KR20010088311A - Thickener composition - Google Patents

Abstract

PURPOSE: To provide a novel tackifier showing a great increase in viscosity at a low addition, and an aqueous emulsion compounded with the tackifier composition, and an aqueous emulsion paint. CONSTITUTION: This tackifier composition contains at least one compound represented by general formula (1), wherein one with c=1 is not less than 35 mass %, one with c=2 is not more than 40 mass %, one with c=3 is not more than 20 mass %, and one with c >= 4 is not more than 15 mass %, and has a weight average molecular weight of 10,000-40,000. (in the formula, X and Z are each a functional group selected from the group consisting of a 6-36C alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, alkylaryl group, arylalkyl group, and arylalkylaryl group, Y is a divalent organic residue derived from an isocyanate compound, OR, OR', and OR" are each a 2-4C oxyalkylene group, a, b, and d are each an integer of 1-500, and c is an integer of 1 or larger).

Description

Thickener Composition {THICKENER COMPOSITION}

The present invention relates to thickeners and, more particularly, to thickeners useful for water-based emulsions, water-based emulsion paints and the like.

As a conventional thickener, natural products, semisynthetic products (hydroxyethyl cellulose, etc.), synthetic products, and many substances are known. 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 coatings, natural products, semi-synthetic products, and polyacrylic acids have poor leveling properties, and polyoxyalkylene glycol derivatives are used to provide leveling properties. As a polyoxyalkylene glycol derivative, many things, such as a urethane modified polyoxyalkylene glycol, ester modified polyoxyalkylene glycol, an epoxy modified polyoxyalkylene glycol, are known. (Special place 52-25840, special publication 1-55292, special place 58-213074, special place 58-164671)

Conventional polyoxyalkylene glycol derivatives have a small thickening force, require a large amount of addition in order to obtain a target thickening property, and cost performance is inferior.

An object of the present invention is to provide a water-based emulsion and an aqueous emulsion paint in which a thickening composition exhibiting a high thickening property with a low addition amount and a corresponding thickening composition are blended.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the compound with a specific requirement met the objective, and reached | attained this invention. That is, the thickening composition of the present invention contains at least one kind of the compound represented by the general formula (1), wherein c is 1 or more and 35 mass% or more, c is 2 or less and 40 mass% or less, c It is characterized by containing 20 mass% or less of thing of 3, 15 mass% or less of thing of c is 4 or more, and a weight average molecular weight is 10,000-40,000.

[Wherein X and Z are functional groups selected from the group consisting of an alkyl group having 6 to 36 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an allyl group, an alkylallyl group, an allylalkyl group and an allylalkylallyl group, and Y is di Is a divalent organic residue derived from an isocyanate compound, OR, OR ', OR "are oxyalkylene groups having 2 to 4 carbon atoms, a, b and d are integers of 1 to 500, and c is an integer of 1 or more.]

Moreover, this invention is an aqueous emulsion which mix | blended 0.01-10 mass% of said thickening composition.

Moreover, this invention is an aqueous emulsion paint which mix | blended 0.01-10 mass% of said thickening composition.

X and Z in the general formula (1) of the present invention are selected from the group consisting of an alkyl group having 6 to 36 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an allyl group, an alkylallyl group, an allylalkyl group, and an allylalkylallyl group It is a hydrophobic functional group.

Examples of the alkyl group having 6 to 36 carbon atoms include hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, donyl group, decyl group, undecyl group, lauryl group, tridecyl group and isotridecyl group , Myristyl group, palmityl group, octadecyl group, isostearyl group and the like.

As a C6-C36 cycloalkyl group, a cyclohexyl group, a cycloheptyl group, a methyl cyclopentyl group, a methyl cyclohexyl group, a methyl cycloheptyl group, etc. are mentioned, for example.

Examples of the alkenyl group having 6 to 36 carbon atoms include hexenyl, hexadienyl, hepdenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, and oleyl. Can be.

