Viscosity modifier for non-aqueous coating material and non-aqueous coating material composition

Abstract

Provided is a polymer-type viscosity modifier for a non-aqueous coating material. The viscosity modifier exhibits good thickening properties and can be added to a coating material at a solid content of 100%. A polymer obtained by reacting a compound (A) with a compound (B) is used as this viscosity modifier for a non-aqueous coating material. The compound (A) is one or more compounds from among: hydroxycarboxylic acids; polyesters obtained by dehydration condensation of a monomer component (A1) including a hydroxycarboxylic acid; and modified polyesters obtained by dehydration condensation of the monomer component (A1) and a modification component (A2). The compound (A) satisfies the condition: the value of hydroxyl value / (acid value + amine value) is 0.5-1.2. The modification component (A2) is a compound having one functional group capable of dehydration condensation with a carboxyl group, and having one or more polar functional groups incapable of dehydration condensation with a carboxyl group. The compound (B) is one or more compounds from among polyisocyanates, derivatives thereof, and polycarboxylic acids having 4-54 carbon atoms.

Description

Viscosity modifiers for non-aqueous coatings and non-aqueous coating compositions

[0001] The present invention relates to viscosity modifiers for non-aqueous coatings and non-aqueous coating compositions.

[0002] Polymer-type viscosity modifiers, consisting of vegetable oils, polymerized oils, waxes, and other non-particulate polymers, are known as viscosity modifiers for non-aqueous paints. Generally, polymer-type viscosity modifiers have functional groups (hereinafter referred to as "adsorption groups") that can adsorb to inorganic fine particles such as pigments, and exert a thickening effect by forming an aggregated structure through adsorption to inorganic fine particles.

[0003] In general, viscosity modifiers often require heating or strong shearing before use. For example, in the case of paste-type viscosity modifiers with amide compound-based (amide) waxes as the active ingredient, strong shearing is necessary to separate the tightly bound particles. One method of applying strong shearing to paste-type viscosity modifiers is the preparation of "pregel." This "pregel" is a high-concentration dispersion of paste-type viscosity modifier in a medium such as a resin solution, and strong shearing is applied to achieve this high-concentration dispersion. In the case of hydrogenated castor oil or amide-based powdered viscosity modifiers, heating the viscosity modifier is necessary to convert (activate) it into an appropriate particle shape (needle-shaped form) that can exert its thickening effect. On the other hand, polymer-type viscosity modifiers do not exist in particle form, and unlike the paste-type and powder-type viscosity modifiers mentioned above, they do not require strong shearing (pregel preparation) or heating, and can exert their thickening effect simply by mixing them with a resin solution at any time. Therefore, polymer-type viscosity modifiers offer greater flexibility in the timing of their addition to paints.

[0004] As an example of such polymer-type viscosity modifiers, Patent Document 1 discloses a sagging prevention agent comprising a polyamide, polyester, or polyurethane obtained using a dimeric acid and / or derivative thereof obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms, wherein the molecule has a dimethylamino group or a diethylamino group at its terminal end.

[0005] Patent Document 2 discloses a thixotropy-imparting agent consisting of a polyamide-polyurethane polymer obtained by reacting 12-hydroxystearic acid and castor oil fatty acid with polyamines and polyisocyanates.

[0006] Patent Document 3 discloses a urea compound obtained by reacting a urethane compound, which is produced by reacting a monohydric alcohol with a diisocyanate, with an amidate, which is produced by reacting a monohydric aliphatic acid with a diamine, in equivalent amounts of isocyanate residue and amine residue.

[0007] Patent Document 4 discloses a thixotropic composition comprising a diurea-diurethane compound having a specific molecular structure (a compound having two urea functional groups and two urethane functional groups) and an aprotic solvent.

[0008] Japanese Patent Publication No. 2003-183583, Japanese Patent Publication No. 2008-115199, Japanese Patent Publication No. Hei 5-247387, Japanese Patent Publication No. 2023-552227

[0009] However, in the anti-sagging agents described in Patent Document 1, those using polyamide and polyurethane as non-particulate polymers have high crystallinity and solidify, making it difficult to add them to paint at 100% solid content. If 100% solid content cannot be added, problems arise such as an increase in the amount of solvent brought into the paint and an increase in transportation costs. On the other hand, those using polyester as the non-particulate polymer can be added to paint at 100% solid content, but they have the problem of poor viscosity when added to paint.

[0010] Furthermore, the thixotropy-imparting agent described in Patent Document 2 uses a solvent during synthesis, resulting in high crystallinity and solidification, making it difficult to add to paints with 100% solid content.

[0011] Furthermore, the anti-sagging agent described in Patent Document 3 and the thixotropic composition described in Patent Document 4 have a high proportion of urethane and urea bonds, resulting in high crystallinity and solidification, making it difficult to add them to paints with 100% solid content.

[0012] Thus, until now, no polymer-type viscosity modifier for non-aqueous paints existed that combined good viscosity-increasing properties with a form that could be added as 100% solids.

[0013] Therefore, the present invention has been made in view of the above circumstances, and aims to provide a polymer-type viscosity modifier for non-aqueous paints that exhibits good viscosity increasing properties and can be added to paints with a solid content of 100%.

[0014] The inventors of the present invention conducted extensive research to solve the above problems and discovered that a viscosity modifier consisting of a polymer obtained by reacting a hydroxycarboxylic acid or its polymer or copolymer with a polyisocyanate or polycarboxylic acid in a specific ratio can exhibit good viscosity increasing properties when added to non-aqueous paints and can be added to paints with 100% solid content. Based on this finding, the inventors completed the present invention.

[0015] In other words, the present invention comprises a polymer (P) obtained by reacting compound (A) and compound (B), wherein compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, wherein monomer component (A1) consists of hydroxycarboxylic acid as an essential component and lactone as an optional component, and modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group, and the monomer - A viscosity modifier for non-aqueous paints, wherein the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, when the hydroxyl group equivalent of compound (A) is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) to compound (B) (mass of compound (A): mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) in terms of polystyrene is 1,000 or more and 100,000 or less.

[0016] In one embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) may have 2 to 24 carbon atoms.

[0017] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the sum of the acid value and amine value of compound (A) may be 10 or more and 200 or less.

[0018] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, compound (B) may be a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups.

[0019] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, compound (B) may be a divalent to tetravalent polycarboxylic acid.

[0020] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the functional group (FG1) may be a hydroxyl group, a primary amino group, or a secondary amino group.

[0021] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the polar functional group (FG2) may be one or more functional groups selected from the group consisting of tertiary amino groups, sulfonic acid groups, and carboxyl groups.

[0022] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, compound (B) may be a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups.

[0023] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, compound (B) may be a divalent to tetravalent polycarboxylic acid.

[0024] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the functional group (FG1) may be a hydroxyl group, a primary amino group, or a secondary amino group.

[0025] In another embodiment of the viscosity modifier for non-aqueous coatings of the present invention, the polar functional group (FG2) may be one or more functional groups selected from the group consisting of tertiary amino groups, sulfonic acid groups, and carboxyl groups.

[0026] Furthermore, the present invention relates to a non-aqueous coating composition containing a viscosity modifier, inorganic fine particles, and a resin component, wherein the viscosity modifier consists of a polymer (P) obtained by reacting compound (A) and compound (B), and compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, the monomer component (A1) consists of hydroxycarboxylic acid as an essential component and lactone as an optional component, and the modified component (A2) has one functional group (FG1) that can undergo dehydration condensation with a carboxyl group, and a polar functional group that cannot undergo dehydration condensation with a carboxyl group ( The compound (A) is a compound having one or more FG2, wherein the percentage of the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of the monomer component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, and the compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, and the water of the compound (A) The non-aqueous paint composition is such that, when the acid group equivalent is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) to compound (B) (mass of compound (A):mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) on a polystyrene basis is 1,000 or more and 100,000 or less.

[0027] In one embodiment of the non-aqueous coating composition of the present invention, the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) may have 2 to 24 carbon atoms.

[0028] In another embodiment of the non-aqueous coating composition of the present invention, the sum of the acid value and amine value of compound (A) may be 10 or more and 200 or less.

[0029] In another aspect of the non-aqueous paint composition of the present invention, the compound (B) may be a polyisocyanate having two or three isocyanate groups and / or a derivative of a polyisocyanate having two or three isocyanate groups.

[0030] In another aspect of the non-aqueous paint composition of the present invention, the compound (B) may be a divalent to tetravalent polycarboxylic acid.

[0031] In another aspect of the non-aqueous paint composition of the present invention, the functional group (FG1) may be a hydroxyl group, a primary amino group or a secondary amino group.

[0032] In another aspect of the non-aqueous paint composition of the present invention, the polar functional group (FG2) may be one or more functional groups selected from the group consisting of a tertiary amino group, a sulfonic acid group and a carboxyl group.

[0033] In another aspect of the non-aqueous paint composition of the present invention, the compound (B) may be a polyisocyanate having two or three isocyanate groups and / or a derivative of a polyisocyanate having two or three isocyanate groups.

[0034] In another aspect of the non-aqueous paint composition of the present invention, the compound (B) may be a divalent to tetravalent polycarboxylic acid.

[0035] In another aspect of the non-aqueous paint composition of the present invention, the functional group (FG1) may be a hydroxyl group, a primary amino group or a secondary amino group.

[0036] In another aspect of the non-aqueous paint composition of the present invention, the polar functional group (FG2) may be one or more functional groups selected from the group consisting of a tertiary amino group, a sulfonic acid group and a carboxyl group.

[0037] In another aspect of the non-aqueous paint composition of the present invention, the content of the viscosity modifier may be 0.1% by mass or more and 20% by mass or less based on the total amount of the non-aqueous paint composition.

