KR100799514B1 - Thickening agent for printing paste and composition for printing paste containing thickening agent therefor - Google Patents

Abstract

The present invention relates to a thickener for printing paste containing a urethane-based thickener as an essential component. The present invention also provides a thickening agent for a printing paste having excellent thickening property and viscosity stability over time and a composition for a printing paste containing the printing agent thickening agent.

Urethane thickener, thickener for printing paste

Description

Printing paste composition containing thickener for printing paste and thickener for printing paste {THICKENING AGENT FOR PRINTING PASTE AND COMPOSITION FOR PRINTING PASTE CONTAINING THICKENING AGENT THEREFOR}

The present invention relates to a thickener for printing paste and a composition for printing paste containing the same.

Conventionally, as a printing paste for textile processing, natural starch paste, processed starch paste, synthetic paste (water-soluble polymer), carboxymethyl cellulose (CMC), water-soluble cellulose, emulsion pool, resin emulsion pool, and the like have been used. 2-91282, JP-A-5-263367, etc.).

In addition to the viscosity stability, permeability, and detergency of the paste itself, the printing paste is required for dyeing at the time of dyeing, homogeneity, processing uniformity, paste removal property, fiber processing, sharpness, and sharpness.

As mentioned above, although there are many types of printing paste, they are rarely used alone and are often used in combination.

Among them, emulsion pools are mainly emulsions adjusted as water, tarpen oils, and emulsifiers. In order to obtain good printing results, stability of the emulsion pools is important. The type of emulsion is determined according to the emulsifier, and there is an O / W type or a W / O type, and usually an O / W type. It is difficult to obtain the desired viscosity only by emulsion in practical use, and it is difficult to obtain celluloses such as carboxymethyl cellulose or hydroxyethyl cellulose, natural grass such as starch, seaweed, natural gum, synthetic grass such as polyvinyl alcohol, polyacrylic acid, ester compound Etc. are used together as a thickener and a viscosity regulator.

However, it is a reality that not all are fully satisfied with the above demands, and in particular, thickening and viscosity stability over time have often been insufficient.

Therefore, the object of the present invention is excellent in permeability, cleaning ability, dyeing at the time of dyeing, uniformity, processing uniformity, paste removal property, fiber processing, sharpness, sharpness, especially thickening and viscosity stability over time An excellent printing paste thickener and a composition for printing paste containing the thickener for printing paste are provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor was able to solve the conventional subject as mentioned above.

That is, this invention provides the thickener for printing pastes which contain a urethane type thickener as an essential component.

In addition, the present invention is to provide a thickener for printing paste, characterized in that the urethane-based thickener contains one or two or more of the compounds represented by the following formula (1).                     

(In formula, R <^1> , R <^2> and R <^4> represent the hydrocarbon group which may be mutually different or same, R <^3> represents the hydrocarbon group which has a hydrocarbon group or a urethane bond, R <^5> is a linear, branched or secondary hydrocarbon group. Or a phenyl group having a substituent, m is two or more numbers, h is one or more numbers, and k and n are numbers within the range of 1 to 500).

In addition, the present invention is to provide a thickener for the printing paste, characterized in that the urethane-based thickener contains one or two or more of the compounds represented by the following formula (2).

(In formula, R <^6> , R <^7> and R <^8> represent the hydrocarbon group which may be same or different, x shows the number of 1-2, y shows the number of 1-1000.

In addition, the present invention is to provide a thickener for printing paste, characterized in that the urethane-based thickener contains one or two or more of the compounds represented by the following formula (3).                     

(In formula, R <^9> , R <^10> and R <^11> represents the hydrocarbon group which may be same or different, a shows the number of 2-4, b shows the number of 1-1000.

In addition, the present invention is to provide a thickener for printing paste, characterized in that the urethane-based thickener contains one or two or more of the compounds represented by the following formula (4).

[In formula, R <^19> and R <^20> represents a hydrocarbon group, R <^21> represents a hydrocarbon group or a hydrocarbon group which has a urethane bond, X is group represented by following formula (5) and / or following formula (6), and all X is simultaneously S represents 2 or more numbers, p represents 0 or 1 or more numbers, and r represents 1 or more numbers.]

(Wherein R ²² and R ²³ represent a hydrocarbon group)

(Wherein R ²⁴ and R ²⁵ represent a hydrocarbon group and t represents 0 or 1 or more numbers)

In addition, the present invention is to provide a composition for printing paste comprising the thickener for printing paste.

Best Mode for Carrying Out the Invention

Thickening agent for printing

The thickener for printing paste of this invention contains a urethane type thickener as an essential component. The urethane type thickener used by this invention should just have a urethane bond in the structure, For example, the compound represented by the said General formula (1), 2, 3, 4 is mentioned.

The compound represented by the formula (1) used as the urethane-based thickener is, for example, one or two or more polyether polyol compounds represented by the following general formula (A), one or two or more polyisocyanate compounds represented by the following general formula (B), It is obtained by reacting 1 type (s) or 2 or more types of polyethermonol compounds represented by following General formula (C) by a conventional method.                     

In formula (1), R ¹ , R ² and R ⁴ represent a hydrocarbon group which may be different or identical to each other, R ³ represents a hydrocarbon group having a hydrocarbon group or a urethane bond, and R ⁵ represents a linear, branched or secondary hydrocarbon group. A petyl group which has a group or a substituent is represented, m is two or more numbers, h is one or more numbers, and k and n are numbers in the range of 1-500.