Examples of the cycloalkenyl group having 6 to 36 carbon atoms include 2,4-cyclohexadienyl group, cyclohexenyl group, cyclohepdenyl group, methylcyclopentenyl group, methylcyclohexenyl group, and methylcyclo. Heptenyl group etc. are mentioned.

As a C6-C36 allyl group, a phenyl group, ( alpha )-naphthyl group, ( beta ) -naphthyl group, anthryl group, a pyrenyl group, etc. are mentioned, for example.

Examples of the alkyl allyl group having 6 to 36 carbon atoms include toluyl group, cysylyl group, gumenyl group, mesityl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentyltenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, Decylphenyl group, undecylphenyl group, dodecylphenyl group, tridecylphenyl group, etc. are mentioned.

As a C6-C36 allylalkyl group, a benzyl group, a benzhydryl group, etc. are mentioned, for example.

As a C6-C36 allyl alkyl allyl group, a stylene phenyl group, a benzyl phenyl group, etc. are mentioned, for example.

Preferred among these are 8 to 26 hydrophobic functional groups, and more preferably 12 to 24 carbon atoms are hydrophobic functional groups. If the carbon number is less than 6, the thickening effect is small, and if the carbon number is more than 36, the raw material is expensive and is poor in cost performance. X and Z may be the same or may be a combination of different kinds.

Y in General formula (1) of this invention is a divalent organic residue derived from the diisocyanate compound, and it does not specifically limit as a diisocyanate compound. As a diisocyanate compound, an aliphatic diisocyanate compound, an aromatic diisocyanate compound, an alicyclic diisocyanate compound, etc. are mentioned, for example.

As the aliphatic diisocyanate compound, for example, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonnamethylene di Isocyanate, decamethylene diisocyanate, dipropyl ether diisocyanate, 2, 2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, 2, 2, 4-trimethylpentane diisocyanate, 3-butoxyhexane diisocyanate, 1 , 4-butylene glycol dipropyl ether diisocyanate, metha xylene diisocyanate, para xylene diisocyanate tetramethyl xylene diisocyanate, etc. are mentioned.

As an aromatic diisocyanate compound, for example, metaphenylene diisocyanate, paraphenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, Biphenyl diisocyanate, tridine diisocyanate, 3, 3'- dimethoxy biphenyl diisocyanate, naphthalene diisocyanate, 4, 4- diphenylmethane diisocyanate, 2, 2'- dimethyl diphenylmethane-4, 4'- Diisocyanate, 3, 3'-dimethoxydiphenylmethane 4, 4'-diisocyanate, 4, 4'-dimethoxydiphenylmethane-3, 3'-diisocyanate, 4-4'diethoxydiphenylmethane- 3, 3'- diisocyanate, 2, 2'- dimethyl-5, 5'- dimethoxy diphenylmethane-4, 4'- diisocyanate, etc. are mentioned.

Examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane-4, and 4'-diisocyanate.

OR, OR ', OR "in General formula (1) of this invention are C2-C4 oxyalkyrene groups, and when carbon number exceeds 2 and 4, thickening will fall. As a C2-C4 oxyalkylene group, Oxyethylene group, oxypropylene group, oxybutylene group, etc. Among these, an oxyethylene group is essential.The ratio of an oxyethylene group is preferably 60 weight% or more of all the oxyalkylene groups, More preferably, all oxy 80 wt% or more of the alkylene group, particularly preferably 90 wt% or more of the total oxyalkylene group. The viscosity decreases when the oxyethylene group is less than 60 wt%. OR, OR ', and OR' 'are two or more kinds of oxy Alkylene groups may be linked in blocks or randomly. (OR) a, (OR ') b, and (OR ") d may be homogeneous or a combination of heterogeneous.

A, b, d in General formula (1) of this invention represent the repeating unit of OR, OR ', OR ", respectively, It is an integer of 1-500, Preferably it is 2-400, More preferably, it is 2- 300. If it is less than 1 and out of 500, the viscosity decreases.

C in General formula (1) of this invention is

It represents an internal repeating unit and is an integer of 1 or more.

