JP2022133099A - Viscosity-improving agent - Google Patents

Abstract

To provide a viscosity-improving agent excellent in thixotropy.SOLUTION: A viscosity-improving agent as a viscosity-improving agent for a composition containing organic fluid and fine particles contains carboxylic acid amide of polyamine. The carboxylic acid amide of polyamine is preferably amide of a formula (1), wherein, R1, R6 are acyl groups, hydrogen atoms, hydrocarbon groups, hydroxyalkyl groups, or hydroxy polyoxyalkylene groups, at least one of the R1, R6 is an acyl group, R2-R5 are hydrogen atoms, hydrocarbon groups, hydroxyalkyl groups or hydroxy polyoxyalkylene groups, R7 is a hydrocarbon group, x is 1-5, y is 0-10, and the sum of x and y is at least 2.SELECTED DRAWING: None

Description

The present invention relates to viscosity improvers.

"(A) 3 to 50% by mass of red phosphorus, (B) a polyurethane flame retardant composition containing 0.2 to 15% by mass of an anti-settling agent (the anti-settling agent is carbon black, finely divided silica, hydrogenated castor oil wax , at least one selected from fatty acid amide waxes and organic clays)” (claims 1 and 2 of Patent Document 1), and it is believed that this anti-settling agent acts as a viscosity improver.

JP 2012-219127 A

Conventional anti-settling agents have the problem of insufficient thixotropy. An object of the present invention is to provide a viscosity improver with excellent thixotropy.

A feature of the viscosity improver of the present invention is that it is a viscosity improver for a composition comprising an organic fluid and fine particles, and comprises a carboxylic acid amide (A) of a polyamine.

The feature of the premix composition for polyurethane production of the present invention is summarized in that it comprises a polyoxyalkylene compound and/or polyester polyol, fine particles and the viscosity improver described above.

The viscosity improver of the present invention can impart excellent thixotropic properties to a composition comprising an organic fluid and fine particles.

Since the premix composition for polyurethane production of the present invention contains the above viscosity improver, it is excellent in thixotropy.

The polyamine carboxylic acid amide (A) includes a compound obtained by a known amidation reaction between a polyamine and a carboxylic acid.

Polyamines are not particularly limited, but include (poly)alkylene polyamines (alkylene having 2 to 3 carbon atoms) and modifications thereof.

From the viewpoint of thixotropy, the (poly)alkylenepolyamine is preferably (poly)ethylenepolyamine, more preferably diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, particularly preferably triethylenetetramine and pentaethylenehexamine. is.

Modified (poly)alkylene polyamines include N-alkyl modified, N-alkenyl modified, N-aryl modified, N-hydroxyalkyl modified and N-hydroxypolyoxyalkylene (an alkylene group having 2 to 2 carbon atoms). 4) Modified products are included.

Carboxylic acids are not particularly limited, but include mono- to bivalent carboxylic acids. The carboxylic acid amide of the polyamine preferably contains at least an amide with a monovalent carboxylic acid.

As monovalent carboxylic acids, saturated or unsaturated fatty acids having 8 to 22 carbon atoms can be used, including caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, Arachidic acid, henicosyl acid, behenic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid and ricinol acids and the like. In addition to these, natural oil fatty acids can also be used, such as coconut oil fatty acid, peanut oil fatty acid, palm oil fatty acid, castor oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, soybean oil fatty acid, and sunflower oil fatty acid. and cottonseed oil fatty acids. Among these, oleic acid and coconut oil fatty acid are preferred from the viewpoint of thixotropy.

As the divalent carboxylic acid, a saturated or unsaturated dicarboxylic acid having 4 to 38 carbon atoms can be used, including succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and isophthalic acid. , terephthalic acid and dimer acid (mixture of dibasic acid obtained by dimerization of unsaturated fatty acid having 18 carbon atoms, hereinafter the same), and the like. When the carboxylic acid amide of the polyamine contains an amide with a divalent carboxylic acid, adipic acid and dimer acid are preferred among these from the viewpoint of thixotropy.

As the polyamine carboxylic acid amide (A), an amide represented by formula (1) can be preferably exemplified.

