JP2008115199A - Thixotropy-imparting agent, skin roughening-preventing type thixotropy-imparting agent, and methods for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thixotropy-imparting agent reducing drooping down of a coated film, and simultaneously reducing the roughening of the coated film when the drooping down has occurred, to provide a skin roughening-preventing type thixotropy-imparting agent, and to provide methods for producing them. <P>SOLUTION: The thixotropy-imparting agent is obtained by reacting a reaction product of 12-hydroxystearic acid and a castor oil fatty acid with polyamines (ethylenediamine or the like), with polyisocyanates (tolylenediisocyanate or the like). Preferably, when the total proportion of the 12-hydroxystearic acid and the castor oil fatty acid is 100 mass%, the proportion of the caster oil fatty acid is 5-95 mass%. In another embodiment, the thixotropy-imparting agent is obtained by reacting the reaction product of the castor oil fatty acid with the polyamines, with the polyisocyanates. The skin roughening-preventing type thixotropy-imparting agent is obtained by reacting the reaction product of the 12-hydroxystearic acid with the polyamines, with the polyisocyanates. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to thixotropic agents, rough skin-suppressing thixotropic agents, and methods for producing them. More specifically, a thixotropic agent and a rough skin-suppressing thixotropic agent that suppresses dripping of the coating film of the solvent-based paint and suppresses roughening of the surface of the coating film (roughness of the skin) when dripping, and their roughening imparting agent. It relates to a manufacturing method.

  When a paint or the like is applied to a material to be coated, the coating film may flow and droop before drying. In order to suppress the sagging of the coating film, a thixotropic agent is often added to the paint, and conventionally, a thixotropic agent such as a polyamide type is used (for example, see Patent Document 1). In addition, thixotropic agents such as polyethylene oxide that are often used as pigment anti-settling agents are also used (for example, see Patent Document 2). Furthermore, a thixotropic agent obtained by reacting an amide derivative with a polyisocyanate is also known (for example, see Patent Document 3).

Japanese Patent Laid-Open No. 60-223876 U.S. Pat. No. 3,212,488 Japanese Patent Laid-Open No. 48-8398

  However, for example, with a polyamide thixotropic agent, the sagging of the coating film can be suppressed, but once sagging has occurred, there is a problem that the surface of the fluidized coating film becomes rough and the appearance deteriorates. In addition, with polyethylene oxide-based thixotropic agents, the appearance of the coating when sagging occurs is better than when polyamide-based thixotropic agents are used, but the ability to suppress sagging is polyamide-based thixotropic. It is inferior to the imparting agent.

Furthermore, the thixotropic agent obtained by reacting a polyisocyanate with an amide derivative described in Patent Document 3 is easy to volatilize xylene or the like as a solvent for a coating material in a total amount or in a large mass ratio, and has a dissolving power. Since a strong solvent was used, the surface roughness of the coating was not a problem. However, in recent years, use of xylene or the like as a solvent in solvent-based paints is avoided as much as possible due to adverse effects on human bodies and environmental pollution. Therefore, there is a tendency that a solvent containing no xylene or a low content is used, but when using such a solvent, a thixotropic agent obtained by reacting an amide derivative with a polyisocyanate is used. It was unclear whether surface roughness of the coating film occurred.
In this way, even when a solvent that does not contain xylene or the like or has a low content is used, dripping of the coating film is suppressed, and the surface roughness of the coating film when dripping occurs is sufficient. There are no thixotropic agents that can be suppressed, and further improvements to the thixotropic agents are needed.

  The present invention has been made in view of the above-described conventional situation, and in particular, a thixotropic agent that suppresses dripping of a coating film of a solvent-based paint and suppresses roughening of the coating film surface when dripping. It is another object of the present invention to provide a rough skin-suppressing thixotropic agent and a method for producing the same.

The present invention is as follows.
1. A thixotropic agent characterized by reacting a reaction product of 2-hydroxystearic acid and castor oil fatty acid with a polyamine and a polyisocyanate.
2. When the total of the 12-hydroxystearic acid and the castor oil fatty acid is 100% by mass, the castor oil fatty acid is 5 to 95% by mass. The thixotropic agent described in 1.
3. 2. The castor oil fatty acid is 25 to 75% by mass. The thixotropic agent described in 1.
4). A thixotropic agent characterized by reacting a reaction product of castor oil fatty acid and polyamines with polyisocyanates.
5. Above 1. To 4. It is a manufacturing method of the thixotropic imparting agent of any one of these, Comprising: The said polyisocyanate is added to the said reaction product in the temperature range of 105-135 degreeC, and it is 95-125 degreeC after that. And the manufacturing method of the thixotropic agent characterized by including the process made to react in the temperature range 5-20 degreeC lower than the temperature of the said addition.
6). 4. The reaction time is 2 to 4 hours. A method for producing a thixotropic agent according to claim 1.
7. A rough skin-suppressing thixotropic agent characterized by reacting a reaction product of 12-hydroxystearic acid and polyamines with polyisocyanates.
8). 6. The above-mentioned 7. used for a solvent-type paint having a toluene and / or xylene content of 10% by mass or less when the total amount of the solvent is 100% by mass. The rough skin-suppressing thixotropic agent described in 1.
9. The solvent is a mixed solvent containing an aromatic solvent having 9 or more carbon atoms and an aliphatic solvent as another solvent excluding the toluene and / or the xylene, and the boiling point of the mixed solvent is 140 ° C. The above 8. The rough skin-suppressing thixotropic agent described in 1.
10. Above 7. To 9. It is a manufacturing method of the rough skin suppression type thixotropy imparting agent of any one of these, Comprising: The said polyisocyanate is added to the said reaction product in the temperature range of 105-135 degreeC, Then, 95-125 A method for producing a rough skin-suppressing thixotropic agent, characterized by comprising a step of reacting in a temperature range of 5 ° C to 20 ° C lower than the temperature of the addition.
11. 10. The reaction is performed for 20 minutes to 4 hours. A method for producing a rough skin-suppressing thixotropic agent as described in 1. above.