As the constitution of c, 35 mass% or more containing c is 1, 40 mass% or less containing c is 2, 20 mass% or less containing c is 3, and 15 mass% or less containing c is 4 or more. do. Preferably it contains 40 mass% or more that c is 1, contains 35 mass% or less for c is 2, 15 mass% or less for c is 3, and contains 10 mass% or less for c is 4 or more. . More preferably, 45 mass% or more of c is 1, 35 mass% or less of c is 2, 15 mass% or less of c is 3, and 10 mass% or less of c is 4 or more do. When it contains less than 35 mass% that c is 1, thickening property falls, and when c contains 4 or more than 15 mass%, thickening property falls.

In General formula (1) of this invention, the weight average molecular weights of a thickening composition are 10,000-40,000, Preferably it is 15,000-35,000, More preferably, it is 20,000-30,000. If the weight average molecular weight is less than 10,000 and more than 40,000, the thickening property is lowered.

The weight average molecular weight and the weight average molecular weight distribution (distribution of c) of the thickening composition in this invention can be measured using gel permeation chromatography (G.P.C.) as a reference material using molecular weight known polystyrene. For example, it can measure on the following conditions using the gel permeation chromatography (G.P.C) of Tosoh Corporation make, model HLC-8120GPC. As a column, a plasticizer, type SuperH-4000x2 and type SuperH-3000x1 are used.The column temperature is 40 ° C, the detector uses a differential refractometer (RI detector), and the THF (reagent 1, Kadayama Chemical Co., Ltd.) is used as the eluent. The flow rate is 0.5 ml / min, sample concentration is 1%, reagent solution injection amount is 10 µl, and the data processor is manufactured by Tosoh Corporation as a standard material of polystyrene of Tosoh Corporation, Model SC-8020, molecular weight base. TSK standard polystyrene is used.

As a method for synthesizing the thickening composition of the present invention, a well-known urene carbonization reaction may be used. For example, polyether monool, polyether diol, and diisocyanate are reacted for 2 to 10 hours to be synthesized. For example, when synthesize | combining from polyethermonol, polyetherdiol, and diisocyanate, the synthetic | combination method of batch injection may also be sufficient, and also the method of synthesize | combining by making polyetherdiol and diisocyanate react, and then reacting with polyethermonol, or polyether The reaction may be carried out by reacting monool with diisocyanate and then reacting with polyetherdiol. Although some by-products may arise by reaction, the main product is a compound of General formula (1), and can be used in mixture with a by-product.

Reaction temperature is 40-130 degreeC, Preferably it is 70-100 degreeC. If the temperature is lower than 40 ° C, the reaction is delayed and takes a long time, and abnormal side reactions occur at temperatures higher than 130 ° C, which is not preferable.

In these reactions, the solvent used as needed does not contain active hydrogen, for example, toluene, xylene, etc., for an aromatic solvent, petroleum ether, n-hexane, etc., for an aliphatic solvent, etc., seek as an alicyclic solvent. Examples of ester solvents such as chloroform, carbon tetrachloride, ethylene dichloride, and chlorobenzene include halogenated solvents such as hexane, cyclohexanone, and decalin, and ethyl acetate, butyl acetate, pentyl acetate, methyl ethyl ketone and di Ethyl ketone, methyl isobutyl tetone, etc. are mentioned.

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 hydroxide, for example as an amine compound. Examples of the containing heap include tin chloride, tin chloride, tin octylate, lead octylate, dibutyl tin dilaurate, cobalt naphthenate, lead naphthenate, potassium naphthenate, and antimony trichloride. Catalyst addition amount is 0.001-1 mass% with respect to the total mass injected. The addition method is added at the beginning of the total reaction, but may be added separately during the reaction.

Next, an aqueous emulsion and an aqueous emulsion paint containing the thickening composition of the present invention will be described.

The aqueous emulsion of this invention mix | blends 0.01-10 mass% of thickening compositions with respect to an aqueous emulsion, Preferably it mix | blends 0.05-5 mass%. If the blending amount is less than 0.01% by mass, the thickening effect is not expressed. If the blending amount exceeds 10% by mass, the thickening becomes excessive.