R ¹ and R ⁶ are an acyl group having 8 to 22 carbon atoms, a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms or a hydroxypolyoxyalkylene group (an alkylene group having 2 carbon atoms 4), at least one of R ¹ and R ⁶ is an acyl group having 8 to 22 carbon atoms, R ² to R ⁵ are hydrogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, and 2 carbon atoms. ~ 4 hydroxyalkyl group or hydroxypolyoxyalkylene group (alkylene group has 2 to 4 carbon atoms), R ⁷ is a hydrocarbon group having 2 to 36 carbon atoms, x is an integer of 1 to 5, y is 0 to 10 The sum of the integers x and y (x+y) is at least two.

Among R ¹ and R ⁶ , acyl groups having 8 to 22 carbon atoms include octanoyl, octenoyl, nonanoyl, nonenoyl, decanoyl, decenoyl, undecanoyl, undecenoyl, dodecanoyl, dodecenoyl, tetradecanoyl, tetradecenoyl, pentadecanoyl, and pentadecenoyl. , hexadecanoyl, hexadecenoyl, heptadecanoyl, heptadecenoyl, octadecanoyl, octadecenoyl, hydroxyoctadecenoyl, octadecadienoyl, octadecantrienoyl, nonadecanoyl, nonadesenoyl, icosanoyl, icosenoyl, icosadienoyl, icosatrienoyl, icosatetraenoyl , henicosanoyl and docosanoyl.

Hydrocarbon groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, vinyl, 2-propenyl, isopropenyl, 3-butenyl, 2-butenyl and 1-butenyl. , 1-methyl-2-propenyl, 1-methyl-1-propenyl, 1-ethyl-1-ethenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 4-pentenyl, 1-hexenyl, cyclo hexenyl, ethynyl, 2-propynyl, 1-butynyl, 1-hexynyl, cyclohexynyl, phenyl and the like.

Examples of hydroxyalkyl groups having 2 to 4 carbon atoms include hydroxyethyl, hydroxypropyl and hydroxybutyl.

Further, as the hydroxypolyoxyalkylene group (alkylene group having 2 to 4 carbon atoms), a plurality of oxyalkylene groups having 2 to 4 carbon atoms (oxyethylene, oxypropylene and oxybutylene) (oxyalkylene group repeating number 2 50) are chemically bonded to the polyoxyalkylene chain. The polyoxyalkylene chain may be composed of one type of oxyalkylene group, or may be composed of two or more types of polyoxyalkylene groups. When composed of two or more types, the bonding mode may be block or random. and a mixture thereof.

From the viewpoint of thixotropy, among R ¹ and R ⁶ , acyl groups having 8 to 22 carbon atoms are preferred, acyl groups having 8 to 18 carbon atoms are more preferred, and octadecenoyl groups are particularly preferred. R ¹ and R ⁶ may be the same or different.

Among R ² to R ⁵ , the hydrocarbon group having 1 to 6 carbon atoms, the hydroxyalkyl group having 2 to 4 carbon atoms and the hydroxypolyoxyalkylene group (alkylene group having 2 to 4 carbon atoms) are the same as above. be.

Among R ² to R ⁵ , from the viewpoint of thixotropy, a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms, hydroxyethyl, hydroxypropyl and a hydroxypolyoxyalkylene group (an alkylene group having 2 to 4 carbon atoms, oxyalkylene 2 to 50 repeating groups), more preferably hydrogen atom, methyl, hydroxyethyl and hydroxypolyoxyalkylene groups (alkylene group having 2 to 4 carbon atoms, oxyalkylene group having 2 to 50 repeating numbers). R ² to R ⁵ may be the same or different.

Hydrocarbon groups having 2 to 36 carbon atoms (R ⁷ ) include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, Reactive residues of icosylene, phenylene and dimer acid (residues obtained by removing two carboxyl groups from dimer acid; dimer acid is a mixture and it is extremely difficult to identify the chemical structure), etc., preferably butylene group and the reactive residue of the dimer acid.

x is an integer of 1 to 5, preferably an integer of 2 to 5, more preferably an integer of 3 to 5, from the viewpoint of thixotropy.

y is an integer of 0 to 10, preferably an integer of 0 to 6, more preferably an integer of 0 to 4, particularly preferably an integer of 0 to 2, from the viewpoint of thixotropy.

