KR100625035B1 - Low temperature thickener - Google Patents

Abstract

The present invention provides a thickening agent having a small change in the thickening effect due to temperature change (low temperature), excellent coloration and gloss retention, and an aqueous emulsion and an aqueous emulsion coating material comprising the same.

It contains at least 1 type of the compound represented by General formula (1), The cloud point of 0.5 weight% aqueous solution is 60-120 degreeC, The weight average molecular weight is 1-80,000, The low temperature thickening agent characterized by the above-mentioned.

[Wherein X, Z is an organic group having 4 to 14 carbon atoms containing oxygen or nitrogen or a straight chain hydrocarbon group having 4 to 14 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ' , OR "is a C2-C4 oxyalkylene group, a, b, d is an integer of 1-500, c is an integer of 1 or more.]

Low Temperature Thickener, Aqueous Emulsion, Aqueous Emulsion Paint, Coloration, Gloss

Description

Thermophilic Thickener {THICKNER HAVING A LOW THERMOSENSITIVITY}

The present invention relates to hypothermic thickeners. More particularly, the present invention relates to a low temperature thickener useful for water-based emulsions, water-based emulsion paints, and the like.

Conventionally, many thickeners are known as natural products and semisynthetic products (hydroxyethyl cellulose, etc.). Among synthetic products, many are known, such as polyacrylic acids and polyoxyalkylene glycol derivatives. For example, when these thickeners are used for water-based emulsion paints, polyoxyalkylene glycol derivatives are used for natural products, semi-synthetic products, and polyacrylic acids in order to provide poor leveling properties and to provide leveling properties. As the polyoxyalkylene glycol derivatives, urethane-modified polyoxyalkylene glycols, ester-modified polyoxyalkylene glycols, epoxy-modified polyoxyalkylene glycols and the like are known in many cases (Japanese Patent Application No. 52-25840, Japanese Patent Publication No. 1-55292). No. 58-213074, Japan No. 52-164671).

Conventional polyoxyalkylene glycol derivatives have a drawback that the thickening action changes significantly with the temperature change in the temperature range (0 to 50 ° C.) used. For example, when the water-based emulsion paint containing a conventional thickener is applied outdoors, the thickening action is also changed by the external temperature, and the viscosity of the paint is greatly changed, so that the viscosity of the paint is lowered in summer, causing a problem of flowing down. In winter, there was a problem in actual workability, such as the viscosity of the paint increased and the complexity of dilution with water occurred. Moreover, in the water-based emulsion paint which mix | blends the conventional thickener, it tended to worsen the color tone of a coating film, or to produce gloss fall, and was not satisfied.

(Means to solve the task)

An object of the present invention is to provide a thickener having a small change in the thickening effect due to temperature change (lower temperature), excellent color tone and gloss retention, and an aqueous emulsion and an aqueous emulsion coating material comprising the same.

That is, the low-temperature thickener of the present invention contains at least one of the compounds represented by the formula (1), and the cloud point of the 0.1 wt% aqueous solution is 60 to 120 ° C, and the weight average molecular weight is 1 to 80,000.

(Formula 1)

[Wherein X, Z is an organic group having 4 to 14 carbon atoms containing oxygen or nitrogen or a straight chain hydrocarbon group having 4 to 14 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ' , OR "is a C2-C4 oxyalkylene group, a, b, d is an integer of 1-500, c is an integer of 1 or more.]

Preferably, X and Z in general formula (1) are a C4-C14 linear hydrocarbon group, and Y is a divalent organic residue derived from a C4-C10 diisocyanate compound.

Moreover, this invention is an aqueous emulsion which mix | blends 0.01-10 weight% of said low temperature thickeners.

Furthermore, this invention is an aqueous emulsion coating material which mix | blends 0.01-10 weight% of said low temperature thickeners.

Embodiment of the Invention

X, Z in the general formula (1) of the present invention is an organic group having 4 to 14 carbon atoms containing oxygen or nitrogen, or a straight chain hydrocarbon group having 4 to 14 carbon atoms. Among these, Preferably, they are a C4-C14 linear hydrocarbon group, More preferably, they are a C8-13 linear hydrocarbon group, Especially preferably, they are a C10-C12 linear hydrocarbon group. X and Z may be the same kind, and may be a different kind of combination. If the carbon number is less than 4, the thickening effect is small. If the carbon number is more than 14, the temperature sensitivity is increased, the color tone is deteriorated, and the gloss decreases. Carbon number here shows a weight average carbon number.