The aqueous emulsion paint of the present invention is a blend of 0.01 to 10% by mass of the thickening composition with respect to the aqueous emulsion paint, preferably 0.05 to 5% by mass. If the blending amount is less than 0.01% by mass, the thickening effect is not expressed. If the blending amount exceeds 10% by mass, the thickening becomes excessive.

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

The aqueous emulsion furnace which can use the thickening composition of this invention is an acrylic resin emulsion, a vinyl acetate resin emulsion, a vinyl chloride resin emulsion, an acryl styrene resin emulsion, a silicone resin emulsion, a urethane resin emulsion, an epoxy resin emulsion, a fluororesin emulsion , SB latex, SBR latex, ABS latex, NBR latex and CR latex.

An aqueous emulsion paint that can use the thickening composition of the present invention is usually composed of an aqueous emulsion, a pigment, water, and an additive. As the aqueous emulsion, acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic styrene resin emulsion, silicone resin emulsion, urethane resin emulsion, epoxy resin emulsion, fluororesin emulsion, SB latex, SBR latex, ABS latex, NBR latex, CR latex and so on.

Examples of the pigment include inorganic pigments such as calcium carbonate, titanium oxide, satin white, barium lactate, talc, zinc oxide, gypsum, silica and ferrite, and organic pigments such as polystyrene-based plastic pigments. As a method of producing an aqueous emulsion paint, a pigment is dispersed (grinding stage) using a ball mill, a sand grinding mill, or the like, followed by blending (latting down stage) an aqueous emulsion.

Aqueous emulsions other than the aqueous emulsions and aqueous emulsion paints in which the thickening composition of the present invention is useful include aqueous coating compositions, cleaning agents, adhesives, waxes, abrasives, cosmetics, toiletries, pharmaceuticals, pesticides, etc. for paper, leather and textile industries. Can be.

(Example)

Although an Example demonstrates this invention again below, this invention is not limited to this. In the content, "parts" or "%" means parts by mass or% by mass.

(Example A-N)

The thickening composition of Example A-N of this invention was obtained by manufacture example A-N.

(Manufacture example A)

300 parts of polyethylene glycol 6000 (molecular weight 6000) and 494 parts of polyether monool having 50 moles of ethylene oxide were added to an octadecyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Next, the mixture was cooled to 70 DEG C and 28.2 parts of xylene diisocyanate was added, and reacted at 90 to 95 DEG C under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product in the pale yellow viscous liquid phase (Example A) Got.

(Manufacture example B)

480 parts of polyethylene glycol 6000 (molecular weight 6000) and 249 parts of polyether monool having 5 mole parts of ethylene oxide were added to an isosil alcohol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 and 53.8 parts of hexamethylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours), and the reaction product as a pale yellow viscous liquid (Example B) )

(Manufacture example C)

Into a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a high viscosity stirrer, 240 parts of polyethylene glycol 6000 (molecular weight 6000) and 423 parts of polyether monool having 20 mole parts of ethylene oxide in hexylphenol were added. The resultant was dehydrated at 80 to 90 ° C. for 3 hours at 5-10 mmHg, and the water content of the system was 0.03%. Subsequently, the mixture was cooled to 70 DEG C, and 40.3 parts of hexamethylene diisocyanate was added thereto, followed by reaction at 85 to 90 DEG C under nitrogen stream until the isocyanate content became 0% (3 hours), and the reaction product as a pale yellow viscous liquid (Example C) Got.

(Manufacture example D)

300 parts of polyethylene glycol 20000 (molecular weight 20000) and 355 parts of polyether monool having 5 mole parts of ethylene oxide were added to a styrene sulfonate in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 ° C., and 28.7 parts of triylene diisocyanate was added. The reaction product was reacted at 80 to 85 ° C. under nitrogen stream until the isocyanate content became 0% (2 hours), and the reaction product (Example D) in light yellow viscous liquid was obtained. Got it.