The sum of x and y (x+y) is at least 2, preferably at least 3 from the viewpoint of thixotropy.

When x is 2 or more, a plurality of R ³ and R ⁵ are present in the molecule, and when y is 2 or more, a plurality of x, R ² , R ³ and R ⁷ are present in the molecule. They can be the same or different.

The amide represented by formula (1) is an amide in which at least one of R ¹ and R ⁶ is an acyl group having 8 to 22 carbon atoms, and the primary amino group of the (poly)alkylenepolyamine is amidated. However, amides in which any one of R ² to R ⁵ is an acyl group, that is, amides in which the secondary amino group of (poly)alkylenepolyamine is amidated, etc., as long as the effects of the present invention are not impaired. It may be contained as an impurity.

Carboxylic acid amide (A) of polyamine can be easily obtained by a known method, for example, (poly)alkylene polyamine and carboxylic acid are dehydrated by heating (for example, 60 to 250° C. under reduced pressure or normal pressure). It is obtained by a method of amidation, or a method of reacting a (poly)alkylene polyamine with a carboxylic acid halide or a carboxylic acid ester to dehydrohalogenate or dealcoholize.

When the polyamine carboxylic acid amide (A) consists of a modified (poly)alkylene polyamine and a carboxylic acid, <1> may be modified after amidation as described above, or <2> (poly)alkylene It may be obtained by obtaining a modified polyamine and then amidating it with a carboxylic acid.

<1> In the case of modification after amidation, the amide is reacted with an alkylating agent, an alkenylating agent and an arylating agent (an alkyl halide, an alkenyl halide, an aryl halide, an alkyl sulfate, etc.) by a known method. N-alkyl modified products, N-alkenyl modified products and N-aryl modified products can be obtained. In addition, N-hydroxyalkyl modified products and N-hydroxypolyoxyalkylene modified products (where the alkylene group has 2 to 4 carbon atoms) can be obtained by reacting an amide with an alkylene oxide by a known method.

<2> When a modified form of a (poly)alkylene polyamine is obtained and then amidated with a carboxylic acid, the (poly)amine, an alkylating agent, an alkenylating agent and an arylating agent (halogenated alkyl, alkenyl halide, aryl halide, alkyl sulfuric acid, etc.) to give N-alkyl modified products, N-alkenyl modified products and N-aryl modified products. Further, by a known method, a (poly)amine and an alkylene oxide can be reacted to obtain an N-hydroxyalkyl modified product and an N-hydroxypolyoxyalkylene (alkylene group having 2 to 4 carbon atoms) modified product. .

(Poly)alkylene polyamines are susceptible to amidation of primary amino groups and are also susceptible to modification. When amidating or modifying a secondary amino group, protect the primary amino group with a ketone (acetone, methyl isobutyl ketone, etc.) (generate ketimine), then perform amidation or modification, then hydrolyze the ketimine. to convert the protecting group (imino group) to a primary amino group (the primary amino group can then be modified or amidated).

The polyamine carboxylic acid amide (A) may be purified into a single component, or may be a mixture of a plurality of polyamine carboxylic acid amides. In addition, it may contain unreacted substances and by-products as long as they do not impair the effects of the present invention.

Organic fluids to which the viscosity improver of the present invention can be applied are not particularly limited, and include fluid organic substances, ie, non-aqueous fluids, and are particularly effective for polyoxyalkylene compounds and/or polyester polyols. Applicable to organic solvents (amides, alcohols, ketones, esters, ethers, aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, etc.) in addition to polyoxyalkylene compounds and/or polyester polyols as organic fluids. can.

Examples of polyoxyalkylene compounds include compounds containing repeating units of oxyalkylene having 2 to 4 carbon atoms, monoalcohols, monocarboxylic acids or monoamine alkylene oxide (2 to 4 carbon atoms) adducts, divalent to hexavalent Alkylene oxide (2 to 4 carbon atoms) adducts of polyols, esters of these alkylene oxide adducts with fatty acids, hydrolyzable silyl group-containing alkylene oxide adducts (JP-A-52-73998, etc.) and these and a reactant (urethane prepolymer, ie, isocyanate oligomer) of an alkylene oxide adduct of and isocyanate.