[0038] According to the present invention, as the non-particulate polymer constituting the viscosity modifier for non-aqueous paints, by using a polymer obtained by reacting a hydroxycarboxylic acid or its polymer or its copolymer with a polyisocyanate or a polyvalent carboxylic acid, it is possible to exhibit good thickening properties and to provide a polymer-type viscosity modifier for non-aqueous paints in a form that can be added to the paint at 100% solids content.

[0039] It is a schematic diagram conceptually showing the molecular structure of the polymer used as the viscosity modifier of the present invention. It is a schematic diagram conceptually showing an example of the mechanism of action of the thickening effect of the viscosity modifier of the present invention. It is a schematic diagram conceptually showing another example of the mechanism of action of the thickening effect of the viscosity modifier of the present invention.

[0040] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In this specification and the drawings, components denoted by the same reference numerals shall have substantially the same structure or function.

[0041] [Viscosity Modifier for Non-Aqueous Paints] The viscosity modifier for non-aqueous paints according to the present invention is composed of a polymer (P) obtained by reacting a compound (A) and a compound (B). In the viscosity modifier according to the present invention, as will be described in detail later, the hydroxyl group of the compound (A) reacts with the isocyanate group (hereinafter sometimes referred to as "NCO group") or carboxyl group of the compound (B) described later, whereby a polymer (P) in which the compound (A) and the compound (B) are crosslinked by a urethane bond or an ester bond is obtained. Since this polymer (P) has a carboxyl group derived from the compound (A) or a polar functional group (FG2) derived from the modified component (A2), by adsorbing to inorganic fine particles, which are components of the non-aqueous paint, using these carboxyl groups or the polar functional group (FG2) derived from the modified component (A2) as adsorption groups, the effect of thickening the paint is exhibited. Hereinafter, the compound (A) and the compound (B) will be described in detail.

[0042] (Compound (A)) Compound (A) is one or more compounds selected from the group consisting of a hydroxycarboxylic acid, a polyester (PE1) obtained by dehydration condensation of monomer component (A1), and a modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and is an essential component in polymer (P) of the present invention.

[0043] <Hydroxycarboxylic Acids> Specific examples of hydroxycarboxylic acids that can be used as compound (A) include monohydroxymonocarboxylic acids such as 12-hydroxystearic acid (hereinafter referred to as "12-HSA"), ricinoleic acid (also called "ricinoleic acid"), glycolic acid, lactic acid, 3-hydroxybutanoic acid, 4-hydroxyundecanoic acid, and cerebronic acid. In addition, hydroxycarboxylic acids with two or more hydroxyl groups or carboxyl groups may be used. Such hydroxycarboxylic acids are not particularly limited, but examples include dihydroxystearic acid, tartaric acid, malic acid, citric acid, and dimethylolpropionic acid. Compound (A) may be one of these hydroxycarboxylic acids used alone, or two or more may be used in combination. However, from the viewpoint of making it easier to adjust the range of "hydroxyl value / (acid value + amine value)" described later to 0.5 or more and 1.2 or less, it is preferable to use monohydroxymonocarboxylic acids as described above.

[0044] <Monomer Component (A1)> Monomer component (A1) consists of a hydroxycarboxylic acid as an essential component and a lactone as an optional component. That is, there are two ways to use monomer component (A1) when synthesizing compound (A) of the present invention: using only a hydroxycarboxylic acid, and using a combination of a hydroxycarboxylic acid and a lactone. Examples of hydroxycarboxylic acids that can be used as monomer component (A1) are the same as those described above. Examples of lactones that can be used as monomer component (A1) include ε-caprolactone, β-butyrolactone, γ-butyrolactone, α-angelicalactone, γ-valerolactone, γ-nonalactone, γ-decalactone, δ-decalactone, and γ-undecalactone.

[0045] <Polyester (PE1)> Polyester (PE1) is a polyester obtained by dehydrating and condensing the monomer component (A1) described above. Specific examples of polyester (PE1) include self-condensates of one of the hydroxycarboxylic acids described above (e.g., self-condensates of 12-HSA, self-condensates of ricinoleic acid, etc.), condensates of two or more of the hydroxycarboxylic acids described above (e.g., condensates of 12-HSA and other hydroxycarboxylic acids, condensates of ricinoleic acid and other hydroxycarboxylic acids, etc.), and condensates of one or more of the hydroxycarboxylic acids described above and lactones. Compound (A) may be one of these polyesters (PE1) used alone, or two or more may be used in combination. Alternatively, compound (A) may be a combination of the hydroxycarboxylic acid (monomer) described above and one or more of the polyesters (PE1).

[0046] <Modified component (A2)> Modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group, and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group, and is an optional component in polymer (P) of the present invention. By incorporating modified component (A2) when synthesizing polymer (P), the functional group (FG1) undergoes dehydration condensation with the carboxyl group of compound (A), converting the adsorption group to inorganic fine particles of polymer (P) from a carboxyl group to a polar functional group (FG2).

[0047] <<Functional group capable of dehydration condensation with a carboxyl group>> The functional group (FG1) is not particularly limited as long as it is a functional group capable of dehydration condensation with a carboxyl group, but examples include a hydroxyl group, a primary amino group, or a secondary amino group.

[0048] <<Polar functional groups that cannot undergo dehydration condensation with carboxyl groups>> The polar functional group (FG2) is not particularly limited as long as it is a polar functional group that cannot undergo dehydration condensation with a carboxyl group, but examples include one or more functional groups selected from the group consisting of tertiary amino groups, sulfonic acid groups, and carboxyl groups. Examples of the above tertiary amino groups include dimethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, as well as tertiary amino groups that constitute the ring of nitrogen-containing heterocyclic compounds such as morpholino group and piperidino group.

[0049] <<Specific Examples of Modified Components (A2)>> Specific examples of the modified components (A2) mentioned above include dimethylaminopropylamine (DMAPA), diethylaminopropylamine, dimethylaminoethanol (DMAE), 2-aminoethylsulfonic acid, 2-dimethylaminoethylamine, 2-diethylaminoethylamine, 2-diisopropylaminoethylamine, dibutylaminopropylamine, 3-(diisobutylamino)propylamine, 3-(2-dimethylaminoethoxy)propylamine, 2-aminomethylpiperidine, 4-aminomethoxypiperidine, N-methylpiperazine, N-aminopropylmorpholine, 2-morpholinoethanol, and 3-morpholinopropylamine.

[0050] <<Amount of Modified Component (A2)>> The percentage of the ratio of the amount of substance of Modified Component (A2) n(A2) to the amount of substance of Monomer Component (A1) n(A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less. That is, the amount of substance of Monomer Component (A1) (mol) : amount of substance of Modified Component (A2) (mol) = 100:0 to 100:100. In other words, in the viscosity modifier of the present invention, the conversion rate of carboxyl groups derived from Monomer Component (A1) (= adsorption groups to inorganic fine particles in the paint) to polar functional groups (FG2) derived from Modified Component (A2) is 0 to 100%. As described above, by incorporating Modified Component (A2) when synthesizing Polymer (P), the adsorption groups to inorganic fine particles that Polymer (P) has can be converted from carboxyl groups to polar functional groups (FG2). This conversion rate may be 0% (i.e., all adsorbent groups remain carboxyl groups), or, depending on the surface state of the inorganic fine particles, the adsorbent groups of the polymer (P) may be converted from carboxyl groups to any polar functional group (FG2) up to a conversion rate of 100% in order to increase the adsorption force to the inorganic fine particles. This greatly increases the freedom of paint formulations in which the viscosity modifier can exhibit a thickening effect, and significantly enhances the versatility of the viscosity modifier of the present invention.

[0051] <Modified Polyester (PE2)> Modified polyester (PE2) is obtained by dehydrating and condensing the monomer component (A1) and the modified component (A2) described above, and is a polyester in which the carboxyl groups of polyester (PE1) are converted to polar functional groups (FG2). When polyester (PE1) is used as compound (A), the ends of the polymer (P) are carboxyl groups derived from polyester (PE1), so depending on the surface condition of the inorganic fine particles, polymer (P) may not be able to adsorb to the inorganic fine particles. However, even in such cases, by converting the carboxyl groups to polar functional groups (FG2) with the modified component (A2), polymer (P) can be adsorbed to various inorganic fine particles. Therefore, the degree of freedom in paint formulations in which the viscosity modifier of the present invention can exhibit a thickening effect is increased, and the versatility of the viscosity modifier can be enhanced. As compound (A), one of these modified polyesters (PE2) may be used alone, or two or more may be used in combination. Furthermore, compound (A) may be a combination of the above-mentioned hydroxycarboxylic acid (monomer) and one or more types of modified polyester (PE2). In addition, compound (A) may be a combination of the above-mentioned hydroxycarboxylic acid (monomer), one or more types of polyester (PE1), and one or more types of modified polyester (PE2).

[0052] <Method for synthesizing polyester (PE1) and modified polyester (PE2)> Polyester (PE1) can be synthesized by blending hydroxycarboxylic acid and lactone as monomer components (A1) in a desired ratio and carrying out a condensation polymerization reaction while heating. Modified polyester (PE2) can be synthesized by blending monomer components (A1) and modified components (A2) in a desired ratio and carrying out a condensation polymerization reaction while heating. The reaction temperature and reaction time can be appropriately set so that the resulting polyester (PE1) and modified polyester (PE2) have the desired hydroxyl equivalents, but for example, a reaction temperature of 150 to 250°C and a reaction time of 1 to 24 hours are preferred. The higher the reaction temperature and the longer the reaction time, the greater the hydroxyl equivalents of polyester (PE1) and modified polyester (PE2) can be (the higher the degree of polymerization).

[0053] <Hydroxyl value / (acid value + amine value)> Furthermore, for compound (A), its hydroxyl value / (acid value + amine value) (hereinafter, "hydroxyl value / (acid value + amine value)") is referred to as R ｈ／ａ It may be written as follows: ) The compound must satisfy the condition that the ratio is between 0.5 and 1.2.