(Manufacture example E)

360 parts of pentadecyl alcohol with a molecular weight of 6,000 polyetherdiol obtained by random copolymerization of ethylene oxide and butylene oxide in a weight ratio of 88:12 in a 1000-mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer 372 parts of polyether monool having 30 mol parts of ethylene oxide was added thereto, dehydrated at 80 to 90 ° C. for 3 hours under low pressure (5-10 mmHg), and the water content of the system was 0.03%. Subsequently, the mixture was cooled to 70 DEG C, and 30.2 parts of hexamethylene diisocyanate was added and reacted under nitrogen stream until the content of 85 to 90 DEG C isocyanate became 0% (2 hours) to give a reaction product of the pale yellow viscous liquid (Example E). Got it.

(Manufacture example F)

439 parts of a polyetherdiol having a molecular weight of 7300 obtained by random copolymerization of ethylene oxide and propylene oxide in a ratio of 84:16 by weight in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, 258 parts of polyether monool having 20 mole parts of ethylene oxide was added to anthrol, and dehydrated at 80 to 90 ° C. under low pressure (5-10 mmHg) for 3 hours to make the water content of the system 0.03%. Subsequently, the mixture was cooled to 70 DEG C and 31.3 parts of trienedic isocyanate was added and reacted under nitrogen stream at 80 to 85 DEG C until the isocyanate content became 0% (3 hours), whereby a reaction product of a pale yellow viscous liquid (Example F) was obtained. Got it.

(Manufacture example G)

400 parts of polyethylene glycol 4000 (molecular weight 4000) and 340 parts of polyether monool having 10 mole parts of ethylene oxide were added to octacosyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, the reaction mixture was cooled to 70 DEG C and 42 parts of tetramethylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours). Got.

(Manufacture example H)

6 parts of polyethylene glycol 1000 (molecular weight 1000) and 674 parts of polyether monool having 420 mole parts of ethylene oxide were added to a octadecyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 and 4.2 parts of trienedic isocyanate was added and reacted under nitrogen flow at 80 to 85 DEG C until the isocyanate content became 0% (3 hours). The reaction product as a pale yellow viscous liquid (Example H) was obtained. Got it.

(Manufacture example I)

446 parts of a molecular weight 7400 polyetherdiol obtained by random copolymerization of ethylene oxide and butylene oxide in a weight ratio of 71:29 in a four-necked flask equipped with a thermometer, a nitrogen introduction tube, and a high viscosity stirrer at a weight ratio of 71:29. 217 parts of polyether monool having 10 mole parts of ethylene oxide was added to the aliphatic alcohol, and dehydrated at 80 to 90 ° C. under low pressure (5-10 mmHg) for 3 hours to make the water content of the system 0.03%. Subsequently, the mixture was cooled to 70 DEG C, and 34.6 parts of hydrogenated xylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours). The reaction product in the pale yellow viscous liquid phase (Example I) Got.

(Manufacture example J)

In a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer, 240 parts of polyethylene glycol 6000 (molecular weight 6000) and 50 moles of ethylene oxide were added to hexadecyl alcohol, followed by 15 moles of propylene oxide. 530 parts of polyether monools are put, dehydrated at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of a system is made into 0.03%. Subsequently, the mixture was cooled to 70 DEG C and 20.2 parts of hexamethylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours). Got.

(Manufacture example K)

270 parts of polyethylene glycol 6000 (molecular weight 6000) and 20 mole parts of ethylene oxide were added to styrene sulfonate, followed by 5 mole parts of propylene oxide in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. 384 parts of polyether monools are put, dehydration is carried out at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and the water content of a system is made into 0.03%. Subsequently, the mixture was cooled to 70 DEG C, and 22.2 parts of hexamethylene diisocyanate was added thereto, followed by reacting at 85 to 90 DEG C under nitrogen stream until the isocyanate content became 0% (3 hours). Got.

(Production example L)

480 parts of polyethylene glycol 6000 (molecular weight 6000) and 174 parts of polyether monool having 5 mole parts of ethylene oxide were added to a triphenylphenol in a 1000-neck four-necked flask equipped with a thermometer, a nitrogen introducing pipe and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 and 40.3 parts of hexamethylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours). Got.