Examples of polyester polyols include reactants of dicarboxylic acids and diols (polyesters having at least two hydroxyl groups, in which some of the diols may be replaced with triols), and the like.

Fine particles to which the viscosity improver of the present invention can be applied are not particularly limited, and in particular carbon fine particles (fine particles such as carbon black), metal carbonate fine particles (fine particles such as calcium carbonate) and phosphorus compound fine particles (red phosphorus, ammonium polyphosphate, etc.) fine particles). In addition to these, metal hydroxide fine particles (fine particles such as aluminum hydroxide or magnesium hydroxide), metal oxide fine particles (fine particles such as titanium oxide or aluminum oxide), metal sulfate fine particles (calcium sulfate, barium sulfate, etc.) or fine particles such as cerium sulfate), metal silicate fine particles (fine particles such as aluminum silicate, potassium silicate, calcium silicate or magnesium silicate), metal fine particles (fine particles such as gold, rhodium, palladium or platinum), nitriding fine particles (melamine, melamine polyphosphate, aluminum nitride, boron nitride, silicon nitride, etc.) and composite fine particles containing these (sepiolite, zeolite, cordierite, boehmite, imogolite, sericite, alloys, diatomaceous earth, hydrotalcite , clay, talc, mica or glass particles), etc.

Preferably, the viscosity improver of the present invention further contains an amine (B). Amines (B) include monoamines and polyamines.

Examples of monoamines that can be used include aliphatic monoamines having 2 to 6 carbon atoms, alicyclic monoamines having 3 to 6 carbon atoms and aromatic monoamines having 5 to 8 carbon atoms.

Aliphatic monoamines include ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, dimethylethanolamine and diethylethanolamine.

Alicyclic monoamines include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 1,4-ethylenepiperazine, diazabicycloundecene and diazabicyclononene.

Aromatic monoamines include aniline, pyridine, piperidine, benzylamine and phenylenediamine.

As the polyamine, those similar to those described above {the polyamine is not particularly limited, but (poly)alkylene polyamine (alkylene having 2 to 3 carbon atoms) and modified products thereof} and the like can be used.

Among these, aliphatic monoamines and polyamines are preferred, and (poly)ethylenepolyamine, ethanolamine, diethanolamine and triethanolamine are more preferred.

When the viscosity improver of the present invention further contains an amine (B), the content (% by weight) of the carboxylic acid amide (A) is 50 to 50% based on the weight of the carboxylic acid amide (A) and the amine (B). 99 is preferred, and 75-90 is more preferred. The content (% by weight) of the amine (B) is preferably 1-50, more preferably 10-25, based on the weight of the carboxylic acid amide (A) and the amine (B). Within this range, the thixotropy is further improved.

When the amine (B) is included, the viscosity improver of the present invention can be prepared by uniformly mixing the polyamine carboxylic acid amide (A) and the amine (B). When the viscosity improver of the present invention contains an amine (B) and the amine (B) is a polyamine, the carboxylic acid amide (A) of the polyamine is prepared by using an excess amount of the polyamine to contain the unreacted polyamine as it is. You may let

If the premix composition for polyurethane production of the present invention contains a polyoxyalkylene compound and/or polyester, fine particles, and the above-mentioned viscosity improver, in addition to these, additives used for polyurethane (foam stabilizer agent, antidegradation agent, plasticizer, curing agent, foaming agent, etc.) and the like.

Examples of foam stabilizers include dimethylsiloxane foam stabilizers and polyether-modified dimethylsiloxane foam stabilizers. Antidegradation agents include triazole antidegradation agents and benzophenone antidegradation agents. Examples of plasticizers include phthalates and adipates. Curing agents include amino compounds, tin compounds, bismuth compounds, acetylacetone metal salts, and the like. Examples of blowing agents include water, halogenated hydrocarbons, low-boiling hydrocarbons, liquefied carbon dioxide gas, and the like.

