JP2002234940A - Polypropylene glycol compound and dispersing agent using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which excels in dispersion activity without selecting a dispersing agent depending on a dispersion medium, and has excellent heat resistance and does not cause agglomeration, and to provide a dispersing agent. SOLUTION: A polypropylene glycol compound has propylene oxide as the main skeleton, and an amino group and hydroxyl groups added thereto and is represented by formula (1) (wherein X is a 1-10C alkoxide group, a halogen or a phenoxide group; Y is hydrogen, a 1-20C alkyl group or a phenyl group; W and U are each a 1-10C alkoxide group, a halogen, a phenoxide group, hydrogen, a 1-20C alkyl group or a phenyl group; p is an integer of 0-10; q is an integer of 5-400; r is an integer of 2-100; s is an integer of 1-3; and t is an integer of 0-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polypropylene glycol compound used as a raw material for paints, inks and pastes used in the field of electronic materials and the like, and a dispersant using this compound. More specifically, a polypropylene glycol compound used as a raw material for a black dispersion for a resin black matrix, a black dispersion for an antistatic roller, an antistatic paint for a CRT, an electromagnetic wave shielding paint, a paste for screen printing, a paint for inkjet, and the like. The present invention relates to a dispersant using a compound.

[0002]

2. Description of the Related Art In the field of electronic materials, paints, inks and pastes are mainly used for black dispersions for resin black matrix, black dispersions for antistatic rollers, antistatic paints for cathode ray tubes, magnetic wave shielding paints, pastes for screen printing, and the like. Used as ink-jet paints. For example, a black dispersion liquid for a resin black matrix is used to prevent light from leaking between drive electrodes in a liquid crystal display element. A black matrix is formed. The color filter that becomes the liquid crystal display element is on a transparent substrate such as glass or plastic sheet,
A black matrix is formed in a prescribed pattern, pixels of three colors of red (R), green (G), and blue (B) are formed at predetermined positions on the black matrix, and then a transparent electrode is formed. It is obtained by forming an alignment film thereon and rubbing the alignment film.

[0003] A black dispersion liquid for a resin black matrix is prepared by adding a powder of, for example, lower titanium oxide (titanium black) or carbon black as a coloring component to a dispersion medium and dispersing the powder in the dispersion medium. Is used. Usually, a dispersant is added to such a dispersion together with the powder. The reason why the dispersant is added to the dispersion liquid is to further improve the dispersibility of the powder, and has an effect of preventing agglomeration of the powder by increasing the repulsion between the powders.

[0004]

However, in the case of the conventional dispersant, it is necessary to select the dispersant according to the type of the dispersion medium. Specifically, for example, when the dispersant is dissolved in a dispersion medium containing a highly polar alcohol as a main solvent, it is possible to uniformly mix the powder in this dispersion medium, but the main solvent is a ketone. In such a case, there is a problem that the powder is agglomerated and cannot be uniformly dispersed in the dispersion medium. In particular, when the dispersing agent is dissolved in a dispersion medium containing a lower alcohol such as ethanol or methanol as a main solvent, propylene glycol monomethyl ether acetate (hereinafter, referred to as a propylene glycol monomethyl ether acetate even if the powder can be uniformly dispersed in the dispersion medium). When esters such as PGMEA) and ketones such as methyl ethyl ketone (hereinafter referred to as MEK) were used as main solvents, the powder could not be uniformly dispersed. Conversely, a dispersing agent that dissolves in a dispersion medium containing PGMEA as a main solvent can be dispersed in a dispersion medium containing ethanol as a main solvent even if powder can be uniformly mixed and dispersed in this dispersion medium. Therefore, there is a problem that a dispersant must be selected each time.

An object of the present invention is to provide a polypropylene glycol compound which is excellent in dispersing effect without selecting a dispersant according to the type of dispersion medium, and a dispersant using this compound. Another object of the present invention is to provide a polypropylene glycol compound having heat resistance and not causing aggregation, and a dispersant using the compound.

[0006]

According to the first aspect of the present invention,
It is a compound having propylene oxide as a main skeleton and is a polypropylene glycol-based compound represented by the following formula (1) in which an amino group and a hydroxyl group are added to propylene oxide.

[0007]

Embedded image

Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen,
To 20 alkyl groups or phenyl groups, W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, phenoxide groups, hydrogen, alkyl groups or phenyl groups having 1 to 20 carbon atoms, p is an integer of 0 to 10, q Is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, and t is an integer of 0 to 10.

