibility and paint stability (storage stability), for example, 0.3 or more, preferably 0.5 or more, more preferably 1.0 or more, even more preferably 1.5 or more, particularly preferably 2.0 or more, and most preferably 2.1 or more; and, from the viewpoints of weather resistance and paint stability (storage stability), for example, 20.0 or less, preferably 15.0 or less, more preferably 10.0 or less, even more preferably 7.0 or less, particularly preferably 5.0 or less, and most preferably 3.0 or less.

[0168] <Additives> The non-aqueous dispersion type resin composition may contain additives in an appropriate proportion as needed. Examples of additives include drying agents, anti-sagging agents, anti-rust agents, plasticizers, coating surface conditioners, antioxidants, ultraviolet absorbers, and surfactants. The additives may be used alone or in combination of two or more.

[0169] <Production of non-aqueous dispersion type resin composition> The non-aqueous dispersion type resin composition can be obtained by mixing an organic solvent, a non-aqueous dispersion type resin, a hindered amine light stabilizer, and additives that are blended as required.

[0170] Furthermore, a non-aqueous dispersion type resin composition can also be produced by blending a hindered amine light stabilizer and optional additives after the second step in the method for producing a non-aqueous dispersion type resin.

[0171] The non-aqueous dispersion type resin composition has a hindered amino group, and the acid value of the shell is 0.5 mgKOH / g or more and 4.0 mgKOH / g or less, the acid value of the non-aqueous dispersion type resin is 0.5 mgKOH / g or more and 6.0 mgKOH / g or less, and the amine value of the non-aqueous dispersion type resin is 0.2 mgKOH / g or more and 4.0 mgKOH / g or less. Therefore, the weather resistance of the non-aqueous dispersion type resin composition, a paint containing this non-aqueous dispersion type resin composition, and ultimately a coating film formed using this paint, and pigment dispersibility in the paint can be all achieved.

[0172] Therefore, the non-aqueous dispersion type resin composition can be suitably used particularly for producing a paint. The paint containing the non-aqueous dispersion type resin composition will be described in detail below.

[0173] 2.Paint The paint contains a non-aqueous dispersion type resin composition and a pigment.

[0174] The pigment is not particularly limited. Examples of the pigment include carbon black, titanium oxide, calcium carbonate, iron oxide, barium sulfate, silica, clay, talc, quinacridone pigments, azo pigments, nitroso pigments, and phthalocyanine pigments. The pigments can be used alone or in combination of two or more.

[0175] The content of the pigment is, for example, 20 to 80 parts by mass, preferably 30 to 70 parts by mass, and more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the non-aqueous dispersion type resin composition.

[0176] The pigment content is, for example, 80 to 400 parts by mass, preferably 200 to 300 parts by mass, relative to 100 parts by mass of the solid content of the non-aqueous dispersion type resin composition (specifically, the total amount of the non-aqueous dispersion type resin, the hindered amine light stabilizer, and additives blended as necessary).

[0177] The coating preferably includes a dispersant.

[0178] The dispersant is not particularly limited. Examples of dispersants include phosphoric acid-based dispersants such as phosphoric acid, monoalkyl phosphate esters, dialkyl phosphate esters, and phosphate polyesters, alkali metal salts such as polyphosphoric acid, polycarboxylic acid-based dispersants, and nonionic dispersants. The dispersants can be used alone or in combination of two or more types.

[0179] Furthermore, the coating material may contain the above shell polymer in an appropriate proportion, if necessary.

[0180] The paint may contain a known colorant in an appropriate proportion, if necessary.

[0181] The paint is produced by mixing the non-aqueous dispersion type resin composition, the pigment, the dispersant which is optionally blended, the shell polymer which is optionally blended, and the colorant which is optionally blended, and stirring it as necessary.

[0182] The paint contains a non-aqueous dispersion type resin composition, and therefore has excellent weather resistance and pigment dispersibility.

[0183] When the core polymerization component contains a hydroxyl group-containing vinyl monomer, the non-aqueous dispersion-type resin composition can also be used by blending a curing agent (for example, a polyisocyanate compound).