The premix composition for polyurethane production of the present invention can be mixed with an isocyanate and then cured to prepare a polyurethane.

Isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified polyisocyanates of these polyisocyanates.

In the premix composition for polyurethane production of the present invention, the content (% by weight) of the viscosity modifier is preferably 0.01 to 10, more preferably 0.01 to 10, based on the weight of the polyoxyalkylene compound, polyester and flame retardant. is 0.1 to 9, particularly preferably 0.2 to 8.

Hereinafter, unless otherwise specified, parts means parts by weight, and % means % by weight. The symbols and contents in { } correspond to formula (1).

<Example 1>
1 mol part of tetraethylenepentamine and 1 mol part of oleic acid were subjected to a dehydration reaction to prepare a polyamine carboxylic acid amide (A1), which was used as the viscosity improver (1) of the present invention. As a result of liquid chromatography analysis and ¹ H-NMR spectrum analysis (the same shall apply hereinafter), this amide (A1) is a bisamide {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom, x: 4, y: 0}, monoamide {R ¹ : octadecenoyl, R ⁴ ·R ⁵ ·R ⁶ : hydrogen atom, x: 4, y: 0} and a statistical mixture of tetraethylenepentamine (molar ratio 1: 1:1) was the major component.

<Example 2>
One mol part of tetraethylenepentamine and 2 mol parts of oleic acid were dehydrated to prepare a polyamine carboxylic acid amide (A2), which was used as the viscosity improver (2) of the present invention. This amide (A2) is N,N''''-dioctadecenoyltetraethylenepentamine {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom, x: 4, y: 0 } was the main component.

<Example 3>
One mol part of diethylenetriamine and 2 mol parts of oleic acid were subjected to a dehydration reaction to prepare a polyamine carboxylic acid amide (A3), which was used as the viscosity improver (3) of the present invention. The main component of this amide (A3) is N,N''-dioctadecenoyldiethylenetriamine {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom, x: 2, y: 0}. there were.

<Example 4>
2 mol parts of tetraethylenepentamine, 1 mol part of adipic acid and 2 mol parts of oleic acid are dehydrated to prepare a polyamine carboxylic acid amide (A4), which is used as the viscosity improver (4) of the present invention. did. This amide (A4) is a tetraamide {R ¹ ·R ⁶ : octadecenoyl, R ² ·R ³ ·R ⁴ ·R ⁵ : hydrogen atom, R ⁷ : butylene, x: 4, y: 1} were the main components.

<Example 5>
3 mol parts of tetraethylenepentamine, 2 mol parts of dimer acid (Halidimer 200, Harima Kasei Co., Ltd.) and 2 mol parts of oleic acid are subjected to a dehydration reaction to prepare a polyamine carboxylic acid amide (A5), which is used in the present invention. This is the viscosity improver (5) of the invention. This amide (A5) is a hexaamide {R ¹ ·R ⁶ : octadecenoyl, R ² ·R ³ ·R ⁴ ·R ⁵ : hydrogen atom, R ⁷ : hydrocarbon group having 34 carbon atoms, x: 4, y: 2} were the main components.

<Example 6>
1 mol part of tetraethylenepentamine and 1 mol part of coconut oil fatty acid (coconut oil fatty acid, NOF Corporation) are subjected to a dehydration reaction to prepare polyamine carboxylic acid amide (A6), which is used as the viscosity-improving agent of the present invention. Agent (6). This amide (A6) is a bisamide {R ¹ ·R ⁶ : acyl group having 8 to 18 carbon atoms, R ⁴ ·R ⁵ : hydrogen atom, x: 4, y: 0}, monoamide {R ¹ : carbon number 8 to 18 acyl groups, R ⁴ ·R ⁵ ·R ⁶ : hydrogen atoms, x: 4, y: 0} and a statistical mixture of tetraethylenepentamine (molar ratio 1:1:1) as the main component Met.