[Formula A]

R^One[-(O-R²)_k-OH]_m                          (A)

(Wherein R ¹ , R ² , m and k represent the same meaning as above)

[Formula B]

R³(-NCO)_{h + 1}                                                   (B)

(Wherein R ³ and h have the same meaning as above)

[Formula C]

HO- (R⁴-O)_n-R⁵                          (C)

(Wherein R ⁴ , R ⁵ and n represent the same meaning as above)

The polyether polyol compound represented by the formula (A), which is preferably used for obtaining the compound represented by the formula (1), is not particularly limited as long as it is a polyether of m-valent alcohol. Such a compound can be obtained by addition polymerization of m-valent polyol represented by R ¹ (-OH) _m with alkylene oxide or styrene oxide.

Especially, as polyol, the alcohol of 2-8 (wherein m is a range of 2-8) is preferable, For example, dihydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentylglycol, etc. ; Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4 -Butanetriol, 2-ethyl-1,2,3, -butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5- Heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane Trihydric alcohols such as trimethylolpropane; Pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol Tetrahydric alcohols such as these; Pentahydric alcohols such as adonite, arabbit and xylite; Hexavalent alcohol, such as dipentaerythritol, sorbet, a mannite, and an diet; And octahydric alcohols such as sucrose.

Further, R ² is determined by alkylene oxide, styrene oxide, etc. to be added, and alkylene oxide, styrene oxide and the like suitable for addition polymerization with the polyol are, for example, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin. Etc. can be mentioned. Among these, alkylene oxides having 2 to 4 carbon atoms (wherein R ² is an alkylene group having 2 to 4 carbon atoms) or styrene oxide are preferred because they exhibit excellent thickening effect and viscosity stability over time.

The addition polymerization reaction of the polyol with alkylene oxide or styrene oxide may be homopolymerization, two or more types of random polymerization or block polymerization. The method of addition polymerization may be a conventional method. Further, the degree of polymerization k is 1 to 500, preferably 1 to 200, and more preferably 10 to 200. Further, if the proportion of the styrene group in R ² is preferably 50 to 100% by weight, more preferably 65 to 100% by weight of the total R ² , excellent thickening and stability of viscosity over time can be obtained. .

In addition, the molecular weight of the polyether polyol compound of the general formula (A) is preferably 500 to 50,000, particularly preferably 1000 to 20,000.

The polyisocyanate compound represented by the formula (B) which can be preferably used to obtain the compound represented by the formula (1) is not particularly limited as long as it has two or more isocyanate groups (wherein h is 1 or more) in a molecule. . For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, tetraisocyanate, etc. are mentioned.

As aliphatic diisocyanate, For example, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2, 2- dimethylpentane diisocyanate, 3-methoxyhexanediisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol di Propyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, para xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned.

As aromatic diisocyanate, for example, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, dimethylene benzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tridine diisocyanate, 1, 4- naphthalene Diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, etc. are mentioned.

As alicyclic diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, etc. are mentioned, for example.

As biphenyl diisocyanate, biphenyl diisocyanate, 3,3'- dimethyl biphenyl diisocyanate, 3,3'- dimethoxy biphenyl diisocyanate, etc. are mentioned, for example.

Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate and diphenyldimethylmethane-4,4'-diisocyanate. , 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, cyclohexylbis (4-isocytriphenyl) methane, 3,3'-dimethoxydiphenylmethane- 4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2 ' -Dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone-3,3'-di Isocyanate etc. are mentioned.

Examples of the triisocyanate include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalenetriisocyanate and biphenyl- 2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, 1,6,11- undecane triisocyanate, 1,8- diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, etc. are mentioned.

Moreover, you may use as a dimer and trimer (isocyanurate bond) of these polyisocyanate compounds, and you may react with an amine and use it as a biuret.

And polyisocyanate compound which has a urethane bond which made these polyisocyanate compound and polyol react can also be used. As a polyol, a bivalent thing is preferable, and the polyol mentioned above is preferable. And when using the polyisocyanate compound more than trivalence (when h is 2 or more) as a polyisocyanate compound of the said Formula B, the polyisocyanate compound which has this urethane bond is preferable.                     

The polyether monoalcohol compound represented by the formula (C) which can be preferably used to obtain the compound represented by the formula (1) is not particularly limited as long as it is a polyether of linear, branched or secondary monohydric alcohol or phenol having a substituent. Do not. Such compounds include phenols having a linear, branched or secondary monohydric alcohol or substituent represented by R ⁵ -OH, and alkylene oxides or styrene oxides or epichlorohexes such as ethylene oxide, propylene oxide and butylene oxide. It can be obtained by addition polymerization of the compound or the like.

Examples of the branched alcohol herein include those represented by the following general formula (7).

Moreover, what is represented by following formula (8) with a secondary alcohol is mentioned.

Examples of the straight alcohol include those represented by the following general formula (9).

R ¹⁷ -OH (9)

Moreover, what is represented by following formula (10) is mentioned with the phenol which has a substituent.

Therefore, R ⁵ of the formula (1) is a group except for the hydroxyl group in the formulas 7, 8, 9 and 10. In Chemical Formulas 7, 8, 9 and 10, R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are hydrocarbon groups, for example, an alkyl group, an alkenyl group, an alkaryl group, a cycloalkyl group, a cycloalkenyl group Etc. can be mentioned.