[0184] 3. Effects The non-aqueous dispersion type resin composition has a hindered amino group, and the acid value of the shell is 0.5 mgKOH / g or more and 4.0 mgKOH / g or less, the acid value of the non-aqueous dispersion type resin is 0.5 mgKOH / g or more and 6.0 mgKOH / g or less, and the amine value of the non-aqueous dispersion type resin is 0.2 mgKOH / g or more and 4.0 mgKOH / g or less. Therefore, the weather resistance of the non-aqueous dispersion type resin composition, a paint containing this non-aqueous dispersion type resin composition, and ultimately a coating film formed using this paint, and pigment dispersibility in the paint can be all achieved.

[0185] Conventionally, paints have been proposed that contain a pigment, a base resin (synthetic resin), and a dispersant (pigment dispersant), and that contain a non-aqueous dispersion type resin as the base resin.

[0186] On the other hand, weather resistance is required for paints depending on their purpose and use, and therefore, from the viewpoint of improving weather resistance, the incorporation of hindered amine light stabilizers into paints has been considered.

[0187] However, it was found that the incorporation of a hindered amine light stabilizer into a paint causes a problem of reduced pigment dispersibility. It is presumed that this problem occurs because the incorporation of a hindered amine light stabilizer changes the interaction between the dispersant and the pigment in the presence of a non-aqueous dispersion-type resin, resulting in a reduction in pigment dispersibility. When pigment dispersibility is reduced, a problem occurs in which color unevenness occurs in the paint film after the paint is applied to form a paint film.

[0188] On the other hand, in the non-aqueous dispersion type resin composition, the acid value of the shell, the acid value of the non-aqueous dispersion type resin, and the amine value of the non-aqueous dispersion type resin are adjusted to the above ranges. This adjusts the above-mentioned interaction that is changed by blending a hindered amine light stabilizer. As a result, the above-mentioned weather resistance and pigment dispersibility can be simultaneously achieved.

[0189] Furthermore, in the non-aqueous dispersion type resin composition, the acid value of the shell, the acid value of the non-aqueous dispersion type resin, and the amine value of the non-aqueous dispersion type resin are adjusted to the above-mentioned ranges. When the acid value of the shell, the acid value of the non-aqueous dispersion type resin, and the amine value of the non-aqueous dispersion type resin are adjusted to the above-mentioned ranges, if the solubility parameters of the shell and the core are each within the above-mentioned ranges, the above-mentioned weather resistance and pigment dispersibility can be more reliably achieved.

[0190] Incidentally, even in the above-mentioned paints that do not contain a dispersant, the problems caused by blending a hindered amine light stabilizer into the paint similarly occur, although the mechanism is not clear. In paints having such a configuration, by adjusting the acid value of the shell in the non-aqueous dispersion-type resin composition, the acid value of the non-aqueous dispersion-type resin, and the amine value of the non-aqueous dispersion-type resin within the above-mentioned ranges, it is possible to achieve both the above-mentioned weather resistance and pigment dispersibility, even if a hindered amine light stabilizer is blended into the paint.

[0191] 4. Variations In the above description, the non-aqueous dispersion type resin composition contains a hindered amine-based light stabilizer, and thus the non-aqueous dispersion type resin composition has a hindered amino group derived from the hindered amine-based light stabilizer. However, the present invention is not limited to this, and a modified example is also possible in which the shell polymerization component contains a hindered amino group-containing (meth)acrylate, and thus the non-aqueous dispersion type resin composition has a hindered amino group derived from the hindered amino group-containing (meth)acrylate. This modified example will be described below.

[0192] Examples of the hindered amino group-containing (meth)acrylate include 1,2,2,6,6-pentamethyl-4-piperidyl(meth)acrylate (e.g., Adekastab LA82, manufactured by ADEKA Corporation) and 2,2,6,6-tetramethyl-4-piperidyl(meth)acrylate. Examples of the hindered amino group-containing (meth)acrylate include preferably 1,2,2,6,6-pentamethyl-4-piperidyl(meth)acrylate. Examples of the hindered amino group-containing (meth)acrylate include more preferably 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate.

[0193] The hindered amino group-containing (meth)acrylates can be used alone or in combination of two or more kinds.

[0194] The content of the hindered amino group-containing (meth)acrylate relative to the shell polymerization component is, for example, 0.1 mass % to 5.0 mass %, preferably 0.5 mass % to 4.0 mass %, more preferably 1.0 mass % to 3.0 mass %, and even more preferably 1.5 mass % to 2.5 mass %.