<Example 7>
After 1 mol part of diethylenetriamine and 2 mol parts of acetone are reacted to protect the primary amino group with ketimine, 1 mol part of ethylene oxide is subjected to addition reaction to the secondary amino group in the presence of potassium hydroxide catalyst, and ketimine is formed by hydrolysis. After deprotection, N'-hydroxyethyldiethylenetriamine was prepared. Then, 1 mol part of N'-hydroxyethyldiethylenetriamine and 1 mol part of oleic acid were subjected to a dehydration reaction to prepare a polyamine carboxylic acid amide (A7), which was used as the viscosity improver (7) of the present invention. This amide (A7) is a bisamide {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom, another R ⁵ : hydroxyethyl, x: 2, y: 0}, monoamide {R ¹ : Octadecenoyl, R ⁴ ·R ⁵ ·R ⁶ : hydrogen atom, another R ⁵ : hydroxyethyl, x: 2, y: 0} and a statistical mixture of N′-hydroxyethyldiethylenetriamine (molar ratio 1:1 : 1) was the main component.

<Example 8>
After 1 mol part of diethylenetriamine and 2 mol parts of acetone are reacted to protect the primary amino group with ketimine, 40 mol parts of propylene oxide is added to the secondary amino group in the presence of potassium hydroxide catalyst, and ketimine is obtained by hydrolysis. was deprotected to prepare N'-hydroxypolyoxypropylene (40 mol) diethylenetriamine. Next, 1 mol part of N'-hydroxypolyoxypropylene (40 mol) diethylenetriamine and 2 mol parts of oleic acid are subjected to a dehydration reaction to prepare polyamine carboxylic acid amide (A8), which is used as the viscosity improver of the present invention. (8). This amide (A8) is N,N''-dioctadecenoyl-N'-hydroxypolyoxypropylene (40 mol) diethylenetriamine {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom , another R ⁵ : hydroxypolyoxypropylene, x: 2, y: 0} was the main component.

<Example 9>
After reacting 1 mol part of diethylenetriamine and 2 mol parts of acetone to protect the primary amino group with ketimine, the secondary amino group is methylated with dimethylsulfuric acid, and the protection of the ketimine is removed by hydrolysis to obtain N'-methyl. Diethylenetriamine was prepared. Then, 1 mol part of N'-methyldiethylenetriamine and 1 mol part of oleic acid were subjected to a dehydration reaction to prepare a polyamine carboxylic acid amide (A9), which was used as the viscosity improver (9) of the present invention. This amide (A9) is a bisamide {R ¹ ·R ⁶ : octadecenoyl, R ⁴ ·R ⁵ : hydrogen atom, another R ⁵ : methyl, x: 2, y: 0}, monoamide {R ¹ : octadecenoyl , R ⁴ ·R ⁵ ·R ⁶ : hydrogen atom, another R ⁵ : methyl, x: 2, y: 0} and a statistical mixture of N′-methyldiethylenetriamine (molar ratio 1:1:1) was the main component.

<Example 10>
81 parts of amide (A1) and 19 parts of amine (B1; diethanolamine, Tokyo Kasei Kogyo Co., Ltd.) were uniformly mixed to obtain the viscosity improver (10) of the present invention.

<Example 11>
77 parts of amide (A2) and 23 parts of amine (B1) were homogeneously mixed to obtain the viscosity improver (11) of the present invention.

<Example 12>
75 parts of amide (A3) and 25 parts of amine (B1) were homogeneously mixed to obtain the viscosity improver (12) of the present invention.

<Example 13>
90 parts of amide (A1) and 10 parts of amine (B2; tetraethylenepentamine, Tokyo Kasei Kogyo Co., Ltd.) were uniformly mixed to obtain the viscosity improver (13) of the present invention.

<Example 14>
90 parts of amide (A3) and 10 parts of amine (B3; diethylenetriamine, Tokyo Kasei Kogyo Co., Ltd.) were uniformly mixed to obtain the viscosity improver (14) of the present invention.

<Example 15>
50 parts of the amide (A4) and 50 parts of the amine (B1) were uniformly mixed to obtain the viscosity improver (15) of the present invention.

<Example 16>
99 parts of the amide (A4) and 1 part of the amine (B2) were homogeneously mixed to obtain the viscosity improver (16) of the present invention.

