Viscosity modifier, method for producing same, curable composition, and non-aqueous paint composition

Abstract

Provided are a viscosity modifier and a method for producing the same, the viscosity modifier comprising a mixture (M) obtained by melting and mixing compounds including: a diamide compound (A) obtained by condensing a diamine component and a monocarboxylic acid component (A-c); a diamide compound (B) obtained by condensing a diamine component and a monocarboxylic acid component (B-c); and a diamide compound (C) obtained by condensing a diamine component and a monocarboxylic acid component (C-c). The monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) have mutually different numbers of carbon atoms, and at least one of the monocarboxylic acid component (A-c), the monocarboxylic acid component (B-c), and the monocarboxylic acid component (C-c) contains a hydrogenated castor oil fatty acid. Also provided are a curable composition and a non-aqueous paint composition in which the viscosity modifier is used.

Description

Viscosity modifier, its manufacturing method, curable composition, and non-aqueous coating composition

[0001] The present invention relates to a viscosity modifier, a method for producing the same, and a curable composition and a non-aqueous coating composition that use the viscosity modifier.

[0002] Sealants that use polyoxyalkylenes with reactive silyl groups at the ends as the base polymer are called modified silicone sealants. Modified silicone sealants are widely used due to their excellent durability and cost-effectiveness, but they have problems with poor weather resistance and heat resistance in the sealant's usage environment. Therefore, from the perspective of reducing environmental impact, there is a demand for sealants that can be used for longer periods than modified silicone sealants.

[0003] In response to this, by changing the backbone of the main chain from polyoxyalkylene to (meth)acrylic polymer, it is possible to give the sealant high weather resistance and high heat resistance that cannot be achieved with modified silicone sealants. This sealant is called a silylated acrylate sealant, and its high weather resistance allows it to be used for a long period of time, extending the maintenance period and reducing the environmental impact. In this way, silylated acrylate sealants can reduce the amount of raw materials used for the sealant because they can extend the maintenance period, and in light of recent trends such as the SDGs, it is a product whose usage is expected to increase in the future.

[0004] Furthermore, various viscosity modifiers (thixotropy modifiers) may be added to sealants to impart viscosity. One such viscosity modifier is an amide-based viscosity modifier primarily composed of a fatty acid diamide (see, for example, Patent Documents 1 to 3). Patent Document 1 discloses a powdered anti-sagging agent for addition to a non-aqueous anti-corrosion coating material with a low solvent content, which is prepared by melt-mixing (A) a condensate of a mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids (C2-C22 acids) not containing hydrogenated castor oil fatty acid with a diamine, (B) a condensate of one or more aliphatic monocarboxylic acids (C2-C22 acids) with a diamine, and (C) a carboxyl group-containing polyolefin wax. This powdered anti-sagging agent is said to have excellent anti-sagging properties and storage stability even when dispersed at low temperatures. Patent Document 2 discloses a thixotropic agent obtained by reacting a mixture of hydrogenated castor oil fatty acids and alkanoic acids (C6-C12) with EDA and 1,4-DAB. This thixotropic agent is said to swell and remain stable even at dispersion temperatures of 50-70°C and in organic vehicles with low dissolving power. Patent Document 3 discloses a polyamide composition comprising a diamine (EDA or HMDA), a linear monocarboxylic acid (having 1-5 carbon atoms, particularly a C2 acid, a C3 acid, or a combination thereof), and a fatty acid (12-HSA, lesquerolic acid, or a combination thereof). This polyamide composition is said to be easily activatable, thereby suppressing viscosity changes and gloss loss over time.

[0005] JP 2013-49761 A JP 56-112977 A U.S. Pat. No. 10,894,900 A

[0006] However, silylated acrylate sealants having a (meth)acrylic polymer as the main skeleton have low compatibility with the amide viscosity modifiers described in Patent Documents 1 to 3. Therefore, when an amide viscosity modifier is added to a silylated acrylate sealant, the swelling of the fatty acid diamide becomes insufficient, making it difficult to exert the viscosity-imparting effect.

[0007] Furthermore, in order to reduce the energy consumed during production, the production of modified silicone sealants using a cold process (low-temperature kneading), which minimizes heating, is being widely studied and is becoming mainstream worldwide. Furthermore, if the cold process becomes possible, modified silicone sealants can be produced even in places that do not have heating equipment. Even when modified silicone sealants and amide viscosity modifiers are kneaded at low temperatures using this cold process, the fatty acid diamides are less likely to swell, and the viscosity-imparting effect of the amide viscosity modifier is less likely to be achieved.

[0008] Furthermore, in non-aqueous paints such as epoxy paints used for marine or heavy-duty anti-corrosion paints, the trend is to reduce the amount of organic solvents in the paint from the viewpoint of reducing the environmental load, particularly the emission of volatile organic compounds (VOCs).Even when an amide-based viscosity modifier is added to so-called ultra-high solid (UHS) paints or solvent-free paints, which are paints with reduced organic solvent content, the fatty acid diamides are less likely to swell, and the viscosity-imparting effect of the amide-based viscosity modifier is less likely to be exhibited.

[0009] In all of the above cases, when an amide-based viscosity modifier is added, the fatty acid diamide is difficult to swell, and the viscosity-imparting effect is difficult to exhibit. Therefore, there is a need for the development of an amide-based viscosity modifier that can sufficiently swell the fatty acid diamide and exhibit the viscosity-imparting effect even under these harsh conditions.

[0010] The present invention has been made in view of the above circumstances, and aims to provide a viscosity modifier that allows fatty acid diamides to swell sufficiently and exhibits a viscosity-imparting effect even in the following cases (i) to (iii), a method for producing the same, and a curable composition and a non-aqueous paint composition that use the viscosity modifier: (i) When an amide-based viscosity modifier is added to a silylated acrylate-based sealant; (ii) When a modified silicone-based sealant and an amide-based viscosity modifier are kneaded by a cold process; and (iii) When an amide-based viscosity modifier is added to a non-aqueous paint containing a reduced amount of organic solvent.

[0011] As a result of intensive research to solve the above problems, the present inventors have found that by using a mixture obtained by melt-mixing at least two kinds of diamide compounds having different chain lengths, in which the mixture contains a diamide compound obtained by using hydrogenated castor oil fatty acid, as a viscosity adjuster, the fatty acid diamide can be sufficiently swelled and can exhibit a viscosity-imparting effect even in the above cases (i) to (iii), and have completed the present invention based on this finding.

[0012] That is, the present invention relates to a viscosity modifier comprising a mixture (M) obtained by melt-mixing two or more compounds including a diamide compound (A), a diamide compound (B), and an optional diamide compound (C), wherein the diamide compound (A) is a diamide obtained by condensing a diamine component (A-a) with a monocarboxylic acid component (A-c), the diamide compound (B) is a diamide obtained by condensing a diamine component (B-a) with a monocarboxylic acid component (B-c), the diamide compound (C) is a diamide obtained by condensing a diamine component (C-a) with a monocarboxylic acid component (C-c), the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) are monocarboxylic acids having different numbers of carbon atoms, and at least one of the monocarboxylic acid component (A-c), the monocarboxylic acid component (B-c), and the monocarboxylic acid component (C-c) contains a hydrogenated castor oil fatty acid.

[0013] In one embodiment of the viscosity modifier of the present invention, it is preferable that the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) are both monocarboxylic acids having 2 to 18 carbon atoms.

[0014] In another embodiment of the viscosity modifier of the present invention, the difference in carbon number between the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) is preferably 16 or less.

[0015] In another aspect of the viscosity modifier of the present invention, it is preferable that the monocarboxylic acid component (Ac) contains at least a linear saturated fatty acid (a), and the monocarboxylic acid component (Bc) contains at least a linear saturated fatty acid (b).

[0016] In another embodiment of the viscosity modifier of the present invention, when the monocarboxylic acid component (Ac) contains hydrogenated castor oil fatty acid and the monocarboxylic acid component (Bc) does not contain hydrogenated castor oil fatty acid and does not contain the diamide compound (C), it is preferable that the mixing ratio (A / B) of the diamide compound (A) to the diamide compound (B) is 95 / 5 to 55 / 45.

[0017] In another embodiment of the viscosity modifier of the present invention, the diamine component (Aa) and the diamine component (Ba) are preferably the same type of diamine.

[0018] The present invention also provides a viscosity modifier comprising: a mixing step of melt-mixing two or more compounds including a diamide compound (A), a diamide compound (B), and an optional diamide compound (C); and a micronization step of micronizing the mixture (M) obtained in the mixing step to obtain a viscosity modifier, wherein the diamide compound (A) is a diamide obtained by condensing a diamine component (A-a) with a monocarboxylic acid component (A-c), and the diamide compound (B) is a diamide obtained by condensing a diamine component (Ba) with a monocarboxylic acid component (B-c). the diamide compound (C) is a diamide obtained by condensing a diamine component (Ca) with a monocarboxylic acid component (C-c); the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) are monocarboxylic acids having different numbers of carbon atoms; and at least one of the monocarboxylic acid component (A-c), the monocarboxylic acid component (B-c), and the monocarboxylic acid component (C-c) contains a hydrogenated castor oil fatty acid.

[0019] In one embodiment of the method for producing a viscosity modifier of the present invention, it is preferable that the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) are both monocarboxylic acids having 2 to 18 carbon atoms.

[0020] In another aspect of the method for producing a viscosity modifier of the present invention, the difference in carbon number between the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) is preferably 16 or less.

[0021] In another aspect of the method for producing a viscosity modifier of the present invention, it is preferable that the monocarboxylic acid component (Ac) contains at least a linear saturated fatty acid (a), and the monocarboxylic acid component (Bc) contains at least a linear saturated fatty acid (b).

[0022] In another embodiment of the method for producing a viscosity modifier of the present invention, when the monocarboxylic acid component (Ac) contains hydrogenated castor oil fatty acid and the monocarboxylic acid component (Bc) does not contain hydrogenated castor oil fatty acid and does not contain the diamide compound (C), it is preferable that the mixing ratio (A / B) of the diamide compound (A) to the diamide compound (B) is 95 / 5 to 55 / 45.

[0023] In another aspect of the method for producing a viscosity modifier of the present invention, the diamine component (Aa) and the diamine component (Ba) are preferably the same type of diamine.

[0024] The present invention also provides a curable composition comprising the viscosity modifier described above and a resin component.

[0025] The present invention also relates to a non-aqueous coating composition containing the viscosity modifier described above, a resin component, and an optional volatile solvent, wherein the content of the volatile solvent is 15 mass % or less based on the total amount of the non-aqueous coating composition.

[0026] According to the present invention, by using as a viscosity modifier a mixture obtained by melt-mixing at least two kinds of diamide compounds having different chain lengths, in which the mixture contains a diamide compound obtained by using hydrogenated castor oil fatty acid, it becomes possible to obtain a sufficient viscosity-imparting effect in comparison with the amide-based viscosity modifiers disclosed in the prior art documents, even in the above cases (i) to (iii).