According to the thixotropic agent of the present invention using 12-hydroxystearic acid and castor oil fatty acid in combination as the fatty acid, dripping of the coating film of the solvent-based paint is sufficiently suppressed (anti-dripping property) and dripping. Roughness of the coating film surface at the time is also suppressed (skin roughness suppression property), and a coating film having an excellent appearance can be formed.
In addition, when the total of 12-hydroxystearic acid and castor oil fatty acid is 100% by mass, when castor oil fatty acid is 5 to 95% by mass, it is more excellent in both sagging prevention property and skin roughness inhibiting property, Furthermore, a thixotropic agent capable of forming a film having an excellent appearance can be obtained.
Furthermore, when castor oil fatty acid is 25-75 mass%, it can be set as the thixotropy imparting agent which has the especially favorable anti-sagging property, and the outstanding skin roughness suppression property.
According to the other thixotropic agent of the present invention using castor oil fatty acid as the fatty acid, dripping of the coating film of the solvent-type paint is sufficiently suppressed, and the roughness of the coating film surface when dripping is also suppressed, A film having an excellent appearance can be formed.
According to the method for producing the thixotropic agent of the present invention, the thixotropic agent of the present invention and the other thixotropic agent of the present invention are obtained by adding and reacting polyisocyanates in a specific temperature range. It can be manufactured easily.
Moreover, when the reaction time is 2 to 4 hours, a thixotropic agent having better performance can be produced.
According to the rough skin-suppressing thixotropic agent of the present invention, it is possible to sufficiently suppress the roughening of the coating film particularly when the solvent-based coating film drips, and to form a coating film having an excellent appearance.
In addition, when the total amount of the solvent is 100% by mass, the content of toluene and / or xylene is used in a solvent-type paint whose content is 10% by mass or less, and the solvent is other than toluene and / or xylene. When the solvent is a mixed solvent containing an aromatic solvent having 9 or more carbon atoms and an aliphatic solvent, and the boiling point of the mixed solvent is 140 ° C. or higher, it is less likely to evaporate than toluene and xylene. In addition, although the solvent is weak and the solvent tends to cause rough skin, the rough skin can be sufficiently suppressed.
According to the method for producing a rough skin-suppressing thixotropic agent of the present invention, by adding and reacting polyisocyanates in a specific temperature range, the rough skin-suppressing thixotropic agent of the present invention is easily produced. can do.
Moreover, when the reaction time is 20 minutes to 4 hours, a rough skin-suppressing thixotropic agent having better performance can be produced.

The present invention will be described in detail below.
[1] Thixotropic agent and skin roughness-suppressing type thixotropic agent The thixotropic agent of the present invention reacts a reaction product of 12-hydroxystearic acid and castor oil fatty acid with polyamines, and a polyisocyanate. Let me.
Another thixotropic agent of the present invention is obtained by reacting a reaction product of castor oil fatty acid and polyamines with polyisocyanates.
The rough skin-suppressing thixotropic agent of the present invention is obtained by reacting a reaction product of 12-hydroxystearic acid and polyamines with polyisocyanates.

  The “12-hydroxystearic acid” is a saturated fatty acid having 18 carbon atoms in which one hydroxyl group is bonded to the carbon atom at the 12-position, and 12-hydroxystearic acid generally provided in the present invention is particularly limited. Can be used without any problem. As this 12-hydroxystearic acid, 12-hydroxystearic acid obtained by hydrogenating ricinoleic acid, which is a castor oil fatty acid, is often used. Moreover, an oligomer can also be used as 12-hydroxystearic acid. As this oligomer, a 2-7mer, especially a 3-5mer is preferable, and it can also be set as a multimer.

  The “castor oil fatty acid” is a fatty acid obtained from castor oil, and is usually a mixture of ricinoleic acid and oleic acid. This castor oil fatty acid may be ricinoleic acid alone. Moreover, an oligomer can also be used as a castor oil fatty acid. As this oligomer, a 2-7mer, especially a 3-5mer is preferable, and it can also be set as a multimer.

  The mass ratio of 12-hydroxystearic acid and castor oil fatty acid used in the thixotropic agent of the present invention is not particularly limited, but when the total of 12-hydroxystearic acid and castor oil fatty acid is 100% by mass, castor The oil fatty acid is preferably 5 to 95% by mass, particularly preferably 25 to 75% by mass. 12-hydroxystearic acid is also preferably 5 to 95% by mass, particularly preferably 25 to 75% by mass. If each mass ratio is 5-95 mass%, it can be set as the thixotropic agent which has sufficient dripping prevention property and skin roughness inhibitory property together. Moreover, if the mass ratio of a castor oil fatty acid is 25-75 mass%, it can be set as the thixotropic agent which has the especially outstanding dripping prevention property.

The “polyamines” include at least one of an amino group (—NH ₂ ) and a secondary amine structure [—NHR (where R is a hydrocarbon residue)], an amino group, a secondary amine structure, Polyamines having a total of 2 or more can be used. As the polyamines, polyamines having an amino group are preferable, and polyamines having two or more amino groups are more preferable. Polyamines having an amino group are highly reactive and can efficiently produce a reaction product obtained by reacting polyamines with 12-hydroxystearic acid and / or castor oil fatty acid. As the polyamines, any of aliphatic polyamines, aromatic polyamines and alicyclic polyamines can be used. Of these, aliphatic polyamines are preferred.

  The aliphatic polyamine is not particularly limited, and various aliphatic polyamines can be used. The aliphatic polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, iminobispropylamine, methyliminobispropylamine, bisaminopropyl. Examples include propylene diamine and hydroxyethyl ethylene diamine (aminoethyl ethanol amine).

  Also, the aromatic polyamine is not particularly limited, and various aromatic polyamines can be used. As this aromatic polyamine, phenylenediamine (any of o-form, m-form and p-form), xylylenediamine (any of o-form, m-form and p-form) may be used. Examples include 4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, and the like.