In said Formula (7), R <^14> is a hydrocarbon group, For example, an alkylene group, an alkenylene group, an alkyl arylene group, a cycloalkylene group, a cycloalkenylene group, etc. are mentioned.

In addition, R ⁵ is preferably an alkyl group, more preferably an alkyl group having 8 to 36 carbon atoms in total, and particularly preferably an alkyl group having 12 to 24 carbon atoms in total.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, isicosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2- Tetradecyloctadecyl, monomethyl branched-isostearyl, and the like.

Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and dodecenyl And tetradecenyl, oleyl and the like.

Examples of the alkylaryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamil, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl and pentylphenyl , Hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, α-naphthyl, β-naphthyl group and the like.

Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl and methylcyclo Hexenyl, a methylcycloheptenyl group, etc. are mentioned.

Moreover, homopolymerization, two or more types of random polymerization, or block polymerization may be sufficient as addition polymerization reaction of monoalcohol represented by said R <^5> -OH, alkylene oxide, or styrene oxide. The addition method may be a conventional method. The polymerization degree n is 1 to 500, preferably 1 to 200, and more preferably 10 to 200. Further, if 50 to 100% by weight of the ethylene group is preferably a full-R ⁴ ratio, more preferably from 65 to 100% by weight occupied by R ^4, it is possible to obtain the viscosity stability with good thickening with time.

Although the method of manufacturing the compound represented by General formula (1) used as a urethane type thickener is not specifically limited, It can carry out using a well-known method.

In addition, when the polyether polyol compound represented by the formula (A), the polyisocyanate compound represented by the formula (B), and the polyether monoalcohol compound represented by the formula (C) are reacted, Some may be byproducts. For example, when the diisocyanate is used as the polyisocyanate compound B, the main product is a CBABC type compound represented by the formula (1), but other compounds such as CBC type and CB- (AB) _x -ABC type are byproducts have. In this case, it can be used as a thickener for printing paste in the form of a mixture containing a compound of the general formula (1) without separating only the compound of the general formula (1).

The compound represented by the formula (2) used as a urethane-based thickener is, for example, one or two or more monoisocyanate compounds represented by the following general formula (D) and one or two or more mono or dihydroxy compounds represented by the following formula (E). It is obtained by making it react.

In general formula (2), R <^6> , R <^7> and R <^8> represents the hydrocarbon group which may be same or different, x shows the number of 1-2, y shows the number of 1-1000.

[Formula D]

R ⁶ -NCO (D)

(Wherein R ⁶ represents the same meaning as above)

[Formula E]

R⁷[-(O-R⁸)_y-OH]_x                          (E)

(Wherein R ⁷ , R ⁸ , x and y represent the same meaning as above)

In this case, R <^6> , R <^7> and R <^8> in Formula (2) are determined by the monoisocyanate compound represented by the said Formula (D) and the mono or dihydroxy compound represented by the said Formula (E).

The monoisocyanate compound represented by the formula (D) which can be preferably used to obtain the compound represented by the formula (2) is not particularly limited as long as it has one isocyanate group in the molecule. For example, aliphatic monoisocyanate, aromatic monoisocyanate, alicyclic monoisocyanate, etc. are mentioned.

As said aliphatic monoisocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate, lauryl isocyanate, octadecyl isocyanate, etc. are mentioned, for example.

Moreover, phenyl isocyanate, tolylene isocyanate, etc. are mentioned as said aromatic monoisocyanate, for example.

Moreover, cyclohexyl isocyanate etc. are mentioned as said alicyclic monoisocyanate, for example.

Among them, an aliphatic monoisocyanate having 1 to 24 carbon atoms is preferable for obtaining excellent thickening properties and stability of viscosity over time.

In addition, the mono or dihydroxy compound represented by the formula (E), which is preferably used for obtaining the compound represented by the formula (2), is not particularly limited as long as it is a polyether of a mono or hydroxy compound. Such a compound is addition polymerization of the monovalent or divalent hydroxy compound represented by R ⁷ (-OH) _x (wherein R ⁷ and x represent the same meaning as described above), alkylene oxide or styrene oxide and the like. It can be obtained by.

In the monovalent or divalent hydroxy compound represented by R ⁷ (-OH) _x , one or two hydrogen atoms of a hydrocarbon such as straight chain, branched chain, saturated, unsaturated, aliphatic, alicyclic or aromatic are substituted with hydroxyl groups. If it is, it will not specifically limit. Especially, it is preferable to use monohydric or dihydric alcohol, monovalent or dihydric phenol.

As the monohydric alcohol, for example, methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, lauryl alcohol, tridecanol , Isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacoalol, octacosanol, myrisil alcohol, racerol, tetratricontanol , Allyl alcohol, oleyl alcohol, isostearyl alcohol, cyclopentanol, cyclohexanol and the like.

Moreover, as a dihydric alcohol, ethylene glycol, propylene glycol, 1, 4- butylene glycol, neopentyl glycol, 1, 6- hexamethylene glycol, etc. are mentioned, for example.

Examples of the monovalent phenol include phenol, cresol, ethyl phenol, tert-butyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, styrenated phenol, and paracumyl phenol.

Moreover, as bivalent phenol, catechol, resorcin, hydroquinone, etc. are mentioned, for example.