[0054] In this invention, "hydroxyl value / (acid value + amine value)" (R ｈ／ａ ) indicates the ratio of the number of hydroxyl groups to the number of adsorbent groups (carboxyl groups or polar functional groups (FG2)) in compound (A). In order for the viscosity modifier of the present invention to have an excellent thickening effect and to be in a form that can be added to paint with 100% solid content, R ｈ／ａ It is desirable that R is close to 1. Specifically, in the viscosity modifier of the present invention, ｈ／ａ It must be between 0.5 and 1.2. ｈ／ａ If R is less than 0.5, the number of reaction sites between compound (A) and compound (B), that is, the number of hydroxyl groups in compound (A) that can react with the NCO group or carboxyl group of compound (B), decreases. Therefore, the proportion of compound (A) that can react with compound (B) (effective ingredient ratio) decreases, and although it is possible to make it into a form that can be added to paint with 100% solids, it cannot exhibit a sufficient thickening effect. On the other hand, R ｈ／ａWhen R exceeds 1.2, although a sufficient thickening effect can be obtained, the number of crosslinking bonds and adsorption groups increases, leading to stronger interactions between viscosity modifiers. Consequently, the stringiness becomes too strong, or the crystallinity of the polymer (P) becomes too high, making it impossible to create a form that can be added to paint at 100% solid content. In order to obtain an excellent thickening effect and to create a form that can be added to paint at 100% solid content more reliably, R ｈ／ａ It is preferable that the value is between 0.8 and 1.1.

[0055] The acid value and hydroxyl value in this invention can be measured according to the method described in JIS K0070:1992. The amine value can be measured according to the method described in ASTM D2074-07.

[0056] <Purity of 12-HSA and ricinoleic acid> When high-purity 12-HSA or ricinoleic acid is used as a raw material, when these hydroxycarboxylic acids are condensed, the number of acid groups (carboxyl groups) and hydroxyl groups will be close to the same, R ｈ／ａ The value approaches 1. On the other hand, if the purity of 12-HSA or ricinoleic acid is low, the hydroxyl value / acid value becomes significantly smaller than 1 (see, for example, Comparative Production Example 1 described later). Specifically, when using 12-HSA or ricinoleic acid as the hydroxycarboxylic acid, it is preferable to use raw materials with a purity of 90% or higher. Higher purity is desirable, but 90% or higher is preferable. If the purity of 12-HSA or ricinoleic acid is less than 90%, when such hydroxycarboxylic acids are self-condensed, a considerable number of the resulting compounds (A) will not have hydroxyl groups. In that case, the proportion of compounds (A) that can form crosslinks (urethane bonds or ester bonds) with the NCO group or carboxyl group of compound (B) decreases. As a result, the number of crosslinks in the polymer (P) decreases, and the number of adsorption sites with inorganic fine particles in non-aqueous paints decreases, so a sufficient thickening effect may not be obtained. However, even if the purity of 12-HSA or ricinoleic acid is less than 90%, by adjusting the reaction temperature and reaction time when these hydroxycarboxylic acids self-condense, the above-mentioned Rｈ／ａ It is possible to set the value of ｈ／ａ within the range of 0.5 or more and 1.2 or less. In this case, since the ratio of the compound (A) capable of forming a crosslinked bond with the NCO group or carboxyl group of the compound (B) is sufficiently high, a sufficient thickening effect can be obtained.

[0057] Here, 12-HSA can be obtained as a raw material derived from hydrogenated castor oil by purifying the hydrogenated castor oil fatty acid obtained by hydrolysis of hydrogenated castor oil, and contains 12-HSA at 90% by mass or more and 100% by mass or less. That is, "the purity of 12-HSA is 90% or more" means that the content of 12-HSA contained in the raw material derived from hydrogenated castor oil is 90% by mass or more. As a method for purifying the hydrogenated castor oil fatty acid, for example, a known method such as crystallization can be used (for example, refer to JP-A-02-194099). In addition, commercially available products can also be used as 12-HSA. As commercially available products, there are 12-HSA or products made as hydrogenated castor oil fatty acids, for example, 12-hydroxy acid HP (high-purity 12-HSA manufactured by Ogura Chemical Industry Co., Ltd.).

[0058] Also, ricinoleic acid can be obtained as a raw material derived from castor oil by purifying the castor oil fatty acid obtained by hydrolysis of castor oil, and contains ricinoleic acid at 90% by mass or more and 100% by mass or less. That is, "the purity of ricinoleic acid is 90% or more" means that the content of ricinoleic acid contained in the raw material derived from castor oil is 90% by mass or more. As a method for purifying the castor oil fatty acid, for example, known methods such as distillation, extraction, and crystallization can be used (for example, refer to JP-A-02-194099). In addition, commercially available products can also be used as ricinoleic acid. As commercially available products, there are ricinoleic acid or products made as castor oil fatty acids.

[0059] Incidentally, the purity of 12-HSA and ricinoleic acid can be determined by gas chromatography using these hydroxycarboxylic acids (fatty acids) as methyl esters after conforming to JIS K3331:2009 and using this methyl ester as a measurement sample.

[0060] <Acid Value + Amine Value> The sum of the acid value and amine value of compound (A) is preferably 10 or more and 200 or less. If the sum of the acid value and amine value of compound (A) is less than 10, when the viscosity modifier of the present invention is added to a non-aqueous paint, the stringiness may become too strong, making it impossible to create a form that can be added to the paint with 100% solid content. On the other hand, if the sum of the acid value and amine value of compound (A) exceeds 200, the crystallinity of polymer (P) may become too high, making it impossible to create a form that can be added to the paint with 100% solid content. To obtain an excellent thickening effect and to more reliably create a form that can be added to the paint with 100% solid content, the sum of the acid value and amine value of compound (A) is more preferably 30 or more and 100 or less.

[0061] <Number of carbon atoms in monomers> The number of carbon atoms in the hydroxycarboxylic acid and monomer component (A1) used as compound (A), that is, the number of carbon atoms in compound (A) itself or the hydroxycarboxylic acid and lactone used in the synthesis of compound (A), is not particularly limited, but is preferably 2 to 24. However, if only monomers of hydroxycarboxylic acids with a small number of carbon atoms (short carbon chains) are used as compound (A), the crystallinity of the polymer (P) may increase, and it may not be possible to obtain a form that can be added to paint with 100% solids content. For this reason, it is preferable to use 12-HSA, ricinoleic acid, or polyester (PE1) or modified polyester (PE2) synthesized using these hydroxycarboxylic acids as monomers as compound (A).

[0062] (Compound (B)) Compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, and is an essential component of polymer (P) of the present invention.

[0063] <Polyisocyanates and their derivatives> There are no particular limitations on the polyisocyanates that can be used as compound (B), but examples include various polyisocyanates such as aliphatic polyisocyanates, aromatic polyisocyanates, and alicyclic polyisocyanates. Examples of derivatives of polyisocyanates that can be used as compound (B) include polymers, modified products, blocked polyisocyanates, and urethane prepolymers of the above-mentioned polyisocyanates.

[0064] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate, and trimethylhexamethylene diisocyanate. Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylene diisocyanate, xylylene diisocyanate (XDI), naphthalene diisocyanate, and triphenylmethane diisocyanate. Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate. These polyisocyanates may be used individually or in combination of two or more.

[0065] Examples of polyisocyanate polymers include PDI polymers (pentamethylene diisocyanate polymers) and HDI polymers (hexamethylene diisocyanate polymers). Commercially available PDI polymers can be used, such as Stabio® D-370N and D-376N (manufactured by Mitsui Chemicals, Inc.). Commercially available HDI polymers can also be used, such as Desmodur® N3300 (manufactured by Covestro). Examples of modified polyisocyanates include urethane-modified polyisocyanates, urea-modified polyisocyanates, carbodiimide-modified polyisocyanates, alohanate-modified polyisocyanates, and biuret-modified polyisocyanates. Examples of blocked polyisocyanates include polyisocyanates blocked with blocking agents such as phenol, alcohol, oxime, imide, lactone, mercaptan, imine, and boric acid. These compounds may be used individually, in combination of two or more, or in combination with one or more of the polyisocyanates mentioned above.

[0066] Of the polyisocyanates and polyisocyanate derivatives described above, it is preferable to use either or both of the following as compound (B): a polyisocyanate having two or three NCO groups, and a polyisocyanate derivative having two or three NCO groups. By using a polyisocyanate or polyisocyanate derivative having two or three NCO groups, the stringiness can be weakened compared to one having four or more NCO groups, making it possible to more reliably add the viscosity modifier of the present invention to paints in a form with 100% solid content. On the other hand, if a polyisocyanate or polyisocyanate derivative having four or more NCO groups is used as compound (B), the stringiness tends to increase, and there is a risk that the viscosity modifier of the present invention may not be in a form that can be added to paints in a form with 100% solid content.

[0067] <Polycarboxylic Acids> Examples of polycarboxylic acids (also called "polyvalent carboxylic acids") that can be used as compound (B) include divalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and dimer acid; trivalent carboxylic acids such as trimer acid, tricarbaric acid, and trimellitic acid; and tetravalent carboxylic acids such as pyromellitic acid and 1,2,3,4-butanetetracarboxylic acid. Furthermore, polycarboxylic acids with a valency of 5 or higher may be used as the polycarboxylic acid for compound (B), and polycarboxylic acids having hydroxyl groups such as tartaric acid, malic acid, and citric acid may also be used.

[0068] Of the polycarboxylic acids mentioned above, it is preferable to use a divalent to tetravalent polycarboxylic acid as compound (B), more preferably to use either a dicarboxylic acid or a tricarboxylic acid or both, and most preferably to use a tricarboxylic acid. By using a divalent to tetravalent polycarboxylic acid as the polycarboxylic acid, the stringiness can be weakened compared to a pentavalent or higher polycarboxylic acid, and the viscosity modifier of the present invention can be more reliably added to paints with 100% solid content.