Furthermore, the alicyclic polyamine is not particularly limited, and various alicyclic polyamines can be used. Examples of the alicyclic polyamine include 1,3-bis (aminomethyl) cyclohexane and 4,4′-methylenebis (cyclohexylamine).
These polyamines may be used alone or in combination of two or more. Moreover, when using 2 or more types together, you may use combining 2 or more types among aliphatic polyamines, aromatic polyamines, and alicyclic polyamines.

  As polyamines, polyamines having more amino groups and / or secondary amine structures per molecular weight are preferable. Accordingly, ethylenediamine or the like is preferable as the aliphatic polyamine, and phenylenediamine or the like is preferable as the aromatic polyamine. As the alicyclic polyamine, 1,3-bis (aminomethyl) cyclohexane and the like are preferable.

The “reaction product” is a product obtained by reacting 12-hydroxystearic acid and / or castor oil fatty acid with polyamines. The amount ratio of 12-hydroxystearic acid and / or castor oil fatty acid and polyamines used in the reaction is not particularly limited, but the number of moles of polyamines (M _a ) and 12-hydroxystearic acid and / or castor oil fatty acid. The ratio (M _a / M _h ) to the number of moles (M _h ) is preferably 0.3 to 0.7, particularly 0.4 to 0.6.

The “polyisocyanates” are not particularly limited, and for example, various aliphatic, aromatic and alicyclic polyisocyanates can be used.
Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), crude TDI, 4,4′-diphenylmethane diisocyanate (MDI), crude MDI, hydrogenated MDI, phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and triphenylmethane diisocyanate. Is mentioned. Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate (HDI), crude HDI, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.
These polyisocyanates may be used alone or in combination of two or more. Moreover, when using 2 or more types together, you may use combining 2 or more types among aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

  Polyisocyanates include urethane modified products, dimers, trimers, carbodiimide modified products, allophanate modified products, urea modified products, biuret modified products, blocked products (phenols, oximes) of the above polyisocyanates. , Imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, polyisocyanates blocked with sodium bisulfite, boric acid, etc.), and prepolymers may also be used. it can.

Furthermore, as polyisocyanate, aromatic polyisocyanate is preferable and TDI is more preferable. In addition, TDI includes 2,4-TDI, which is a 2,4-isomer, and 2,6-TDI, which is a 2,6-isomer, and a mixture of these isomers is particularly preferable. . This mixture is preferably a mixture containing 50 to 90% by mass of 2,4-TDI when the total of 2,4-TDI and 2,6-TDI is 100% by mass. %, Particularly a mixture containing 75 to 85% by mass is more preferable. As a mixture of such isomers, commercially available so-called TDI65 (the content of 2,4-TDI is 65% by mass) and TDI80 (containing 80% by mass of 2,4-TDI) are included. TDI80 is more preferable. Moreover, as TDI (TDI80) whose content of 2, 4-TDI is 80 mass%, TDI65 and TDI100 marketed similarly (content of 2,4-TDI is 100 mass%) are used. You may mix and use an appropriate amount.
In particular, when weather resistance is required, non-yellowing polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate can be used.

  As described above in detail, the thixotropic agent according to the present invention, the other thixotropic agent according to the present invention, and the rough surface-suppressing thixotropic agent according to the present invention use ethylenediamine as the polyamine, and polyisocyanates. When a total of 2,4-TDI and 2,6-TDI is 100% by mass, a mixture of TDI containing 70 to 90% by mass, particularly 75 to 85% by mass of 2,4-TDI is used. It is preferable. The thixotropic agent of the present invention using a reaction product of 12-hydroxystearic acid and castor oil fatty acid as a reaction product, and using ethylenediamine as a polyamine and a mixture of the above TDI as a polyisocyanate, In particular, this is preferable because of excellent anti-sagging property. Further, the roughening-suppressing thixotropic agent of the present invention using a reaction product of 12-hydroxystearic acid as a reaction product and using a mixture of the above-mentioned TDI as ethylenediamine and polyisocyanate as polyamines is particularly It is excellent in the rough skin suppression property and is more preferable in this respect.

The thixotropic agent and the rough skin inhibiting thixotropic agent are obtained by reacting a reaction product with polyisocyanates. The amount ratio between the reaction product used for the reaction and the polyisocyanate is not particularly limited, but the ratio (M _r / _m ) of the number of moles of the reaction product (M _r ) and the number of moles of the polyisocyanate (M _i ). M _i ) is preferably 0.9 to 1.2, more preferably 1.0 to 1.1.

  The uses of the thixotropic agent of the present invention, the other thixotropic agent of the present invention, and the rough skin-suppressing thixotropic agent of the present invention are not particularly limited, and include solvent-type paints, sealing materials, waterproofing materials and adhesives. It can be used, the dripping of these coating films is suppressed, and the roughness of the coating film surface when dripping is suppressed. The solvent used for the solvent-type paint or the like is not particularly limited, and an aliphatic solvent, an aromatic solvent, a mixed solvent of an aliphatic solvent and an aromatic solvent, or the like can be used.

  Examples of the aliphatic solvent include aliphatic hydrocarbons such as heptane and hexane, and kerosene and volatile oil mainly composed of aliphatic hydrocarbons. Examples of the aromatic solvent include aromatic hydrocarbons having 9 or more carbon atoms such as xylene, toluene, and trimethylbenzene, Solvesso 100 (registered trademark, almost all of which is aromatic). . Furthermore, the mixed solvent is a low aromatic content (usually 30% by mass or less) mineral spirit (a product with a low aromatic content (Low Aromatic White Spirit), hereinafter referred to as “LAWS” (registered). It is a trademark.) ], Aromatic content (usually 50% by mass or more) Mineral spirit [High Aromatic White Spirit product. ] Etc. are mentioned. These mixed solvents may further contain an alicyclic solvent. Other solvents include alcohols such as ethyl alcohol and isopropyl alcohol, ethers such as tetrahydrofuran, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, ethyl acetate, isopropyl acetate and butyl acetate. Esters, ketones such as acetone, methyl ethyl ketone, and cyclohexanone can also be used.

