JPH09272796A - Novel associative thickener - Google Patents

Abstract

(57) Abstract: A compound obtained by adding one molecule of alkenylsuccinic anhydride or alkylsuccinic anhydride per amino group to polyethylene glycols having at least two amino groups at the ends of the molecule. Effect] A new associative thickener which is excellent as a thickener for latex and water-based paint is provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound obtained by adding an alkenyl succinic anhydride or an alkyl succinic anhydride to polyethylene glycols having at least two amino groups at the end of the molecule; And an aqueous composition such as a latex composition or an aqueous coating composition using the thickener.

[0002]

2. Description of the Related Art Conventionally, water-soluble thickeners have been used in various applications such as latex and water-based paint. Examples include various polyacrylamide polymers, polyethylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, casein, alginic acid, cellulose ethers such as methylcellulose and carboxymethylcellulose, and natural polysaccharides such as gum arabic, tragacanth gum and guar gum. is there. In recent years, associative thickeners (Asso
A group of compounds, collectively referred to as ciative Thickeners, has been developed. Although detailed description is given in US Pat. Nos. 4,426,485 and 4,411,819, it is a nonionic molecule structurally having a higher alkyl group as a hydrophobic group at both ends of polyethylene glycol. A feature of this associative thickener is that it has a large effect as a thickener despite a low molecular weight compound having a molecular weight of about 1,000 to 100,000. Further, functionally, a decrease in solution viscosity with respect to an increase in shearing force can be mentioned. This property exists not only in the aqueous solution of the compound itself, but also in the case of a composition such as latex or water-based paint,
It is a major feature of associative thickeners.

[0003]

The conventional polyether-based associative thickeners have a solution viscosity sensitive to the thickener concentration, and the adjustment of the viscosity by adjusting the concentration was often troublesome. In addition, because of its nonionic nature, the association group is strongly hydrophobic and it took a long time to dissolve in water. Therefore, a method of previously dissolving it in an organic solvent such as methanol and diluting it with water has been used, but mixing of the organic solvent may cause a problem. In addition, in order to facilitate handling, thickeners marketed as an aqueous solution were added with an auxiliary solvent such as propylene glycol to suppress the solution viscosity, but there are still environmental and sanitary problems due to organic solvents. It was happening.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that polyethylene glycols having at least two amino groups at the ends of the molecule are alkenylsuccinic anhydrides. The inventors have found that a compound obtained by adding an alkyl succinic anhydride is effective as an associative thickener and completed the present invention.

That is, the present invention is (a) at least 2
A compound in which one molecule of alkenyl succinic anhydride or alkyl succinic anhydride per amino group is added to polyethylene glycols having one amino group at the terminal of the molecule, (b) Formula (1)

[0006]

Embedded image (N in the formula is an integer of 1 to 2000).

However, A in the formula (1) is represented by the formula (2)
1]

[0008]

Embedded image (Where x is an integer of 1 to 6) or formula (3)

[0009]

Embedded image (Y in the formula is an integer of 0 to 5, Me represents a methyl group), and B in the formulas (2) and (3) is represented by the formula (4)
3]

[0010]

Embedded image COOM—CHRCH ₂ — or COOM—CH ₂ CHR— (4) (R in the formula represents an alkenyl group having 6 to 25 carbon atoms or an alkyl group having 6 to 25 carbon atoms. M represents hydrogen or alkali. Represents a metal, an alkaline earth metal, an ammonium group or an organic base). (C) R in formula (4) is represented by formula (5)

[0011]

Embedded image —CHR ¹ —CH═CH—R ² or —CR ¹ ═CH—CH ₂ —R ² (5) (wherein R ¹ and R ² are independently a hydrogen atom or a carbon number 1).
To a linear alkenyl group having 22 carbon atoms or a linear alkyl group having 1 to 22 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 3
In the range of 22 to 22),
(D) R in formula (4) is represented by formula (6)

[0012]