Examples of the organic group having 4 to 14 carbon atoms containing oxygen include 1-methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, and 1-t. -Butoxy-2-propanol, 3,3-diethoxy-1-propanol, 5-ethyl-1,3-dioxan-5-methanol, 2,2-dimethoxycyclo hexanol, 5,5-dimethyl- 1,3-dioxane-2-ethanol, 2,2-dibutoxyethanol, 5-t-butyl-1-hexanol, 4-t-butoxy-4-methyl-1-pentanol, hexylene glycol mono Alcohol residues of butyl ether, 2,2-di-t-butoxycyclohexanol, hexylene glycol monooctyl ether, and the like.

Examples of the organic group having 4 to 14 carbon atoms containing nitrogen include dimethylaminopropanol, diethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, diethylaminopropanol, 1,3-bis ( Dimethylamino) -2-propanol, diisopropylaminoethanol, diethylaminopentanol, dibutylaminoethanol, dibutylaminobutanol, 1,3-bis (diethylamino) -2-methyl-2-propanol, dibutyl Alcohol residues of aminohexanol, etc. are mentioned.

As a C4-C14 linear hydrocarbon group, it is n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecide, for example. A real group, n-dodecyl group, n-tridecyl group, n-myristyl group, etc. are mentioned. Moreover n stands for straight chain.

Y in the general formula (1) of the present invention is a divalent organic residue derived from a diisocyanate compound. Preferably it is a divalent organic residue derived from a C4-10 diisocyanate compound, More preferably, it is a divalent organic residue derived from a C5-9 diisocyanate compound, Especially preferably, it is a C6-C8 It is a divalent organic residue derived from a diisocyanate compound. If carbon number is less than 4, manufacturing cost will become high, and when carbon number exceeds 10, color tone will deteriorate.

As a diisocyanate compound, For example, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, cyclohexyl diisocyanate, hydrogenated xylene Diisocyanate, xylidene diisocyanate, phenylene diisocyanate, tolylden diisocyanate, naphthalene diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexanediisocyanate, 2,2,4-trimethylpentane diisocyanate, nonnamethylene Diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, dimethylbenzene diisocyanate, ethylbene Diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, isoborone diisocyanate, biphenyl diisocyanate, 3,3'-dimethylbiphenyl diisocyanate, 3,3'-dimethoxybiphenyl diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, methylenebis 4-cycloisocyanate, etc. are mentioned.

OR, OR ', OR "in the general formula (1) of the present invention is an oxyalkylene group having 2 to 4 carbon atoms, and when the carbon number is less than 2 and exceeds 4, the thickening property is lowered. As the oxyalkylene group having 2 to 4 carbon atoms, oxyethylene Group, an oxypropylene group, an oxybutylene group, etc. Among these, an oxyethylene group is essential.The ratio of an oxyethylene group becomes like this. Preferably it is 60 weight% or more of a whole oxyalkylene group, More preferably, it is a total oxyalkylene group. 80% by weight or more, particularly preferably 90% by weight or more of the total oxyalkylene group. If the oxyethylene group is less than 60% by weight, the thermal sensitivity becomes poor. OR, OR ', OR "blocks two or more oxyalkylene groups. Or a random connection. (OR) a, (OR ') b, and (OR ") d may be the same kind, or different kinds of combinations may be used.

A, b, d in the general formula (1) of the present invention represent a repeating unit of OR, OR ', OR ", each is an integer of 1 to 500, preferably 2 to 400, still more preferably 2 to 300 If it is less than 1 and exceeds 500, the thickening property is lowered.

C in Formula 1 of the present invention is

The repeating unit is displayed and is an integer of 1 or more.

The cloud point of the 0.5 wt% aqueous solution of the thickener composition in the general formula (1) of the present invention is 60 to 120 ℃, preferably 65 to 110 ℃, even more preferably 70 to 100 ℃. If the cloud point is less than 60 ° C, the thermosensitivity becomes large, and if it exceeds 120 ° C, the thickness decreases. The cloud point is a numerical value measured by the following measuring method.