  When the main component of the solvent-type paint is a synthetic resin such as unsaturated polyester resin, polyurethane resin, acrylic resin, epoxy resin, alkyd resin, etc., these synthetic resins can be easily dissolved, and the low-viscosity solvent-type paint For example, it is preferable to use a solvent having a strong dissolving power. To that end, it is preferable to use toluene and / or xylene, but these solvents are not preferable from the viewpoints of adverse effects on human bodies and environmental pollution. In this case, you may use an aliphatic solvent and a mixed solvent that have a small adverse effect on the human body and environmental pollution, etc., but are less volatile than toluene and / or xylene and weak in dissolving power. Usually, there is a problem that the coating film tends to sag and the surface of the coating film becomes rough when it sags.

  In the thixotropic agent according to the present invention and the other thixotropic agent according to the present invention, a solvent that does not easily volatilize and has a weak dissolving power, such as the above-mentioned aliphatic solvents and mixed solvents, is used. However, it is difficult for the coating film to sag and the roughness of the coating film surface when it sags is also suppressed. Therefore, from the viewpoint of adverse effects on the human body and environmental pollution, the thixotropic agent of the present invention and the other thixotropic agents of the present invention should use a solvent having a low toluene and / or xylene content. Is preferred. As the solvent having a low content of toluene and / or xylene, the above-mentioned various aliphatic solvents and mixed solvents can be used without any particular limitation.

Further, the rough surface-suppressing thixotropic agent of the present invention is also unlikely to cause roughening of the coating film surface when the coating film drips, like the thixotropic agent of the present invention and other thixotropic agents of the present invention. . In particular, when the total amount of the solvent used is 100% by mass, the content of toluene and / or xylene (the total content when both toluene and xylene are contained) is 10% by mass or less, particularly 7% by mass Hereinafter, further 3% by mass or less [may be 0% by mass (less than the measurement limit value). ], It is difficult for the coating film surface to be roughened. Further, the solvent is a mixed solvent containing an aromatic solvent containing an aromatic hydrocarbon having 9 or more carbon atoms such as trimethylbenzene and an aliphatic solvent as another solvent excluding toluene and / or xylene, And even if it is what is called a weak solvent whose boiling point of a mixed solvent is 140 degreeC or more, roughening of the coating-film surface does not arise easily. Further, even a solvent-type paint having the above-described synthetic resin as a main component, the coating film surface is hardly roughened. Therefore, the rough skin-suppressing thixotropic agent of the present invention is a solvent-type paint, containing the above-described various synthetic resins as a main component, and using the specific solvent as described above as a solvent. Even useful enough.
The mass ratio of the aromatic solvent containing an aromatic hydrocarbon having 9 or more carbon atoms and the aliphatic solvent in the mixed solvent is not particularly limited, but when the total of these is 100 mass%, the carbon number is 9 The aromatic solvent containing the aromatic hydrocarbon may be 20 to 80% by mass, preferably 20 to 60% by mass, particularly 20 to 50% by mass, and more preferably 20 to 40% by mass. The upper limit of the carbon number of the aromatic solvent having 9 or more carbon atoms is not particularly limited, but is usually 9 or 10. Further, the mixed solvent may contain an alicyclic solvent.

[2] Manufacturing method of thixotropic agent and rough skin-suppressing thixotropic agent The manufacturing method of the thixotropic agent of the present invention is not particularly limited. For example, the thixotropic agent of the present invention is manufactured. Can do.
Moreover, the manufacturing method of the rough skin suppression type thixotropic agent of this invention is not specifically limited, For example, it can manufacture with the manufacturing method of the rough skin suppression type thixotropic agent of this invention.
That is, a reaction product of 12-hydroxystearic acid and castor oil fatty acid and polyamines, a reaction product of castor oil fatty acid and polyamines, or a reaction product of 12-hydroxystearic acid and polyamines. A polyisocyanate is added in a temperature range of ˜135 ° C., and then manufactured by a production method comprising a step of reacting in a temperature range of 95 to 125 ° C. and 5 to 20 ° C. lower than the temperature of adding the polyisocyanate. be able to.
In these production methods, the description relating to each of the above [1] can be applied as it is to 12-hydroxystearic acid, castor oil fatty acid, polyamines and polyisocyanates. Moreover, the mass ratio in said [1] can be applied as it is also about the mass ratio of 12-hydroxystearic acid and castor oil fatty acid used in manufacture of the thixotropic agent of this invention.

A method for producing each of the above reaction products is not particularly limited. For example, by adding 12-hydroxystearic acid and / or castor oil fatty acid, and polyamines to a reaction vessel equipped with a stirrer, a cooler, etc., stirring while heating, and reacting while removing generated water Can be produced. The reaction atmosphere may be an inert atmosphere or an air atmosphere, but the reaction is preferably performed in an inert atmosphere such as a nitrogen gas atmosphere or an inert gas atmosphere such as an argon gas atmosphere. The reaction temperature and reaction time are not particularly limited, and the reaction temperature is preferably 150 to 250 ° C., particularly 170 to 230 ° C., and the reaction time is preferably 2 to 6 hours, particularly 3 to 5 hours.
Regarding the quantitative ratio (molar ratio) between 12-hydroxystearic acid and / or castor oil fatty acid and polyamines in the method for producing the reaction product, the description in [1] can be applied as it is.

  A reaction product is prepared as described above, and then a solvent is added to the reaction product to dissolve it, and then the solution in which the reaction product is dissolved is heated to gradually raise the temperature, and then polyisocyanate A thixotropy imparting agent or a rough skin-suppressing thixotropic agent can be produced by gradually adding and reacting. The reaction atmosphere may be an inert atmosphere or an air atmosphere, but the reaction is preferably performed in an inert atmosphere such as a nitrogen gas atmosphere or an inert gas atmosphere such as an argon gas atmosphere. That is, it is preferable to continuously produce a thixotropic agent or a rough skin-suppressing thixotropic agent while maintaining the inert atmosphere in the production of the reaction product.