Embedded image —CH ₂ —C (Me) ═CH—C (Me) H—R ³ (6) (In the formula, R ³ is a hydrogen atom or a compound represented by formula (7)

[0013]

Embedded image (B) is an alkyl group represented by the formula, n is an integer of 1 to 6, and (e) R in the formula (4) is represented by the formula (8)

[0014]

Embedded image _{-CH 2 C (Me) = CH} (C (Me) 2 CH 2) n H (8) ( wherein, n is an integer from 1 to 5) or the formula (9)
[Chemical 18]

[0015]

Embedded image _{-CH 2 C (= CH 2)} CH 2 (C (Me) 2 CH 2) n H (9) ( wherein, n a is an integer of 1 to 5) represented by (b) Described compound, (f) (a) to (e) to (g) an associative thickener comprising the compound according to any one of (t) (a) to
(E) An aqueous composition comprising the compound according to any one of (a) to (c) or the associative thickener according to (f),
(H) The composition according to (G), wherein the solution viscosity can be adjusted by adding a polyvalent metal salt.
(I) The composition according to (g) or (h), wherein the aqueous composition is a latex composition or an aqueous coating composition.

One of the features of the present invention is that the structure of the thickener has a succinic acid half amide group as a connecting group between the hydrophilic main chain of polyethylene glycol and the hydrophobic group. This linking group has a neighboring amide group (-CONH-) and a carboxyl group (-COOH) as hydrophilic groups, and has a nonionic linking group that is stable and has high heat resistance even in an acid or alkali. It has improved properties over the agent.

This compound is swollen or slowly dissolved in water when its carboxyl group is an acid type (-COOH), but it is rapidly dissolved in water by adding a base such as an aqueous solution of caustic soda or ammonium water. . When a compound having a basic carboxyl group (-COOM, M is a counterion such as an alkali metal, an alkaline earth metal, an ammonium group or an organic base) is used, it can be easily dissolved in water. Therefore, it is no longer necessary to use it by dissolving it in an organic solvent in advance as in the conventional case.

Another feature is that when a polyvalent metal salt containing a polyvalent cation is added to the aqueous solution, the viscosity of the solution increases depending on the amount added. That is Be
²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Cu ²⁺ , Z
n ²⁺ , Cd ²⁺ , Hg ²⁺ , Sn ²⁺ , Fe ²⁺ , Al ³⁺ , Fe
By adding polyvalent metal salts containing polyvalent cations such as ³⁺ and Cr3 ⁺ to the aqueous solution, the solution viscosity can be increased while the concentration of the thickener is almost constant. That is,
It has an effect that the preparation of the aqueous solution of the thickener and the aqueous composition containing the thickener becomes extremely easy, and the use of the auxiliary solvent is not necessary.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The polyethylene glycols having at least two amino groups at the ends of the molecule (hereinafter abbreviated as PEG diamine) used in the present invention are:
Formula (10) [Chemical formula 19]

[0020]

Embedded image NH ₂ (CH ₂ ) _x (OCH ₂ CH ₂ ) _n O (CH ₂ ) _{x ′} NH ₂ (10) (wherein x and x ′ are integers of 1 to 6 and n is 1 to 200)
0) or formula (11) [Chemical formula 20]

[0021]

Embedded image NH ₂ CHMeCH ₂ (OCHMeCH ₂ ) _y (OCH ₂ CH ₂ ) _n (OCHMeCH ₂ ) _{y ′} OCH ₂ CHMeNH ₂ (11) (where y and y ′ are integers from 0 to 5 and n is 1-200
An example is a compound represented by an integer of 0 and Me is a methyl group.