[0027] Preferred embodiments of the present invention will now be described in detail.

[0028] [Viscosity Modifier] The viscosity modifier of the present invention comprises a mixture (M) obtained by melt-mixing two or more compounds, including a diamide compound (A) as an essential component, a diamide compound (B) as an essential component, and a diamide compound (C) as an optional component. By including the components described in detail below in the mixture (M), the fatty acid diamide can be sufficiently swollen and activated even in the following cases (i) to (iii). Therefore, the viscosity modifier of the present invention can exhibit a sufficient viscosity-imparting effect compared to the amide-based viscosity modifiers disclosed in the prior art documents mentioned above. (i) When a fatty acid diamide viscosity modifier is added to a silylated acrylate sealant. (ii) When a modified silicone sealant and a fatty acid diamide viscosity modifier are kneaded using a cold process (generally, about 50°C to 60°C) or at a temperature lower than the cold process (for example, room temperature, about 20°C to 30°C). (iii) When a fatty acid diamide viscosity modifier is added to a non-aqueous paint with a reduced amount of organic solvent.

[0029] The principle by which amide-based viscosity modifiers exert their viscosity-imparting effect is as follows. The fatty acid diamide, the main component of amide-based viscosity modifiers (the diamide compounds (A), (B), and (C) in the present invention are also fatty acid diamides), changes from a particulate to a needle-like shape upon swelling and becomes activated. The activated fatty acid diamide can impart stable viscosity to systems such as curable compositions, such as sealants, and non-aqueous paint compositions, such as marine or heavy-duty anticorrosion paints. As a result, a sufficient viscosity-imparting effect is exhibited. However, under conditions in which the fatty acid diamide is difficult to swell and activate, such as in the above cases (i) to (iii), it is presumed that the fatty acid diamide powder (solid particles) tends to aggregate and form aggregates. In this aggregate state, the fatty acid diamide is difficult to assume an acicular shape (i.e., is difficult to activate). However, the present inventors speculate that the viscosity adjuster of the present invention uses a mixture obtained by melt-mixing at least two diamide compounds having different chain lengths, in which the diamide compound obtained using hydrogenated castor oil fatty acid is contained, and that the fatty acid diamide is easily activated as a result of the interaction between the respective components.

[0030] Furthermore, in the case of the above (iii), it has been found that the use of the viscosity modifier of the present invention not only provides a sufficient viscosity-imparting effect, but also improves the effect of improving the impediment to overcoatability caused by an increase in the contact angle of a coating film formed using a non-aqueous paint containing a reduced amount of organic solvent. In other words, the viscosity modifier of the present invention can achieve both a sufficient viscosity-imparting effect and an effect of improving the impediment to overcoatability, even in the case of the above (iii).

[0031] Here, paints are generally applied in multiple layers for purposes such as surface protection, imparting design, and functionality. For example, in marine or heavy-duty anticorrosion paints, two coats of paint are often applied, and then another coat is applied on top of that, in order to increase the thickness of the paint film and thereby improve corrosion resistance. In such cases, poor adhesion at the coating interface between each coating film can cause the coating to peel off.

[0032] Here, fatty acid diamides, which are produced by reacting hydrogenated castor oil fatty acids or linear saturated fatty acids with diamines, have low surface tension and may bleed onto the surface after application of a non-aqueous paint. For example, when a solvent-containing paint is applied, convection occurs within the paint film during curing due to solvent evaporation after application, making the fatty acid diamide particularly susceptible to bleeding. Furthermore, when a solvent-free paint is applied, convection occurs within the paint film due to the settling of pigments and fillers after application and before curing, causing the fatty acid diamide to bleed. This bleeding of the fatty acid diamide results in an increased contact angle of the paint film. When the contact angle of the paint film increases, droplets of another paint applied to the surface of the cured paint film do not wet and spread, reducing the contact area at the paint film interface, reducing interlayer adhesion and hindering the paint film's recoatability. This increases the risk of the recoat film peeling.

[0033] In contrast, by adding the viscosity modifier of the present invention to a non-aqueous paint, the problem of impaired recoatability of the paint film caused by an increase in the paint film contact angle as described above can be alleviated.

[0034] (Diamide Compound (A)) The diamide compound (A) is an essential component of the viscosity modifier according to the present invention, and is a diamide (fatty acid diamide) obtained by condensing a diamine component (A-a) with a monocarboxylic acid component (A-c). Raw materials for obtaining the diamide compound (A) according to the present invention include the diamine component (A-a) and a monocarboxylic acid component (A-c) selected from the group consisting of hydrogenated castor oil fatty acid (hereinafter sometimes referred to as "oxy acid" or "OX acid"), saturated fatty acid, and unsaturated fatty acid. Examples of the diamine component (A-a) and the monocarboxylic acid component (A-c) include the compounds exemplified below. The conditions for the condensation reaction (e.g., reaction temperature, compounding ratio of each component) can be appropriately set by known methods.

[0035] <Diamine Component (A-a)> As the diamine component (A-a) according to the present invention, for example, one or more diamines selected from the group consisting of diamines having 2 to 12 carbon atoms can be used. Examples of such diamines include aliphatic diamines such as ethylenediamine (EDA), propylenediamine, tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), octamethylenediamine (OMDA), and dodecamethylenediamine (DMDA); aromatic diamines such as orthoxylenediamine, metaxylenediamine (MXDA), paraxylenediamine (PXDA), diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, and methylenebischloroaniline; and alicyclic diamines such as piperazine and isophoronediamine.

[0036] <Monocarboxylic Acid Component (A-c)> The monocarboxylic acid component (A-c) of the present invention can be a monocarboxylic acid selected from the group consisting of hydroxy acids, saturated fatty acids, and unsaturated fatty acids. Examples of hydroxy acids (hydrogenated castor oil fatty acids) include fatty acids having a hydroxy group, such as 12-hydroxystearic acid obtained by saponifying hydrogenated castor oil. Examples of saturated fatty acids include saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid (behenic acid), 2-ethylhexanoic acid, isostearic acid, cyclopentanoic acid, cyclohexanoic acid, and cycloheptanoic acid. Examples of unsaturated fatty acids include unsaturated aliphatic monocarboxylic acids such as oleic acid, linoleic acid, ricinoleic acid, linolenic acid, eicosenoic acid, erucic acid, and mixed fatty acids obtained from natural fats and oils (tall oil fatty acid, rice bran fatty acid, soybean oil fatty acid, beef tallow fatty acid, etc.).

[0037] In order to enhance the viscosity-imparting effect and the effect of improving topcoatability inhibition, it is preferable that the monocarboxylic acid component (A-c) contains at least a straight-chain saturated fatty acid (a) (hereinafter, straight-chain saturated fatty acid may be referred to as "alkanoic acid"). Examples of the straight-chain saturated fatty acid (a) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid.

[0038] From another viewpoint of enhancing the viscosity-imparting effect and the effect of improving inhibition of overcoatability, the monocarboxylic acid component (Ac) is preferably a monocarboxylic acid having 2 to 18 carbon atoms, more preferably a monocarboxylic acid having 2 to 14 carbon atoms, and even more preferably a monocarboxylic acid having 2 to 12 carbon atoms.

[0039] <Method for Synthesizing Diamide Compound (A)> The diamide compound (A) according to the present invention can be obtained by adding the diamine component (A-a) to the monocarboxylic acid component (A-c) in an amount that is half the amount of the monocarboxylic acid component (A-c) (i.e., 1 molar equivalent per 2 molar equivalents of the monocarboxylic acid component (A-c)), and carrying out a condensation polymerization (amidation) reaction at 150 to 200°C. For example, the diamine component (A-a) and the monocarboxylic acid component (A-c) as raw materials are placed in a reaction vessel such as a four-necked flask, and the raw materials are stirred in an inert gas atmosphere (e.g., under a nitrogen gas flow) to form a mixture. The raw material mixture is then heated and subjected to a condensation polymerization reaction at 150 to 200°C for 4 to 10 hours, thereby synthesizing the diamide compound (A).

[0040] (Diamide Compound (B)) The diamide compound (B) is an essential component of the viscosity modifier according to the present invention, and is a diamide (fatty acid diamide) obtained by condensing a diamine component (Ba) with a monocarboxylic acid component (B-c). Raw materials for obtaining the diamide compound (B) according to the present invention include the diamine component (Ba) and a monocarboxylic acid component (B-c) selected from the group consisting of hydroxy acids, saturated fatty acids, and unsaturated fatty acids. Examples of the diamine component (Ba) and the monocarboxylic acid component (B-c) include the compounds exemplified below. The conditions for the condensation reaction (such as the reaction temperature and the blending ratio of each component) can be appropriately set by known methods.

[0041] <Diamine Component (Ba)> As the diamine component (Ba) according to the present invention, the same diamines as those used for the diamine component (Aa) can be used.

[0042] Here, in order to enhance the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, it is preferable that the diamine component (Aa) and the diamine component (Ba) are the same type of diamine.

[0043] <Monocarboxylic Acid Component (Bc)> As the monocarboxylic acid component (Bc) according to the present invention, the same monocarboxylic acids as those used for the monocarboxylic acid component (Ac) can be used.

[0044] In order to enhance the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, it is preferable that the monocarboxylic acid component (B-c) contains at least a linear saturated fatty acid (b). Examples of the linear saturated fatty acid (b) are the same as the examples of the linear saturated fatty acid (a) described above.

[0045] From another standpoint of enhancing the viscosity-imparting effect and the effect of improving inhibition of overcoatability, it is preferred that the monocarboxylic acid component (Bc) be a monocarboxylic acid having 2 to 18 carbon atoms.

[0046] In the viscosity modifier of the present invention, in order to exert a sufficient viscosity-imparting effect and an effect of improving inhibition of overcoatability, the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) must be monocarboxylic acids having different numbers of carbon atoms. If the number of carbon atoms of the monocarboxylic acid component (A-c) is the same as the number of carbon atoms of the monocarboxylic acid component (B-c), the sufficient viscosity-imparting effect and effect of improving inhibition of overcoatability intended by the present invention cannot be exerted.