[0195] The content of the hindered amino group-containing (meth)acrylate relative to the shell polymerization component is, from the viewpoint of weather resistance, for example, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and even more preferably 1.5 mass% or more, and from the viewpoint of facilitating control of viscosity and molecular weight when polymerizing the shell polymerization component, for example, 5.0 mass% or less, preferably 4.0 mass% or less, more preferably 3.0 mass% or less, and even more preferably 2.5 mass% or less.

[0196] In such cases, the shell polymerization component contains a hindered amino group-containing (meth)acrylate and forms a shell polymer containing structural units derived from the hindered amino group-containing (meth)acrylate, so that the non-aqueous dispersion resin, and ultimately the non-aqueous dispersion resin composition, has a hindered amino group derived from the hindered amino group-containing (meth)acrylate. Furthermore, in such cases, as described above, it is presumed that the interaction between the dispersant and the pigment in the presence of the non-aqueous dispersion resin changes, resulting in a more pronounced problem of reduced pigment dispersibility in the paint.

[0197] In the non-aqueous dispersion type resin composition having such a configuration, the hindered amino group-containing (meth)acrylate is incorporated into the non-aqueous dispersion type resin as a structural unit derived from the hindered amino group-containing (meth)acrylate, and therefore can be said to be a reactive hindered amine light stabilizer (HALS).

[0198] Furthermore, when the non-aqueous dispersion-type resin composition contains a hindered amine-based light stabilizer and the shell polymerization component contains a hindered amino group-containing (meth)acrylate, the non-aqueous dispersion-type resin composition can have a hindered amino group derived from the hindered amine-based light stabilizer and a hindered amino group derived from the hindered amino group-containing (meth)acrylate.

[0199] Preferably, from the viewpoint of weather resistance, the non-aqueous dispersion type resin composition contains a hindered amine-based light stabilizer, and the non-aqueous dispersion type resin composition has a hindered amino group derived from the hindered amine-based light stabilizer.

[0200] Specifically, when a non-aqueous dispersion type resin composition contains a hindered amine light stabilizer, the hindered amine light stabilizer is independent and not linked to the non-aqueous dispersion type resin. That is, the hindered amine light stabilizer is unreacted with the non-aqueous dispersion type resin. In other words, the hindered amine light stabilizer is an additive to the non-aqueous dispersion type resin in the non-aqueous dispersion type resin composition. Therefore, when a coating material containing the non-aqueous dispersion type resin composition is applied to form a coating film, a high proportion of the hindered amine light stabilizer is present on the surface of the coating film. As a result, the weather resistance of the coating film can be further improved.

[0201] On the other hand, since the hindered amine light stabilizer is independent of the non-aqueous dispersible resin, it is presumed that the interaction between the dispersant and the pigment in the presence of the non-aqueous dispersible resin changes, resulting in a more pronounced decrease in pigment dispersibility.

[0202] However, as described above, in the non-aqueous dispersion-type resin composition, the acid value of the shell, the acid value of the non-aqueous dispersion-type resin, and the amine value of the non-aqueous dispersion-type resin are adjusted to fall within predetermined ranges, so that both weather resistance and pigment dispersibility can be achieved even if the effect of adding a hindered amine light stabilizer, i.e., the effect of reducing pigment dispersibility, becomes more pronounced. [Example]

[0203] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0204] 1. Examination of the acid value of Shell and NAD resin and the amine value of NAD resin Example 1 <Ingredient details> ADK STAB LA82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, manufactured by ADEKA Corporation Tinuvin 292: a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by BASF

[0205] <Synthesis of alkyd resin> The following mixture and 86.0 parts by mass of xylene as a reflux solvent were charged into a reaction vessel, and the temperature was raised to 250°C. While removing water from the reaction system using a water separator, the mixture was reacted until the acid value reached 15 mgKOH / g or less, thereby producing a xylene solution of an alkyd resin. {mixture} Linseed oil: 1080 parts by mass (38.2% by mass) Dehydrated castor oil fatty acids: 363 parts by mass (12.8% by mass) Glycerin: 52 parts by mass (1.8% by mass) Pentaerythritol: 492 parts by mass (17.4% by mass) Phthalic anhydride: 800 parts by mass (28.3% by mass) Benzoic acid: 43 parts by mass (1.5% by mass)

[0206] Next, when the acid value of the xylene solution of the alkyd resin reached 15 mg KOH / g or less, the xylene was removed by vacuum distillation and the mixture was allowed to cool. The resulting alkyd resin was then diluted with 1624 parts by mass of mineral spirits to obtain a mineral spirits solution of the alkyd resin (solids concentration 60.0 mass%). The acid value of the mineral spirits solution of the alkyd resin was 9.5 mg KOH / g.