Of course, the polyethylene glycols used in the present invention are not particularly limited to the above-exemplified compounds, and poly (methylene) is formed at both ends of a poly (oxyethylene) chain having a repeating unit of about 1 to 2000. Polyethylene glycols in which amino groups are connected to sandwich a divalent group having a hydrophobic or amphipathic property and having about 1 to 18 carbon atoms, such as a group or a poly (oxypropylene) group, may be used.
If the number of carbon atoms of the divalent group is too large, the solubility of the product in water is lowered, which is not preferable. A poly (methylene) group suitably has up to 6 carbon atoms, and a poly (oxypropylene) group suitably has up to 18 carbon atoms. It is more preferable that the poly (methylene) group has 3 carbon atoms, and the poly (oxypropylene) group has 3 to 6 carbon atoms. The alkenyl succinic anhydride or alkyl succinic anhydride (both abbreviated as ASA hereinafter) used in the present invention has the formula (12)

[0023]

[Chemical 21] The compound represented by these is mentioned. However, R has 6 to 6 carbon atoms
25 represents an alkenyl group having 25 or an alkyl group having 6 to 25 carbon atoms. ASA can be further classified into several types according to the type of R. For example, R is represented by the formula (5)

[0024]

Embedded image —CHR ¹ —CH═CH—R ² or —CR ¹ ═CH—CH ₂ —R ² (5) (wherein R ¹ and R ² are independently a hydrogen atom or a carbon number 1).
To a linear alkyl group having 22 to 22 or a linear alkenyl group having 1 to 22 carbons, and the total number of carbon atoms of R ¹ and R ² is 3
The ethylene-based ASA represented by
R is the formula (6)

[0025]

Embedded image —CH ₂ —C (Me) ═CH—C (Me) H—R ³ (6) (In the formula, R ³ is a hydrogen atom or a compound represented by formula (7)

[0026]

Embedded image Is an alkyl group represented by the formula (n is an integer of 1 to 6) and R is represented by the formula (8).
[Chemical 25]

[0027]

Embedded image _{-CH 2 C (Me) = CH} (C (Me) 2 CH 2) n H (8) ( wherein, n is an integer from 1 to 5) or the formula (9)
[Chemical 26]

[0028]

Embedded image _{-CH 2 C (= CH 2)} CH 2 (C (Me) 2 CH 2) n H (9) ( wherein, n a is an integer of 1 to 5) isobutene system represented by ASA Etc.

More specifically, examples of the ethylene-based ASA include n-hexenyl succinic anhydride, n-octenyl succinic anhydride, n-decenyl succinic anhydride, n-dodecenyl succinic anhydride and n- Tetradecenyl succinic anhydride, n-hexadecenyl succinic anhydride, n-octadecenyl succinic anhydride, n-dococenyl succinic anhydride, 4,9-decadiene-1,2-dicarboxylic anhydride, sec-hexadecenyl succinic acid Anhydrous, sec-
Octadecenyl succinic anhydride, etc.
Examples of A include dipropenyl succinic anhydride, tripropenyl succinic anhydride, tetrapropenyl succinic anhydride, pentapropenyl succinic anhydride, and hexapropenyl succinic anhydride, and examples of isobutene-based ASA include diisobutenyl succinic acid. Acid anhydrides, triisobutenyl succinic anhydrides, tetraisobutenyl succinic anhydrides, pentaisobutenyl succinic anhydrides, hexaisobutenyl succinic anhydrides, etc., and other ASAs include n-octyl succinic anhydride. , N-decyl succinic anhydride, n-
Dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, n-octadecyl succinic anhydride, isooctadecyl succinic anhydride, n-eicosyl succinic anhydride and the like can be mentioned.

ASA can be easily obtained by adding a terminal olefin or an internal olefin to maleic anhydride. Also, some ASAs are already manufactured industrially. Of course, the ASA used in the present invention is not particularly limited in its manufacturing method. ASA is a structural isomer resulting from the position of the carbon-carbon double bond in the alkenyl group (alkene-1-yl / alkene-2-yl, etc.) or a structural isomer resulting from the rotation of the carbon-carbon double bond. (E-form / Z-form) may exist, but in the present invention, any of these isomers or a mixture of these isomers at any ratio may be used.