What dissolved the thickener composition in ion-exchange water so that it may become 0.5 weight% is used as a measurement sample. Store the sample in a capillary tube with an internal diameter of 1 mm and a depth of 60 mm, attach it to the thermostat of the alcohol thermometer, place it in an oil bath, gradually heat it, and store the temperature when the sample begins to cloud. It is done.

In the general formula (1) of the present invention, the weight average molecular weight of the thickener composition is 1 to 80,000, preferably 1.5 to 70,000, even more preferably 2 to 60,000. If the weight average molecular weight is less than 10,000 and more than 80,000, the thickening property is lowered.                     

In the present invention, the weight average molecular weight of the thickener can be measured using gel permeation chromatography (G.P.C.) as a reference material based on molecular weight known polystyrene. For example, it can measure on condition of the following using gel permeation chromatography (G.P.C) of the type HLC-8120 GPC made from Tosoh Corporation. The column uses a plasticizer, two types Super H-4000 × and one type Super H-3000 × 1, the column temperature is 40 ° C, the detector is a differential refractometer (RI detector), and the THF (reagent 1 class, Kadayama) as eluent. Kagaku Kogyo Co., Ltd., the flow rate is 0.5 ml / min, the sample concentration is 1%, the sample solution injection amount is 10 µl, and the data processor is manufactured by Tosoh Corporation, type SC-8020, molecular weight known polystyrene. As manufactured by Tosoh Corporation, TSK standard polystyrene is used.

As a method of synthesize | combining the thickener of this invention, it can synthesize | combine using a well-known urethanation reaction. For example, polyether monool, polyetherdiol, and diisocyanate can be reacted for 2 to 10 hours to synthesize. For example, when synthesize | combining from polyethermonol, polyetherdiol, and diisocyanate, the synthesis method by batch injection may also be sufficient, Moreover, after making polyetherdiol and diisocyanate react, it is made to react with polyethermonol and synthesize | combining Or a method of synthesizing by reacting polyethermonol and diisocyanate and then reacting with polyetherdiol. Some by-products may be generated by the reaction, but the main product is a compound of Formula 1, and may be used in a mixture with the by-products.

Reaction temperature is 40-130 degreeC, Preferably it is 70-100 degreeC. Below 40 ° C, there is a drawback that the reaction is slow and takes too long, and at temperatures higher than 130 ° C, strange side reactions occur, which is undesirable.

In these reactions, the solvent used as needed requires no active hydrogen, for example, an aromatic solvent such as toluene, xylene, aliphatic solvents, such as petroleum ether, n-hexane, alicyclic solvents, etc. As a halogen-containing solvent, such as cyclohexane, cyclohexanone, decalin, etc., chloroform, carbon tetrachloride, ethylene dichloride, chlorobenzene, etc. As an ester solvent, ethyl acetate, butyl acetate, a pentyl acetate, methyl ethyl ketone , Diethyl ketone, methyl isobutyl ketone and the like.

Moreover, as a catalyst used for a urethanation reaction as needed, it is a metal, such as triethylamine, triethylenediamine, heptamethyldiethylene triamine, N-methylmorpholine, benzyl triethylammonium hydrooxide, for example as an amine compound. Examples of the compound include stannous chloride, stannous chloride, tin octylate, lead octylate, dibutyl tin dilaurate, cobalt naphthenate, lead naphthenate, potassium naphthenate, and antimony trichloride. The amount of catalyst added is 0.001 to 1% by weight based on the total weight of charge. The addition method is usually added at the beginning of the reaction, but may be added separately during the reaction.

Next, the water-based emulsion and water-based emulsion paint which mix | blend the low temperature thickening agent of this invention are demonstrated.

The aqueous emulsion of this invention mix | blends 0.01-10 weight% of hypothermic thickener with respect to an aqueous emulsion, Preferably 0.05-5 weight% is mix | blended. If the blended amount is less than 0.01% by weight, no thickening effect is expressed, and if the amount exceeds 10% by weight, the amount is excessively thickened.                     

The aqueous emulsion paint of the present invention is a blend of 0.01 to 10% by weight of the low temperature thickener with respect to the aqueous emulsion paint, preferably 0.05 to 5% by weight. If the blending amount is less than 0.01% by weight, no thickening effect is expressed, and if the amount exceeds 10% by weight, the thickening effect is excessively increased.