[0207] <Production of non-aqueous dispersion type resin composition> (1st step) 13.4 parts by mass of the mineral spirit solution of the alkyd resin obtained in the above Synthesis Example (solid content concentration 60.0% by mass) and 420.5 parts by mass of mineral spirit were charged into a reaction vessel, and the mixture was stirred while passing nitrogen gas through and heated to 105°C.

[0208] Next, the following shell polymerization components and 4.8 parts by mass of t-butylperoxyisopropyl monocarbonate (polymerization initiator) were added dropwise to the reaction vessel over 2.5 hours while maintaining the temperature at 105° C. Note that the proportions in parentheses for the shell polymerization components indicate the proportion of each component when the total amount of the shell polymerization components is taken as 100% by mass. {Shell polymer component} Isobutyl methacrylate: 302.6 parts by mass (59.3% by mass) 2-Ethylhexyl acrylate: 39.8 parts by mass (7.8% by mass) 2-Ethylhexyl methacrylate: 59.8 parts by mass (11.7% by mass) 2-Hydroxyethyl acrylate: 31.7 parts by mass (6.2% by mass) Styrene: 76.6 parts by mass (15.0% by mass) Methacrylic acid: 0.3 parts by mass (0.05% by mass)

[0209] After the dropwise addition of the shell polymerization components was completed, the reaction was carried out for 4.5 hours at 105° C. After the reaction, 55.4 parts by mass of mineral spirits was added to the reaction vessel while cooling, to obtain a solution containing a shell polymer.

[0210] (2nd process) 422.3 parts by mass of a solution containing a shell polymer (solid content concentration 51.9% by mass) and 195.6 parts by mass of mineral spirits were placed in a reaction vessel, and the mixture was stirred while passing nitrogen gas through it and heated to 112°C.

[0211] Next, the following core polymerization component and 2.9 parts by mass of t-butylperoxyisopropyl monocarbonate (polymerization initiator) were added dropwise to the reaction vessel over 2.5 hours while maintaining the temperature at 112° C. Note that the percentages in parentheses for the core polymerization component indicate the percentage of each component when the total amount of the core polymerization components is taken as 100% by mass. {Core polymer component} Methyl methacrylate: 97.8 parts by mass (36.4% by mass) Isobutyl methacrylate: 70.4 parts by mass (26.2% by mass) Acrylonitrile: 0.3 parts by mass (0.1% by mass) 2-Hydroxyethyl acrylate: 21.9 parts by mass (8.2% by mass) N,N-dimethylaminoethyl methacrylate: 0.4 parts by mass (0.2% by mass) Styrene: 24.4 parts by mass (9.1% by mass) Acrylic acid: 0.3 parts by mass (0.1% by mass) Methacrylic acid: 0.3 parts by mass (0.1% by mass) n-Butyl acrylate: 52.8 parts by mass (19.7% by mass)

[0212] After the dropwise addition of the core polymerization component was completed, the mixture was reacted at 112°C for 4.5 hours. After the reaction, heating was stopped, and 33.9 parts by mass of mineral spirits, 50.5 parts by mass of Ipsol 100 (manufactured by Idemitsu Kosan Co., Ltd.), and 2.0 parts by mass of Tinuvin 292 as a hindered amine light stabilizer were added to the reaction vessel and stirred. This produced a non-aqueous dispersion type resin composition (solid content concentration 49.5% by mass).

[0213] Examples 2 to 14 and Comparative Examples 1 to 3 Non-aqueous dispersion-type resin compositions were produced using the same procedure as in Example 1. However, the blending ratio of each component was changed based on the descriptions in Tables 1 to 4. In Tables 1 to 4, the numerical values ​​for the core polymerization component indicate the ratio of each component when the total amount of the core polymerization component is 100% by mass. In Tables 1 to 4, the numerical values ​​for the shell polymerization component indicate the ratio of each component when the total amount of the shell polymerization component is 100% by mass. In Tables 1 to 4, the numerical values ​​for the hindered amine light stabilizer indicate the content ratio of the hindered amine light stabilizer relative to 100 parts by mass of the core polymerization component. In Examples 11 and 12, ADK STAB LA82 was blended as a hindered amino group-containing (meth)acrylate into the shell polymerization component, but a hindered amine light stabilizer (Tinuvin 292) was not blended.