[0069] The number of carbon atoms in the polycarboxylic acid used as compound (B) ranges from 4 to 54, but the number of carbon atoms in the polycarboxylic acid has almost no effect on the thickening effect, stringiness, or whether it can be added in a form with 100% solid content in the present invention. This is because the effect of the number of carbon atoms in the polycarboxylic acid on the crystallinity of polymer (P) and the interaction between polymers (P) is relatively small compared to the effect of the type and number of adsorption sites for inorganic fine particles in the paint, as well as the branching of the polymer.

[0070] (Mixing ratio of compound (A) and compound (B)) When synthesizing polymer (P) using compound (A) and compound (B), let EqA be the hydroxyl group equivalent of compound (A) and EqB be the NCO equivalent or carboxyl group equivalent of compound (B). Compound (A) and compound (B) are reacted such that the charging ratio (mass of compound (A):mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2). Here, "charging ratio of compound (A) and compound (B)" means the ratio of the mass of compound (A) to the mass of compound (B) used in the synthesis of polymer (P) (=mass of compound (A):mass of compound (B)).

[0071] Furthermore, the statement that "the mixing ratio of compound (A) to compound (B) is EqA:α×EqB (0.1≦α≦1.2)" indicates that the ratio of (number of hydroxyl groups in compound (A)) to (number of NCO groups or carboxyl groups in compound (B)) is in the range of 1:0.1 to 1:1.2. If α is less than 0.1, it is possible to create a form that can be added to paint with 100% solids, but it will not exhibit sufficient thickening effect. On the other hand, if α exceeds 1.2, although sufficient thickening effect can be obtained, it may become too stringy or the crystallinity of polymer (P) may become too high, making it impossible to create a form that can be added to paint with 100% solids. In addition, if α exceeds 1.2, there is a possibility of concerns such as harmful effects from residual isocyanates and adverse effects on the paint to which it is added. In order to obtain an excellent thickening effect and to ensure that the product can be added to paints with 100% solid content, it is preferable that α is between 0.4 and 1.0 (0.4 ≤ α ≤ 1.0), and more preferably between 0.5 and 1.0 (0.5 ≤ α ≤ 1.0).

[0072] Here, hydroxyl group equivalent refers to the molecular weight per hydroxyl group. The hydroxyl group equivalent EqA of compound (A) can be calculated from the hydroxyl value of compound (A) using the following formula (1): EqA = 56100 / hydroxyl value of compound (A) ... (1)

[0073] Furthermore, NCO equivalent refers to the molecular weight per NCO group. The EqB (NCO equivalent) of compound (B) can be calculated from the NCO content (NCO%) of compound (B), determined according to the method described in JIS K6860:1974, using the following formula (2): EqB (NCO equivalent) = (42 / NCO%) × 100 ... (2)

[0074] Furthermore, the equivalent weight of a carboxyl group refers to the molecular weight per carboxyl group. The EqB (equivalent weight of carboxyl groups) of compound (B) can be calculated from the acid value of compound (B) using the following formula (3). Note that the method for measuring the acid value of compound (B) is the same as for compound (A). EqB (equivalent weight of carboxyl groups) = 56100 / acid value of compound (B) ... (3)

[0075] (Molecular weight of polymer (P)) The weight-average molecular weight Mw of the polymer (P) constituting the viscosity modifier according to the present invention, in terms of polystyrene equivalent, is 1,000 or more and 100,000 or less. If the weight-average molecular weight Mw of polymer (P) is less than 1,000, a sufficient thickening effect cannot be achieved. On the other hand, if the weight-average molecular weight Mw of polymer (P) exceeds 100,000, a sufficient thickening effect can be obtained, but the stringiness becomes too strong, making it impossible to create a form that can be added to paint with 100% solid content. In order to obtain an excellent thickening effect and to create a form that can be added to paint with 100% solid content more reliably, the weight-average molecular weight Mw of polymer (P) is preferably 2,000 or more and 30,000 or less.

[0076] <Method for measuring molecular weight> The weight-average molecular weight Mw of the polymer (P) in this invention shall be the value calculated from the chromatogram measured by gel permeation chromatography (GPC) based on the molecular weight of standard polystyrene.

[0077] (Molecular structure of polymer (P)) Next, with reference to Figure 1, the molecular structure of polymer (P) used as a viscosity modifier in the present invention will be described. Figure 1 is a schematic diagram conceptually showing the molecular structure of polymer (P). In Figure 1, as an example of polymer (P), a self-condensate of hydroxycarboxylic acid is used as compound (A), and a polyisocyanate containing an isocyanuric ring having three NCO groups is used as compound (B), and polymer (P) obtained by reacting these compounds (A) and (B) is shown.

[0078] As shown in Figure 1, polymer (P) is formed by linking the oligomer chain 1 of the hydroxycarboxylic acid self-condensate with the isocyanuric ring 2 of the polyisocyanate via a crosslinking bond 3, thereby crosslinking the hydroxycarboxylic acid self-condensate with the polyisocyanate. Crosslinking bond 3 is a urethane bond formed by the reaction of a hydroxyl group derived from the hydroxycarboxylic acid self-condensate with an NCO group derived from the polyisocyanate. Note that if polycarboxylic acid is used instead of polyisocyanate as compound (B), crosslinking bond 3 becomes an ester bond formed by dehydration condensation of a hydroxyl group derived from the hydroxycarboxylic acid self-condensate with a carboxyl group derived from the polycarboxylic acid.

[0079] Furthermore, polymer (P) has an adsorption group 4 for inorganic fine particles in the paint at the end of the oligomer chain 1 opposite to the crosslinking bond 3. If the modifying component (A2) is not used during the synthesis of polymer (P), all of the adsorption groups 4 become carboxyl groups derived from the self-condensate of hydroxycarboxylic acid. On the other hand, if the modifying component (A2) is used during the synthesis of polymer (P), the functional group (FG1) of the modifying component (A2) undergoes dehydration condensation with the carboxyl group derived from the self-condensate of hydroxycarboxylic acid, thereby converting the carboxyl group into a polar functional group (FG2). Therefore, depending on the mixing ratio of monomer component (A1) and modifying component (A2), some or all of the adsorption groups 4 become polar functional groups (FG2).

[0080] (Effects of the viscosity modifier of the present invention) According to the viscosity modifier for non-aqueous paints of the present invention as described above, a polymer (P) is obtained by reacting a compound (A) whose "hydroxyl value / (acid value + amine value)" (Rh / a) value is close to 1 (i.e., the number of hydroxyl groups and carboxyl groups, etc., is close to the same number) and a compound (B) which has multiple functional groups (NCO groups or carboxyl groups) that can undergo dehydration condensation with the hydroxyl groups of compound (A). Since this polymer (P) has many crosslinked bonds (urethane bonds or ester bonds) formed by the reaction of hydroxyl groups derived from compound (A) and NCO groups or carboxyl groups derived from compound (B), the numerous terminal adsorbent groups present on polymer (P) chemically adsorb onto inorganic fine particles in non-aqueous paints, and the viscosity modifier of the present invention consisting of this polymer (P) exhibits a good thickening effect. Furthermore, the viscosity modifier according to the present invention has low crystallinity and weak stringiness of polymer (P), making it possible to add it to paint in a form that is 100% solids. By making it possible to add it to paint in a form that is 100% solids, the amount of solvent that needs to be brought into the paint is eliminated, and transportation costs can be reduced.

[0081] <Mechanism of Action of the Viscosity Modifier of the Present Invention> Here, with reference to Figures 2 and 3, the mechanism of action of the viscosity modifier of the present invention that exhibits a thickening effect will be described. Figures 2 and 3 are schematic diagrams conceptually illustrating an example of the mechanism of action of the viscosity modifier of the present invention that exhibits a thickening effect, illustrating the state in which the polymer (P) shown in Figure 1 is adsorbed onto inorganic fine particles 10 in the paint.

[0082] As shown in Figure 2, the viscosity modifier of the present invention, which consists of a polymer (P), is adsorbed onto inorganic fine particles 10 in the paint by adsorption groups 4. The polymer (P) used as this viscosity modifier has multiple adsorption groups 4 in its molecule, so it crosslinks multiple inorganic fine particles 10 and constructs a three-dimensional network. More specifically, in the viscosity modifier of the present invention, for example, a first adsorption group 4 located at the end of a first oligomer chain 1, an isocyanuric ring 2 linked to the first oligomer chain 1 by a first crosslinking bond 3, a second oligomer chain 1 linked to the isocyanuric ring 2 by a second crosslinking bond 3, and a second adsorption group 4 located at the end of the second oligomer chain 1 all constitute a crosslinked portion. In this case, the first adsorption group 4 is adsorbed onto the first inorganic fine particles 10, and the second adsorption group 4 is adsorbed onto the second inorganic fine particles 10, so that the first inorganic fine particles 10 and the second inorganic fine particles 10 are crosslinked by the above-mentioned crosslinked portion. By forming such crosslinks between multiple other inorganic microparticles 10, a three-dimensional network is constructed.

[0083] Furthermore, the inventors believe that, in addition to the adsorption force of the polymer (P) to the inorganic fine particles 10, the strength of the three-dimensional network described above also influences the viscosity-enhancing effect of the viscosity modifier of the present invention. That is, as shown in Figure 3, in the viscosity modifier of the present invention, strong interactions act between the crosslinking bonds 3 (urethane bonds in the example of Figure 3), which strengthens the cohesive force between the polymers (P), and this cohesive force is thought to contribute to reinforcing the construction of the three-dimensional network. This interaction between the crosslinking bonds 3 also acts when the crosslinking bonds 3 are ester bonds, but it is stronger when the crosslinking bonds 3 are urethane bonds than when they are ester bonds. This is because, generally, the cohesive energy of urethane bonds is greater than the cohesive energy of ester bonds. In this sense, it is preferable to use polyisocyanate as compound (B).