[0047] In order to enhance the viscosity-imparting effect and the effect of improving overcoatability inhibition, it is preferable that the difference in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) is 16 or less. There is no particular restriction on the lower limit of the difference in the number of carbon atoms, and the difference in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) may be 1. In order to further enhance the viscosity-imparting effect and the effect of improving overcoatability inhibition, it is more preferable that the difference in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) is 1 or more and 14 or less, even more preferably 1 or more and 12 or less, even more preferably 1 or more and 10 or less, and most preferably 1 or more and 8 or less. Note that, when an oxyacid is used as the monocarboxylic acid component (A-c) or the monocarboxylic acid component (B-c), the "difference in the number of carbon atoms" referred to here means the difference in the number of carbon atoms of the monocarboxylic acid other than the oxyacid. For example, in the viscosity modifier of Production Example 1 listed in the Examples below, the difference in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) is the difference between the number of carbon atoms of acetic acid (C2), a monocarboxylic acid other than the oxyacid used in Synthesis Example A1, and the number of carbon atoms of caproic acid (C6), a monocarboxylic acid used in Synthesis Example B1, and is therefore 4. When multiple monocarboxylic acids other than oxyacids are used as the monocarboxylic acid component (A-c) or the monocarboxylic acid component (B-c), the difference in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) will be multiple. Furthermore, in the present invention, when there are multiple differences in the number of carbon atoms between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c), if at least one of the differences in the number of carbon atoms is not 0 (zero), the number of carbon atoms of the monocarboxylic acid component (A-c) and the number of carbon atoms of the monocarboxylic acid component (B-c) are considered to be different from each other. For example, when hydrogenated castor oil fatty acid and acetic acid are used as the monocarboxylic acid component (A-c), and caproic acid and lauric acid are used as the monocarboxylic acid component (B-c), the difference in the number of carbon atoms will be either 4 or 10. In this case, it is presumed that the viscosity-imparting effect and the effect of improving inhibition of topcoatability depend on the molar fraction of caproic acid and lauric acid.For example, if the compounding ratio of the monocarboxylic acid component (B-c) is 60 mol% caproic acid and 40 mol% lauric acid, it is considered that the effect when the difference in carbon number is 4 contributes to 60% of the total effect, and the effect when the difference in carbon number is 10 contributes to 40% of the total effect. Furthermore, for example, if hydrogenated castor oil fatty acid and acetic acid are used as the monocarboxylic acid component (A-c), and acetic acid and caproic acid are used as the monocarboxylic acid component (B-c), the difference in carbon number will be either 0 or 4. In this case, since the difference in carbon number may not be 0, it can be said that the carbon number of the monocarboxylic acid component (A-c) and the carbon number of the monocarboxylic acid component (B-c) are different from each other. In this case, too, the contribution of the effect differs depending on the molar fraction of acetic acid and caproic acid in the monocarboxylic acid component (B-c). Therefore, as the molar fraction of caproic acid decreases, its contribution to the effect decreases accordingly.

[0048] <Method for synthesizing diamide compound (B)> The diamide compound (B) according to the present invention can be synthesized by the same method as that for synthesizing the diamide compound (A) described above.

[0049] (Diamide Compound (C)) The diamide compound (C) is an optional component of the viscosity modifier according to the present invention, and is a diamide (fatty acid diamide) obtained by condensing a diamine component (Ca) with a monocarboxylic acid component (C-c). One or more fatty acid diamides can be used as the diamide compound (C) contained in the mixture (M). The diamide compound (C) is a fatty acid diamide different from both the diamide compound (A) and the diamide compound (B). The raw materials for obtaining the diamide compound (C) according to the present invention include the diamine component (Ca) and a monocarboxylic acid component (C-c) selected from the group consisting of hydroxy acids, saturated fatty acids, and unsaturated fatty acids. Examples of the diamine component (Ca) and the monocarboxylic acid component (C-c) include the compounds exemplified below. The conditions for the condensation reaction (e.g., reaction temperature, compounding ratio of each component) can be appropriately set by a known method.

[0050] <Diamine Component (Ca)> As the diamine component (Ca) according to the present invention, the same diamines as those used as the diamine component (Aa) can be used.

[0051] Here, in order to enhance the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, it is preferable that the diamine component (Ca) is the same type of diamine as the diamine components (Aa) and (Ba).

[0052] <Monocarboxylic Acid Component (Cc)> As the monocarboxylic acid component (Cc) according to the present invention, the same monocarboxylic acids as those used for the monocarboxylic acid component (Ac) can be used.

[0053] However, the number of carbon atoms of the monocarboxylic acid component (C-c) is not particularly limited, and may be the same as or different from the number of carbon atoms of the monocarboxylic acid component (A-c) or the monocarboxylic acid component (B-c). Furthermore, the monocarboxylic acid component (C-c) may or may not contain an alkanoic acid.

[0054] On the other hand, in order to enhance the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, the monocarboxylic acid component (Cc) is preferably a monocarboxylic acid having 2 to 18 carbon atoms.

[0055] In the viscosity modifier according to the present invention, at least one of the monocarboxylic acid component (A-c), the monocarboxylic acid component (B-c), and the monocarboxylic acid component (C-c) must contain hydrogenated castor oil fatty acid. In other words, the mixture (M) must contain a diamide compound obtained by using hydrogenated castor oil fatty acid as the monocarboxylic acid component. Otherwise, the viscosity modifier will not be able to exhibit the sufficient viscosity-imparting effect and the effect of improving overcoatability inhibition intended by the present invention.

[0056] A typical case in which the viscosity modifier of the present invention contains a diamide compound (C) is when neither the monocarboxylic acid component (A-c) nor the monocarboxylic acid component (B-c) contains hydrogenated castor oil fatty acid, and when the monocarboxylic acid component (C-c) contains a diamide compound (C) containing hydrogenated castor oil fatty acid. However, the case in which the viscosity modifier of the present invention contains a diamide compound (C) is not limited to the above case.

[0057] <Method for synthesizing diamide compound (C)> The diamide compound (C) according to the present invention can be synthesized by the same method as that for synthesizing the diamide compound (A) described above.

[0058] (Mixing Ratio of Diamide Compound (A) and Diamide Compound (B)) The mixing ratio of the diamide compound (A) and the diamide compound (B) contained as essential components in the mixture (M) (hereinafter, in this specification, this may also be read as the "blending ratio" during the production of the viscosity modifier) ​​is not particularly limited. For example, the mixing ratio of the diamide compound (A) to the diamide compound (B) (hereinafter, referred to as the "mixing ratio A / B") can be 99 / 1 to 1 / 99. From the viewpoint of enhancing the viscosity-imparting effect and the effect of improving inhibition of overcoatability, the mixing ratio A / B is preferably 95 / 5 to 5 / 95. Furthermore, from the viewpoint of further enhancing the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, when the monocarboxylic acid component (A-c) contains hydrogenated castor oil fatty acid and the monocarboxylic acid component (B-c) does not contain hydrogenated castor oil fatty acid and does not contain the diamide compound (C), the mixing ratio A / B is preferably 95 / 5 to 55 / 45. To further enhance the viscosity-imparting effect and the effect of improving the inhibition of overcoatability, the mixing ratio A / B is more preferably 95 / 5 to 60 / 40, even more preferably 95 / 5 to 70 / 30 or 90 / 10 to 60 / 40, even more preferably 90 / 10 to 70 / 30, and most preferably 80 / 20 to 70 / 30.

[0059] (Amount of Diamide Compound (C)) The amount of diamide compound (C) mixed in the viscosity modifier of the present invention (hereinafter, in this specification, this may also be read as the "amount blended" during production of the viscosity modifier) ​​is not particularly limited, and may be, for example, more than 0 parts by mass and not more than 900 parts by mass per 100 parts by mass of the total amount of diamide compound (A) and diamide compound (B). From the viewpoint of enhancing the viscosity-imparting effect and the effect of improving inhibition of overcoatability, the amount of diamide compound (C) mixed is preferably more than 0 parts by mass and not more than 400 parts by mass, more preferably 100 parts by mass or more and not more than 200 parts by mass per 100 parts by mass of the total amount of diamide compound (A) and diamide compound (B).

[0060] (Other Components (D)) The mixture (M) may contain a component (D) other than the diamide compound (A), diamide compound (B), and diamide compound (C) described above, as long as the effects of the present invention are not impaired. Examples of such component (D) include polyamide, hydrogenated castor oil, and other polymers. The amount of component (D) contained in the viscosity modifier of the present invention (hereinafter, this may also be interpreted as the "blended amount" during the production of the viscosity modifier) ​​is not particularly limited, and may be, for example, more than 0 parts by mass and not more than 900 parts by mass per 100 parts by mass of the total amount of diamide compound (A), diamide compound (B), and diamide compound (C). From the viewpoint of enhancing the effect of adding component (D), the amount of component (D) contained is preferably more than 0 parts by mass and not more than 400 parts by mass, more preferably 1 part by mass or more and not more than 50 parts by mass, per 100 parts by mass of the total amount of diamide compound (A), diamide compound (B), and diamide compound (C).

[0061] <Polyamide> The polyamide is a polyamide obtainable by polycondensation of an amine component and a carboxylic acid component. In the present invention, the amine component includes, for example, at least one amine selected from the group consisting of diamines having 2 to 54 carbon atoms and triamines having 2 to 54 carbon atoms. The carboxylic acid component includes, for example, at least one carboxylic acid selected from dicarboxylic acids having 4 to 54 carbon atoms and tricarboxylic acids having 4 to 54 carbon atoms. The polyamide usable as component (D) of the present invention may have any chemical structure, as long as it is a polymer compound obtainable by polycondensation of the above-mentioned amine component and carboxylic acid component and has an amide bond (—CONH—).

[0062] The amine component can be, for example, at least one amine selected from the group consisting of diamines having 2 to 54 carbon atoms and triamines having 2 to 54 carbon atoms. Examples of the diamines include aliphatic diamines such as ethylenediamine (EDA), propylenediamine, tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), octamethylenediamine (OMDA), and dodecamethylenediamine (DMDA); aromatic diamines such as orthoxylenediamine, metaxylenediamine (MXDA), paraxylenediamine (PXDA), diaminodiphenylmethane, diaminodiphenylether, diaminodiphenylsulfone, and methylenebischloroaniline; and alicyclic diamines such as piperazine and isophoronediamine. Examples of the triamines include aliphatic triamines such as diethylenetriamine.

[0063] Furthermore, as the amine component, diamines or triamines derived from polymerized fatty acids, which are polymerized fatty acid derivatives, can also be used. Examples of such polymerized fatty acid derivatives include dimer diamine (DDA), which is a dimer acid derivative (described in detail below), and trimer triamine (TTA), which is a trimer acid derivative (described in detail below). Dimer diamine is a dimer acid derivative in which the two terminal carboxyl groups of a dimer acid are substituted with primary aminomethyl groups or amino groups, and commercially available products can be used. Trimer triamine is a trimer acid derivative in which the three terminal carboxyl groups of a trimer acid are substituted with primary aminomethyl groups or amino groups, and commercially available products can be used.

[0064] As the amine component, a monoamine may be used in combination with the diamine and / or triamine. Examples of monoamines that can be used as the amine component include ethylamine, monoethanolamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, and behenylamine.

[0065] The compounds used as the amine components described above can be used either alone or in combination of two or more.