(Production example M)

300 parts of polyethylene glycol 10000 (molecular weight 10000) and 505 parts of polyether monool having 30 moles of ethylene oxide were added to a tribenzyl phenol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, it cooled to 70 degreeC, 33.8 parts of xylene diisocyanate was added, and it reacted under nitrogen stream at 90-95 degreeC until the isocyanate content became 0% (3 hours), and the reaction product of a pale yellow viscous liquid (Example M) was obtained. Got it.

(Manufacture example N)

Into a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube, and a high viscosity stirrer, 240 parts of polyethylene glycol 6000 (molecular weight 6000) and 395 parts of polyether monool having 50 moles of ethylene oxide in isostearyl alcohol were added. And dehydration at 80-90 degreeC under low pressure (5-10 mmHg) for 3 hours, and let the water content of a system be 0.03%. Subsequently, the mixture was cooled to 70 DEG C and 20.2 parts of hexamethylene diisocyanate was added and reacted at 90 to 95 DEG C under nitrogen stream until the isocyanate content became 0% (3 hours). Got.

(Comparative Example O-U)

The thickening composition of the comparative example O-U of this invention was obtained by manufacture example O-U.

(Manufacture example O)

540 parts of polyethylene glycol 6000 (molecular weight 6000) and 281 parts of polyether monool having 30 mole parts of ethylene oxide were added to hexadecyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introducing pipe and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 and 31.3 parts of trienedic isocyanate was added and reacted under nitrogen stream at 80 to 85 DEG C until the isocyanate content became 0% (3 hours), whereby the reaction product (Comparative Example O) in light yellow viscous liquid was obtained. Got it.

(Manufacture example P)

480 parts of polyethylene glycol 6000 (molecular weight 6000) and 305 parts of polyether monool having 20 mol parts of ethylene oxide in butyl alcohol were put into a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introducing pipe and a high viscosity stirrer. The resultant was dehydrated at 80 to 90 ° C. for 3 hours at 5-10 mmHg, and the water content of the system was 0.03%. 40.3 parts of hexamethylene diisocyanate was then cooled to 70 DEG C, and reacted at 85 to 90 DEG C under nitrogen stream until the isocyanate content became 0% (3 hours), and a reaction product of a pale yellow viscous liquid (Comparative Example P) Got.

(Manufacture example Q)

400 parts of polyethylene glycol 20000 (molecular weight 20000) and 370 parts of polyether monool having 100 mole parts of ethylene oxide were added to a pentadecyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introducing pipe and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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 and 11.3 parts of xylene diisocyanate was added and reacted at 90 to 95 DEG C under nitrogen stream until the isocyanate content became 0% (3 hours) to give the reaction product (Comparative Example Q) in a pale yellow viscous liquid. Got it.

(Manufacture example R)

600 parts of polyethylene glycol 6000 (molecular weight 6000) and 33 parts of polyether monool having 5 moles of ethylene oxide were added to a octadecyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out 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, and 25.6 parts of hydrogenated xylene diisocyanate was added and reacted under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (3 hours) to give a reaction product of light yellow viscous liquid (Comparative Example R). Got.

(Production example S)

400 parts of polyethylene glycol 4000 (molecular weight 4000) and 388 parts of polyether monool having 10 mole parts of ethylene oxide in octyl phenol were placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. The resultant was dehydrated at 80 to 90 ° C. for 3 hours at 5-10 mmHg, and the water content of the system was 0.03%. Subsequently, the mixture was cooled to 70 DEG C and 69.6 parts were added to the mixture, and reacted under nitrogen stream at 80 to 85 DEG C until the isocyanate content became 0% (2 hours). The reaction product (Comparative Example S) in light yellow viscous liquid was obtained. Got it.