As a method for adding the low temperature thickener of the present invention, the additive may be added directly to an aqueous emulsion and an aqueous emulsion paint, or may be added after diluting the thickener with water or a solvent so as to have a suitable viscosity before addition. For example, the emulsion paint may be added to the grinding stage (kneading step) or may be added to the let down stage (adjusting step).

Examples of the aqueous emulsion which can use the low temperature thickener of the present invention include acrylic resins, emulsions, vinyl acetate resin emulsions, vinyl chloride resin emulsions, acrylic styrene resin emulsions, silicone resin emulsions, urethane resin emulsions, epoxy resin emulsions, and fluororesins. Resin emulsion, SB latex, SBR latex, ABS latex, NBR latex, CR latex and the like.

The aqueous emulsion paint which can use the low temperature thickener of this invention consists of an aqueous emulsion, a pigment, water, and an additive normally. Examples of the aqueous emulsion include acrylic resin emulsions, vinyl acetate resin emulsions, vinyl chloride resin emulsions, acrylic resin emulsions, silicon resin emulsions, urethane resin emulsions, epoxy resin emulsions, and fluorine resin emulsions. Examples of the pigment include inorganic pigments such as potassium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica and ferrite, and organic pigments such as polystyrene plastic pigments. As a manufacturing method of an aqueous emulsion paint, a pigment is disperse | distributed (grinding stage) using a ball mill, a sand grind mill, etc., and then it mixes and manufactures a resin emulsion (let down stage).

Aqueous resin compositions other than the resin emulsions and resin emulsion paints in which the thickener of the present invention is useful include water-based coating compositions, cleaning agents, adhesives, waxes, abrasives, cosmetics, toiletries, pharmaceuticals, pesticides, etc. for the paper, leather, and textile industries. have.

Hereinafter, although an Example demonstrates this invention again, this invention is not limited to this. As used herein in parts or percent means parts by weight or weight percent.

(Manufacture example A of the thickener of this invention)

A polyethermonol obtained by adding 500 parts of polyethylene glycol 10000 (molecular weight 10000) and 20 moles of ethylene oxide to n-lauryl alcohol in a 1000-mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 17.4 parts of tolylene diisocyanate were added, and it reacted at 80-85 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example B of the thickener of this invention)

360 parts of polyethylene glycol 6000 (molecular weight 6000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and a polyether monool obtained by adding 50 mol of ethylene oxide to n-lauryl alcohol was 285. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 22.6 parts of xylidene diisocyanate was added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example C of the thickener of this invention)

A polyethermonol obtained by adding 600 parts of polyethylene glycol 6000 (molecular weight 6000) and 5 moles of ethylene oxide to n-tridecyl alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction pipe and a high viscosity stirrer 28 The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 22.4 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example D of the thickener of this invention)

420 parts of polyethylene glycol 6000 (molecular weight 6000) and 145 parts of polyether monool having 20 moles of ethylene oxide added to n-decyl alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 24.4 parts of tolylene diisocyanate were added, and it reacted at 80-85 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.                     

(Manufacture example E of the thickener of this invention)

400 parts of polyethylene glycol 20000 (molecular weight 20000) and 100 parts of polyethermonol with 100 moles of ethylene oxide added to n-octyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 7 parts of tolylene diisocyanate was added, and it reacted at 80-85 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example F of the thickener of this invention)

450 parts, n-tree, of polyetherdiol having a molecular weight of 6000 with random copolymerization of ethylene oxide and propylene oxide in a ratio of 82:18 by weight in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 150 parts of polyether monool which added 20 mol of ethylene oxides to decyl alcohol was put, and it dehydrated at 80-90 degreeC for 3 hours under low pressure (5-10 mmHg), and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 19.6 parts of tetramethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example G of the thickener of this invention)

339 polyethermonol with 300 parts of polyethylene glycol 6000 (molecular weight 600) and 150 moles of ethylene oxide added to n-lauryl alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at low pressure (5-10 mmHg) at 80-90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 12.6 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example H of the thickener of this invention)

360 parts of polyethylene glycol 6000 (molecular weight 6000) in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, 50 moles of ethylene oxide and 20 moles of propylene oxide in n-tridecyl alcohol 142 parts of copolymerized polyether monool was put, and it dehydrated at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 13.4 parts of hexamethylene diisocyanate were added, and it reacted at 90-95 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid phase was obtained.