[0214] <Evaluation> (Weight average molecular weight) The weight-average molecular weight of the shell polymer and non-aqueous dispersion resin of each example and each comparative example was measured by gel permeation chromatography (GPC). Specifically, the sample was dissolved in tetrahydrofuran and measured using a GPC equipped with a refractive index detector (RID) under the following conditions. The weight-average molecular weight was then calculated from the obtained chromatogram (chart) using standard polystyrene as a calibration curve. The results are shown in Tables 1 to 4. {conditions} Equipment: Tosoh HLC-8420GPC Detector: Differential refractive index detector Column: Two TSKgel SuperHZM-H columns manufactured by Tosoh Corporation Mobile phase: tetrahydrofuran Column temperature: 40℃ Sample concentration: 0.8% by mass Flow rate: 1.0mL / min Injection volume: 100μL Standard polystyrene for calibration: Tosoh product name "TSKgel Standard Polystyrene"

[0215] (acid number) The acid values ​​of the shells (shell polymers) and non-aqueous dispersion resins of each Example and Comparative Example were measured based on the solid content of the shell polymer and non-aqueous dispersion resin in accordance with JIS K 0070-1992 (neutralization titration method). The results are shown in Tables 1 to 4.

[0216] (Hydroxyl value) The hydroxyl values ​​of the shells (shell polymers) and non-aqueous dispersion resins of each Example and Comparative Example were measured based on the solid content of the shell polymer and non-aqueous dispersion resin in accordance with JIS K 0070-1992 (neutralization titration method). The results are shown in Tables 1 to 4.

[0217] (amine value) The amine value of the shell (shell polymer), non-aqueous dispersion type resin, and hindered amine light stabilizer of each Example and Comparative Example was measured based on the solid content of the shell polymer, non-aqueous dispersion type resin, and hindered amine light stabilizer according to JIS K-7237-1995 (potentiometric titration method). The results are shown in Tables 1 to 4.

[0218] (glass transition temperature) The glass transition temperatures of the cores (core polymers) and shells (shell polymers) of the examples and comparative examples were calculated based on the Fox equation shown below in (3). The results are shown in Tables 1 to 4.

[0219] 1 / Tg=W1 / Tg1+W2 / Tg2++Wn / Tgn (3) [Wherein, Tg is the glass transition temperature of the core polymer or shell polymer (unit: K), Tgi (i = 1, 2, . . . n) is the glass transition temperature (unit: K) when monomer i forms a homopolymer. Wi (i = 1, 2,...n) represents the mass fraction of monomer i in all monomers.

[0220] For special monomers with unknown glass transition temperatures, such as ADK STAB LA82, if the total amount of monomers with unknown glass transition temperatures is 5.0 mass% or less, calculations were made using only monomers with known glass transition temperatures.

[0221] (Solubility parameter) The solubility parameters (SP values) of the cores (core polymers) and shells (shell polymers) of each Example and Comparative Example were determined. Specifically, the SP values ​​were calculated by substituting the cohesive energy constants of each Hoy atomic group into the Small formula (1) above. The results are shown in Tables 1 to 4.

[0222] For special monomers (atomic groups) with unknown cohesive energy constants, such as ADK STAB LA82, if the total amount of monomers with unknown cohesive energy constants is 5.0 mass% or less, calculations were made using only monomers with known cohesive energy constants.

[0223] (Paint manufacturing) 21.5 parts by mass of the shell polymer of Example 6 (solid content concentration 51.9% by mass), 12.7 parts by mass of mineral spirits, 24.8 parts by mass of titanium oxide JR-603 (manufactured by Teika Corporation) as a pigment, and 41.0 g of glass beads were added and dispersed using a homodisper at a rotation speed of 3,000 rpm for a treatment time of 20 minutes. The beads were then removed using a wire mesh. This yielded a composition.

[0224] Next, 47.6 parts by weight of the above composition, 42.3 parts by weight of the non-aqueous dispersion type resin composition (solid content concentration 49.5% by weight) of each Example and Comparative Example, and 10.1 parts by weight of mineral spirits were mixed at 1,500 rpm for 5 minutes, and 2.0 parts by weight each of UNILANT 55 (manufactured by Yokohama Chemical Industry Co., Ltd.) black, ochre, and red rust colorants were added and mixed at 1,500 rpm for 5 minutes. Next, hexamethylene diisocyanate (manufactured by Asahi Chemical Industry Co., Ltd., "Duranate TPA-100") was added as a curing agent to achieve an NCO / OH ratio of 1.0. This produced the paints of each Example and Comparative Example.