[0066] The carboxylic acid component can be, for example, at least one carboxylic acid selected from dicarboxylic acids having 4 to 54 carbon atoms and tricarboxylic acids having 4 to 54 carbon atoms. Examples of the dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and dimer acid. Dimer acids are polymerized fatty acids obtained by polymerizing (dimerizing) unsaturated fatty acids (e.g., unsaturated fatty acids having 18 or 22 carbon atoms) obtained from vegetable oils such as soybean oil, tall oil, linseed oil, and cottonseed oil. Dimer acids having 36 or 44 carbon atoms are generally commercially available. Commercially available dimer acids contain monomeric acids and trimer acids in addition to dimer acids, but those with a high dimer acid content are preferred.

[0067] Examples of the tricarboxylic acid include trimer acid and trimesic acid. Trimer acid is a polymerized fatty acid obtained by increasing the trimer acid content from a dimer acid by distillation or other purification, and trimer acid having 54 carbon atoms is generally commercially available. Commercially available trimer acids contain monomeric acid and dimer acid in addition to trimer acid, but those with a high trimer acid content are preferred.

[0068] The carboxylic acid component may be a monocarboxylic acid in combination with the dicarboxylic acid and / or tricarboxylic acid. Examples of the monocarboxylic acid that can be used as the carboxylic acid component include saturated aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated castor oil fatty acid, arachidic acid, and behenic acid (behenic acid), and unsaturated aliphatic monocarboxylic acids such as oleic acid, linoleic acid, ricinoleic acid, linolenic acid, eicosenoic acid, erucic acid, and mixed fatty acids obtained from natural fats and oils (tall oil fatty acid, rice bran fatty acid, soybean oil fatty acid, beef tallow fatty acid, etc.).

[0069] The compounds used as the carboxylic acid component described above can be used either alone or in combination of two or more.

[0070] The polyamide usable in the present invention can be synthesized by polycondensation of the amine component and carboxylic acid component described above under known reaction conditions. For example, the raw materials, amine component and carboxylic acid component, are placed in a reaction vessel such as a four-neck flask and stirred in an inert gas atmosphere (e.g., under a nitrogen gas flow) to form a mixture. The raw material mixture is then heated and subjected to polycondensation at 150°C to 200°C for 2 to 10 hours to synthesize the polyamide.

[0071] <Hydrogenated Castor Oil> Hydrogenated castor oil is a triglyceride of saturated fatty acids obtained by hydrogenating castor oil. Commercially available hydrogenated castor oils can be used, and examples of commercially available hydrogenated castor oils include C-Wax (manufactured by Kokura Synthetic Industries, Ltd.), Kaowax 85P (manufactured by Kao Corporation), Castor Hydrogenated Oil A (manufactured by Ito Oil Mills, Ltd.), Castor Hydrogenated Oil (manufactured by Yamakei Sangyo Co., Ltd.), and Royal Castor Products' Hydrogenated Castor Oil "B" Grade.

[0072] <Other Polymers> Examples of other polymers include ethylene acrylic acid copolymers, polyethylene oxide, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, polyurea, ethylene-vinyl acetate copolymers, poly(meth)acrylic acid, and (meth)acrylic acid copolymers.

[0073] (Properties of Viscosity Modifier) ​​The viscosity modifier according to the present invention is a powdered (fine powder) viscosity modifier obtained by atomizing the mixture (M). The size of the powdered viscosity modifier is not particularly limited, and may be adjusted to, for example, a median diameter of about 0.1 to 100 μm. As the viscosity modifier of the present invention, a powdered viscosity modifier may be used as is, or a liquid or paste-like viscosity modifier obtained by dispersing or dissolving a powdered viscosity modifier in a solvent may be used. Therefore, for example, when the viscosity modifier of the present invention is added to a curable composition or a non-aqueous coating composition described below, the powdered viscosity modifier may be kneaded with the base polymer and other components of the sealant, or the liquid or paste-like viscosity modifier may be kneaded with the base polymer and other components of the sealant.

[0074] (Method for Producing Viscosity Adjuster) The method for producing the viscosity adjuster according to the present invention described above includes the mixing step and the atomization step described below.

[0075] <Mixing Step> In the mixing step, two or more compounds (including at least the diamide compound (A) and the diamide compound (B) as essential components, the diamide compound (C) as an optional component, and optionally other components (D) are melt-mixed to obtain a molten mixture (M). Specifically, for example, some components, such as the diamide compound (A) and the diamide compound (B), are heated to a molten state, and then the remaining components are added and melt-mixed. The melting temperature at this time may be set to be equal to or higher than the melting points of all components contained in the mixture (M).

[0076] <Atomization Process> In the atomization process, the mixture (M) obtained in the above-mentioned mixing process is atomized to obtain a powdered viscosity modifier, or a liquid or paste-like viscosity modifier in which the powdered viscosity modifier is dispersed or dissolved in a solvent. The atomization method is not particularly limited, but for example, a powdered viscosity modifier is produced by extracting the molten mixture (M) obtained in the mixing process as a solid and pulverizing the solid mixture (M) to a desired particle size. Known methods can be used to pulverize the solid mixture (M), such as a jet mill. Another atomization method is, for example, adding the molten mixture (M) obtained in the mixing process to a precipitation medium such as an organic solvent, a low-viscosity polymer, or a resin solution (varnish), and precipitating the powdered mixture (M) in the solution of the precipitation medium, thereby producing a liquid or paste-like viscosity modifier. The organic solvent, low viscosity polymer, and resin solution (varnish) that can be used as the deposition medium are not particularly limited, but the following examples can be used.

[0077] 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); acetonitrile, propionitrile, and the like. The above organic solvents may be used alone or in combination of two or more kinds.

[0078] Examples of low-viscosity polymers include polyalphaolefins, polyalkylene oxides, polyesters, epoxy resins, urethane resins, acrylic resins, aliphatic or aromatic high-boiling oils, phenol-modified aliphatic or aromatic polymers, xylene resins, and toluene resins, all of which have a viscosity of 1 to 200 cps at 25°C and a heating residue of 90% or more.

[0079] Examples of resin solutions include solutions obtained by diluting alkyd resin, acrylic resin, acrylic urethane resin, melamine resin, urethane resin, epoxy resin, coumarone resin, urea resin, phenolic resin, vinyl chloride resin, phenoxy resin, silicone resin, fluororesin, nylon resin, styrene butadiene resin, nitrile butadiene resin, petroleum resin, rosin, drying oil, boiled oil, acetyl cellulose, nitrocellulose, or the like with an organic solvent.

[0080] (Uses of Viscosity Modifier) ​​The viscosity modifier according to the present invention is suitable for use as an additive in curable compositions, which will be described later, or non-aqueous paint compositions such as marine or heavy-duty anticorrosion paints.

[0081] [Curable Composition] The curable composition of the present invention contains the above-described viscosity modifier and a resin component as essential components. The curable composition of the present invention may further contain other additives, such as a plasticizer, a filler, and a dehydrating agent or an adhesion promoter, as optional components. The content of the viscosity modifier of the present invention varies depending on the type of resin component in the curable composition and the formulation of fillers such as pigments. However, it is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the total resin solids in the curable composition. By setting the content of the viscosity modifier within the above range, the fatty acid diamide can be sufficiently activated and a sufficient viscosity-imparting effect can be obtained even under conditions such as (i) and (ii) above, where the fatty acid diamide is unlikely to swell and a sufficient viscosity-imparting effect is unlikely to be exhibited. Furthermore, depending on the blending composition of the curable composition according to the present invention and the composition of the viscosity modifier according to the present invention, even under conditions in which the components of the curable composition are kneaded at room temperature (for example, about 25°C, which is even lower than the cold process of (ii)), the fatty acid diamide can be sufficiently activated and a sufficient viscosity-imparting effect can be obtained.

[0082] (Resin Component) Examples of the resin component of the curable composition of the present invention include modified silicone resins. Modified silicone resins are primarily composed of silyl-terminated polyethers (e.g., polyoxyalkylenes) with reactive silyl groups introduced at the terminals. Sealants using such modified silicone resins as the base polymer are called modified silicone sealants. For example, when modified silicone resins are used as the resin component of curable compositions such as sealants, the modified silicone resins preferably cure in the presence of moisture to form siloxane bonds. Examples of modified silicone resins include silyl-modified polymers formed by introducing silyl groups into the hydroxyl terminals of a linear or branched polyoxyalkylene polymer as the main chain. Other examples of silyl-modified polymers include silyl-modified polyurethanes, silyl-modified polyesters, and silyl-terminated polyisobutylenes. Modified silicone resins may be those obtained by known synthesis methods or commercially available products. Commercially available modified silicone resins include, for example, MS Polymer S203H and MS Polymer S303H manufactured by Kaneka Corporation, and Exestar manufactured by AGC.

[0083] Another example of the resin component of the curable composition is a (meth)acrylic polymer having a hydrolyzable silyl group (hereinafter referred to as a "silylated (meth)acrylate polymer"). A silylated (meth)acrylate polymer is a resin in which the main chain of a modified silicone resin is changed from polyoxyalkylene to a (meth)acrylic polymer. A sealant using this silylated (meth)acrylate polymer as the base polymer is called a silylated acrylate sealant. Note that "(meth)acrylic" and "(meth)acrylate" refer to "acrylic or methacrylic" and "acrylate or methacrylate," respectively. Using a silylated (meth)acrylate polymer as the base polymer of a sealant can impart high weather resistance and high heat resistance to the sealant. Therefore, a silylated acrylate sealant can be used for a long period of time, extending the maintenance period and reducing environmental impact. The silylated (meth)acrylate polymer may be one obtained by a known synthesis method, or may be one available as a commercially available product. Examples of commercially available silylated (meth)acrylate polymers include TA Polymer SB802S manufactured by Kaneka Corporation, ARUFON (registered trademark) US-6000 series (manufactured by Toagosei Co., Ltd.), and Actflow (registered trademark) series (manufactured by Soken Chemical & Engineering Co., Ltd.).

[0084] The resin component of the curable composition may contain other resins in addition to the modified silicone resin or silylated (meth)acrylate polymer described above, as long as the effects of the present invention are not impaired.

[0085] (Plasticizer) Examples of plasticizers include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), isononyl 1,2-cyclohexanedicarboxylate (DINCH), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), Dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid esters, dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipates, dibutyl diglycol adipate (BXA), bis(2-ethylhexyl) azelaate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dibutyl maleate ( DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris(2-ethylhexyl)phosphate (TOP), tri(chloroethyl)phosphate (TCEP), trisdichloropropyl phosphate (CRP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl)phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (CDP), acetyltriethyl citrate, acetyltributyl citrate, trimellitic acid-based plasticizers, polyester-based plasticizers, polyether-based plasticizers, epoxy-based plasticizers, chlorinated paraffin, stearic acid-based plasticizers, dimethylpolysiloxane, process oil, and the like.