[0084] Furthermore, as shown in the dashed box in Figure 2, the carboxyl group, sulfonic acid group, tertiary amino group, etc., acting as adsorbent groups 4, are thought to contribute not only to adsorption onto the inorganic fine particles 10, but also to the construction of a three-dimensional network among the viscosity modifiers through acid-base interactions between these functional groups (for example, acid-base interactions between the carboxyl group and the tertiary amino group, and acid-base interactions between the sulfonic acid group and the tertiary amino group). It is believed that the adsorption force of these adsorbent groups 4 onto the inorganic fine particles 10, as well as the strength and diversity of the interactions among the viscosity modifiers, contribute to good viscosity increasing properties and the versatility of the viscosity modifiers described above. The adsorption force of the adsorbent groups of the viscosity modifier of the present invention onto the inorganic fine particles is mainly determined by the balance between the acidic-basic properties of the surface of the inorganic fine particles (i.e., the ratio of acidic adsorption sites to basic adsorption sites on the surface of the inorganic fine particles) and the acidic-basic properties of the adsorbent groups of the viscosity modifier (i.e., the ratio of acidic functional groups to basic functional groups that the viscosity modifier has as adsorbent groups). Basically, it is thought that basic adsorption groups (e.g., tertiary amino groups) of viscosity modifiers are adsorbed to acidic adsorption sites on the surface of inorganic microparticles, and acidic adsorption groups (e.g., carboxyl groups, sulfonic acid groups) of viscosity modifiers are adsorbed to basic adsorption sites on the surface of inorganic microparticles. Depending on the type of inorganic microparticles added to the paint, the ratio of acidic adsorption sites to basic adsorption sites will differ. For example, if the inorganic microparticles have a high ratio of acidic adsorption sites, a viscosity modifier with a high ratio of basic adsorption groups will have a higher adsorption force to the inorganic microparticles, and if the inorganic microparticles have a high ratio of basic adsorption sites, a viscosity modifier with a high ratio of acidic adsorption groups will have a higher adsorption force to the inorganic microparticles.

[0085] <Forms that can be added as 100% solids> In this invention, "forms that can be added to paint as 100% solids" means "a viscosity modifier in which 100% polymer (P) can be added to paint at room temperature and exhibits a thickening effect when added." If it is not possible to synthesize polymer (P) in a state of 100% solids, or even if it can be synthesized, if the viscosity modifier does not exhibit a thickening effect when added to paint, or if there are difficulties such as the polymer (P) not dissolving in the paint and remaining as lumps, then it cannot be said to be "a form that can be added to paint as 100% solids." More specifically, as shown in the examples described later, for example, if it is a liquid to soft semi-solid at room temperature and can be added in any amount from a lump sample using a spatula or pipette, then it can be determined to be a form that can be added to paint as 100% solids. On the other hand, if a substance is semi-solid to solid at room temperature and cannot be added in any desired amount unless it is divided by operations such as scraping or crushing, or if it is semi-solid at room temperature but has strong stringiness and is extremely difficult to add in any desired amount, it can be determined that it is "not" in a form that can be added to paint with 100% solid content.

[0086] <Reasons why both a good thickening effect and a form that can be added as 100% solids are possible> Generally, in order to enhance the thickening effect of polymer-type viscosity modifiers, it is desirable to strengthen the three-dimensional network constructed between the polymer and inorganic fine particles by increasing the number of polymer branches and the number of adsorbent groups located at the polymer ends. In addition, the three-dimensional network can be reinforced by increasing the number of crosslinking bonds and increasing the cohesive force. However, if there are too many crosslinking bonds in the polymer, the crystallinity of the polymer will increase, and the viscosity modifier will no longer be in a form that can be added to paint as 100% solids. In other words, there is a trade-off between "improving the thickening effect" and "making it a form that can be added to paint as 100% solids". According to the present invention, it is possible to combine these two characteristics that are in a trade-off relationship. The reasons why the present invention can combine these two characteristics that are in a trade-off relationship are described below.

[0087] First, we will list the factors that affect the thickening effect and the form that can be added with 100% solids content. (1) Strongly interacting sites Examples of strongly interacting sites in polymers include urethane bonds and amide bonds. These sites contribute to a strong thickening effect, but when the solids content of the polymer is increased, the crystallinity of the polymer increases, which can lead to solidification or increased stringiness. (2) Weakly interacting sites Examples of weakly interacting sites in polymers include ester bonds and alkyl chains. These sites contribute little to the thickening effect, but even when the solids content of the polymer is increased, the crystallinity of the polymer can be kept low, making it easier to maintain fluidity and weak stringiness. (3) Molecular weight and number of branches Regarding the molecular weight and number of branches of a polymer, the larger the molecular weight and the more branches there are, the greater the contribution to the thickening effect, but when the solids content of the polymer is increased, this can lead to increased stringiness.

[0088] In view of the above factors, one reason why the viscosity modifier according to the present invention can achieve both a good thickening effect and a form that can be added with 100% solids content is, for example, that the proportion of strongly interacting sites in the polymer (P) is low. As a result, aggregation of viscosity modifiers is prevented, and low crystallinity and weak stringiness can be maintained, so even if the solids content of the polymer is increased, it is less likely to solidify and fluidity can be maintained. Another factor is that in polymer (P), while the number of crosslinking bonds can be increased and the molecular weight can be increased, strongly interacting sites such as urethane bonds are concentrated locally, as in block copolymers. The inventors speculate that, compared to the case where such strongly interacting sites are evenly distributed throughout the polymer (P) molecule, the interactions only act locally, which prevents aggregation of viscosity modifiers and makes it less likely for the polymer (P) to solidify. However, in the viscosity modifier of the present invention, if the number of crosslinking bonds, such as urethane bonds and ester bonds, obtained by the reaction between the hydroxyl group of compound (A) and the NCO group or carboxyl group of compound (B) is too large, it will no longer be in a "form that can be added with 100% solid content." For this reason, as described above, the charging ratio of compound (A) and compound (B) is limited to a predetermined range. From a similar viewpoint, it is preferable that the number of NCO groups or carboxyl groups is not too large (there are 2 or 3 NCO groups in one polyisocyanate molecule, and 2 to 4 carboxyl groups in one polycarboxylic acid molecule).

[0089] Furthermore, with the viscosity modifier according to the present invention, particularly when the modified component (A2) is used, the carboxyl groups derived from compound (A) can be converted into various functional groups, as described above. Therefore, the adsorption groups for inorganic fine particles in the paint can be diversified, and furthermore, by diversifying the interactions between viscosity modifiers, including the acid-base interactions between the functional groups described above, the effects of the present invention can be demonstrated in a wide range of paint formulations.

[0090] [Method for producing a viscosity modifier for non-aqueous paints] The method for producing a viscosity modifier for non-aqueous paints according to the present invention includes a polymer synthesis step for synthesizing the polymer (P) described above.

[0091] (Polymer Synthesis Process) In the polymer synthesis process, compound (A) and compound (B) are charged as raw materials for synthesizing polymer (P). Then, polymer (P) is obtained by reacting these raw materials at a predetermined temperature for a predetermined time while stirring. The reaction conditions at this time are not particularly limited, but for example, when polyisocyanate and its derivatives are used as compound (B), it is preferable to set the reaction temperature to 50°C to 150°C and the reaction time to 1 hour to 8 hours. When polycarboxylic acid is used as compound (B), it is preferable to set the reaction temperature to 150°C to 250°C and the reaction time to 1 hour to 24 hours.

[0092] [Method of Use of Viscosity Modifier for Non-Aqueous Paints] The viscosity modifier of the present invention obtained by the manufacturing method described above can be mixed with other components of non-aqueous paints (inorganic fine particles, resin components, etc.) in a solid content of 100% without any further processing and uniformly dispersed, or it can be added in a pre-dispersed mixture of other components of non-aqueous paints in a solid content of 100% and uniformly dispersed.

[0093] [Applications of the viscosity modifier for non-aqueous paints] The viscosity modifier according to the present invention can be suitably used as an additive for non-aqueous paints. Examples of applications for non-aqueous paints include marine paints, heavy-duty anticorrosive paints, woodworking paints, architectural paints, automotive paints, plastic paints, concrete paints, floor paints, and oil-based inks, but are not limited to these applications and can be used in various applications where non-aqueous paints are generally applicable.

[0094] [Non-aqueous paint composition] The non-aqueous paint composition according to the present invention contains the above-mentioned viscosity modifier for non-aqueous paints, inorganic fine particles, and a resin component as essential components. In the present invention, the content of the viscosity modifier in the non-aqueous paint composition is not particularly limited, but generally, it is preferable to be 0.1% by mass or more and 20% by mass or less based on the total amount of the non-aqueous paint composition. If the content of the viscosity modifier is less than 0.1% by mass, the effect of the viscosity modifier (thickening effect) is weak, and if it exceeds 20% by mass, the thickness of the paint increases significantly, which may make it difficult to disperse the viscosity modifier in the paint, handle the paint, and apply the paint.

[0095] The non-aqueous coating composition of the present invention may be a solvent-free coating that does not contain a solvent, or a solvent-containing coating that contains a non-aqueous solvent. Solvent-free coatings have the advantage of contributing to low VOCs because there is no need to volatilize the solvent during film formation. Also, because they contain almost no volatile solvent components, the thickness applied is almost the same as the thickness after drying, making them suitable for coating applications where a large coating film thickness is desired. On the other hand, solvent-containing coatings have the advantage of excellent applicability because the viscosity of the coating can be appropriately adjusted during application.