Among these, in the monovalent hydroxy compound, those having 1 to 36 carbon atoms are preferable, and in the divalent hydroxy compound, those having 2 to 4 carbon atoms are preferable.

Further, R ⁸ is determined by alkylene oxide, styrene oxide, or the like added, and alkylene oxide, styrene oxide, etc. suitable for addition polymerization with the hydroxy compound represented by R ⁷ (-OH) _x are, for example, ethylene oxide. , Propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and the like. Among them, alkylene oxides having 2 to 4 carbon atoms (wherein R ⁸ is an alkylene group having 2 to 4 carbon atoms) exhibit excellent thickening effects and stability over time, and are therefore easy to obtain. Do.

The addition polymerization reaction such as the hydroxy compound represented by R ⁷ (-OH) _x and alkylene oxide or styrene oxide may be homopolymerization, two or more types of random polymerization or block polymerization. The addition method may be a conventional method. Moreover, the said polymerization degree y is 1-1000, Preferably it is 5-800, More preferably, 20-500 is good. The proportion of ethylene chains in R ⁸ is preferably 50 to 100% by weight, more preferably 65 to 100% by weight of the total R ⁸ , and is excellent in good viscosity and viscosity stability over time.

The method for producing the compound represented by the formula (2) used as the urethane-based thickener is not particularly limited, and the monoisocyanate compound represented by the formula (D) and the mono or dihydroxy compound represented by the formula (E) are known polyether and isocyanate. It can be made to react by the same method as the reaction method of the above.

The compound represented by the above formula (3) used as the urethane-based thickener is, for example, alkyl to one or two or more polyisocyanate compounds represented by the following formula (F) and one or two or more monovalent hydroxy compounds represented by the following formula (G). It is obtained more preferably by reacting the polyether monool compound which made styrene oxide, styrene oxide, etc. react.

In general formula (3), R <^9> , R <^10> and R <^11> represents the hydrocarbon group which may be same or different, a shows the number of 2-4, and b shows the number of 1-1000.

Formula F]

R⁹(-NCO)_a                          (F)

(Wherein R ⁹ and a have the same meaning as above)

[Formula G]

R ¹⁰ -O- (R ¹¹ -O) _b -H (G)

(Wherein R ¹⁰ , R ¹¹ and b have the same meaning as above)

In this case, R ⁹ , R ¹⁰ and R ¹¹ in Formula 3 are determined by the Formulas F and G used.

The a-valent polyisocyanate compound represented by the formula (F) which can be used to obtain the compound of the formula (3) is not particularly limited as long as it has 2 to 4 (when a is 2 to 4) isocyanate groups in the molecule. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, tetraisocyanate, etc. are mentioned.

Here, as aliphatic diisocyanate, methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2, 2- dimethylpentane, for example Diisocyanate, 3-methoxyhexanediisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butyl Lenglycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, para xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned.

And as aromatic diisocyanate, for example, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylene benzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate , Tridine diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, etc. are mentioned.

And as alicyclic diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, etc. are mentioned, for example.

Moreover, as biphenyl diisocyanate, biphenyl diisocyanate, 3,3'- dimethyl biphenyl diisocyanate, 3,3'- dimethoxy biphenyl diisocyanate, etc. are mentioned, for example.

As the diisocyanate of phenylmethane, for example, diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'- Diisocyanate, 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, cyclohexylbis (4-isocyanotriphenyl) methane, 3,3'-dimethoxydiphenyl Methane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2, 2'-dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone-3,3 ' -Diisocyanate etc. are mentioned.

As the triisocyanate, for example, 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalenetriisocyanate, ratio Phenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4'-triisocyanate, 1,6,11-undecanetriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptane triisocyanate, tris (Isocyanate phenyl) thiophosphate etc. are mentioned.

Moreover, you may use as a dimer and trimer (isocyanurate bond) of these polyisocyanate compounds, and you may react with an amine and use it as a biuret.

The polyether monool compound represented by the formula (G) which can be preferably used to obtain the compound of the formula (3) is not particularly limited as long as it is a polyether of a hydroxy compound. Such a compound can be obtained by addition polymerization of a monovalent hydroxy compound represented by R ¹⁰ -OH and alkylene oxide or styrene oxide. Moreover, R <^11> is determined by the alkylene oxide, styrene oxide, etc. which are added.

The monovalent hydroxy compound represented by R ¹⁰ -OH is not particularly limited as long as one hydrogen atom of a hydrocarbon such as straight chain, branched chain, saturated, unsaturated, aliphatic, alicyclic or aromatic is substituted with a hydroxyl group. Especially, monohydric alcohol and monohydric phenol can be used.

For example, methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, lauryl alcohol, tridecanol, isotridecyl alcohol , Myristyl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, myrisil alcohol, raceol, tetratricontanol, allyl alcohol, oleic Monohydric alcohols such as monoalcohol, isostearyl alcohol, cyclopentanol and cyclohexanol; Monohydric phenols such as phenol, cresol, ethylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, styrenated phenol and paracumylphenol. Among these, those having 1 to 36 carbon atoms are preferable, and those having 8 to 36 carbon atoms are more preferable.

Moreover, alkylene oxide, styrene oxide, etc. which are suitable for addition polymerization with the monovalent hydroxy compound represented by said R <^10> -OH are, for example, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide and the like. Can be mentioned. Among these, alkylene oxides having 2 to 4 carbon atoms (wherein R ¹¹ is an alkylene group having 2 to 4 carbon atoms) exhibit excellent thickening effects and viscosity stability over time, and thus, are obtained. Is also easy.