<Comparative Example 1>
"Anti-settling agent J: Fatty acid amide wax, Kusumoto Kasei Co., Ltd. 'Disparlon A603-20X', active ingredient 20%" used in the example of Patent Document 1 "Fatty acid amide wax (ALFLOW H-50S, NOF Corporation, "ALFLOW" is a registered trademark of the same company.) 20 parts and xylene (first grade, Kanto Kagaku Co., Ltd.) 80 parts uniformly mixed solution] was used as a viscosity improver for comparison (H1) .

<Evaluation 1>
Organic fluid (1; p-phthalate polyester polyol, Kawasaki Kasei Co., Ltd., Maximol RFK-505, "Maximol" is a registered trademark of the company.) 40.1 parts, fine particles (1; ammonium polyphosphate flame Retardant, Clariant Produkte (Deutschland) Gesellschaft Mitt Beschlenktel Haftung, Exolite AP 422, "Exolite" is a registered trademark of the same company.) 26.7 parts, evaluation sample {viscosity modifiers (1) to (16), comparative Viscosity modifier (H1)} 1 part, liquid flame retardant (tris (chloropropyl) phosphate flame retardant, Daihachi Chemical Industry Co., Ltd., TMCPP) 16 parts, blowing agent (1; Honeywell International Inc., Solstice LBA , "SOLSTICE" is a registered trademark of the company.) 11.4 parts, silicone foam stabilizer (Dow Toray Co., Ltd., SH-193) 0.9 parts, water 1.1 parts, curing catalyst (1; N -Methyldicyclohexylamine, Air Products and Chemicals Inc., POLYCAT 12, "POLYCAT" is a registered trademark of the company.) 1.3 parts and curing catalyst (2; tertiary amine, Tosoh Corporation, TOYOCAT- DM-70 and "TOYOCAT" are registered trademarks of the company.) 1.3 parts were uniformly mixed to prepare premix compositions (1-1) to (1-16) and (1-16) for evaluation polyurethane production. 1-H1) was obtained.

<Evaluation 2>
Organic fluid (1) 40.1 parts, fine particles (1) 20 parts, fine particles (2; red phosphorus, Rin Kagaku Kogyo Co., Ltd., Novaled 120 UFA, "Novaled" is a registered trademark of the company) 6.7 part, evaluation sample {any of viscosity improvers (3), (4), (14), viscosity improver for comparison (H1)} 1 part, liquid flame retardant 16 parts, blowing agent (1) 11.4 parts, 0.9 parts of a silicone foam stabilizer, 1.1 parts of water, 1.3 parts of curing catalyst (1) and 1.3 parts of curing catalyst (2) were uniformly mixed to obtain a polyurethane production preform for evaluation. Mix compositions (2-3), (2-4), (2-14) and (2-H1) were obtained.

<Evaluation 3>
Organic fluid (2; polyoxypropylene glyceryl ether, Sanyo Chemical Industries, Ltd., Sannix GP-600, "Sannix" is a registered trademark of the company.) 60 parts, organic fluid (3; polyoxypropylene glycol, Sanyo Kogyo Co., Ltd., Sannics PP-400) 40 parts, fine particles (1) 20 parts, fine particles (2) 6.7 parts, evaluation samples {viscosity modifiers (3), (4), (14), for comparison Viscosity improver (H1)} 1 part, liquid flame retardant 16 parts, foaming agent (2: cyclopentane, Nippon Zeon Co., Ltd., Zeon Solve HP, "Zeon Solve" is a registered trademark of the company.) 15.7 2 parts of silicone foam stabilizer, 2.7 parts of water, 1.3 parts of curing catalyst (1) and 1.3 parts of curing catalyst (2) are uniformly mixed to prepare a premix composition for producing polyurethane for evaluation. Products (3-3), (3-4), (3-14) and (3-H1) were obtained.

Premix composition for polyurethane production for evaluation (1-1) to (1-16), (1-H1), (2-3), (2-4), (2-14), (2- H1), (3-3), (3-4), (3-14) and (3-H1) were measured using a viscoelasticity measuring device (rotational rheometer, Physica MCR301, Anton Paar). Viscosity at a speed of 1 s ^-1 (η1; 15 ° C., Pa s) and viscosity at 100 s ^-1 (η2; 15 ° C., Pa s) are measured, respectively, and the thixotropy index (TI) is calculated from the following formula. It was calculated and shown in the table below.