[0096] Generally speaking, "solvent-free paint" refers to a paint that does not contain volatile solvents used to dissolve the resin in the paint, and may contain liquid components (components that remain in the paint film) such as reactive diluents, non-reactive diluents, and silane coupling agents as needed. Therefore, in this invention as well, "solvent-free paint" does not mean a completely solvent-free paint that does not contain any liquid components that can function as a solvent, but rather a paint that contains the above-mentioned components that remain in the paint film. Examples of reactive diluents include acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and phenyl glycidyl ether acrylate; urethane prepolymers such as hexamethylene diisocyanate urethane prepolymer and phenyl glycidyl ether toluene diisocyanate urethane prepolymer; glycidyl ethers such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether stearate, styrene oxide, phenyl glycidyl ether, nonylphenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, and diethylene glycol diglycidyl ether; and chlorostyrene, methoxystyrene, butoxystyrene, and vinyl benzoic acid. Furthermore, non-reactive diluents such as petroleum resin-based diluents can be suitably used. Examples of petroleum resin-based diluents include aliphatic or aromatic high-boiling-point oils, phenol-modified aliphatic or aromatic polymers, xylene resins, and toluene resins.

[0097] (Solvent) The solvent in this invention is an organic solvent, for example, and is not particularly limited as long as it is used in the field of paints.

[0098] Examples of organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, 1-butanol (n-butanol), 2-butanol, 1-pentanol, octyl alcohol, benzyl alcohol, glycerin, ethylene glycol, and propylene glycol; carboxylic acids such as acetic acid; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; aromatic hydrocarbons such as toluene and xylene; amides such as dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and acetanilide; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogens such as methylene chloride and chloroform; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl butyrate, and propylene glycol monomethyl ether acetate (PMA); ethers such as propylene glycol monomethyl ether (PM); and acetonitrile and propionitrile. The solvents mentioned above may be used individually or in combination of two or more.

[0099] (Organic media) In the non-aqueous coating composition (solvent-containing coating) containing the solvent of the present invention, an organic media containing a reactive functional group or a non-reactive organic media may be used in conjunction with the solvent described above.

[0100] Examples of organic media containing reactive functional groups include acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and phenyl glycidyl ether acrylate; urethane prepolymers such as hexamethylene diisocyanate urethane prepolymer and phenyl glycidyl ether toluene diisocyanate urethane prepolymer; and n-butyl glycidyl ether and 2-ethylhexyl. Examples of glycidyl ethers include glycidyl ethers, alkyl (C8-C18) glycidyl ethers (alkyl glycidyl ethers with an alkyl chain length of C8-C18, i.e., alkyl glycidyl ethers with 8 to 18 carbon atoms in the alkyl group), glycidyl stearate ether, styrene oxide, phenyl glycidyl ether, nonylphenyl glycidyl ether, butylphenyl glycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and other glycidyl ethers; chlorostyrene, methoxystyrene, butoxystyrene, vinylbenzoic acid, and others.

[0101] Furthermore, suitable non-reactive organic media include, for example, petroleum resin-based organic media with a viscosity of 1 to 200 cps at 25°C and a heating residue of 90% or more. Examples of petroleum resin-based organic media include aliphatic or aromatic high-boiling-point oils, phenol-modified aliphatic or aromatic polymers, xylene resins, and toluene resins.

[0102] (Inorganic Fine Particles) Examples of inorganic fine particles contained in the non-aqueous coating composition of the present invention include extender pigments, coloring pigments, and metallic pigments. The inclusion of these pigments can improve the appearance and properties of the coating film formed using the non-aqueous coating composition of the present invention.

[0103] Examples of inorganic fine particles of the present invention include extender pigments such as calcium carbonate (heavy calcium carbonate (GCC), precipitated calcium carbonate (PCC), etc.), barium sulfate, silicon dioxide, aluminum hydroxide, talc, organic fibers, and glass powder; titanium dioxide, carbon black, lead yellow, cadmium yellow, ochre, titanium yellow, zinc chromate, iron oxide, aluminosilicate; and metallic pigments such as aluminum flakes, copper flakes, mica-like iron oxide, mica, and flaky powders of mica coated with metal oxides.

[0104] From the viewpoint of achieving the purpose of adding inorganic fine particles, the inorganic fine particles in the non-aqueous coating composition of the present invention are preferably contained in an amount of 0.001 to 80% by mass.

[0105] (Resin component) The non-aqueous paint composition of the present invention contains a resin component for forming a paint film. The resin component of the non-aqueous paint composition of the present invention is not particularly limited as long as it is a resin that has been conventionally used as a base resin for non-aqueous paints, and various resins can be blended into the non-aqueous paint composition. Examples of base resins for non-aqueous paints that can be used with the non-aqueous paint composition of the present invention include alkyd resins, acrylic resins, acrylic urethane resins, melamine resins, urethane resins, epoxy resins, coumarone resins, urea resins, phenolic resins, vinyl chloride resins, phenoxy resins, silicone resins, fluororesins, nylon resins, styrene-butadiene resins, nitrile-butadiene resins, petroleum resins, rosin, drying oils, boiled oils, acetylcellulose, and nitrocellulose. These resins may be heat-curable, UV-curable, electron-beam-curable, oxidative-curable, photocationic-curable, peroxide-curable, or acid / epoxy-curable, curing types that involve chemical reactions in or without the presence of a catalyst. Alternatively, they may be resins with high glass transition temperatures that do not involve chemical reactions and form a film simply by the evaporation of the diluent solvent. Examples of curing agents include amino resins, melamine resins, isocyanate compounds, blocked isocyanate compounds, and epoxy compounds. Only one base resin may be used, or two or more may be used in combination.

[0106] From the viewpoint of film-forming properties and other factors, the resin component content in the non-aqueous paint composition is preferably 20 to 99.5% by mass.

[0107] (Other Additives) The non-aqueous coating composition of the present invention may contain other substances, such as dehydrating agents (e.g., silane coupling agents), adhesion enhancers, surfactants, curing catalysts, plasticizers, film-forming aids, dryers, anti-fouling agents, sensitizers, antioxidants, light stabilizers, UV absorbers, water-resistant agents, anti-corrosion and anti-fungal agents, defoaming agents, leveling agents, dispersants, flame retardants, antistatic agents, release agents, deodorizers, and fragrances, to the extent that their properties and the objectives of the present invention are not impaired.

[0108] [Method for producing a non-aqueous paint composition] The method for producing the non-aqueous paint composition of the present invention is not particularly limited, but the viscosity modifier described above may be added to the resin in advance and uniformly dispersed, and then blended with the remaining raw materials, or it may be added and mixed together with various additives, solvents, and resin when preparing the non-aqueous paint composition. If the dispersion of the viscosity modifier in the non-aqueous paint composition is insufficient, the effects of the present invention may not be fully exhibited.

[0109] [Method of using the non-aqueous paint composition] The non-aqueous paint composition of the present invention can be used in the form of a dispersion, or it can be used as a dried powdered non-aqueous paint composition by removing liquid components such as solvents from the dispersion through drying treatment or the like.

[0110] The non-aqueous coating composition of the present invention can be applied to the surface of various substrates to a desired film thickness by known application methods, such as roller coating, brush coating, air spraying, airless spraying, and electrostatic coating. Furthermore, by curing the non-aqueous coating composition applied to the surface of the substrate, a coated article having a coating film made of the cured non-aqueous coating composition can be obtained.

[0111] Examples of substrates include metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, galvanized steel, zinc alloys (Zn-Al, Zn-Ni, Zn-Fe, etc.), and plated steel; plastic materials such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, epoxy resin, and various types of FRP; and inorganic materials such as glass, cement, and concrete, which may be surface-treated.

[0112] [Uses of Non-Aqueous Paint Compositions] The non-aqueous paint composition according to the present invention can be used, for example, in marine paints, heavy-duty anticorrosive paints, woodworking paints, architectural paints, automotive paints, plastic paints, concrete paints, floor paints, oil-based inks, etc., but is not limited to these uses and can be used in various applications where non-aqueous paints are generally applicable.

[0113] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the embodiments described above. That is, other embodiments or various modifications that a person skilled in the art could conceive of within the scope of the invention as described in the claims are also understood to fall within the technical scope of the present invention.

[0114] Specifically, the invention includes the following: (1) A polymer (P) obtained by reacting compound (A) and compound (B), wherein compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, wherein monomer component (A1) consists of hydroxycarboxylic acid as an essential component and lactone as an optional component, and modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group. A viscosity modifier for non-aqueous paints, wherein the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of the monomer component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, the compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, when the hydroxyl group equivalent of compound (A) is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) and compound (B) (mass of compound (A): mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) in terms of polystyrene is 1,000 or more and 100,000 or less. (2) The viscosity modifier for non-aqueous paints according to (1), wherein the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) have 2 to 24 carbon atoms. (3) The viscosity modifier for non-aqueous paints according to (1) or (2), wherein the sum of the acid value and amine value of compound (A) is 10 or more and 200 or less. (4) The viscosity modifier for non-aqueous paints according to any one of (1) to (3), wherein compound (B) is a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups.(5) The viscosity modifier for non-aqueous paints according to any one of (1) to (4), wherein the compound (B) is a divalent to tetravalent polycarboxylic acid. (6) The viscosity modifier for non-aqueous paints according to any one of (1) to (5), wherein the functional group (FG1) is a hydroxyl group, a primary amino group, or a secondary amino group. (7) The viscosity modifier for non-aqueous paints according to any one of (1) to (6), wherein the polar functional group (FG2) is one or more functional groups selected from the group consisting of a tertiary amino group, a sulfonic acid group, and a carboxyl group. (8) A non-aqueous coating composition comprising a viscosity modifier, inorganic fine particles, and a resin component, wherein the viscosity modifier comprises a polymer (P) obtained by reacting compound (A) and compound (B), and compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, the monomer component (A1) comprises hydroxycarboxylic acid as an essential component and lactone as an optional component, and the modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group. A non-aqueous paint composition wherein the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of the monomer component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, the compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, when the hydroxyl group equivalent of compound (A) is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) to compound (B) (mass of compound (A): mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) in terms of polystyrene is 1,000 or more and 100,000 or less.(9) The non-aqueous paint composition according to (8), wherein the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) have 2 to 24 carbon atoms. (10) The non-aqueous paint composition according to (8) or (9), wherein the sum of the acid value and amine value of compound (A) is 10 or more and 200 or less. (11) The non-aqueous paint composition according to any one of (8) to (10), wherein compound (B) is a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups. (12) The non-aqueous paint composition according to any one of (8) to (11), wherein compound (B) is a divalent to tetravalent polycarboxylic acid. (13) The non-aqueous paint composition according to any one of (8) to (12), wherein the functional group (FG1) is a hydroxyl group, a primary amino group, or a secondary amino group. (14) The non-aqueous paint composition according to any one of (8) to (13), wherein the polar functional group (FG2) is one or more functional groups selected from the group consisting of a tertiary amino group, a sulfonic acid group, and a carboxyl group. (15) The non-aqueous paint composition according to any one of (8) to (14), wherein the content of the viscosity modifier is 0.1% by mass or more and 20% by mass or less based on the total amount of the non-aqueous paint composition.