[0086] (Filler) Examples of fillers 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; color pigments such as titanium dioxide, carbon black, yellow lead, cadmium yellow, ochre, titanium yellow, zinc chromate, red iron oxide, aluminosilicate, quinacridone-based, phthalocyanine-based, anthroquinone-based, diketopyrrolopyrrole-based, benzimidazolone-based, and isoindolinone-based; and metallic pigments such as aluminum flakes, copper flakes, micaceous iron oxide, mica, and scaly powder of mica coated with a metal oxide.

[0087] (Other Additives) The curable composition of the present invention may contain other substances, such as dehydrating agents (e.g., silane coupling agents), adhesion improvers, surfactants, curing catalysts, film-forming aids, driers, antifouling agents, sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, water-resistant agents, antiseptic and antifungal agents, antifoaming agents, leveling agents, dispersants, flame retardants, antistatic agents, release agents, deodorizers, and fragrances, within the scope of not impairing the properties of the curable composition of the present invention or the object of the present invention.

[0088] (Method for Producing Curable Composition) The curable composition of the present invention can be produced in accordance with known sealant production methods. For example, the curable composition of the present invention is produced by mixing the above-mentioned resin components, plasticizer, filler, viscosity modifier, and other components using a three-roll mill or dissolver, followed by kneading under reduced pressure while heating. The kneading temperature may be appropriately set depending on the equipment used in production, production costs, allowable energy consumption, and the like. The curable composition of the present invention may also be obtained by kneading the components at room temperature (e.g., about 20 to 30°C) without heating. Therefore, with a curable composition containing a viscosity modifier of the present invention, the viscosity-imparting effect can be achieved by kneading while maintaining room temperature (about 25°C), even in warm regions where a temperature rise due to the heat generated by dispersion of the components can deteriorate the quality of the composition, or where heat cannot be obtained. Furthermore, in cold regions, the viscosity-imparting effect can be achieved even in cold regions where the temperature is about 0°C and the temperature during kneading only rises to about 20 to 30°C, even if heat is generated during dispersion of the components.

[0089] (Uses of Curable Composition) A cured product of the curable composition of the present invention can be used as a sealant for buildings, ships, automobiles, roads, medical equipment, etc.

[0090] [Non-aqueous Paint Composition] The non-aqueous paint composition of the present invention contains the above-mentioned viscosity modifier and a resin component as essential components. The amide-based viscosity modifier is activated by heat dispersion in the non-aqueous paint, exhibiting a viscosity-imparting effect. However, the degree of activation is affected by the paint formulation and heat dispersion conditions (temperature, dispersion shear, dispersion time, etc.). On the other hand, when the paint formulation and heat dispersion conditions are the same, the ease of activation is determined by the viscosity modifier composition, so the effects of the present invention are not limited by the content of viscosity modifier in the paint. However, if the content of viscosity modifier in the paint is too low, the viscosity modifier's effect as a viscosity modifier is weak. On the other hand, if the content of viscosity modifier in the paint is too high, the paint will thicken significantly, making dispersion of the viscosity modifier in the paint, handling of the paint, and application difficult. Therefore, the content of viscosity modifier in the non-aqueous paint composition is preferably 0.2% to 5% by mass. Furthermore, by setting the content of the viscosity modifier within the above range, it is possible to achieve both the effect of imparting viscosity and the effect of improving overcoating inhibition, even in the case of (iii) above.

[0091] The non-aqueous coating composition of the present invention is an ultra-high solids coating or a solventless coating. Ultra-high solids coatings are coatings in which the content of volatile solvents in the coating is reduced as much as possible. In this invention, coatings in which the content of volatile solvents in the coating is 15 mass% or less based on the total amount of the non-aqueous coating composition are referred to as "ultra-high solids coatings." Solventless coatings are coatings that do not contain volatile solvents (organic solvents, etc.) to dissolve the resin in the coating, and have the advantage of contributing to low VOCs because there is no need to volatilize the solvent during coating film formation. Furthermore, because they do not contain volatile solvent components, the applied thickness is almost the same as the thickness after drying, making them suitable for coating applications in areas where a large coating thickness is desired.

[0092] In general, as mentioned above, "solvent-free paint" refers to paint that does not contain volatile solvents in the paint, but it may contain liquid components (components that remain in the paint film) such as reactive organic media such as reactive diluents, non-reactive organic media such as non-reactive diluents, and silane coupling agents, as necessary. Therefore, in the present invention, "solvent-free paint" includes not only completely solvent-free paints that are completely free of liquid components that can function as solvents, but also paints that contain the above-mentioned components that remain in the paint film and do not contain volatile solvents.

[0093] (Solvent) The solvent in the present invention, that is, the volatile solvent for dissolving the resin in the coating material, may be, for example, an organic solvent, and is not particularly limited as long as it is used in the coating material field. 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); acetonitrile, propionitrile, and the like. The above-mentioned solvents may be used alone or in combination of two or more kinds.

[0094] (Organic Medium) In the non-aqueous coating composition containing the solvent of the present invention (solvent-containing coating), an organic medium containing a reactive functional group or a non-reactive organic medium may be used in combination with the above-mentioned solvent.

[0095] 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 acrylate toluene diisocyanate urethane prepolymer; n-butyl glycidyl ether, 2-ethylhexyl Examples of suitable alkyl (C8-C18) glycidyl ethers include glycidyl ethers such as glycidyl ether, alkyl (C8-C18) glycidyl ether (an alkyl glycidyl ether having an alkyl chain length of C8-C18, i.e., an alkyl glycidyl ether having 8 to 18 carbon atoms in the alkyl group), glycidyl ether of stearic acid, 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; chlorostyrene, methoxystyrene, butoxystyrene, and vinyl benzoic acid. Of the alkyl (C8-C18) glycidyl ethers listed above, commonly used are C12-C14 mixed alkyl glycidyl ethers (a mixture of alkyl glycidyl ethers having alkyl chain lengths of C12, C13, and C14, also known as "aliphatic glycidyl ether (C12-14)") and lauryl glycidyl ether.

[0096] Suitable examples of non-reactive organic media include petroleum resin-based organic media having 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 oils, phenol-modified aliphatic or aromatic polymers, xylene resins, and toluene resins.

[0097] (Resin Component) The resin component of the non-aqueous coating composition of the present invention is not particularly limited as long as it is a resin conventionally used as a base resin for non-aqueous coatings, and various resins can be incorporated into the non-aqueous coating composition. Examples of base resins for non-aqueous coatings that can be used with the non-aqueous coating 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 oil, boiled oil, acetyl cellulose, nitrocellulose, etc. These resins may be cured with a chemical reaction in the presence or absence of a catalyst, such as heat-curable, ultraviolet-curable, electron beam-curable, oxidation-curable, photocation-curable, peroxide-curable, and acid / epoxy-curable resins, or may be resins with a high glass transition point that form a coating simply by volatilizing the diluting solvent without a chemical reaction. Examples of the curing agent include amino resins, melamine resins, isocyanate compounds, blocked isocyanate compounds, and epoxy compounds. Only one type of base resin may be used, or two or more types may be used in combination.

[0098] From the viewpoint of film-forming properties, the content of the resin in the non-aqueous coating composition is preferably 20 to 99.5% by mass.

[0099] (Filler) The non-aqueous coating composition of the present invention may further contain fillers such as extender pigments, color pigments, metallic pigments, etc., from the viewpoint of improving the appearance and properties of the coating film. Examples of fillers 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; color pigments such as titanium dioxide, carbon black, yellow lead, cadmium yellow, ochre, titanium yellow, zinc chromate, red iron oxide, aluminosilicate, quinacridone, phthalocyanine, anthroquinone, diketopyrrolopyrrole, benzimidazolone, and isoindolinone; and metallic pigments such as aluminum flakes, copper flakes, micaceous iron oxide, mica, and scaly powder of mica coated with a metal oxide.

[0100] The non-aqueous coating composition of the present invention does not necessarily need to contain a filler, but from the viewpoint of achieving the purpose of adding the filler, the content of the filler in the non-aqueous coating composition is preferably 0.001 to 80 mass %.

[0101] (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 improvers, surfactants, curing catalysts, plasticizers, film-forming aids, driers, antifouling agents, sensitizers, antioxidants, light stabilizers, ultraviolet absorbers, water-resistant agents, antiseptic and antifungal agents, antifoaming agents, leveling agents, dispersants, flame retardants, antistatic agents, release agents, deodorizers, fragrances, and the like, to the extent that the properties of the non-aqueous coating composition of the present invention and the objects of the present invention are not impaired.

[0102] (Method for producing non-aqueous coating composition) The method for producing the non-aqueous coating composition of the present invention is not particularly limited, but the viscosity modifier may be added to the resin in advance, and the resulting homogeneous dispersion may be blended with the remaining raw materials, or may be added and mixed together with various additives, solvents, and resins when preparing the non-aqueous coating composition. If the viscosity modifier is not sufficiently dispersed in the non-aqueous coating composition, the effects of the present invention may not be fully exhibited.

[0103] (Method of using non-aqueous coating composition) The non-aqueous coating composition of the present invention can be used in the form of a dispersion, or it can be used as a dried powdery non-aqueous coating composition after removing liquid components such as the solvent from the dispersion by drying treatment or the like.

[0104] 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 coating methods, such as roller coating, brush coating, air spraying, airless spraying, electrostatic coating, etc. Furthermore, by curing the non-aqueous coating composition applied to the surface of a substrate, a coated article having a coating film consisting of a cured product of the non-aqueous coating composition can be obtained.

[0105] Examples of the substrate include metal materials such as iron, aluminum, brass, copper, stainless steel, tinplate, zinc-plated steel, zinc alloys (Zn—Al, Zn—Ni, Zn—Fe, etc.), and plated steel; plastic materials such as resins such as polyethylene resin, polypropylene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, and epoxy resin, and various FRPs; and inorganic materials such as glass, cement, and concrete, which may be surface-treated or the like.

[0106] (Uses of non-aqueous coating composition) The non-aqueous coating composition of the present invention can be used, for example, as a marine paint or a heavy-duty anticorrosion paint, but is not limited to these uses and can be used in various uses to which non-aqueous coatings are generally applicable.

[0107] While the preferred embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments. In other words, it is understood that other embodiments or various modifications that can be conceived by a person skilled in the art within the scope of the invention described in the claims also fall within the technical scope of the present invention.

[0108] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In the examples, "%" and "parts" refer to "% by mass" and "parts by mass" unless otherwise specified.

[0109] [Synthesis of Diamide Compound (A)] The diamine component (A-a) and the monocarboxylic acid component (Ac) shown in Table 1 were reacted under a nitrogen gas flow at 190°C for 6 hours while removing the generated water, to obtain the diamide compounds (A) of Synthesis Examples A1 to A16.

[0110]

[0111] [Synthesis of Diamide Compound (B)] The diamine component (Ba) and the monocarboxylic acid component (Bc) shown in Table 2 were reacted under a nitrogen gas flow at 190°C for 6 hours while removing the generated water, to obtain the diamide compounds (B) of Synthesis Examples B1 to B12.