The temperature at which the polyisocyanates are gradually added is 105 to 135 ° C, preferably 110 to 130 ° C. Moreover, the reaction temperature of a reaction product and polyisocyanate is 95-125 degreeC, and it is preferable to set it as 100-115 degreeC. Furthermore, the reaction time is not particularly limited, and in the case of a thixotropic agent, it is preferably 2 to 4 hours, particularly 2.2 to 3.8 hours. In the case of a rough skin suppressing thixotropic agent, it is preferably 20 minutes to 4 hours, particularly 1 to 4 hours. This reaction time may be 20 to 30 minutes, but if it is 1 hour or longer, it can be more stably a rough skin-suppressing thixotropic agent having a predetermined performance. Furthermore, the reaction temperature between the reaction product and the polyisocyanate is preferably 5 to 20 ° C., particularly 7 to 15 ° C. lower than the temperature at which the polyisocyanate is added.
Regarding the quantitative ratio (molar ratio) between the reaction product and the polyisocyanate in the method for producing the thixotropic agent and the rough skin suppressing thixotropic agent, the description in [1] can be applied as it is.

  Each of the methods for producing the thixotropic agent of the present invention, the other thixotropic agent of the present invention, and the rough skin-suppressing thixotropic agent of the present invention includes various steps in addition to the above steps. You may prepare. Further, the thixotropic agent or the rough skin-suppressing type thixotropic agent produced by the respective production methods can be used as it is by mixing it with a solvent-type paint or the like, and is adjusted to an appropriate concentration by adding a solvent. It can also be used as a thixotropic agent or a rough skin suppressing thixotropic agent. For example, it can also be used as a solution containing a nonvolatile content of about 10 to 30% by mass. The solvent used for the concentration adjustment is not particularly limited. For example, alcohols such as benzyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and n-butyl acetate Esters such as propylene glycol monomethyl ether acetate, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, and mixed solvents such as the above-mentioned “LAWS” can be used.

Hereinafter, the present invention will be described specifically by way of examples.
[1] Preparation of rough skin-suppressing thixotropic agent and thixotropic agent Example 1
A reactor equipped with a stirrer, a thermometer, a water-cooled condenser, a dropping funnel and a nitrogen gas inlet was charged with 217 g (0.70 mol) of 12-hydroxystearic acid and 21 g (0.35 mol) of ethylenediamine. Thereafter, the mixture was heated to gradually raise the temperature, and reacted at 200 ° C. for 4 hours while distilling off the water produced by the reaction to produce a reaction product. Next, 560 g of mineral spirit was added to dissolve the reaction product, and tolylene diisocyanate (an isomer mixture containing 80% by mass of the 2,4-isomer was used) in a solution adjusted to 120 ° C. 55 g (0.325 mol) was added dropwise and then reacted at 110 ° C. for 3 hours to produce a rough skin-suppressing thixotropic agent. Then, benzyl alcohol was added and diluted to adjust the nonvolatile content concentration to 20% by mass.

Example 2
A thixotropic agent was produced in the same manner as in Example 1 except that 108.5 g (0.35 mol) of 12-hydroxystearic acid and 108.5 g (0.35 mol) of castor oil fatty acid were used as fatty acids. In the same manner, benzyl alcohol was added and diluted to adjust the nonvolatile content concentration to 20% by mass.

Example 3
A thixotropic agent was produced in the same manner as in Example 1 except that 217 g (0.70 mol) of castor oil fatty acid was used as the fatty acid. It adjusted to the mass%.
Hereinafter, the rough skin suppression type thixotropic agent of Example 1 and the thixotropic agents of Example 2 and Example 3 are collectively referred to as thixotropic agents.

[2] Performance evaluation (1) Manufacture of test paints Thixotropic properties of thixotropic agents of Examples 1 to 3 and commercially available thixotropic agents (in Tables 1 to 3, evaluation was made based on the sagging limit film thickness). And the coating material for a test for evaluating rough skin suppression property was manufactured as follows.
57 parts by mass of acrylic resin (Dainippon Ink Chemical Co., Ltd., trade name “Acridic A-188”), 17 parts by mass of mineral spirit (Shell Chemicals Japan Co., Ltd., trade name “LAWS”), and white pigment ( 26 parts by mass of Ishihara Sangyo Co., Ltd., trade name “Typaque R-930”) was placed in a batch sand grinder using glass beads having a diameter of 2 mm, and dispersed and mixed. The glass beads were then removed from the mixture to produce a white test paint.

(2) Production of Examples 1 to 3 and Comparative Examples 1 to 4 blended with LAWS products, thixotropic agents, and thixotropic agents of Examples 1 to 3 were added to the test paints produced in (1) above. The commercially available thixotropic agent used in Comparative products 1 to 4 was dispersed and mixed for 15 minutes at a rotational speed of 3000 rpm using a disper so that the thixotropic agent was 0.75 mass% as an active ingredient. It was. That is, in the case of a thixotropic agent having an active ingredient content of 20% by mass, 3.75 parts by mass of the test coating is blended with 3.75 parts by mass of the thixotropic agent and 3.75 parts by mass of LAWS. And mixed. Further, in the case of a thixotropic agent having an active ingredient content of 10% by mass, 7.50 parts by mass of the thixotropic agent was mixed with 92.50 parts by mass of the test coating material, and dispersed and mixed.

The commercially available thixotropic agents used for the production of the above comparative products 1 to 4 are as follows.
Thioxide imparting agent used in Comparative Product 1; Fatty acid amide-based swelling paste (non-volatile content: 20% by mass), a product of another company other than Ito Oil Co., Ltd. -Based composite paste containing polyethylene oxide and non-volatile content of 10% by mass
Thixotropic agent used in Comparative Product 3; fatty acid amide-based swelling paste, nonvolatile content 20% by mass, manufactured by Ito Oil Co., Ltd., trade name “A-S-A T-380-20BS”
Thixotropic agent used in Comparative Product 4; fatty acid amide-based swelling paste, 10% by mass of non-volatile content, manufactured by Ito Oil Co., Ltd., trade name “A-S-A T-380-10BS”
The “LAWS product” shown in Table 1 is a comparative product prepared by blending 92.50 parts by mass of the test paint with 7.50 parts by mass of LAWS and using no thixotropic agent.