[0115] The present invention will be described in detail below with reference to examples. However, the present invention is not limited in any way to these examples. In addition, unless otherwise specified, "%" and "parts" in the examples refer to "mass%" and "parts by mass," respectively.

[0116] (Synthesis of Compound (A)) Compounds A1 to A17 and comparative synthesis examples A1 to A2 were synthesized by preparing the raw materials and amounts shown in Table 1 and carrying out a condensation reaction at the reaction temperature and reaction time shown in Table 1. Synthesis example A1 is a monomer of 12-HSA that has not undergone self-condensation. Here, as 12-HSA in Table 1, 12HSA-A (purity approximately 86%) manufactured by Royal Castor Products was used, and as ricinoleic acid, a reagent (ricinoleic acid purity approximately 86%) manufactured by Tokyo Chemical Industry Co., Ltd. was used. Furthermore, these hydroxycarboxylic acids were purified to increase their purity. Specifically, 500 g of 12-HSA-A (purity approximately 86%) was added to 600 g of n-hexane, left at 35°C for 1 hour, and then filtered. The obtained solid was dried to obtain high-purity 12-HSA. According to JIS K3331:2009, 12-HSA was converted to a methyl ester, and this methyl ester was used as a sample for gas chromatography, resulting in a purity of 97%. Furthermore, 500g of 12-HSA-A (approximately 86% purity) was recrystallized using 1kg of acetone to obtain high-purity 12-HSA. According to JIS K3331:2009, 12-HSA was converted to a methyl ester, and this methyl ester was used as a sample for gas chromatography, resulting in a purity of 92%. In addition, 200g of ricinoleic acid (approximately 86% purity) was mixed vigorously with 400g of n-hexane, allowed to stand, and then the layers were separated to recover the ricinoleic acid. This procedure was repeated three times to obtain high-purity ricinoleic acid. According to JIS K3331:2009, ricinoleic acid was converted to a methyl ester, and then this methyl ester was analyzed by gas chromatography as a sample, revealing a purity of 95%.

[0117] In Table 1, reagents from Tokyo Chemical Industry Co., Ltd. were used for dimethylolpropionic acid and ε-caprolactone, reagents from Fujifilm Wako Pure Chemical Industries, Ltd. were used for glycolic acid, and reagents from Kanto Chemical Co., Ltd. were used for 3-(dimethylamino)propylamine and 2-dimethylaminoethanol. The acid value and hydroxyl value were measured according to the method described in JIS K0070:1992. Furthermore, the hydroxyl equivalent was calculated from the hydroxyl value measured as described above using formula (1) above. The amine value was measured according to the method described in ASTM D2074-7.

[0118]

[0119] (Synthesis of Compound (B)) As shown in Table 3, the following reagents were prepared for compound (B): ・IPDI (isophorone diisocyanate): Reagent manufactured by Tokyo Chemical Industry Co., Ltd. ・MDI (diphenylmethane diisocyanate): Millionate® NM manufactured by Tosoh Corporation ・HDI (hexamethylene diisocyanate): Reagent manufactured by Tokyo Chemical Industry Co., Ltd. ・Trimer acid: Tsunodaimm® 346 manufactured by Tsukuno Foods Industry Co., Ltd. ・Sebacic acid: Grade 1 reagent manufactured by Kanto Chemical Co., Ltd. ・PDI-type polyisocyanate (PDI-type polymer): Stavio® D-370N manufactured by Mitsui Chemicals, Inc. ・HDI-type polyisocyanate (HDI-type polymer): Desmodur® N3300 manufactured by Covestro Furthermore, as shown in Table 2, 100 g of polypropylene glycol (Sannix® PP-2000 manufactured by Sanyo Chemical Industries, Ltd.) and 22.5 g of IPDI were charged and reacted at a reaction temperature of 80°C for 3 hours to synthesize the urethane prepolymer of Synthesis Example B1. The NCO equivalent of this urethane prepolymer was calculated from the NCO amount (NCO%) determined by the method described in JIS K6806:1974 using formula (2) described above.

[0120]

[0121]

[0122] (Synthesis of viscosity modifiers) Compound (A) and compound (B) shown in Table 3 were mixed in a mass ratio of EqA:α×EqB and reacted to obtain viscosity modifiers for Production Examples 1-30 and Comparative Production Examples 1-4. When polyisocyanate was used as compound (B) (Production Examples 1-22, Production Examples 25-30, Comparative Production Examples 2-4), the reaction temperature was 80°C and the reaction time was 3 hours. When polycarboxylic acid was used as compound (B) (Production Examples 23, 24), the reaction temperature was 200°C and the reaction time was 12 hours. The equivalent amount of carboxyl groups was calculated from the acid value of compound (B), which was measured in the same manner as in Table 1, using formula (3) described above.

[0123] Furthermore, the viscosity modifier for Comparative Production Example 5 was obtained by the same method as in Production Example 1 of Patent Document 1 (up to the point before adding the mixed solvent of methyl n-amyl ketone and n-butanol). In addition, the viscosity modifier for Comparative Production Example 6 was obtained by the same method as in Example 1 of Patent Document 2 (up to the point before adding benzyl alcohol).

[0124] The weight-average molecular weight Mw of the polymer-type viscosity modifiers produced in Production Examples 1-30 and Comparative Production Examples 1-6, as described above, was measured. More specifically, the weight-average molecular weight Mw was defined as the value calculated from the chromatogram measured by GPC, using the molecular weight of standard polystyrene as a reference. The GPC measuring instrument used was "HLC-8320GPC" (manufactured by Tosoh Corporation, product name), and three columns were used: one "GPCKF-801" and two "GPCKF-802" (both manufactured by Shodex, product names). The weight-average molecular weight was measured under the following conditions: mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1 cc / min, detector: RI. The measurement results are shown in Table 3.

[0125] [Test Example 1: Example of a One-Component Paint] Non-aqueous paint compositions for the examples and comparative examples were prepared using the non-aqueous paint formulations (Formulation 1 and Formulation 2) shown in Table 4 as follows, and the thickening effect, stringiness, and feasibility of adding these non-aqueous paint compositions in a 100% solids form were evaluated.

[0126] (Preparation of Non-Aqueous Paint Compositions) For Formulation 1, as shown in Table 4, 25 parts of ACRYDIC A-801 (acrylic resin manufactured by DIC Corporation), 73 parts of JR-600A (rutile-type titanium dioxide manufactured by Teika Co., Ltd.) as a pigment, and 1.0 part of a viscosity modifier were added and dispersed for 5 minutes using a dissolver (with a blade diameter of 3 cm) to obtain the non-aqueous paint compositions of the Examples and Comparative Examples. For Formulation 2, as shown in Table 4, 39 parts of refined castor oil (ester resin manufactured by Ogura Synthetic Industry Co., Ltd.) as a resin, 59 parts of JR-600A (rutile-type titanium dioxide manufactured by Teika Co., Ltd.) as a pigment, and 1.0 part of a viscosity modifier were added and dispersed for 5 minutes using a dissolver (with a blade diameter of 3 cm) to obtain the non-aqueous paint compositions of the Examples and Comparative Examples.

[0127]

[0128] (Evaluation Method) The non-aqueous paint compositions of the examples and comparative examples obtained as described above were evaluated for their thickening effect and their suitability for addition to paint in a 100% solids form. In addition, the evaluation of the stringiness of the viscosity modifiers of the production example and comparative production example obtained as described above was also taken into consideration in determining whether they could be added to paint in a 100% solids form. The evaluation results are shown in Table 5.

[0129] <Thickening Effect (Viscosity)> The viscosity of the non-aqueous paint composition was used to evaluate the thickening effect. A rheometer AR-G2 (manufactured by TA Instruments) was used to measure the viscosity, and a cone plate with a diameter of 20 mm and a geometry of 1° between the generatrix and the circular surface of the cone was used as the jig, with a shear rate (shear rate) of 0.1 s. －１ The viscosity at 25°C was used as the measured value.

[0130] <Stringability> Using the NEVA METER (manufactured by Ishikawa Iron Works Co., Ltd.), a device for measuring stringability, spindle strength, and coagulation, the string length of the viscosity modifier was measured at 25°C and evaluated according to the following criteria: A: String length of 0 mm to 29.9 mm B: String length of 30.0 mm to 59.9 mm C: String length of 60.0 mm to 79.9 mm D: String length of 80.0 mm to 100 mm E: Sample is solid and cannot be measured

[0131] <Feasibility of Addition in 100% Solid Content Form> The following criteria were used to determine whether the viscosity modifier can be added to a non-aqueous paint composition in a 100% solid content (active ingredient) state. "Forms that can be added in 100% solid content form": A form that is liquid to soft semi-solid at room temperature, and in which any amount can be added from a lump sample using a spatula or pipette. "Forms that cannot be added in 100% solid content form": The following forms (i) or (ii) (i) Semi-solid to solid at room temperature, and in which any amount cannot be added unless divided by operations such as scraping or crushing (ii) Semi-solid at room temperature, highly stringy, and in which it is extremely difficult to add any amount

[0132]

[0133] (Evaluation Results) As is clear from Table 5, all of the non-aqueous paint compositions of Examples 1 to 24 were in a form that could be added with 100% solid content and showed good stringability. In addition, both formulation 1 and formulation 2 of the non-aqueous paint compositions of Examples 1 to 24 had a good thickening effect.