(Manufacture example T)

490 parts of molecular weight 7000 polyetherdiol obtained by random copolymerization of ethylene oxide and propylene oxide at a weight ratio of 50:50 in a four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer at a weight ratio of 50:50, and ethylene to pentadecyl alcohol. 178 parts of polyether monool having 10 mole parts of oxide was added thereto, dehydrated at 80 to 90 ° C. 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 35.3 parts of hexamethylene diisocyanate were added, it was made to react 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 (comparative example T) Got.

(Manufacture example U)

12 parts of polyethylene glycol 2000 (molecular weight 2000) and 638 parts of polyether monool having 600 moles of ethylene oxide in lauryl alcohol were placed in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen introduction tube and a high viscosity stirrer. Under low pressure (5-10 mmHg), dehydration was carried out at 80 to 90 ° C. for 3 hours, and the water content of the system was 0.03%. Subsequently, the reaction mixture was cooled to 70 DEG C and 2.5 parts of tetramethylene diisocyanate was added thereto, followed by reaction under nitrogen flow at 85 to 90 DEG C until the isocyanate content became 0% (2 hours). Got.

Table 1 shows the weight average molecular weight and the weight average molecular weight distribution (distribution of c) of Examples A-N and Comparative Examples O-U of the thickener of the present invention.

TABLE 1

Weight average molecular weight and weight partial molecular weight distribution (distribution of c):

Measurements in Gel Permeation Chromatography

The performance of Example A-N and Comparative Example O-U was evaluated by the following method. The results are shown in Table 2.

30 parts of thickeners, 20 parts of butyltriglycol ethers and 50 parts of water of Example A-N and Comparative Example O-U of the present invention were uniformly blended to obtain respective thickener solutions.

Evaluation example: evaluation of thickening in water-based emulsion paint

254 parts of titanium dioxide (manufactured by Seokwon Industrial Co., Ltd., R-630), 10 parts of dispersant (manufactured by Sanofco Co., Ltd., SN-dispersant 5040), 0.5 part of antifoaming agent (Henkel KGaA, dihydrane 1620) , Antifoaming agent (manufactured by Sanofco Co., Ltd., SN Deformer 380) 8 parts, Preservative (Santofco Co., Ltd., Nofcoside SN-215) 1 part, Water 163 parts, Emulsion for single layer elastic paint (Acrylic Styrene system) 531 parts, 10 parts of ethylene glycol, film forming aid (Eastman Chemical Company, Texanol) 22 parts, 9 parts SN SNEKNER 634 (manufactured by Sanofco Co., Ltd.) and 16 parts thickener solution Emulsion paint was prepared. Moreover, the thing which did not mix | blend the thickener solution was made into the blank. Subsequently, after adjusting the temperature to 25 degreeC, the viscosity (B-type viscometer by Tokyo Co., Ltd.) was measured at 20 rpm.

Thickening property: The viscosity is high, so that it is high, compared with the blank in 25 degreeC.

TABLE 2

An effect of the present invention is to provide a water-based emulsion and an aqueous emulsion paint in which a novel thickening composition and a thickening composition exhibiting a high thickening property with a low addition amount. Aqueous emulsion paints containing the thickeners of the present invention have a very high cost performance and industrially useful characteristics because they reach the target paint viscosity with a low additive amount.

Claims (3)

One or more of the compounds represented by the general formula (1) is contained, among them, c is 1, containing 35% by mass or more, c is 2, containing 40% by mass or less, and c is 3, 20% by mass or less It contains 15 mass% or less that c is 4 or more, and a weight average molecular weight is 10,000-40,000, The thickener composition characterized by the above-mentioned. [Wherein X and Z are functional groups selected from the group consisting of an alkyl group having 6 to 36 carbon atoms, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an allyl group, an alkylallyl group, an allylalkyl group and an allylalkylallyl group, and Y is It is a divalent organic residue derived from a diisocyanate compound, OR, OR ', OR "is a C2-C4 oxyalkylene group, a, b, d are integers of 1-500, c is an integer of 1 or more. ] The aqueous emulsion of Claim 1 which mix | blends 0.01-10 mass% of said thickening compositions. The aqueous emulsion coating according to claim 1, wherein the thickening composition is blended with 0.01 to 10% by mass.