A compound of the present invention in which one molecule of alkenyl succinic anhydride or alkyl succinic anhydride per amino group is added to polyethylene glycols having at least two amino groups at the ends of the molecule (hereinafter referred to as PEG-A).
SA is abbreviated as SA) is obtained by reacting these PEG diamines (hereinafter represented by NH ₂ —X—NH _{2 in the} chemical formula) with ASA in a suitable solvent or without solvent. The reaction is represented by the formula (13)

[0032]

Embedded image 2ASA + NH ₂ -X-NH ₂ → B-CONH-X-NHCO-B (13) However, B in the formula is the formula (14)

[0033]

Embedded image COOH—CHRCH ₂ — or COOH—CH ₂ CHR— (14) (wherein R is an alkenyl group). When PEG diamine is added to ASA, two kinds of structural isomers represented by the formula (14) are generated because there are two kinds of carbonyl groups to which the amino nitrogen can be bonded. The ratio of the two differs depending on the reaction conditions and the substituent R, but in the present invention, these isomers can be used without distinction.

The PEG-ASA represented by the formula (14) is in the acid form. By neutralizing the PEG-ASA with an appropriate base, B in the formula (13) is replaced by the formula (14 ') ] The base type PEG-ASA represented by this is obtained.

[0035]

Embedded image COOM-CHRCH ₂ — or COOM-CH ₂ CHR- (14 ′) where M is an alkali metal such as Li, Na, K, Rb, or Cs, or Be, Mg, Ca, Sr, Ba, or the like. Represents an alkaline earth metal, ammonium group or various organic bases. The manufacturing method will be described below. A raw material PEG diamine, ASA, and, if necessary, a solvent are charged into a reaction vessel having a stirrer.

The amount of ASA is 0.5 to 2 moles, more preferably 0.8 to 2 moles per mole of amino groups of PEG diamine.
1.5 mol, more preferably 0.9 to 1.2 mol is suitable. If the amount of ASA is much less than 0.5 mol, P
ASA cannot be added to both ends of EG diamine. On the other hand, if the amount is much more than 2 mol, unreacted ASA will increase, which is uneconomical. The raw materials may be charged all at once, or one or both of the raw materials may be divided or continuously charged.

The reaction may be carried out without a solvent, but as a solvent, an alcohol solvent such as methanol, a ketone solvent such as dimethyl ketone, an ester solvent such as ethyl acetate, an aromatic solvent such as xylene, and a heptane solvent can be used. A general organic solvent such as an aliphatic solvent, an ether solvent such as THF, or a mixed solvent thereof can be used. The amount of solvent used is 1 with respect to 100 parts by weight of PEG diamine.
About 0 to 500 parts by weight is suitable. If the amount of the solvent is too large, the reaction becomes slow, which is not preferable. Since the melt viscosity increases as the molecular weight of PEG diamine as a raw material increases, in that case the reaction is easier using a solvent, but the use of a solvent does not particularly limit the present invention.

While the reaction vessel is kept at room temperature to about 100 ° C., the reaction is continued with stirring to carry out the reaction. Since most PEG diamines are solid at room temperature, when the reaction is carried out without a solvent, the reaction is carried out by melting the PEG diamine by heating above the melting point (often about 30 to 70 ° C. although it varies depending on the molecular weight etc.).
This is not the case when a solvent is used. As for the reaction temperature, if the mixture of the raw materials is in a liquid state, the reaction temperature sufficiently proceeds even at about room temperature, but it can be heated up to about 100 ° C. to accelerate the reaction. More preferably, the reaction is performed at about 30 to 70 ° C. If the reaction temperature is much higher than 100 ° C., side reaction may occur, which is not preferable. The reaction time is not particularly limited and may be 10 minutes to 5 hours, although it varies depending on the amount of the solvent used, the reaction temperature and the like.

The atmosphere in the reaction vessel is not particularly limited,
When an organic solvent is used, it is better to replace air with an inert gas such as nitrogen gas. The pressure in the reaction vessel is not particularly limited, but normal pressure or weakly pressurized state is suitable. The acid-type PEG-ASA can be synthesized by the above operation. This product is subjected to solvent removal, drying,
It can be made into a product by an operation such as crushing.