(Manufacture example I of the thickener of this invention)

30 parts of polyethylene glycol 1000 (molecular weight 1000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube, and a high viscosity stirrer, and a polyether monool obtained by adding 250 moles of ethylene oxide to n-tridecyl alcohol. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 10.1 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.                     

(Manufacture example J of the thickener of this invention)

600 parts of polyethylene glycol 6000 (molecular weight 6000) was added to a four-necked flask of 1000 ml with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and 60.6 polyether monool having 5 moles of ethylene oxide added to n-lauryl alcohol. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 28.8 parts of hydrogenated xylidene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example K of the thickener of this invention)

A polyethermonol obtained by adding 500 parts of polyethylene glycol 10000 (molecular weight 10000) and 10 moles of ethylene oxide to n-tridecyl alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, the hydrogenated xylidene diisocyanate was added 14.4 parts, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example L of the thickener of this invention)

A polyethermonol with 300 parts of polyethylene glycol 6000 (molecular weight 6000) and 50 moles of ethylene oxide added to hexylene glycol monooctyl ether was added to a four-necked flask with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 122 parts were put, dehydration was carried out at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 12.6 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example M of the thickener of this invention)

600 parts of polyethylene glycol 6000 (molecular weight 6000) and ethylene ethylene oxide were added to 2,2-di-t-butoxycyclohexanol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 46 parts of mole-added polyether monools were put, it dehydrated at 80-90 degreeC for 3 hours under low pressure (5-10 mmHg), and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 23.2 parts of tolylene diisocyanate were added, and it reacted at 80-85 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example N of the thickener of this invention)

Polyethermono obtained by adding 420 parts of polyethylene glycol 6000 (molecular weight 6000) and 20 mol of ethylene oxide to 2- (dibutylamino) ethanol in a four-necked flask of 1000 ml with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 147 parts of balls were put and dehydrated at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 24.4 parts of tolylene diisocyanate were added, and it reacted at 70-80 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of light yellow viscous liquid was obtained.                     

(Manufacture example O of the thickener of this invention)

360 parts of polyethylene glycol 6000 (molecular weight 6000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and 50 mol of ethylene oxide was added to 6- (dibutylamino) hexanol. 145 parts of polyether monools were put, dehydration was carried out at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, the mixture was cooled to 70 DEG C and 15.1 parts of hexamethylene diisocyanate was added, followed by reacting at 70 to 80 DEG C under nitrogen stream until the isocyanate content became 0% (2 hours), to obtain a pale yellow viscous liquid reaction product.

(Manufacture example P of the thickener of this invention)

300 parts of polyethylene glycol 6000 (molecular weight 6000) and 142 parts of polyether monool having 30 moles of ethylene oxide added to n-hexyl alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 17.4 parts of tolylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example Q of the thickener of this invention)

300 parts, n-tree, of polyetherdiol having a molecular weight of 6000 with random copolymerization of ethylene oxide and butylene oxide in a ratio of 88:12 by weight in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 108 parts of polyether monool which added 20 mol of ethylene oxides to decyl alcohol was dehydrated, and it dehydrated at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 14 parts of tetramethylene diisocyanate were added, and it reacted at 90-95 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example R of the thickener of this invention)

400 parts of polyethylene glycol 4000 (molecular weight 4000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high viscosity stirrer, and a polyether monool obtained by adding 20 moles of ethylene oxide to n-lauryl alcohol was 210. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 37.6 parts of xylidene diisocyanate were added, and it reacted at 90-95 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example S of the thickener of this invention)

520 parts of polyethylene glycol 13000 (molecular weight 13000) and 20 mol of ethylene oxide in 2,2-di-t-butoxycyclohexanol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer 30 parts of added polyether monool was put, dehydration was carried out at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 7.5 parts of tetramethylene diisocyanate were added, and it reacted at 90-95 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example T of the thickener of this invention)                     

25 parts of polyethylene glycol 2000 (molecular weight 2000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high viscosity stirrer, and 500 parts of polyether monool having 450 moles of ethylene oxide added to n-trialcohol. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 4.7 parts of xylidene diisocyanate were added, and it reacted at 90-95 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture Example A of Comparative Product)

600 parts of polyethylene glycol 6000 (molecular weight 6000) and 5 moles of ethylene oxide were added to n-octyl decyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 34.8 parts of tolylene diisocyanate were added, and it reacted at 80-85 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example B of a comparative product)