(3) Performance Evaluation The LAWS product, the practical products 1 to 3 and the comparative products 1 to 4 manufactured in the above (2) are allowed to stand at 25 ° C. for 24 hours, and then the KU value, the viscosity, the T.P. I. Values and gloss were measured. Moreover, sagging limit film thickness and rough skin suppression property were evaluated. Each measuring method and evaluation method are as follows.
(A) KU value It measured at 25 degreeC using the Stormer viscometer.
(B) Viscosity and T.I. I. Value After stirring for 1 minute using a B-type viscometer, the viscosity and T.I. I. The value was measured.
(C) Sagging limit film thickness Using a sag tester, a plurality of strip-like coatings having different thicknesses are formed on the surface of the test paper from one side to the other side, and the test paper is immediately placed with the thick film side downward. Vertically placed vertically. Then, after the flow of the paint stopped, the state of the paint flow was visually observed, and it was assumed that there was no dripping when the paint did not flow out to the unpainted portion between the belt-like coating films. A comb-shaped wet film thickness meter was lightly pressed at right angles to the maximum thickness of the coatings without sagging, and the thickness was measured. This film thickness is defined as the sagging limit film thickness.
(D) Gloss Each paint was applied to a glass plate using an applicator to form a coating film having a thickness of 150 μm. For each paint, a coating film is formed on two glass plates, one is set horizontally and the other is set vertically, and after the coating is dried, the gloss of the coating film is 20 ° and 60 ° with respect to the glass plate. Was measured using a digital variable angle gloss meter (model “UGV-5D” manufactured by Suga Test Instruments Co., Ltd.).
(E) Gloss retention and skin roughness suppression An appropriate amount of each paint is placed on one end of the same glass plate as used in (d) above, and the paint is flowed vertically by placing the paint on the upper side. (This is referred to as “Drip coating” in Table 1.) After the paint was dried, the gloss of the fluidized coating film was measured from the direction of 20 ° and 60 ° with respect to the glass plate using the same apparatus as in the above (d). Further, the gloss retention rate was calculated from the gloss of the fluidized coating film and the gloss of the coating film in the above (d) according to the following formula, and used as an index for rough skin suppression.
Gloss retention (%) = [Glossiness of fluidized coating film / Glossiness of coating film in (d) above] × 100
In addition, rough skin suppression property was evaluated by this gloss retention rate and the observation result by visual observation of the coating film in said (d).
The evaluation results are shown in Table 1.

(4) Preparation of diluted products and performance evaluation Tables 2 and 3 of Comparative Examples 1, 3 and 4 manufactured in (2) above and KU values (25 ° C) of 75 were prepared by LAWS. The diluted product described in Table 3 and the KU value (25 ° C.) adjusted to 70 were prepared. Further, using these diluted products, the viscosity, T.I. I. The value and the gloss were measured, and the sagging limit film thickness and the rough skin suppression were evaluated. Each measurement method and evaluation method are as described in (3) above.
The evaluation results when the KU value (25 ° C.) is 75 are shown in Table 2, and the evaluation results when the KU value (25 ° C.) is 70 are shown in Table 3, respectively.
In addition, the evaluation result of the rough skin suppression property described in Tables 1 to 3 is as follows: ◎: There is no pattern on the surface of the coating film and is smooth, ◯: A slight pattern is seen on the surface of the coating film, Δ: Coating film A three-dimensional rough pattern is seen on the surface, but it is not in a state where film breakage occurs. X; There is a part where film breakage occurs and the underlying glass plate is exposed.
Moreover, since the film | membrane cut | disconnection generate | occur | produced and there exists a part which the base glass plate is exposed, it is glossy that the numerical value of drip coating and gloss retention of comparative product 1 in Tables 1-3 is attached. This is because the measured value is not sufficiently determined.

Effects of Examples According to the results of Tables 1 to 3, the thixotropic agent of Example 1 used in Example 1 has a large sagging limit film thickness, excellent thixotropic properties, and gloss. It can be seen that the retention rate is also high, and it has sufficient rough skin inhibiting properties. Further, the thixotropic agent of Example 2 used in Example 2 and used in combination with 12-hydroxystearic acid and castor oil fatty acid has a lower viscosity than the commercially available thixotropic agent used in Comparative Product 1. Nevertheless, it can be seen that the sagging limit film thickness is thicker than that of Comparative Product 1 and the skin roughness suppression property is also superior, and it has both excellent thixotropy and skin roughness suppression properties. Furthermore, in the thixotropic agent of Example 3 used in Example 3, the sagging limit film thickness is thicker than that in Example 1 and has better thixotropic properties, and is equivalent to Example 2. It can be seen that it has a gloss retention and also has sufficient skin roughness inhibiting properties.

  On the other hand, the LAWS products shown in Table 1 are not blended with a thixotropic agent and are only diluted with a solvent. Therefore, the sagging limit film thickness is extremely inferior to 25 μm or less, and the rough skin inhibiting property is Although it is good, it cannot be put to practical use. Moreover, in the commercially available thixotropic agent used for the comparative product 1, the sagging limit film thickness is superior to that of the practical product 1, but the gloss retention is extremely low, and it is found that the skin roughness inhibiting property is inferior.

  Furthermore, although the commercially available thixotropic agent used for the comparative product 2 has a low dripping limit film thickness although it has a low viscosity, it cannot be said to be a sufficient thickness and has poor skin roughness suppression properties. In addition, the commercially available thixotropic agent used for the comparative product 3 has a very low sag limit film thickness even though the viscosity is not so low, and also has poor skin roughness suppression properties. Further, the commercially available thixotropic agent used for the comparative product 4 has a good sagging limit film thickness as compared with the comparative product 3, but is inferior in skin roughness suppression (low gloss retention), and practically. That's not enough.