Acid-type PEG-ASA is LiOH, NaO.
Alkali metal hydroxides such as H, KOH, RbOH, CsOH, Be (OH) ₂ , Mg (OH) ₂ , Ca (O
H— ₂ , Sr (OH) ₂ , Ba (OH) ₂ and other alkaline earth metal hydroxides, ammonia, or organic bases such as organic amines, and other types of bases to neutralize the base type PEG-ASA Can be obtained. Of these, alkali metal hydroxides are particularly preferable as the base. Neutralization can be easily performed by adding an amount of a base necessary for neutralization to an aqueous solution of an acid PEG-ASA or a solution of an organic solvent.

The associative thickener obtained in the present invention has a weight average molecular weight of about 500 to 100,000. If the molecular weight is less than 500, a sufficient thickening effect cannot be obtained. Also one
If it exceeds 0,000, the solubility will decrease and it is often not suitable for use as an associative thickener.

When the solution viscosity is measured with a B-type viscometer at 6 rpm, a compound having a range of about 10 to 1,000,000 cp (centipoise) is obtained with a 5% aqueous solution. The viscosity varies greatly depending on the molecular weight of the thickener and the type of ASA. It is one of the features of the present invention that a thickener having a desired viscosity can be used depending on the purpose of use.

The thickener of the present invention should be added in an amount of about 0.1 to 10% by weight to various aqueous compositions containing water as a dispersion medium, such as aqueous paints in which various latexes and various pigments are dissolved or dispersed. Thereby, effects such as prevention of dripping and improvement of coating property can be exhibited. Specifically, not only the viscosity of the composition increases by adding a thickener, but also the viscosity is relatively high at low shear stress and it is difficult for liquid to drip, and the viscosity relatively decreases at high shear stress to apply the composition. Will be easier.

The above water-based composition to which the thickener of the present invention is added is Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , C.
u ²⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Sn ²⁺ , Fe ²⁺ and Al
By adding a polyvalent metal salt containing a polyvalent cation such as ³⁺ , Fe ³⁺ , Cr ³⁺ or the like, or an aqueous solution of the polyvalent metal salt to this composition, the viscosity of the solution remains almost constant and the viscosity of the solution is kept constant. Can be increased, and the viscosity of the aqueous composition containing the thickener can be adjusted very easily. Of course, as the thickener, the associative thickener of the present invention may be used in combination with a conventional associative thickener or other thickeners such as cellulose ethers, polyacrylamide polymers, and polyethylene oxide.

[0045]

The present invention will be described in detail below with reference to Examples.
Of course, the present invention is not limited to these examples. In the following,% is based on weight. Molecular weight is GPC
By analysis, polyethylene glycol was determined as a standard in THF solvent. The solution viscosity was measured at 25 ° C. using a B-type viscometer (6 rpm). For the IR spectrum, a film was formed on a silicon wafer, and this was measured by FT-IR. The unit of the analysis value is cm ⁻¹ , the symbol in parentheses represents the peak relative intensity, and becomes weaker in the order of s>m> w. b represents a broad peak. In the following, the amine value is PEG-
It is the number of moles of monobasic acid required to neutralize the amino groups in 1 g of diamine. (Production of PEG-ASA) [Example 1] PEO amine 6 manufactured by Kawaken Fine Chemical Co., Ltd. as PEG-diamine in a 300 ml round bottom flask.
000 (the molecular structure is represented by the formula (10), the weight average molecular weight is 7,800, the dispersity is 1.3, and the amine value is 0.217 mmo.
(1 / g) 10.0 g, as sec-octadecenyl succinic anhydride manufactured by Mitsubishi Petroleum (in formula (5), R ¹ and R ² are both alkyl groups, and the total number of carbon atoms of R ¹ and R ² is No. 15. 0.76 g of trade name Pavelas-NP) and 50 g of xylene as a solvent were charged, and the mixture was heated to 70 ° C. with stirring under a nitrogen blanket. Stirring was continued while heating for 1 hour. The product was transferred to a beaker and the solvent xylene was distilled off while heating to 70 ° C. in a vacuum oven. Acid-type PEG-ASA (weight average molecular weight 9,000, dispersity 1.3) was obtained in a yield of 16.3 g.