R ¹⁰ -OH The addition polymerization reaction such as the hydroxy compound and alkylene oxide or styrene oxide represented by the above may be homopolymerization, two or more types of random polymerization or block polymerization. The addition method may be a conventional method. Moreover, the said polymerization degree b is 1-1000, Preferably it is 5-800, More preferably, it is 10-200. The proportion of ethylene chains in R ¹¹ is preferably 50 to 100% by weight, more preferably 65 to 100% by weight of the entire R ¹¹ , thereby exhibiting good thickening and viscosity stability over time.

The method for producing the compound represented by the general formula (3) used as the urethane-based thickener is not particularly limited, and the polyisocyanate compound represented by the general formula (F) and the polyether monool compound represented by the general formula (G) include known polyethers and isocyanates. It can be made to react by the same method as the reaction method of the above.

The compound represented by the formula (4) used as the urethane-based thickener is one or two or more polyether polyol compounds represented by the following formula (H), one or two or more polyisocyanate compounds represented by the following formula (I), The secondary amine represented by the general formula (J) and / or the polyethermonool compound represented by the following general formula (K) can be obtained by reacting with a conventional urethane-urea reaction.

In formula (4), R ¹⁹ and R ²⁰ represent a hydrocarbon group, R ²¹ represents a hydrocarbon group or a hydrocarbon group having a urethane bond, and X represents a group represented by the formula (5) and / or the formula (6), provided that all X At the same time except for the group represented by the following formula (6), s represents two or more numbers, p represents zero or one or more numbers, and r represents one or more numbers. In the formulas (5) and (6), R ²² , R ²³ , R ^24, and R ²⁵ represent a hydrocarbon group, and t represents 0 or 1 or more numbers.

[Formula H]

R¹⁹[-(O-R²⁰)_p-OH]_s                          (H)

(R ¹⁹ , R ²⁰ , p and s have the same meaning as above)

[Formula I]

R²¹(-NCO)_{r + 1}                                                   (I)

(R ²¹ , r represents the same meaning as above)

[Formula J]

(Wherein R ²² and R ²³ represent the same meaning as above)

[Formula K]

H- (O-R²⁴)_t-O-R²⁵                          (K)

(Wherein, R ²⁴ , R ²⁵ and t represent the same meanings as above)

The polyether compound represented by the formula (H), which is preferably used to obtain the compound represented by the formula (4), is, for example, R ¹⁹ (-OH) _s (wherein R ¹⁹ and s represent the same meaning as described above). It can obtain by addition-polymerizing polyol and alkylene oxide, styrene oxide, etc. which are represented.

Especially, as a polyol, the alcohol of 2-8 (the formula is s is the number of 2-8) is preferable.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentylglycol, 1,6-hexanediol, 1,2-octanediol, sorbite, hydrogenated bisphenol A, and the like. Can be mentioned.

Examples of the trihydric alcohol include glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, and 2-methyl -2,3,4-butanetriol, 2-ethyl-1,2,3, -butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl- 3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentane Triol, trimethylol ethane, trimethylolpropane and the like.                     

As the tetrahydric alcohol, for example, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4 , 5-hexanetetrol, diglycerin, sorbitan and the like.

As a pentahydric alcohol, adonitol, arabitol, xylitol, triglycerine, etc. are mentioned, for example. Examples of the hexavalent alcohols include dipentaerythritol, sorbitol, mannitol, iditol, inositol, darcitol, taros, and aros. Examples of the octal alcohol include sucrose and the like. Polyglycerol etc. are mentioned as other trivalent or more alcohol.

Since these polyols are easy to obtain industrially, preferred are ethylene, glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, Sorbite, (poly) glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, dipentaerythritol, sorbitol and the like.

(OR ²⁰ ) _p in the compound of Formula H is determined by addition polymerization of a polyol represented by R ¹⁹ (-OH) _s with an alkylene oxide or styrene oxide. The hydrocarbon group of R ²⁰ is preferably an alkylene group or an arylene group, more preferably an alkylene group having 2 to 4 carbon atoms. Therefore, alkylene oxide or styrene oxide, etc. which can be preferably used include, for example, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin and the like. Among them, alkylene oxides having 2 to 4 carbon atoms are preferred because of their excellent thickening effect and viscosity stability over time.

The addition polymerization reaction of the polyol and alkylene oxide or styrene oxide represented by the above-mentioned R ¹⁹ (-OH) _s may be homopolymerization, two or more types of random polymerization, block copolymerization or random / block copolymerization. Moreover, the said polymerization degree p shows the number of 0 or 1 or more, Preferably it is 1-1000, More preferably, it is 10-800, Most preferably, it is 50-700. Further, if the proportion of the ethylene group occupied by R ²⁰ preferably from 50 to 100% by weight of the total R ^20, more preferably from 65 to 100% by weight, it is possible to obtain the viscosity stability with the excellent thickening with time.

The polyisocyanate compound represented by the formula (I) which can be preferably used to obtain the compound represented by the formula (4) is not particularly limited as long as it has two or more isocyanate groups (wherein r is 1 or more) in the molecule. . In formula, R <^21> is a hydrocarbon group, Specifically, it is a residue of polyisocyanate. As a preferable polyisocyanate compound, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, etc. are mentioned, for example.

Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diiso cyanate, and 2,2-dimethylpentanedi. Isocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene Glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, para xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned.

As aromatic diisocyanate, for example, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylene benzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tri Din diisocyanate, 1, 4- naphthalene diisocyanate, 1, 5- naphthalene diisocyanate, 2, 6- naphthalene diisocyanate, 2, 7- naphthalene diisocyanate, etc. are mentioned.

As alicyclic diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, etc. are mentioned, for example.

As biphenyl diisocyanate, biphenyl diisocyanate, 3,3'- dimethyl biphenyl diisocyanate, 3,3'- dimethoxy biphenyl diisocyanate, etc. are mentioned, for example.

Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4'-diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate and diphenyldimethylmethane-4,4'-diisocyanate. , 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, cyclohexylbis (4-isocytriphenyl) methane, 3,3'-dimethoxydiphenylmethane- 4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, 4,4'-diethoxydiphenylmethane-3,3'-diisocyanate, 2,2 ' -Dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate, benzophenone-3,3'-di Isocyanate etc. are mentioned.

Examples of the triisocyanate include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalenetriisocyanate and biphenyl- 2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, 1,6,11- undecane triisocyanate, 1,8- diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, etc. are mentioned.

Among these, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4'- diisocyanate , 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate and the like are preferable.

Moreover, these polyisocyanate compounds may be used as a dimer and a trimer (isocyanurate bond), and may be used as a biuret by making it react with an amine.

And the polyisocyanate compound which has the urethane bond which made the said polyisocyanate compound and polyol react can also be used. As the polyol, the above-mentioned divalent to octavalent polyols are preferable. Specifically, the glycerin-tolylene diisocyanate reactant, the glycerin-hexamethylene diisocyanate reactant, etc. are mentioned. When using a triisocyanate or more polyisocyanate compound, it is preferable to use the urethane bond containing polyisocyanate compound which made diisocyanate react with polyol.

X represented by the formula (4) is a group represented by the formula (5) and / or a group represented by the formula (6).

In general formula (5), R <^22> and R <^23> is a hydrocarbon group, As a hydrocarbon group, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, etc. are mentioned, for example.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tert-pentyl, hexyl, secondary hexyl, heptyl, Secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, Secondary tridecyl, tetradecyl, secondary tetradecyl, hexadecyl, secondary hexadecyl, stearyl, isocyl, docosyl, tetracosyl, triacyl, 2-butyloctyl, 2-butyldecyl, 2-hex Cyl octyl, 2-hexyldecyl, 2-octyldecyl, 2-decyl tetradecyl, 2-dodecyl hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl octadecyl, monomethyl branched-isostearyl, etc. are mentioned. Can be.

Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, desenyl, undecenyl, dodecenyl, tetradecenyl, Olerail, etc. are mentioned.

As the aryl group, for example, phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamil, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexyl Phenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, β-naphthyl group and the like. have.

Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, and methylcyclohexenyl Cenyl, a methylcycloheptenyl group, etc. are mentioned.

That is, as a compound which gives the group represented by general formula (5), the secondary amine represented by the said general formula (J) is mentioned.

Particularly preferred secondary amines are, for example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dioctylamine, di-2 Ethylhexylamine, dilaurylamine, ditridecylamine, diisotridecylamine, dimyristylamine, dipalmitylamine, distearylamine, dioleylamine, diallylamine, diphenylamine, methyllauryl Amine, ethyl lauryl amine, isopropyl lauryl amine, butyl lauryl amine, isobutyl lauryl amine, 2-ethylhexyl lauryl amine, octyl lauryl amine, isotridecyl lauryl amine, myristyl lauryl amine, palmi Thilaurylamine, stearyllaurylamine, oleyllaurylamine, allyllaurylamine, phenyllaurylamine, methyl-2-ethylhexylamine, ethyl-2-ethylhexylamine, isopropyl-2-ethylhexylamine, butyl -2-ethylhexylamine, isobutyl-2-ethylhexylamine, octyl-2-ethylhexylamine, Ristil-2-ethylhexylamine, palmityl-2-ethylhexylamine, stearyl-2-ethylhexylamine, oleyl-2-ethylhexylamine, allyl-2-ethylhexylamine, phenyl-2-ethylhexyl Amine, methyloleylamine, ethyloleylamine, isopropyloleylamine, butyloleylamine, isobutyloleylamine, octyloleylamine, myristyloleylamine, palmityloleylamine, allyloleylamine , Phenyl oleyl amine or a mixture thereof.

Among these, in order to exhibit especially excellent thickening property and stability of viscosity over time, as R <^22> and R <^23> , an alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group of 4 or more carbon atoms is more preferable.

In addition, X may be a contribution represented by the formula (6). In Formula (6), R ²⁵ and R ²⁴ are hydrocarbon groups, and t represents 0 or 1 or more numbers.

As R <^25> , it is a hydrocarbon group similar to said R <^22> or R <^23> , For example, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a cycloalkenyl group, etc. are mentioned. Especially, an alkyl group or an alkenyl group is preferable. Examples of R ²⁴ is preferably an alkylene group or an arylene group as in the R ^20, and more preferably an alkylene group of carbon atoms 2-4. Moreover, 0-500 are preferable, as for t, 0-300 are more preferable, and 0-200 are the most preferable.