(5) Vividness Using the products 1 and 2 and the comparative products 1 and 3 when the KU value (25 ° C) prepared in (4) is 75, the same as (3) and (d) above. A coating film was formed on the surface of the glass plate. Then, it was left to stand obliquely below the fluorescent lamp so that the coating film surface became the upper surface, and the clarity was evaluated by the clarity of the fluorescent lamp reflected on the coating film surface.
FIG. 1 shows the results when the product 1 was used, FIG. 2 shows the product 2 used, FIG. 3 shows the comparison product 1, and FIG. 4 shows the comparison product 3.
According to FIGS. 1 to 4, it can be seen that in the working products 1 and 2, the fluorescent lamp is reflected quite clearly, the visibility is high, and the rough skin is sufficiently suppressed. On the other hand, in comparative product 1, the rough skin is extremely severe, and it is almost impossible to confirm that a fluorescent lamp is reflected, and the sharpness is extremely inferior. Moreover, although the thing like a fluorescent lamp is reflected in the comparative product 3, it cannot be confirmed at all that it is a plurality of fluorescent lamps, and it turns out that the rough skin is severe and the sharpness is inferior.

(6) Evaluation of sagging prevention property and skin roughness inhibition property when the mass ratio of 12-hydroxystearic acid and castor oil fatty acid is changed in the thixotropic agent of the present invention Experimental Examples 1 to 11
A thixotropic agent was produced in the same manner as in Example 2 except that the mass ratio of 12-hydroxystearic acid and castor oil fatty acid was changed as shown in Table 4, and benzyl alcohol was similarly used. The non-volatile content concentration was adjusted to 20% by mass by adding and diluting. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 4.

In Table 4, “12HSA” is 12-hydroxystearic acid, “CO-FA” is castor oil fatty acid, “EDA” is ethylenediamine, and “T-80” is 80% by mass of 2,4-TDI. TDI.

  According to the result of Table 4, sufficient sag prevention property and rough skin suppression property are obtained in all the compositions of Experimental Examples 1 to 11. Moreover, in Experimental Examples 4-8 whose mass ratio of castor oil fatty acid is 30-70 mass%, it turns out that it is especially excellent in sagging prevention property.

(7) Evaluation of sagging prevention property and skin roughness inhibition property when the type of polyamines or polyisocyanates is changed in the thixotropic agent of the present invention Experimental Examples 12 to 19
A thixotropic agent was produced in the same manner as in Example 2 except that the polyamines or polyisocyanates were changed as shown in Table 5. Similarly, benzyl alcohol was added and diluted, and the nonvolatile content concentration was adjusted. It adjusted to 20 mass%. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 5.

In Table 5, “12HSA” is 12-hydroxystearic acid, “CO-FA” is castor oil fatty acid, “EDA” is ethylenediamine, “TMDA” is tetramethylenediamine, “HMDA” is hexamethylenediamine, “MXDA”. "Metaxylenediamine", "PXDA" is paraxylenediamine, "1,3-BAC" is 1,3 bis (aminomethyl) cyclohexane, "T-80" is 80% by mass of 2,4-TDI. TDI, “T-100” is TDI having a total amount of 2,4-TDI, and “T-65” is TDI containing 65% by mass of 2,4-TDI.

  According to the results of Table 5, the polyisocyanates were T-80, and in Experimental Examples 12 to 17 in which the types of polyamines were changed, the polyisocyanates had sufficient sagging prevention properties regardless of the types of polyamines. It also has excellent resistance to rough skin. Moreover, EDA has the outstanding dripping prevention property, and it turns out that it is preferable polyamines. Furthermore, in Experimental Examples 18 and 19 in which the polyamines were changed to EDA and the polyisocyanates were changed, sufficient performance was obtained, but the overall evaluation was slightly inferior to T-80. It turns out that it is a more preferable polyisocyanate.

(8) Evaluation of sagging prevention property and skin roughness inhibition property when polyisocyanate addition temperature, reaction temperature and reaction time are changed in thixotropic agent of the present invention Experimental Examples 20 to 28
A thixotropic agent was produced in the same manner as in Example 2 except that the temperature, reaction temperature, and reaction time when adding polyisocyanates were changed as shown in Table 6, and benzyl alcohol was added in the same manner. And diluted to adjust the non-volatile content concentration to 20% by mass. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 6.

In Table 6, “12HSA” is 12-hydroxystearic acid, “CO-FA” is castor oil fatty acid, “EDA” is ethylenediamine, and “T-80” is 80% by mass of 2,4-TDI. TDI.

  According to the results in Table 6, in Experimental Examples 20 to 22 in which the addition temperature of T-80 and the reaction temperature were changed, the rough skin suppression was excellent regardless of the temperature, but the drooping prevention was greatly affected by the temperature. Experimental Examples 20 and 21 having an addition temperature of 115 to 120 ° C. and a reaction temperature of 100 to 110 ° C. are good, and in Experimental Example 22 at a higher temperature, the performance is degraded. In addition, in Experimental Examples 23 to 28 in which the addition temperature was 120 ° C., the reaction temperature was 110 ° C., and the reaction time was changed, the skin roughness suppression property was excellent regardless of the time, and the sagging prevention property was a reaction time of 2.5 hours. In the case of Experimental Examples 25 and 26 for 3.5 hours, it can be seen that the results are particularly excellent.

(9) Evaluation of sagging prevention property and skin roughness inhibition effect when polyamines are changed in another thixotropic agent of the present invention Experimental Examples 29 to 34
A thixotropic agent was produced in the same manner as in Example 3 except that the polyamines were changed as shown in Table 7. Similarly, benzyl alcohol was added and diluted to make the nonvolatile content concentration 20% by mass. It was adjusted. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 7.

In Table 7, “CO-FA” is castor oil fatty acid, “EDA” is ethylenediamine, “TMDA” is tetramethylenediamine, “HMDA” is hexamethylenediamine, “MXDA” is metaxylenediamine, and “PXDA” is Paraxylenediamine, “1,3-BAC” is 1,3 bis (aminomethyl) cyclohexane, and “T-80” is TDI containing 80% by mass of 2,4-TDI.