12 parts of polyethermonol with 400 parts of polyethylene glycol 20000 (molecular weight 20000) and 10 moles of ethylene oxide added to n-decyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 5 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Manufacture example C of a comparative product)

300 parts of polyethylene glycol 2000 (molecular weight 2000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and 298 parts of a polyethermonol obtained by adding 20 moles of ethylene oxide to n-octyl alcohol. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 50.4 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example D of a comparative product)

A polyethermonool containing 400 parts of polyethylene glycol 4000 (molecular weight 4000) and 10 moles of ethylene oxide added to a secondary alcoholol having 14 carbon atoms in a four-necked flask with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 130 parts was put, it dehydrated at 80-90 degreeC for 3 hours under low pressure (5-10 mmHg), and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 37.6 parts of xylidene diisocyanate was added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

(Production Example E of Comparative Product)

420 parts of polyethylene glycol 6000 (molecular weight 6000) and 148 parts of polyether monool having 20 moles of ethylene oxide added to hexylphenol were placed in a four-necked flask of 1000 ml with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), it dehydrated at 80-90 degreeC for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 23.5 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example F of a comparative product)

610 parts, n-tree of 9000 polyetherdiol having a molecular weight of 9000 which was randomly copolymerized with ethylene oxide and propylene oxide in a ratio of 60:40 by weight in a 1000-mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 90 parts of polyether monool which added 10 mol of ethylene oxides to decyl alcohol was put, it dehydrated at 80-90 degreeC for 3 hours under low pressure (5-10 mmHg), and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 23.5 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example G of a comparative product)

480 parts of polyethylene glycol 6000 (molecular weight 6000) were added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and polyether monool obtained by adding 5 mol of ethylene oxide to n-tetradecyl alcohol was added. The mixture was dehydrated at low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, the mixture was cooled to 70 DEG C, 40 parts of 4,4-diphenylmethane diisocyanate was added, and reacted at 80 to 85 DEG C under nitrogen stream until the isocyanate content became 0% (2 hours). The product was obtained.

(Manufacture Example H of Comparative Product)

480 parts of polyethylene glycol 6000 (molecular weight 6000) and 150 parts of polyethermonol with 20 moles of ethylene oxide added to propyl alcohol were placed in a four-necked flask with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), it dehydrated at 80-90 degreeC for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, and 26.9 parts of hexamethylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of light yellow viscous liquid was obtained.

(Manufacture example I of a comparative product)

80 parts of polyethylene glycol 4000 (molecular weight 4000) was added to a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, and 530 parts of a polyether monool having 600 moles of ethylene oxide added to n-hexanol. The mixture was dehydrated at 80 to 90 ° C. under low pressure (5 to 10 mmHg) for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC and 5.2 parts of tolylene diisocyanate were added, and it reacted at 85-90 degreeC under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product of the pale yellow viscous liquid phase was obtained.

Table 1 shows the weight average molecular weights and cloud points of the thickeners obtained in Production Examples A to O of the thickener of the present invention and Production Examples A to H of the comparative product.                     

(Examples A-T, Comparative Examples A-I)

40 parts of thickeners obtained in Production Examples A to T of the thickener of the present invention and Production Examples A to I of the comparative product, 20 parts of butyltriglycol ether and 40 parts of water were uniformly blended, and Examples A to T and Comparative Examples A to I were prepared. Got it.                     

The performance of Examples A-T and Comparative Examples A-T was evaluated by the following method. The results are shown in Tables 2, 3, and 4.

Evaluation Example 1 : Evaluation of Thickening and Temperature Sensitivity in Resin Emulsion

An aqueous emulsion having a solid content of 43% was prepared by blending 100 parts by weight of an acrylic emulsion [commercially available product: concentration 49%], 0.1 part by weight of an antifoaming agent [manufactured by Henkel KGaA, Dehydran 1620] and 0.5 part by weight of a thickener. After mixing for 5 minutes at 3000 rpm in a tabletop homogenizer by the above combination, it was allowed to stand for 12 hours. Thereafter, the blend was temperature-controlled to a predetermined temperature (2,25,40 ° C), and then the viscosity (BM type viscometer manufactured by Tokyo Instruments Co., Ltd.) at 60 rpm was measured.