[0225] (pigment dispersibility) The paints of each example and comparative example were applied in a constant temperature and humidity chamber at 23°C and 50% RH at a coating amount of 100 g / m 2 The coating was applied to a tin plate with a roller so that the dispersion was within ±10%, and then the plate was left to dry. After drying, the presence and number of black raised areas (mottle patterns) on the coating film were checked. The pigment dispersibility was evaluated based on the following criteria. The results are shown in Tables 1 to 4. In addition, if the evaluation was A to C according to the following criteria, it can be evaluated as being at a level that presents no practical problems. {standard} A: There was no difference in color on the coated surface and it was uniform. B: There was a slight difference in color on the coated surface. C: There were some spots on the coated surface that were mottled. D: There were some areas on the coated surface where the mottled pattern was noticeable. E: The coated surface had noticeable mottled patterns all over.

[0226] (weather resistance) The paint of each example and comparative example was applied to a 0.8 mm thick dull steel plate (150 mm × 70 mm) using a No. 75 bar coater. The dull steel plate was then dried for one week indoors at 23°C and 50% RH, and the gloss retention (60°GR) after 2500 hours of exposure under the following conditions was calculated using an Eye Super Xenon Tester XER-W75 (manufactured by Iwasaki Electric Co., Ltd.) according to the following formula (4). Weather resistance was evaluated according to the following criteria. The results are shown in Tables 1 to 4. According to the following criteria, a rating of A to C can be considered to be at a level that is acceptable for practical use. Gloss retention (%) = {Specular gloss of test piece after exposure (60°) / Specular gloss of test piece before exposure (60°)} × 100 (4) {conditions} UV irradiation intensity: 67W / m 2 Wetting time: 18 minutes Drying time: 102 minutes Temperature and humidity: 63°C, 50% RH {standard} A: Gloss retention was 80% or more. B: Gloss retention was 70% or more and less than 80%. C: Gloss retention was 60% or more and less than 70%. D: Gloss retention was 50% or more and less than 60%. E: Gloss retention was less than 50%.

[0227] (Paint stability (storage stability)) The paints of each example and comparative example were left to stand in a thermostatic bath at 23°C, and then their viscosity was measured using an E-type viscometer. They were then stored in a 50°C oven for 5 days, removed from the oven, and stirred. They were then left to stand in a thermostatic bath at 23°C, and their viscosity was measured using an E-type viscometer. The viscosity change rate was calculated based on the following formula (5). The paint stability (storage stability) was evaluated based on the following criteria. The results are shown in Tables 1 to 4. In addition, if the paint is rated A to C according to the following criteria, it can be evaluated as being at a level that presents no practical problems. Viscosity change rate (%) = (| Viscosity after storage - Viscosity before storage | / Viscosity before storage) × 100 (5) {standard} A: There was no significant separation of the pigment, and the viscosity change rate was less than 10%. B: There was no significant separation of the pigment, and the viscosity change rate was 10% or more but less than 20%. C: There was no significant separation of the pigment, and the viscosity change rate was 20% or more but less than 30%. D: There was no significant separation of the pigment, and the viscosity change rate was 30% or more. E: Significant separation and sedimentation of the paint occurred.

[0228] [Table 1]

[0229] [Table 2]

[0230] [Table 3]

[0231] [Table 4]

[0232] 2. Examination of the amine value of hindered amine light stabilizers Examples 15 to 17 A non-aqueous dispersion-type resin composition was produced based on the same procedure as in Example 1. However, the blending ratio of each component was changed based on the description in Table 5. In Table 5, the numerical values ​​for the core polymerization component indicate the ratio of each component when the total amount of the core polymerization component is taken as 100 mass%. In Table 5, the numerical values ​​for the shell polymerization component indicate the ratio of each component when the total amount of the shell polymerization component is taken as 100 mass%. In Table 5, the numerical values ​​for the hindered amine light stabilizer indicate the content ratio of the hindered amine light stabilizer relative to 100 parts by mass of the core polymerization component.