10.0 g of the above acid type PEG-ASA and 0.081 g of caustic soda were placed in a 1 L beaker, and pure water was added to 1
90 g was added and stirred for 1 hour at room temperature. PEG-ASA was uniformly dissolved to obtain a 5% solution of PEG-ASA. The solution viscosity was 300 cp. Take 50g of this solution,
It was dried at 80 ° C. under normal pressure to obtain PEG-ASA sodium salt (base type PEG-ASA).

The analysis results are shown below. 1) IR spectrum of acid type (Fig. 1): 2885 (s), 1966 (b), 17
33 (w), 1672 (w), 1540 (w), 1467 (m), 1360 (m), 1344 (m), 1280
(m), 1235 (w), 1149 (m), 1114 (s), 1061 (m), 947 (m), 843 (m). In addition, 1733, 1672, 1540 cm ^-1 has a succinic acid half amide structure. It is a characteristic peak. 2) IR spectrum of base type (Fig. 2): 2888 (s), 1966 (b),
1729 (w), 1666 (w), 1543 (w), 1467 (m), 1360 (m), 1344 (m), 12
81 (m), 1242 (m), 1149 (m), 1110 (s), 1062 (m), 964 (m), 843
(m). 1729, 1672, and 1540 cm ^-1 are peaks characteristic of the succinic acid half amide structure.

Example 2 P was added to a 300 ml round bottom flask.
Kawaken Fine Chemical Co., Ltd. P as EG-diamine
EO amine 6000 (the molecular structure is represented by the formula (10), the weight average molecular weight is 7,400, the dispersity is 1.3, and the amine value is 0.
185 mmol / g) as an ASA, 3.24 g of n-octadecenyl succinic anhydride (R ¹ = hydrogen, R ² = n-pentadecyl in the formula (5)) manufactured by Tokyo Kasei as ASA, and xylene as a solvent. 50 g was charged and heated to 70 ° C. with stirring under a nitrogen blanket. Stirring was continued while heating for 1 hour. The product was transferred to a beaker and the solvent xylene was distilled off while heating to 70 ° C. in a vacuum oven. Acid-type PEG-ASA (weight average molecular weight 8,700, dispersity 1.3) was obtained with a yield of 52.5 g.

15.0 g of the above acid type PEG-ASA and 0.106 g of caustic soda were placed in a 1 L beaker, and pure water was added to 2
85 g was added and stirred for 1 hour at room temperature. PEG-ASA was uniformly dissolved to obtain a 5% solution of PEG-ASA. The solution viscosity was 400 cp. Take 50g of this solution,
It was dried at 80 ° C. under normal pressure to obtain PEG-ASA sodium salt (base type PEG-ASA).

The analysis results are shown below. 1) IR spectrum of acid type (Fig. 3): 2887 (s), 1966 (b), 17
32 (w), 1674 (w), 1538 (w), 1467 (m), 1360 (m), 1344 (m), 1281
(m), 1242 (m), 1150 (m), 1111 (s), 1062 (m), 964 (m), 843 (m). In addition, 1732, 1674, 1538cm ^-1 succinic acid half amide structure It is a characteristic peak. 2) IR spectrum of base type (Fig. 4): 2886 (s), 1966 (b),
1704 (w), 1666 (w), 1572 (w), 1467 (m), 1360 (m), 1344 (m), 12
81 (m), 1242 (m), 1149 (m), 1114 (s), 1062 (m), 964 (m), 843
(m). 1704, 1674, and 1538 cm ^-1 are peaks characteristic of the succinic acid half amide structure.