Thickening property: The thicker the viscosity, the higher the viscosity is, compared to the case where no thickener is added at 25 ° C.

Temperature Sensitivity: The smaller the ratio of the viscosity of 2 ° C to the viscosity of 40 ° C, the smaller the temperature sensitivity.                     

Evaluation Example 2 : Evaluation of Thickening and Temperature Sensitivity in Water-Based Emulsion Paints

350 parts by weight of titanium dioxide [manufactured by Teika Co., Ltd., JR-600A], 100 parts by weight of calcium carbonate [manufactured by Sankyo Milling Co., Ltd., Escaron # 2000], a dispersant [manufactured by Sannobugo Co., Ltd. 44-C] 4 parts by weight, antifoaming agent [Renkel KGaA, Dehydran 1620] 3 parts by weight, antiseptic [Sanbugo Co., Ltd., Nobugoside SN-215) 2.4 parts by weight, water 100 parts by weight, for glaze paint A resin emulsion paint of the formulation consisting of 605 parts by weight of an emulsion (acrylic), 30 parts by weight of propylene glycol, 15 parts by weight of a film forming aid [Eastman Chemical Company, Dexanol] and 15 parts by weight of a thickener was prepared. Then, after adjusting the creation paint to predetermined temperature (2,25,40 degreeC), the viscosity (BM type viscometer by Tokyo Instruments Co., Ltd.) at 60 rpm was measured.

Thickening property: The thicker the viscosity, the higher the viscosity is, compared to the case where no thickener is added at 25 ° C.

Temperature Sensitivity: The smaller the ratio of the viscosity of 2 ° C to the viscosity of 40 ° C, the smaller the temperature sensitivity.                     

Evaluation Example 3 : Coloration and Gloss Evaluation in Resin Emulsion Paint

<Color tone test> 100 parts by weight of paint used in Evaluation Example 2, antifoaming agent [Henkel KGaA Co., Ltd., Dehydran 1620] 0.2 parts by weight, ocher 2.3 parts by weight, red rust 0.2 parts by weight, black pigment 0.5 parts by weight The mixture was stirred and homogenized at 2000 rpm for 10 minutes as a tabletop homogenizer. This paint is applied to the slate plate with a roller, and A, a touch-up test (after the coating film has been dried once, is partially finished with a brush) B, a rubbing test (rubbing the film surface with a finger) C, spotting The test was carried out (a small amount of paint was dropped on a separate portion of the coating film, and the slate plate was inclined so that the paint was squeezed). After drying, the difference in color with the coating film surface of one coat was observed.

<Gloss Test> The coating material used in Evaluation Example 2 was coated on an glass plate degreased with an applicator (film thickness of 0.152 mm), dried at room temperature for one day, and then measured by a gloss meter to measure 60 degree mirror gloss.                     

The effect of this invention is providing the novel thickener which is excellent in temperature sensitivity, does not deteriorate color tone, and does not reduce glossiness, and the water-based emulsion and water-based emulsion paint which mix this thickener. The resin emulsion paints obtained by blending the thickeners of the present invention have a low temperature dependence of the paint viscosity, have excellent coating workability throughout the year, have a low flow of paints in the summer, and troubles such as dilution of the paints in the winter. It also has the feature of no degree.

Claims (4)

A low temperature thickener comprising at least one of the compounds represented by the formula (1), wherein the cloud point of the 0.5% by weight aqueous solution is 60 to 120 ° C and the weight average molecular weight is 1 to 80,000. (Formula 1)

[Wherein X, Z is an organic group having 4 to 14 carbon atoms containing oxygen or nitrogen or a straight chain hydrocarbon group having 4 to 14 carbon atoms, Y is a divalent organic residue derived from a diisocyanate compound, and OR, OR ' , OR "is a C2-C4 oxyalkylene group, a, b, d is an integer of 1-500, c is an integer of 1 or more.] The low temperature thickener according to claim 1, wherein X and Z in the general formula (1) are linear hydrocarbon groups having 4 to 14 carbon atoms, and Y is a divalent organic residue derived from a diisocyanate compound having 4 to 10 carbon atoms. A water-based emulsion comprising 0.01 to 10% by weight of the low temperature thickener according to claim 1 or 2. 0.01-10 weight% of the low temperature thickener of Claim 1 or 2 is mix | blended, The aqueous emulsion coating material characterized by the above-mentioned.