[0112]

[0113] [Synthesis of Diamide Compound (C)] The diamine component (Ca) and the monocarboxylic acid component (Cc) shown in Table 3 were reacted under a nitrogen gas flow at 190°C for 6 hours while removing the generated water, to obtain the diamide compound (C) of Synthesis Example C1.

[0114]

[0115] [Preparation of Other Component (D)] As shown in Table 4, in addition to the diamide compounds (A), (B), and (C), the components (D) of Synthesis Example D1 and Component Examples D2 and D3 were prepared as other components (D).

[0116]

[0117] (Synthesis Example D1: Polyamide 1) Into a four-neck flask, as raw materials, 55.6g of ethylenediamine as an amine component, 472.2g of polymerized fatty acid A (see Table 5) as a carboxylic acid component, and 472.2g of polymerized fatty acid B (see Table 5) were added, and the mixture was heated under nitrogen gas flow with stirring, and reacted at 150 ° C for 1 hour. Then, the mixture was further reacted at 175 ° C for 2 hours to obtain polyamide 1 of Synthesis Example D1. The weight average molecular weight of polyamide 1 was 7515, and the acid value was 82.4. The weight average molecular weight of Synthesis Example D1 was calculated from the chromatogram measured by GPC based on the molecular weight of standard polystyrene as the weight average molecular weight. The weight average molecular weight was measured using an "HLC-8320GPC" (trade name, manufactured by Tosoh Corporation) as the GPC measuring instrument and three columns, one "GPCKF-801" and two "GPCKF-802" (both trade names, manufactured by Shodex), under the conditions of a mobile phase of tetrahydrofuran, a measurement temperature of 40°C, a flow rate of 1 cc / min, and a detector of RI. The acid value was measured in accordance with "JIS K 0070-1992 Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products."

[0118]

[0119] (Component Example D2: Ethylene-acrylic acid copolymer) AC (registered trademark) 5120 manufactured by Honeywell was prepared as the ethylene-acrylic acid copolymer of Component Example D2.

[0120] (Component Example D3: Hydrogenated Castor Oil) Hydrogenated Castor Oil "B" Grade (abbreviated as "HCO-B Grade" in Table 4) from Royal Castor Products was prepared as hydrogenated castor oil for Component Example D3.

[0121] (Synthesis of diamide compounds of Comparative Synthesis Examples 1 to 3) Furthermore, as diamide compounds not corresponding to the mixture (M) of the present invention, the diamide compounds of Comparative Synthesis Examples 1 to 3 were synthesized. These diamide compounds were obtained by blending two or more monocarboxylic acid components with different carbon numbers, corresponding to the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) of the present invention, together with a diamine component, and simultaneously condensing them. Specifically, the diamine component and the monocarboxylic acid component shown in Table 6 were reacted in a nitrogen gas stream at 190°C for 6 hours while removing the generated water, to obtain the diamide compounds of Comparative Synthesis Examples 1 to 3.

[0122]

[0123] [Production of Viscosity Adjuster] Next, a method for producing the viscosity adjuster will be described.

[0124] (Production Examples 1 to 32, Comparative Production Examples 1 to 6) The diamide compounds (A) of Synthesis Examples A1 to A16, the diamide compounds (B) of Synthesis Examples B1 to B12, the diamide compound (C) of Synthesis Example C1, and the components (D) of Synthesis Example D1 and Component Examples D2 and D3 obtained as described above were melt-mixed according to the formulations shown in Table 6. These molten mixtures were then taken out as solids, and these solid mixtures were pulverized in a pulverizer to have a median diameter in the range of 1 μm to 10 μm, thereby obtaining the viscosity modifiers of Production Examples 1 to 32 and Comparative Production Examples 5 and 6. The diamide compounds of Comparative Synthesis Examples 1 to 3 obtained as described above were pulverized in a pulverizer to have a median diameter in the range of 1 μm to 10 μm, thereby obtaining the viscosity modifiers of Comparative Production Examples 1, 2, and 3. Furthermore, the diamide compound (A) of Synthesis Example A5 was pulverized in a pulverizer so that the median diameter was in the range of 1 μm to 10 μm, thereby obtaining a viscosity modifier of Comparative Production Example 4.

[0125] The components and blending amounts of the viscosity modifiers of Production Examples 1 to 32 and Comparative Production Examples 1 to 6 obtained as described above are shown in Table 7.

[0126]

[0127] [Evaluation of Viscosity Modifiers] The viscosity modifiers of Production Examples 1 to 32 and Comparative Production Examples 1 to 6 obtained as described above were used to evaluate the performance of the viscosity modifiers as shown in the following Test Examples 1 to 4.

[0128] (Test Example 1 Sealant Formulation 1: Silylated Acrylate-Based Sealant) Curable compositions (silylated acrylate-based sealants) of Examples and Comparative Examples were prepared using the sealant formulations shown in Table 8 as follows, and the viscosity-imparting effect of these curable compositions was evaluated.

[0129] <Preparation of curable composition> As shown in Table 8, 80.0 parts of TA polymer SB802S (manufactured by Kaneka Corporation) as a resin component (sealant base polymer), 80.0 parts of Sanso Cizer DINP (manufactured by New Japan Chemical Co., Ltd.) as a plasticizer, 200.0 parts of Ryton S-4 (heavy calcium carbonate: manufactured by Bihoku Funka Kogyo Co., Ltd.) as a filler, 10.0 parts of KRONOS 2190 (titanium dioxide: manufactured by KRONOS), and 11.2 parts of any of the viscosity modifiers of Production Examples 1 to 27 and Comparative Production Example 1 were pre-dispersed using a three-roll mill, and then kneaded at 120 ° C. under reduced pressure using a planetary mixer. To this mixture, 4.0 parts of Silquest A-171 (manufactured by Momentive Corp.) as a dehydrating agent, 4.0 parts of Silquest A-1122 (manufactured by Momentive Corp.) as an adhesion improver, and 3.0 parts of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.) as a curing catalyst were added, and the mixture was kneaded using a planetary mixer to obtain the curable compositions of Examples 1 to 27 and Comparative Example 1. A blank curable composition containing no viscosity modifier was also prepared. Each curable composition was filled into a sealable container.

[0130]

[0131] <Evaluation Method> The viscosity-imparting effect of the viscosity modifiers added to the curable compositions of Examples 1 to 27 and Comparative Example 1 was evaluated based on three items: viscosity, T.I. value, and viscosity index (thickening). Based on the evaluation criteria shown below, it was determined that the effects of the present invention were not achieved when at least one of the viscosity and viscosity index was rated D. Details of the evaluation method for each item are shown below.

[0132] [Viscosity] A rheometer AR2000 (manufactured by TA Instruments) was used, and the geometry (cone-plate) of the jig was 20 mm in diameter and the angle between the generatrix of the cone and the circular surface was 1°. The shear rate was set to 1.0 s －１ The viscosity η at 25 ° C. １ The viscosity was measured and the viscosity imparting effect was evaluated according to the following criteria: A: Viscosity η １ is 2000 or more B+: Viscosity η １ B: Viscosity η is 1000 or more and less than 2000 １ is 500 or more and less than 1000 C: Viscosity η １ is 100 or more and less than 500 D: Viscosity η １ is less than 100

[0133] [T.I. value] In the same manner as in the viscosity measurement above, the shear rate was increased to 10 s －１ The viscosity η at 25 ° C. １０ From these measurement results, the T.I. value (= η １ / η １０ ) was calculated, and the viscosity-imparting effect was evaluated according to the following criteria: A: T.I. is 8 or more; B: T.I. is 5 or more and less than 8; C: T.I. is 3 or more and less than 5; D: T.I. is less than 3.

[0134] [Viscosity Index (Thickening)] First, for each of the curable compositions of the Examples and Comparative Examples, a reference sample was prepared in which only the diamide compound synthesized using a monocarboxylic acid containing hydrogenated castor oil fatty acid was used as a viscosity modifier among the diamide compounds contained in the mixture (M). (In other words, a sample having the same composition as the curable compositions of the Examples and Comparative Examples, except that only the diamide compound synthesized using a monocarboxylic acid containing hydrogenated castor oil fatty acid was used as a viscosity modifier.) Specifically, the reference sample of the curable composition of Example 27 was a curable composition containing only the diamide compound (C) of Synthesis Example C1 as a viscosity modifier. Furthermore, the reference sample of the curable composition of Comparative Example 1 was a curable composition containing only the diamide compound (A) of Synthesis Example A1 as a viscosity modifier. The reference samples of the curable compositions of the other Examples and Comparative Examples were curable compositions containing only the diamide compound (A) as a viscosity modifier. Next, the shear rate was increased to 1.0 s －１ The viscosity η of each standard sample at 25 ° C. s１ The viscosity η of each standard sample was measured. s１ The viscosity η of each curable composition is calculated based on the measured value of 100. １ The relative value of this was taken as the viscosity index I. That is, the viscosity index I is calculated by the following formula (1), and indicates the thickening effect of the viscosity modifier used in the curable compositions of the Examples and Comparative Examples relative to the viscosity modifier used in the reference sample. When the viscosity index I is 100, the viscosity η of the curable composition is １ means that the viscosity of the curable composition is the same as that of the reference sample (no change). １ / η s１ ) × 100 ... (1)

[0135] The viscosity-imparting effect was evaluated according to the value of the viscosity index I according to the following criteria: A: Viscosity index I is 150 or more; B: Viscosity index I is 120 or more and less than 150; C: Viscosity index I is 100 or more and less than 120; D: Viscosity index I is less than 100

[0136] <Evaluation Results> Table 9 shows the evaluation results as described above, as well as the viscosity modifiers used in each curable composition and their blend ratios.

[0137]

[0138] As shown in Table 9, all of the curable compositions of Examples 1 to 27 exhibited a good viscosity-imparting effect (at least the viscosity and viscosity index were rated C or higher). Furthermore, as can be seen from a comparison of Examples 1 to 12, when the carbon numbers of the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) were 2 to 18, a good viscosity-imparting effect was exhibited; when the carbon number was 14 or less, a better viscosity-imparting effect was exhibited; and when the carbon number was 12 or less, an even better viscosity-imparting effect was exhibited. Furthermore, as shown in Examples 2, 5, 13 to 16, etc., when the difference in the carbon numbers between the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) was at least 8 or less, an excellent viscosity-imparting effect was exhibited. Furthermore, as can be seen from a comparison of Examples 5 and 17 to 20, when the monocarboxylic acid component (A-c) contained hydrogenated castor oil fatty acid, the monocarboxylic acid component (B-c) did not contain hydrogenated castor oil fatty acid, and did not contain diamide compound (C), an excellent viscosity-imparting effect was exhibited when the mixing ratio (A / B) of the diamide compound (A) to the diamide compound (B) was 95 / 5 to 60 / 40. Next, as shown in Examples 25 and 26, even when another component (D) was mixed in addition to the diamide compound (A) and the diamide compound (B), an excellent viscosity-imparting effect was maintained. Furthermore, Example 27, in which neither the monocarboxylic acid component (A-c) nor the monocarboxylic acid component (B-c) contained hydrogenated castor oil fatty acid, but the monocarboxylic acid component (C-c) contained hydrogenated castor oil fatty acid, also exhibited an excellent viscosity-imparting effect.