(Adjustment of Viscosity by Calcium Salt) [Example 3] 5% of PEG-ASA obtained in Example 1
The solution was diluted 1/2 with water (2.5%) and adjusted to pH 11 with caustic soda. A predetermined amount of 1M calcium chloride aqueous solution was added to 60 g of this solution and mixed well, and then the solution viscosity was measured (Table 1). Solution viscosity of 3 by adding calcium
The viscosity was increased to 50%.

Example 4 PEG-obtained in Example 2
A predetermined amount of a 1 M calcium chloride aqueous solution was added to 62 g of a 5% solution of ASA (pH 8.4) and mixed well, and then the solution viscosity was measured (Table 1). The solution viscosity could be increased up to 250% by adding calcium.

In Examples 3 to 4, the change in viscosity was shown in a system containing no rubber particles or pigment, but the absolute value of the viscosity also depends on the system in various latex systems or systems in which various pigments are dissolved or dispersed. Needless to say, the same viscosity adjustment is possible, although it is different. In general, in an aqueous composition containing an associative thickener, the viscosity greatly changes due to a slight change in the added amount of the thickener. The fact that the viscosity can be adjusted by adding a small amount of polyvalent metal salts improves the workability of solution preparation and facilitates the quality control of products.

[0054]

[Table 1]

[0055]

The present invention provides a new associative thickener which is excellent as a thickener for latex and water-based paint.

[Brief description of drawings]

FIG. 1 IR spectrum of acid-type PEG-ASA

FIG. 2 IR spectrum of basic PEG-ASA

FIG. 3 IR spectrum of acid-type PEG-ASA

FIG. 4 IR spectrum of basic PEG-ASA

Claims (9)

[Claims] 1. A compound obtained by adding one molecule of alkenyl succinic anhydride or alkyl succinic anhydride per amino group to polyethylene glycols having at least two amino groups at the ends of the molecule. 2. Formula (1) [Chemical Formula 1] (N in the formula is an integer of 1 to 2000).
However, A in the formula (1) is represented by the formula (2). (Where x is an integer of 1 to 6) or formula (3) [Chemical Formula 3] (In the formula, y represents an integer of 0 to 5, Me represents a methyl group), and B in the formulas (2) and (3) is represented by the formula (4) [Chemical Formula 4] [Chemical Formula 4] COOM-CHRCH _2- or COOM-CH ₂ CHR- (4) (wherein R represents an alkenyl group having 6 to 25 carbon atoms or an alkyl group having 6 to 25 carbon atoms. M represents hydrogen, an alkali metal, an alkaline earth metal, It represents an ammonium group or an organic base). Wherein formula (4) R in the formula (5) [Formula 5] embedded image -CHR ¹ -CH = CH-R ² or _{^{-CR 1 = CH-CH 2 -R}} 2 (5) (In the formula, R ¹ and R ² are independently a hydrogen atom or a carbon number 1
To a linear alkenyl group having 22 carbon atoms or a linear alkyl group having 1 to 22 carbon atoms, and the total number of carbon atoms of R ¹ and R ² is 3
To 22)). 4. R in formula (4) is represented by formula (6) [Chemical formula 6]: —CH ₂ —C (Me) ═CH—C (Me) H—R ³ (6) , R ³ is a hydrogen atom or is represented by the formula (7) [Chemical formula 7] Is an alkyl group represented by and n is an integer of 1 to 6). 5. The formula (4) R is the formula (8) formula 8 embedded image _{-CH 2 C (Me) = CH} (C (Me) 2 CH 2) n H (8) ( Formula In the formula, n is an integer of 1 to 5) or the formula (9).
Formula 9 embedded image _{-CH 2 C (= CH 2)} CH 2 (C (Me) 2 CH 2) n H (9) ( wherein, n a is an integer of 1 to 5) are represented by Claim 2
A compound as described. 6. An associative thickener comprising the compound according to claim 1. 7. An aqueous composition comprising the compound according to claim 1 or the associative thickener according to claim 6. 8. The composition according to claim 7, wherein the solution viscosity can be adjusted by adding a polyvalent metal salt. 9. The composition according to claim 7, wherein the aqueous composition is a latex composition or an aqueous coating composition.