X in the general formula (4) may be any of the group represented by the general formula (5) and the group represented by the general formula (6), but not all contributions in which all s × r X are represented by the general formula (6). Among these, in order to exhibit particularly excellent thickening and stability of viscosity over time, all X is a group represented by the formula (5), or a group represented by the formula (5) and R ²⁵ of the formula (6) are branched chains having 4 or more carbon atoms or 2 It is preferable that it is a grade hydrocarbon group.

The method for producing the compound represented by the formula (4) used as the urethane-based thickener is not particularly limited, but the polyether polyol compound of the formula (H), the polyisocyanate compound of the formula (I), the secondary amine of the compound J, and, if necessary, The polyethermonol compound of the formula (K) can be obtained by carrying out the reaction using a known urethane-urea reaction method.

Specific examples of the polyether polyol compound represented by Chemical Formula H include polyethylene glycol (PEG), polypropylene glycol, polyethylene / polypropylene glycol, (preferably a block copolymer of ethylene oxide and propylene oxide), and glycerin-alkyl. Ethylene oxide adduct, neopentyl glycol alkylene oxide adduct, trimethylol ethane alkylene oxide adduct, trimethylol propane alkylene oxide adduct, pentaerythritol alkylene oxide adduct, dipentaerythritol alkylene Oxide adducts, sorbitol-alkylene oxide adducts, and the like. It is preferable that they are the molecular weight 500-50,000, and it is especially preferable that they are 1000-30000. This is because when the molecular weight is too large, the viscosity becomes high, making it difficult to use at the time of manufacture.                     

Then, the polyether polyol compound represented by the formula (H), the polyisocyanate compound represented by the formula (I), and the secondary amine represented by the formula (J) [or the polyether monool compound represented by the formula (K)] are reacted. In this case, compounds other than the structure of general formula (4) may also be by-produced. For example, when polyetherdiol is used as the polyether polyol compound H and diisocyanate is used as the polyisocyanate compound I, as a main product, a compound of the type J (or K) -IHIJ (or K) represented by Formula 4 is produced. And other compounds such as J (or K) -HJ (or K) type and J (or K) -I- (HI) _x -HIJ (or K) type may be by-produced. In this case, in particular, it can be used as a thickener for printing paste in the state of a mixture containing a compound of the general formula (4) without separating only the compound of the general formula (4).

Printing paste composition

The composition for printing pastes of this invention contains the thickener for (A) printing pastes obtained by this invention. The component (A) may be used alone or in combination with other components. The other ingredients that can be blended can be any of those commonly formulated in a printing paste, and examples thereof include natural pastes such as starch, sodium alginate, starch, seaweed, agar, tganth gum, guar gum, locust bean gum, gum arabic and glue. And processed starches such as soluble starch, semisynthetic pastes such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose, and synthetic pastes such as polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate.                     

And dyeing agents such as dyes and pigments, dye dissolving agents such as ethylene glycol, thiodiethylene glycol, urea, moisturizing agents such as urea and glycerin, nonionic surfactants, anionic surfactants and other leveling agents, mildewing agents and penetrants, and sodium hydroxide. Alkali agents such as sodium carbonate, sodium bicarbonate, sodium trichloroacetate, ammonia and the like, and dyeing auxiliaries that assist the fixing of the dyes described above can also be blended.

In addition, additives such as metal ion sequestrants, preservatives, reducing agents, defoamers, plasticizers, antioxidants, and ultraviolet inhibitors can also be blended.

And mineral oils, such as mineral tapene (refined terpene oil), solvents, such as water, and various resin binders can be mix | blended.

Example

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In addition, the part in a following example shows a weight part.

The thickener for printing paste is manufactured by the compounding composition of Table 1, and a comparative product is manufactured by the compounding composition of Table 2.                     

Polyether polyol Mono or polyisocyanate Monools or amines Invention 1 combination PEG6000 Dicyclohexyl methane diisocyanate 50 mole adduct of ethylene oxide of styrenated phenol part 842 73 84 Invention 2 combination PEG6000 Dicyclohexyl methane diisocyanate 20 mole adduct of ethylene oxide of a branched alcohol having 16 carbon atoms part 684 60 256 Invention 3 combination PEG6000 Cyclohexyl isocyanate - part 960.0 40.0 - Invention 4 combination - Dicyclohexyl methane diisocyanate 100 mol addition product of ethylene oxide of C18 branched alcohol part - 53 946 Invention 5 combination PEG20000 Tolylene diisocyanate 8 mole adduct of ethylene oxide of branched alcohol of 20 carbon atoms part 924 16 60 Invention 6 combination PEG20000 Hexamethylene diisocyanate Dilaurylamine part 966 16 18 Invention 7 combination PEG6000 Dicyclohexyl methane diisocyanate 1: 1 mol mixture of ethylene oxide 30 mole adduct of nonylphenol and dilaurylamine part 726.0 63.4 Combination of 186.3 parts of 30 mole adduct of nonylphenol and 22.3 parts of dilaurylamine (1: 1 in molar ratio) Invention 8 combination PEG11000 Isophorone diisocyanate 15 mole adduct of ethylene oxide of branched alcohol having 24 carbon atoms part 850 32 118 Invention 9 combination PEG4000 Tetramethylene diisocyanate 40 mole adduct of ethylene oxide of octylphenol part 852 60 88

Polyether polyol fatty acid Comparative product 1 combination PEG6000 Stearic acid part 912 87 Comparative product 2 combination PEG20000 Lauric acid part 980 20

(Example)

842 parts of polyethylene glycol (PEG) 6000 (molecular weight 6000) and 84 parts of ethylene oxide side (EO) of styrenated phenol were added into a 2000-neck four-necked flask equipped with a thermometer, a nitrogen introduction tube and a stirrer. And 73 parts of dicyclohexyl methane diisocyanate are added, and it reacts by a conventional method. Confirm that the isocyanate content is 0% and obtain a reaction product which is a pale yellow solid at room temperature. This is called invention 1.