[0139] On the other hand, Comparative Example 1, in which a diamide compound not corresponding to the mixture (M) of the present invention was used as a viscosity adjuster, had a low viscosity index and did not exhibit the viscosity-imparting effect required in the present invention.

[0140] (Test Example 2 Sealant Formulation 2: Modified Silicone-Based Sealant) The curable compositions (modified silicone-based sealants) of Examples and Blank were prepared using the sealant formulations shown in Table 10 as follows, and the viscosity-imparting effect of these curable compositions was evaluated.

[0141] <Preparation of Curable Composition (Preparation Example 2-1)> As shown in Table 10, 100.0 parts of MS Polymer S303H (manufactured by Kaneka Corporation) was used as the resin component (sealant base polymer), 60.0 parts of Sanso Cizer DINP (manufactured by New Japan Chemical Co., Ltd.) was used as a plasticizer, 200.0 parts of Ryton S-4 (heavy calcium carbonate: manufactured by Bihoku Funka Kogyo Co., Ltd.) and 10.0 parts of KRONOS 2190 (titanium dioxide: manufactured by KRONOS) were used as fillers, and 14.0 parts of the viscosity modifier of any one of Preparation Examples 3, 5, 7, and 28 was used as a viscosity modifier. These were then pre-dispersed using a three-roll mill, and the mixture was kneaded at 55°C under reduced pressure using a planetary mixer. To this mixture, 4.0 parts of Silquest A-171 (manufactured by Momentive Chemicals) as a dehydrating agent, 4.0 parts of Silquest A-1122 (manufactured by Momentive Chemicals) as an adhesion improver, and 3.0 parts of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.) as a curing catalyst were added, and the mixture was kneaded with a planetary mixer to obtain the curable compositions of Examples 28 to 31. A blank curable composition to which no viscosity modifier was added was also prepared. Each curable composition was filled into a sealable container.

[0142] <Preparation of Curable Composition (Preparation Example 2-2)> The curable compositions of Examples 32 to 34 were obtained in the same manner as in Preparation Example 2-1, except that the kneading temperature under reduced pressure was 25°C and the viscosity modifier used was any of the viscosity modifiers of Preparation Examples 1, 3, and 4. The temperature was maintained at 25°C during kneading (if the kneading temperature rose due to heat of dispersion, it was cooled to 25°C). In addition, as in Preparation Example 2-1, a curable composition to which no viscosity modifier was added was also prepared as a blank, and each curable composition was filled into a sealable container.

[0143]

[0144] The viscosity-imparting effect of the viscosity modifiers added to the curable compositions of Examples 28 to 34 was evaluated based on three items: viscosity, TI value, and viscosity index (thickening property). Details of the evaluation methods for each item are shown below.

[0145] [Viscosity] The same method as in Test Example 1 was used to measure viscosity at a shear rate of 1.0 s －１Viscosity η at 25 ° C. １ was used as the measured viscosity, and the viscosity-imparting effect was evaluated according to the following criteria. Here, the viscosity of a curable composition such as a sealant not only varies in its preferred viscosity range depending on its application and desired function, but also in cases where the viscosity range desired by the user differs even for the same application or function. Furthermore, the viscosity of the curable composition differs depending on its formulation and preparation conditions, and therefore the viscosity of the base composition (the viscosity of a blank that does not contain a viscosity modifier) ​​varies. Therefore, there is no particular problem as long as the viscosity evaluation criteria are set based on the base viscosity and the effect of adding a viscosity modifier can be evaluated relatively. Therefore, there is no particular problem even if the evaluation criteria for Test Example 1 and Test Example 2 are different. A: Viscosity η １ is 1000 or more B: Viscosity η １ is 500 or more and less than 1000 C: Viscosity η １ is 100 or more and less than 500 D: Viscosity η １ is less than 100

[0146] [T.I. Value] The T.I. value was calculated in the same manner as in Test Example 1, and the viscosity-imparting effect was evaluated according to the following criteria: A: T.I. is 8 or more; B: T.I. is 5 or more and less than 8; C: T.I. is 3 or more and less than 5; D: T.I. is less than 3.

[0147] [Viscosity Index (Thickening)] The viscosity index I was determined in the same manner as in Test Example 1, and the viscosity-imparting effect was evaluated according to the following criteria: A: Viscosity index I is 150 or more; B: Viscosity index I is 120 or more but less than 150; C: Viscosity index I is 100 or more but less than 120; D: Viscosity index I is less than 100

[0148] <Evaluation Results> The results of the evaluation of the curable composition of Preparation Example 2-1 (kneaded at 55°C) as described above, as well as the viscosity modifiers used in each curable composition and their blend ratios, are shown in Table 11. Furthermore, the results of the evaluation of the curable composition of Preparation Example 2-2 (kneaded at 25°C) as described above, as well as the viscosity modifiers used in each curable composition and their blend ratios are shown in Table 12.

[0149]

[0150]

[0151] As shown in Tables 11 and 12, the curable compositions of Examples 28 to 34 all exhibited a good viscosity-imparting effect (at least the viscosity and viscosity index were rated C or higher). The viscosity modifier of Production Example 28 was an example in which hydrogenated castor oil (Component Example D3) was further mixed in addition to the same diamide compound (A) and diamide compound (B) as in Production Example 5. Example 31, which used the viscosity modifier of Production Example 28, had a viscosity-imparting effect equal to or greater than that of Example 29, which used Production Example 5. Furthermore, the curable compositions of Examples 32 to 34, in which the viscosity modifiers of Production Examples 1, 3, and 4 were kneaded at 25°C, also exhibited an excellent viscosity-imparting effect.

[0152] (Test Example 3 Sealant Formulation 3: Modified Silicone-Based Sealant) The curable compositions (modified silicone-based sealants) of Examples and Blank were prepared using the sealant formulations shown in Table 13 as follows, and the viscosity-imparting effect of these curable compositions was evaluated.

[0153] <Preparation of curable composition> As shown in Table 13, 100.0 parts of MS Polymer S303H (manufactured by Kaneka Corporation) was used as the resin component (sealant base polymer), 60.0 parts of Sanso Cizer DINP (manufactured by New Japan Chemical Co., Ltd.) was used as the plasticizer, 200.0 parts of Ryton S-4 (heavy calcium carbonate: manufactured by Bihoku Funka Kogyo Co., Ltd.), 60.0 parts of Hakuenka CC-R (synthetic calcium carbonate: manufactured by Shiraishi Kogyo Co., Ltd.), 10.0 parts of KRONOS 2190 (titanium dioxide: manufactured by KRONOS) were used as the filler, and 14.0 parts of the viscosity modifier of any of Production Examples 3, 4, 6, 8, 29 to 32 and Comparative Production Examples 5 and 6 were pre-dispersed using a three-roll mill, and then kneaded under reduced pressure at 25 ° C. using a planetary mixer. During kneading, the temperature was maintained at 25°C (if the kneading temperature rose due to heat of dispersion, it was cooled to 25°C). To this mixture, 4.0 parts of Silquest A-171 (manufactured by Momentive) as a dehydrating agent, 4.0 parts of Silquest A-1122 (manufactured by Momentive) as an adhesion improver, and 3.0 parts of Neostan U-220H (manufactured by Nitto Kasei Co., Ltd.) as a curing catalyst were added, and the mixture was kneaded using a planetary mixer to obtain curable compositions of Examples 35 to 42 and Comparative Examples 2 and 3. A blank curable composition containing no viscosity modifier was also prepared. Each curable composition was filled into a sealable container.

[0154]

[0155] The viscosity-imparting effect of the viscosity modifiers added to the curable compositions of Examples 35 to 42 and Comparative Examples 2 and 3 was evaluated based on three items: viscosity, TI value, and viscosity index (thickening property). Details of the evaluation methods for each item are shown below.

[0156] [Viscosity] The same method as in Test Example 1 was used to measure viscosity at a shear rate of 1.0 s －１ The viscosity η at 25 ° C. １was used as the measured viscosity, and the viscosity-imparting effect was evaluated according to the following criteria. As described above, the viscosity of the curable composition varies depending on the formulation and preparation conditions of the base composition, so there is no particular problem if the viscosity evaluation criteria are set based on the base viscosity, allowing the effect of adding a viscosity modifier to be evaluated relatively. Therefore, there is no particular problem even if the evaluation criteria for Test Example 1 and Test Example 2 are different from those for Test Example 3. A: Viscosity η １ is 2000 or more B: Viscosity η １ is 1000 or more and less than 2000 C: Viscosity η １ D: Viscosity η is 500 or more and less than 1000 １ is less than 500

[0157] [T.I. Value] The T.I. value was calculated in the same manner as in Test Example 1, and the viscosity-imparting effect was evaluated according to the following criteria: A: T.I. is 8 or more; B: T.I. is 5 or more and less than 8; C: T.I. is 3 or more and less than 5; D: T.I. is less than 3.

[0158] [Viscosity Index (Thickening)] The viscosity index I was determined in the same manner as in Test Example 1, and the viscosity-imparting effect was evaluated according to the following criteria: A: Viscosity index I is 150 or more; B: Viscosity index I is 120 or more but less than 150; C: Viscosity index I is 100 or more but less than 120; D: Viscosity index I is less than 100

[0159] <Evaluation Results> Table 14 shows the evaluation results as described above, as well as the viscosity modifiers used in each curable composition and their blend ratios.

[0160]

[0161] As shown in Table 14, the curable compositions of Examples 35 to 42 all exhibited a good viscosity-imparting effect (viscosity, T.I. value, and viscosity index were rated B or higher). Thus, depending on the formulation of the curable composition and the composition of the viscosity modifier, it is possible to activate the fatty acid diamide even at room temperature of 25°C, thereby achieving excellent thickening properties. On the other hand, the curable compositions of Comparative Examples 2 and 3 all exhibited poor viscosity-imparting effects (at least one of viscosity, T.I. value, and viscosity index was rated D).

[0162] (Test Example 4 Non-aqueous paint formulation: ultra-high solids epoxy paint) Non-aqueous paint compositions (ultra-high solids epoxy paints) of Examples and Comparative Examples were prepared using the non-aqueous paint formulations shown in Table 15 as follows, and these non-aqueous paint compositions were evaluated for their viscosity-imparting effect and their effect of improving overcoatability inhibition.