  According to the results of Table 7, in Experimental Examples 29 to 34 in which polyisocyanates are T-80 and the types of polyamines are changed, the rough skin suppression is all good, but the sag prevention is more effective by EDA. It is excellent and it turns out that it is preferable polyamines.

(10) Evaluation of sagging prevention and rough skin suppression when the type of polyamines or polyisocyanates is changed in the rough skin suppressing thixotropic agent of the present invention Experimental Examples 35 to 45
A thixotropic agent was produced in the same manner as in Example 1 except that polyamines or polyisocyanates were changed as shown in Table 8. Similarly, benzyl alcohol was added and diluted, and the nonvolatile content concentration was adjusted. It adjusted to 20 mass%. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 8.

In Table 8, “12HSA” is 12-hydroxystearic acid, “EDA” is ethylenediamine, “TMDA” is tetramethylenediamine, “HMDA” is hexamethylenediamine, “MXDA” is metaxylenediamine, and “PXDA” is Para-xylenediamine, “1,3-BAC” is 1,3-bis (aminomethyl) cyclohexane, “T-80” is TDI containing 80% by mass of 2,4-TDI, “HDI” is hexamethylene diisocyanate "T-100" is a total amount of 2,4-TDI TDI, "Hydrogenated XDI" is a hydrogenated product of metaxylene diisocyanate, "IPDI" is an isophorone diisocyanate, "Hydrogenated MDI" is a hydrogenated diphenylmethane diisocyanate It is a thing.

  According to the results in Table 8, in Experimental Examples 35 to 40 in which the polyisocyanate is T-80 and the type of the polyamine is changed, the polyisocyanate has sufficient sag prevention property regardless of the type of the polyamine. It can be seen that EDA is superior. Moreover, the rough skin suppression property is excellent irrespective of the kind of polyamines. Furthermore, in Experimental Examples 41 to 45 in which polyamines were changed to EDA and the polyisocyanates were changed, the rough skin suppressing property was excellent regardless of the type of polyisocyanates, but the dripping prevention property was T-100. It can be seen that TDI is a preferred polyisocyanate, which is superior to the polyisocyanates of TDI.

(11) Evaluation of sagging prevention and rough skin suppression when the reaction time of the reaction product and the polyisocyanate is changed in the rough skin suppressing thixotropic agent of the present invention Experimental Examples 46 to 51
A thixotropic agent was produced in the same manner as in Example 1 except that the reaction time of the reaction product and the polyisocyanate was changed as shown in Table 9, and was similarly diluted by adding benzyl alcohol. The non-volatile content concentration was adjusted to 20% by mass. Thereafter, the thixotropic agent produced in this manner is dispersed and mixed in the test paint produced in (1) as described in (2) above to prevent dripping as in (3) above. And the rough skin suppression were evaluated.
The results are listed in Table 9.

In Table 9, “12HSA” is 12-hydroxystearic acid, “EDA” is ethylenediamine, and “T-80” is TDI containing 80% by mass of 2,4-TDI.

  According to the results of Table 9, in Experimental Examples 46 to 51 in which the reaction time of T-80 was changed, sufficient performance was obtained for both dripping prevention and rough skin suppression, and in particular, the reaction time was 0.5 to In the case of 3.5 hours, it turns out that the more outstanding dripping prevention property is acquired.

  The thixotropic agent of the present invention and the other thixotropic agent of the present invention and the rough skin suppressing type thixotropic agent are paints, sealing materials, waterproofing materials, adhesives, etc. It can mix | blend especially with solvent-type paints etc., and can use it suitably for the use which suppresses dripping of a coating film and suppresses the rough skin when dripping.

It is explanatory drawing showing the clarity when using the implementation goods 1 (KU value 75). It is explanatory drawing showing the visibility when using the implementation goods 2 (KU value 75). It is explanatory drawing showing the visibility when using the comparative product 1 (KU value 75). It is explanatory drawing showing the clarity when using the comparative product 3 (KU value 75).

Claims (11)

  A thixotropic agent characterized by reacting a reaction product of 12-hydroxystearic acid and castor oil fatty acid with polyamines and polyisocyanates.   The thixotropic agent according to claim 1, wherein the castor oil fatty acid is 5 to 95 mass% when the total of the 12-hydroxystearic acid and the castor oil fatty acid is 100 mass%.   The thixotropic agent according to claim 2, wherein the castor oil fatty acid is 25 to 75% by mass.   A thixotropic agent characterized by reacting a reaction product of castor oil fatty acid and polyamines with polyisocyanates. A method for producing a thixotropic agent according to any one of claims 1 to 4,
Adding the polyisocyanates to the reaction product in a temperature range of 105 to 135 ° C., and then reacting the reaction product in a temperature range of 95 to 125 ° C. and 5 to 20 ° C. lower than the temperature of the addition. A method for producing a thixotropic agent characterized by the above.   The method for producing a thixotropic agent according to claim 5, wherein the reaction time is 2 to 4 hours.   A rough skin-suppressing thixotropic agent characterized by reacting a reaction product of 12-hydroxystearic acid and a polyamine with a polyisocyanate.   The rough skin-suppressing thixotropic agent according to claim 7, which is used for a solvent-type paint having a toluene and / or xylene content of 10% by mass or less when the total amount of the solvent is 100% by mass.   The solvent is a mixed solvent containing an aromatic solvent having 9 or more carbon atoms and an aliphatic solvent as another solvent excluding the toluene and / or the xylene, and the boiling point of the mixed solvent is 140 ° C. The rough skin-suppressing thixotropic agent according to claim 8, which is as described above. A method for producing a rough skin-suppressing thixotropic agent according to any one of claims 7 to 9,
Adding the polyisocyanates to the reaction product in a temperature range of 105 to 135 ° C., and then reacting the reaction product in a temperature range of 95 to 125 ° C. and 5 to 20 ° C. lower than the temperature of the addition. A method for producing a rough skin-suppressing thixotropic agent characterized by the above.   The method for producing a rough skin-suppressing thixotropic agent according to claim 10, wherein the reaction time is 20 minutes to 4 hours.