[0134] In Example 1, the "acid value + amine value" of compound (A) was slightly high, exceeding 100, resulting in a tendency towards strong stringiness. Also, the weight-average molecular weight of polymer (P) was slightly low, less than 2000, resulting in a tendency towards slightly lower viscosity. In Example 4, the "acid value + amine value" of compound (A) was slightly low, less than 30, and the weight-average molecular weight of polymer (P) was slightly high, exceeding 30000, resulting in a tendency towards slightly stronger stringiness. In Example 7, the purity of hydroxycarboxylic acid (12-HSA) was low, less than 90%, resulting in the R of compound (A). ｈ／ａ The R of compound (A) was somewhat small, less than 0.8, and the weight-average molecular weight of polymer (P) was also somewhat small, less than 3000, resulting in a tendency for the viscosity to be somewhat low. In Example 9, the R of compound (A) ｈ／ａIn Example 13, the viscosity tended to be slightly lower because the amount of compound (B) was slightly lower (α value was slightly lower) and the number of crosslinking bonds in polymer (P) was slightly lower. In Example 17, the viscosity tended to be stronger because the amount of compound (B) was slightly higher (α value was slightly higher) and the number of branches in polymer (P) was slightly higher. In Example 18, the viscosity tended to be stronger because the weight-average molecular weight of polymer (P) was large, around 60,000.

[0135] On the other hand, Comparative Example 1, in which compound (B) was not added, and R of compound (A) ｈ／ａ In Comparative Example 3, where the ratio was less than 0.5, a sufficient thickening effect was not obtained. Also, in Comparative Example 2, the amount of compound (B) was too high (α > 1.2), and the R of compound (A) was too high. ｈ／ａ In Comparative Example 4, where the ratio was greater than 1.2, the stringiness was too strong, making it impossible to add the viscosity modifier to the paint in a 100% solid form. Furthermore, in Comparative Example 5, which corresponds to the anti-sagging agent in Patent Document 1, and Comparative Example 6, which corresponds to the thixotropy-imparting agent in Patent Document 2, the stringiness was too strong (in particular, the viscosity modifier in Comparative Example 6 was solid at room temperature), making it impossible to add the viscosity modifier to the paint in a 100% solid form.

[0136] [Test Example 2: Example of a Two-Component Paint] Non-aqueous paint compositions for the examples and comparative examples were prepared using the non-aqueous paint formulation (Formulation 3) shown in Table 6 as follows, and the thickening effect, stringiness, and feasibility of adding these non-aqueous paint compositions in a 100% solids form were evaluated.

[0137] (Preparation of Non-Aqueous Paint Compositions) As shown in Table 6, 30.0 parts of MACRYNAL SM2810 / 75BAC (acrylic polyol resin manufactured by Allnex) was used as the resin, 8.8 parts of butyl acetate as the solvent, 0.4 parts of DA-325 (wetting dispersant manufactured by Kusumoto Chemical Co., Ltd.) as the dispersant, 35.0 parts of R-930 (rutile-type titanium dioxide manufactured by Ishihara Sangyo Co., Ltd.) and 10.0 parts of W-1 (barium sulfate manufactured by Toshin Chemical Co., Ltd.) as pigments were charged and dispersed for 30 minutes using a bead mill. Next, 1.0 part of a viscosity modifier was added to the dispersion solution and dispersed for 10 minutes using a dissolver (with blades 5 cm in diameter) to obtain the main component. 14.9 parts of Desmodur N3300 (polyisocyanate-based curing agent manufactured by Covestro) was added to this main component as a curing agent and mixed to obtain the non-aqueous paint compositions of the examples and comparative examples.

[0138]

[0139] (Evaluation Method) The non-aqueous paint compositions of the examples and comparative examples obtained as described above were evaluated for their thickening effect and their suitability for addition to paint in a 100% solids form, in the same manner as in Test Example 1. The evaluation results are shown in Table 7.

[0140]

[0141] (Evaluation Results) As is clear from Table 7, the non-aqueous paint compositions of Examples 25 to 31 were all in a form that could be added with 100% solid content and showed good stringability. In addition, the non-aqueous paint compositions of Examples 25 to 31 had a good thickening effect. In particular, as can be seen from the comparison between Example 25 and Example 30, or between Example 31 and Examples 27 to 29, in formulations containing inorganic fine particles (barium sulfate) with relatively weak adsorption to carboxyl groups, such as formulation 3, Examples 27 to 30, which contained a viscosity modifier with a modified component (A2), had a better thickening effect than Examples 25 and 31, which contained a viscosity modifier without a modified component (A2).

[0142] On the other hand, in Comparative Example 5, which corresponds to the anti-sagging agent in Patent Document 1, and Comparative Example 6, which corresponds to the thixotropy-imparting agent in Patent Document 2, the stringiness was too strong (in particular, the viscosity modifier in Comparative Example 6 was solid at room temperature), so it was not possible to add the viscosity modifier to the paint in a form with 100% solid content.

[0143] 1. Oligomer chain 2. Isocyanuric ring 3. Crosslinking bond 4. Adsorption group 10. Inorganic microparticles

Claims

1. The polymer (P) is obtained by reacting compound (A) and compound (B), wherein compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, wherein the monomer component (A1) consists of hydroxycarboxylic acid as an essential component and lactone as an optional component, and the modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group. A viscosity modifier for non-aqueous paints, wherein the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of the monomer component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, the compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, when the hydroxyl group equivalent of compound (A) is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) and compound (B) (mass of compound (A): mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) in terms of polystyrene is 1,000 or more and 100,000 or less.

2. The viscosity modifier for non-aqueous paints according to claim 1, wherein the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) have 2 to 24 carbon atoms.

3. The viscosity modifier for non-aqueous paints according to claim 1, wherein the sum of the acid value and amine value of compound (A) is 10 or more and 200 or less.

4. The viscosity modifier for non-aqueous coatings according to claim 1, wherein the compound (B) is a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups.

5. The viscosity modifier for non-aqueous paints according to claim 1, wherein the compound (B) is a divalent to tetravalent polycarboxylic acid.

6. The viscosity modifier for non-aqueous coatings according to claim 1, wherein the functional group (FG1) is a hydroxyl group, a primary amino group, or a secondary amino group.

7. The viscosity modifier for non-aqueous coatings according to claim 1, wherein the polar functional group (FG2) is one or more functional groups selected from the group consisting of tertiary amino groups, sulfonic acid groups, and carboxyl groups.

8. A non-aqueous coating composition containing a viscosity modifier, inorganic fine particles, and a resin component, wherein the viscosity modifier consists of a polymer (P) obtained by reacting compound (A) and compound (B), and compound (A) is one or more compounds selected from the group consisting of hydroxycarboxylic acid, polyester (PE1) obtained by dehydration condensation of monomer component (A1), and modified polyester (PE2) obtained by dehydration condensation of monomer component (A1) and modified component (A2), and satisfies a hydroxyl value / (acid value + amine value) of 0.5 or more and 1.2 or less, the monomer component (A1) consists of hydroxycarboxylic acid as an essential component and lactone as an optional component, and the modified component (A2) is a compound having one functional group (FG1) that can undergo dehydration condensation with a carboxyl group and one or more polar functional groups (FG2) that cannot undergo dehydration condensation with a carboxyl group. A non-aqueous paint composition wherein the ratio of the amount of substance n(A2) of the modified component (A2) to the amount of substance n(A1) of the monomer component (A1) [n(A2) / n(A1)] is 0 mol% or more and 100 mol% or less, the compound (B) is one or more compounds selected from the group consisting of polyisocyanates and their derivatives, and polycarboxylic acids having 4 to 54 carbon atoms, when the hydroxyl group equivalent of compound (A) is EqA and the isocyanate equivalent or carboxyl group equivalent of compound (B) is EqB, the charging ratio of compound (A) to compound (B) (mass of compound (A): mass of compound (B)) is EqA:α×EqB (0.1≦α≦1.2), and the weight-average molecular weight of the polymer (P) in terms of polystyrene is 1,000 or more and 100,000 or less.

9. The non-aqueous coating composition according to claim 8, wherein the hydroxycarboxylic acid used as compound (A) and the monomer component (A1) have 2 to 24 carbon atoms.

10. The non-aqueous coating composition according to claim 8, wherein the sum of the acid value and amine value of compound (A) is 10 or more and 200 or less.

11. The non-aqueous coating composition according to claim 8, wherein the compound (B) is a polyisocyanate having two or three isocyanate groups, and / or a derivative of a polyisocyanate having two or three isocyanate groups.

12. The non-aqueous coating composition according to claim 8, wherein the compound (B) is a divalent to tetravalent polycarboxylic acid.

13. The non-aqueous coating composition according to claim 8, wherein the functional group (FG1) is a hydroxyl group, a primary amino group, or a secondary amino group.

14. The non-aqueous coating composition according to claim 8, wherein the polar functional group (FG2) is one or more functional groups selected from the group consisting of a tertiary amino group, a sulfonic acid group, and a carboxyl group.

15. The non-aqueous paint composition according to claim 8, wherein the content of the viscosity modifier is 0.1% by mass or more and 20% by mass or less based on the total amount of the non-aqueous paint composition.

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