(TI) = (η1)/(η2)

When the viscosity improver of the present invention was used, the thixotropy index (TI) was significantly higher and the thixotropy was extremely excellent compared to when the viscosity improver for comparison was used.
Further, since the premix composition for polyurethane production of the present invention is extremely excellent in thixotropy, fine particles are unlikely to settle, and maintenance of a uniform state can be expected even after long-term storage.

<Evaluation 4>
Organic fluid (4; polypropylene glycol with a weight average molecular weight of 12,000) 27.8 parts, organic fluid (5; polypropylene glycol with a weight average molecular weight of 3000) 18.5 parts, fine particles (4; heavy calcium carbonate, Takehara Chemical Industry Co., Ltd., SL-300) 39.3 parts, fine particles (5; surface-treated synthetic calcium carbonate, Shiraishi Calcium Co., Ltd., Hakuenka CCR, "Hakuenka" is a registered trademark of the company.) 13.9 parts and evaluation samples { Viscosity improvers (1) to (16) and viscosity improver for comparison (H1)} 1.0 parts were uniformly mixed to obtain premix compositions (4-1) to (4-) for producing polyurethane for evaluation. 16) and (4-H1) were obtained.

<Evaluation 5>
Organic fluid (4) 27.8 parts, organic fluid (5) 18.5 parts, fine particles (6; carbon black, Mitsubishi Chemical Corporation, MA100) 53.2 parts and evaluation sample {viscosity modifier (3), comparison 1 part of the viscosity improver (H1) for evaluation was uniformly mixed to obtain premix compositions (5-3) and (5-H1) for polyurethane production for evaluation.

For premix compositions (4-1) to (4-16), (4-H1), (5-3) and (5-H1) for polyurethane production for evaluation, a viscoelasticity measuring device (rotating rheo Using a meter, Physica MCR301, Anton Paar), the viscosity viscosity at a shear rate of 1 s ^-1 (η1; 25 ° C., Pa s) and viscosity at 100 s ^-1 (η2; 25 ° C., Pa s) Each was measured, and the thixotropy index (TI) was calculated from the following formula and shown in the table below.

(TI) = (η1)/(η2)

When the viscosity improver of the present invention was used, the thixotropy index (TI) was significantly higher and the thixotropy was extremely excellent compared to when the viscosity improver for comparison was used.
Further, since the premix composition for polyurethane production of the present invention is extremely excellent in thixotropy, fine particles are unlikely to settle, and maintenance of a uniform state can be expected even after long-term storage. Furthermore, it is expected that the premix composition for polyurethane production of the present invention will not drip easily even if it is applied to a vertical surface or an inclined surface.

Claims (5)

A viscosity modifier for a composition comprising an organic fluid and particulates, characterized in that it comprises a carboxylic acid amide (A) of a polyamine. 2. The viscosity improver according to claim 1, wherein the polyamine carboxylic acid amide (A) is an amide represented by formula (1).

R ¹ and R ⁶ are an acyl group having 8 to 22 carbon atoms, a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms or a hydroxypolyoxyalkylene group (an alkylene group having 2 carbon atoms 4), at least one of R ¹ and R ⁶ is an acyl group having 8 to 22 carbon atoms, R ² to R ⁵ are hydrogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, and 2 carbon atoms. ~ 4 hydroxyalkyl group or hydroxypolyoxyalkylene group (alkylene group has 2 to 4 carbon atoms), R ⁷ is a hydrocarbon group having 2 to 36 carbon atoms, x is an integer of 1 to 5, y is 0 to 10 The sum of the integers x and y (x+y) is at least two. 3. The viscosity improver according to claim 1, further comprising an amine (B). The content of the carboxylic acid amide (A) is 50 to 99% by weight and the content of the amine (B) is 1 to 50% by weight, based on the weights of the carboxylic acid amide (A) and the amine (B). 3. The viscosity improver according to 3. A premix composition for producing polyurethane, comprising a polyoxyalkylene compound and/or polyester polyol, fine particles and the viscosity improver according to any one of claims 1 to 3.