[0233] <Evaluation> The nonaqueous dispersion-type resin compositions of Examples 15 to 17 were evaluated for weight average molecular weight, acid value, hydroxyl value, amine value, glass transition temperature, solubility parameter, pigment dispersibility, weather resistance, and paint stability (storage stability) in the same manner as in Examples 2 to 14 and Comparative Examples 1 to 3. The results of these evaluations are shown in Table 5. [Table 5]

[0234] 3. Examination of the solubility parameters (SP values) of the shell and core Examples 18 to 25 and Comparative Examples 4 and 5 A nonaqueous dispersion-type resin composition was produced based on the same procedure as in Example 1. However, the blending ratio of each component was changed based on the descriptions in Tables 6 and 7. In Tables 6 and 7, the numerical values ​​for the core polymerization component indicate the ratio of each component when the total amount of the core polymerization component is 100 mass%. In Tables 6 and 7, the numerical values ​​for the shell polymerization component indicate the ratio of each component when the total amount of the shell polymerization component is 100 mass%. In Tables 6 and 7, the numerical values ​​for the hindered amine light stabilizer indicate the content ratio of the hindered amine light stabilizer relative to 100 parts by mass of the core polymerization component.

[0235] <Evaluation> The nonaqueous dispersion-type resin compositions of Examples 18 to 25 and Comparative Examples 4 and 5 were evaluated for weight-average molecular weight, acid value, hydroxyl value, amine value, glass transition temperature, solubility parameter, pigment dispersibility, weather resistance, and paint stability (storage stability) in the same manner as in Examples 2 to 14 and Comparative Examples 1 to 3. The results of these evaluations are shown in Tables 6 and 7. [Table 6]

[0236] [Table 7]

[0237] 4. Examination of styrene content in the shell Examples 26 to 29 A non-aqueous dispersion-type resin composition was produced based on the same procedure as in Example 1. However, the blending ratio of each component was changed based on the description in Table 8. In Table 8, the numerical values ​​for the core polymerization component indicate the ratio of each component when the total amount of the core polymerization component is 100 mass%. In Table 8, the numerical values ​​for the shell polymerization component indicate the ratio of each component when the total amount of the shell polymerization component is 100 mass%. In Table 8, the numerical values ​​for the hindered amine light stabilizer indicate the content ratio of the hindered amine light stabilizer relative to 100 parts by mass of the core polymerization component.

[0238] <Evaluation> The nonaqueous dispersion-type resin compositions of Examples 26 to 29 were evaluated for weight average molecular weight, acid value, hydroxyl value, amine value, glass transition temperature, solubility parameter, pigment dispersibility, weather resistance, and paint stability (storage stability) in the same manner as in Examples 2 to 14 and Comparative Examples 1 to 3. The results of these evaluations are shown in Table 8.

[0239] [Table 8]

Claims

1. an organic solvent comprising a hydrocarbon solvent; A non-aqueous dispersion resin composition comprising a core and a non-aqueous dispersion resin having a shell covering the core, the core is a polymer of a core polymerization component, the core polymerization component polymer is substantially insoluble in the organic solvent; the shell is a polymer of a shell polymerization component, the polymer of the shell polymerization component is soluble in the organic solvent, the acid value of the shell is 0.5 mgKOH / g or more and 4.0 mgKOH / g or less; The acid value of the non-aqueous dispersion resin is 0.5 mgKOH / g or more and 6.0 mgKOH / g or less, the amine value of the non-aqueous dispersion resin is 0.2 mgKOH / g or more and 4.0 mgKOH / g or less; The non-aqueous dispersion type resin composition has a hindered amino group.

2. 2. The non-aqueous dispersion type resin composition according to claim 1, wherein the polymer of the core polymerization component is an alkyd-modified acrylic resin.

3. the non-aqueous dispersion resin composition contains a hindered amine light stabilizer, 2. The non-aqueous dispersion resin composition according to claim 1, wherein a ratio of an acid value of the shell to an amine value of the hindered amine light stabilizer is 0.3 or more and 20.0 or less.

4. The solubility parameter of the shell is 7.70 (cal / cm ３ ) １／２ 7.90 (cal / cm) ３ ) １／２ is as follows: The solubility parameter of the core is 7.90 (cal / cm ３ ) １／２ 8.25 (cal / cm) ３ ) １／２ The non-aqueous dispersion resin composition according to claim 1, wherein:

5. The non-aqueous dispersion resin composition according to claim 1 , wherein the shell polymerization component comprises styrene.

6. A paint comprising the non-aqueous dispersion type resin composition according to any one of claims 1 to 5 and a pigment.

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