[0163] <Preparation of Non-Aqueous Coating Composition (Preparation Example 4-1)> As shown in Table 15, 39.1 parts of jER (registered trademark) 806 (an epoxy resin manufactured by Mitsubishi Chemical Corporation) was used as the resin, and LS-632 (a reactive diluent manufactured by Hubei Greenhome Materials) was used. A mixture of 11.3 parts of a bifunctional reactive diluent manufactured by JNC Technology Co., Ltd., 2.3 parts of Sila-Ace (registered trademark) S510 (a silane coupling agent manufactured by JNC Corporation), 2.0 parts of dimethyl carbonate as an organic solvent, 8.8 parts of Talc No. 1 (a body pigment manufactured by Takehara Chemical Industry Co., Ltd.), 15.0 parts of PG-K10 (a body pigment manufactured by Sibelco Japan), 22.1 parts of barium sulfate BA (a body pigment manufactured by Sakai Chemical Industry Co., Ltd.), and 1.3 parts of Typeque (registered trademark) R-820 (a rutile-type titanium oxide manufactured by Ishihara Sangyo Kaisha, Ltd.), and 1.0 part of the viscosity modifier of any of Production Examples 6, 22, and Comparative Production Examples 2 to 4 was charged, and the mixture was dispersed using a dissolver (blade diameter 5 cm) until the temperature of the paint reached 60 ° C. to obtain an epoxy base resin (Part A). To this base resin, 21.5 parts of Ancamine 2644 (an amine-based curing agent manufactured by Evonik Japan Co., Ltd.) was added as PART B, and the mixture was mixed to obtain the non-aqueous coating compositions of Examples 43 and 44 and Comparative Examples 4 to 6. A non-aqueous coating composition to which no viscosity modifier was added was also prepared as a blank.

[0164] <Preparation of Non-Aqueous Coating Composition (Preparation Example 4-2)> The non-aqueous coating compositions of Example 45 and Comparative Example 7 were obtained in the same manner as in Preparation Example 4-1, except that the temperature during dispersion of the coating was 25°C and the viscosity modifier used was either the viscosity modifier of Preparation Example 29 or Comparative Preparation Example 2. The temperature was maintained at 25°C during dispersion (if the dispersion temperature rose due to the heat of dispersion, it was cooled to 25°C). In addition, as in Preparation Example 4-1, a non-aqueous coating composition to which no viscosity modifier was added was also prepared as a blank.

[0165]

[0166] The viscosity modifiers added to the nonaqueous coating compositions of Examples 43 to 45 and Comparative Examples 4 to 7 were evaluated for their viscosity-imparting effect and their effect of improving overcoatability. The viscosity-imparting effect was evaluated based on viscosity, and the effect of improving overcoatability was evaluated based on two items: anti-sagging property and coating contact angle. Details of the evaluation methods for each item are shown below.

[0167] [Viscosity] The day after the non-aqueous coating composition was prepared as described above, the viscosity (P) was measured at 25°C and 60 rpm using a Brookfield viscometer. The higher the viscosity of the non-aqueous coating composition, the greater the viscosity-imparting effect of the viscosity modifier. In this example, a viscosity of 25 P or more as evaluated by the above method was determined to be sufficient to provide the viscosity-imparting effect required in the present invention (acceptable criterion).

[0168] [Sagging Resistance] As an index of sagging resistance, the sagging limit film thickness (μm) of the non-aqueous coating composition prepared as described above was measured. Specifically, using a sag tester (trade name "Sag Tester BOX 100-500, 500-700, 600-1000" manufactured by Taiyu Kizai Co., Ltd.), the non-aqueous coating composition of any of Examples 32, 33 and Comparative Examples 2 to 4 was applied to a sagging test paper (trade name "All Black Measurement Paper" manufactured by Taiyu Kizai Co., Ltd.) at five different film thicknesses (100 μm to 500 μm, 500 μm to 700 μm, 600 μm to 1000 μm) with thicknesses differing by 100 μm. As a result, coating film strips having five different film thicknesses were arranged at predetermined intervals on the sagging test paper. Next, this test paper was stood upright with the thinner coating film band at the top, and air-dried at room temperature, after which the coating film first began to drip over the gap between the coating film bands, and the thickness of the coating film band with a thickness one step thinner than the coating film band where a portion of the coating film that had come into contact with the lower coating film band was observed was taken as the sagging limit thickness (μm). In this example, when the sagging limit thickness evaluated by the above method was 600 μm or more, it was judged that the coating film had sufficient sagging prevention properties (pass criterion) to achieve the effect of improving the overcoatability inhibition required in the present invention.

[0169] [Coating Contact Angle] The non-aqueous coating composition prepared as described above was applied to the surface of a tinplate substrate using a film applicator with a groove depth of 500 μm, and the non-aqueous coating composition was dried and cured at 25°C to obtain a coating film formed on the surface of the tinplate substrate. Next, at 25°C, a 2 μL droplet of n-hexadecane was dropped onto the cured coating film, and the degree of spreading of the droplet (coating contact angle) was evaluated. The coating contact angle (°) was measured using a DM-501 (Kyowa Interface Science Co., Ltd.) and the static contact angle was measured according to the θ / 2 method of the sessile drop method. In this example, when the coating contact angle evaluated by the above method was 15° or less, it was determined that the coating contact angle was sufficiently small to exhibit the effect of improving overcoatability inhibition required in the present invention (acceptance criterion).

[0170] <Evaluation Results> The results of the evaluation of the non-aqueous coating composition of Preparation Example 4-1 (dispersed at 60°C) as described above, as well as the viscosity modifiers used in each non-aqueous coating composition and their blend ratios, are shown in Table 16. Furthermore, the results of the evaluation of the non-aqueous coating composition of Preparation Example 4-2 (dispersed at 25°C) as described above, as well as the viscosity modifiers used in each non-aqueous coating composition and their blend ratios are shown in Table 17.

[0171]

[0172]

[0173] As shown in Tables 16 and 17, the non-aqueous coating compositions of Examples 43 to 45 all exhibited good viscosity-imparting effects and improved recoatability (the evaluations of viscosity, sagging limit film thickness, and coating contact angle all showed values ​​within the pass criteria). On the other hand, Comparative Examples 4 and 5, which used a diamide compound not corresponding to the mixture (M) of the present invention as a viscosity modifier, and Comparative Example 6, which used only diamide compound (A) as a viscosity modifier without diamide compound (B), all exhibited poor evaluations of viscosity, sagging limit film thickness, and coating contact angle, failing to achieve the effects of the present invention. Furthermore, Comparative Example 7, which used a viscosity modifier that did not contain diamide compound (B) and was dispersed at 25°C, exhibited low viscosity and sagging resistance, failing to meet the pass criteria. No increase in coating contact angle was observed in Comparative Example 7. This is presumably because the viscosity value was also low, and the viscosity modifier was not activated at the low dispersion temperature of 25°C, resulting in little viscosity-imparting effect.

Claims

1. A viscosity modifier comprising a mixture (M) obtained by melt-mixing two or more compounds including a diamide compound (A), a diamide compound (B), and an optional diamide compound (C), wherein the diamide compound (A) is a diamide obtained by condensing a diamine component (A-a) with a monocarboxylic acid component (A-c), the diamide compound (B) is a diamide obtained by condensing a diamine component (B-a) with a monocarboxylic acid component (B-c), the diamide compound (C) is a diamide obtained by condensing a diamine component (C-a) with a monocarboxylic acid component (C-c), the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) are monocarboxylic acids having different numbers of carbon atoms, and at least one of the monocarboxylic acid component (A-c), the monocarboxylic acid component (B-c), and the monocarboxylic acid component (C-c) contains a hydrogenated castor oil fatty acid.

2. The viscosity modifier according to claim 1, wherein the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) are both monocarboxylic acids having 2 to 18 carbon atoms.

3. The viscosity modifier according to claim 1, wherein the difference in carbon number between the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) is 16 or less.

4. The viscosity modifier according to claim 1, characterized in that the monocarboxylic acid component (Ac) contains at least a linear saturated fatty acid (a), and the monocarboxylic acid component (Bc) contains at least a linear saturated fatty acid (b).

5. The viscosity modifier according to claim 1, wherein the monocarboxylic acid component (A-c) contains hydrogenated castor oil fatty acid, the monocarboxylic acid component (B-c) does not contain hydrogenated castor oil fatty acid, and the diamide compound (C) does not contain the diamide compound (A), and the mixing ratio (A / B) of the diamide compound (A) to the diamide compound (B) is 95 / 5 to 55 / 45.

6. The viscosity modifier according to claim 1, wherein the diamine component (Aa) and the diamine component (Ba) are the same type of diamine.

7. A method for producing a viscosity modifier, comprising: a mixing step of melt-mixing two or more compounds including a diamide compound (A), a diamide compound (B), and an optional diamide compound (C); and a micronization step of micronizing the mixture (M) obtained in the mixing step to obtain a viscosity modifier, wherein the diamide compound (A) is a diamide obtained by condensing a diamine component (A-a) with a monocarboxylic acid component (A-c), the diamide compound (B) is a diamide obtained by condensing a diamine component (B-a) with a monocarboxylic acid component (B-c), the diamide compound (C) is a diamide obtained by condensing a diamine component (C-a) with a monocarboxylic acid component (C-c), and the monocarboxylic acid component (A-c) and the monocarboxylic acid component (B-c) are monocarboxylic acids having different numbers of carbon atoms, At least one of the monocarboxylic acid component (Ac), the monocarboxylic acid component (Bc), and the monocarboxylic acid component (Cc) contains a hydrogenated castor oil fatty acid.

8. The method for producing a viscosity modifier according to claim 7, wherein the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) are both monocarboxylic acids having 2 to 18 carbon atoms.

9. The method for producing a viscosity modifier according to claim 7, wherein the difference in carbon number between the monocarboxylic acid component (Ac) and the monocarboxylic acid component (Bc) is 16 or less.

10. A method for producing a viscosity modifier according to claim 7, characterized in that the monocarboxylic acid component (A-c) contains at least a linear saturated fatty acid (a), and the monocarboxylic acid component (B-c) contains at least a linear saturated fatty acid (b).

11. The method for producing a viscosity modifier according to claim 7, wherein the monocarboxylic acid component (A-c) contains hydrogenated castor oil fatty acid, the monocarboxylic acid component (B-c) does not contain hydrogenated castor oil fatty acid, and does not contain the diamide compound (C), and the mixing ratio (A / B) of the diamide compound (A) to the diamide compound (B) is 95 / 5 to 55 / 45.

12. The method for producing a viscosity modifier according to claim 7, wherein the diamine component (Aa) and the diamine component (Ba) are the same type of diamine.

13. A curable composition comprising the viscosity modifier according to any one of claims 1 to 6 and a resin component.

14. A non-aqueous coating composition containing the viscosity modifier according to any one of claims 1 to 6, a resin component, and an optional volatile solvent, wherein the content of the volatile solvent is 15 mass% or less based on the total amount of the non-aqueous coating composition.

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