Hereinafter, the inventions 2 to 9 and the comparative products 1 and 2 are obtained by the same method.

The following composition for printing paste is prepared, and the viscosity immediately after preparation and the viscosity (mPa · s) after one month are measured. The viscosity measurement is measured at 10 rpm and 25 degreeC using a Brookfield viscometer. The results are shown in Table 3.

Resin

800 parts of resin binder

(Acrylic acid ester copolymer, NK binder AS-50 (made by Shinnakamura Kagaku))

Pigment paste part 5

(Cibacron Blue 3R (manufactured by Chiba)

40 thickeners for printing paste

(Each invention 1-9 and comparative products 1, 2)

Ammonia water

Mineral oil emulsion system

Mineral tapene 500 parts

(Refined Terepin Oil (Harimakasesei Co., Ltd.))

450 parts of water                     

2.5 parts of polyoxyethylene nonylphenyl ether

(Adecatol NP-700 (manufactured by Asahi Denka Kogyo Co., Ltd.))

Part 3 thickener for printing paste

(Each invention 1-9 and comparative products 1, 2)

5 parts of dye

(Ryudai W tacoise blue FB (made by Dainippon Ink High School))

Pool system

100 parts thickener for printing paste

(Each invention 1-9 and comparative products 1, 2)

10 parts sodium metanitrobenzenesulfonate

Element 50 Part

Neutral 20

60 parts of dye

(Cibacron Pront Turquoise G (made by Chiba Gaigisha))

760 parts of water                     

Thickening agent for printing Resin Mineral oil emulsion system Pool system Immediately after compounding 1 month later Immediately after compounding 1 month later Immediately after compounding 1 month later Invention 1 18000 18000 12000 12000 5000 4800 Invention 2 17000 17000 14000 14000 4200 4200 Invention 3 19000 18000 12000 12000 6100 5900 Invention 4 20000 20000 13000 12000 5700 5700 Invention 5 19000 19000 10000 10000 4500 4500 Invention 6 20000 19000 14000 13000 4900 4800 Invention 7 18000 18000 13000 13000 5300 5100 Invention 8 17000 17000 13000 12000 6000 5900 Invention 9 19000 19000 14000 14000 5100 5100 Comparative product 1 11000   760  5700  2500 2700  290 Comparative product 2  9200   530  6100  1300  200  170

As shown in Table 3 above, the thickener for printing paste of the present invention and the composition for printing paste containing the same have an excellent thickener and viscosity stability over time.

According to the present invention, there is provided a thickener for printing paste having excellent thickening property and stability of viscosity over time, and a composition for printing paste containing the printing paste thickener.

Claims (10)

delete delete delete delete delete delete A printing paste composition having excellent stability over time viscosities, comprising a printing paste thickener containing as an essential component a urethane-based thickener containing one or two or more of the compounds represented by the following formula (1): [Formula 1]

(In formula, R <^1> , R <^2> and R <^4> represent the hydrocarbon group which may be mutually different or same, R <^3> represents the hydrocarbon group which has a hydrocarbon group or a urethane bond, R <^5> is a linear, branched or secondary hydrocarbon group. Or a phenyl group having a substituent, m is two or more numbers, h is one or more numbers, and k and n are numbers in the range of 1 to 500). A printing paste composition having excellent stability over time viscosities, comprising a printing paste thickener containing as an essential component a urethane-based thickener containing one or two or more of the compounds represented by the following formula (2): [Formula 2]

(In formula, R <^6> , R <^7> and R <^8> represents the hydrocarbon group which may be same or different, x shows the number of 1-2, y shows the number of 1-1000. A printing paste composition having excellent stability over time viscosities, comprising a printing paste thickener containing as an essential component a urethane-based thickener containing one or two or more of the compounds represented by the following formula (3): [Formula 3]

(In formula, R <^9> , R <^10> and R <^11> represents the hydrocarbon group which may be same or different, a shows the number of 2-4, b shows the number of 1-1000. A printing paste composition having excellent stability over time viscosities, comprising a printing paste thickener containing as an essential component a urethane-based thickener containing one or two or more of the compounds represented by the following formula (4): [Formula 4]

[In formula, R <^19> and R <^20> represents a hydrocarbon group, R <^21> represents a hydrocarbon group or a hydrocarbon group which has a urethane bond, X is group represented by following formula (5) and / or following formula (6), and all X is simultaneously S represents two or more numbers, p represents zero or one or more numbers, and r represents one or more numbers. [Formula 5]

(Wherein R ²² and R ²³ represent a hydrocarbon group), [Formula 6]

(In formula, R <^24> and R <^25> represents a hydrocarbon group and t represents 0 or 1 or more numbers.).