The invention according to claim 2 is a compound having propylene oxide as a main skeleton, which is a polypropylene glycol compound represented by the following formula (2) wherein propylene oxide is added with an amino group and a hydroxyl group.

[0010]

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Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen,
To 20 alkyl groups or phenyl groups, W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, phenoxide groups, hydrogen, alkyl groups or phenyl groups having 1 to 20 carbon atoms, p is an integer of 0 to 10, q Is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, t is an integer of 0 to 10, and Z is represented by the following formulas (3) and (4). It is a functional group. Note that Z _{1 to} Z ₄ are hydrogen or C _{1 to} C 2.
0 is an alkyl group, i is an integer of 1 to 10, j is 1 to
It is an integer of 10.

[0012]

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[0013]

Embedded image

The invention according to claim 3 is a compound having propylene oxide as a main skeleton, which is a polypropylene glycol compound represented by the following formula (5) wherein propylene oxide is added with an amino group and a hydroxyl group.

[0015]

Embedded image

Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen,
To 20 alkyl groups or phenyl groups, W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, phenoxide groups, hydrogen, alkyl groups or phenyl groups having 1 to 20 carbon atoms, p is an integer of 0 to 10, q Is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, and t is an integer of 0 to 10.

In the invention according to any one of claims 1 to 3, the compound has a heat resistance up to about 100 ° C. since it has a polypropylene glycol compound in its structure.
No aggregation occurs in the solution when heated at 80 ° C. for 2 hours.

The invention according to claim 4 is the invention according to claims 1 to 3
The invention according to any one of the above, wherein the molecular weight is 900 to 200.
00 is a polypropylene glycol-based compound.
In the invention according to claim 4, the molecular weight is 900 to 20,000.
It is. Preferably it is 1000-10000. If the molecular weight is less than 900, sufficient dispersibility and heat resistance cannot be obtained,
When the molecular weight exceeds 20,000, dissolution in a solvent becomes difficult.

The invention according to claim 5 is the invention according to claims 1 to 4
A dispersant using any of the polypropylene glycol-based compounds described above. In the invention according to claim 5, claim 1 is
When the polypropylene glycol-based compound according to any one of to 4 is used as a dispersant, alcohols, ketones,
Dispersion can be performed without selecting a dispersant depending on the type of dispersion medium such as esters.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene glycol compound of the present invention is a compound having a molecular weight of 900 to 20,000 and being liquid at ordinary temperature, and has a structure represented by the aforementioned general formulas (1), (2) and (5). Having. Since a polypropylene glycol-based compound is used as a main skeleton, it is possible to dissolve from a highly polar solvent to a low polar solvent. Therefore, aggregation does not occur even when added to various solvents as a dispersant.

As a method for producing the polypropylene glycol compound of the present invention, an amine is added to a compound having propylene oxide as a main skeleton, followed by a reaction with a silicon compound. Thereby, the compound of the present invention can be produced. Examples of the compound having propylene oxide as a main skeleton include polypropylene glycol. Examples of the amine compound include ethanolamine, trimethylamine, and allylamine. Examples of the silicon compound include silicone oil and silane.

The polypropylene glycol-based compound thus produced has excellent heat resistance and can be dissolved in various solvents such as alcohols, ketones, esters and ethers. Is preferred. The mixing ratio of the dispersion is powder 100
The dispersant is added in a ratio of 0.1 to 80% by weight based on the weight%. In particular, it is preferable to add a dispersant in a ratio of 10 to 30% by weight. When the amount of the dispersant is less than 0.1% by weight, the effect of adding the dispersant is not exhibited, and when the amount of the dispersant exceeds 80% by weight, problems such as high viscosity are caused. Further, a mixture is obtained by adding a dispersion medium so that the concentration of the powder contained in the dispersion is 5 to 85% by weight. The lower limit of the powder concentration here is not particularly limited. However, if the value exceeds the upper limit, the viscosity becomes high, and problems such as deterioration of the recovery rate of the dispersion liquid are caused. More preferable conditions are 70% by weight or less. This mixed solution is charged together with the small spheres into a container of an Attritor device, which is a type of ball mill having a rotating impeller in the container, and the impeller is rotated for a certain period of time, for example, about 2 hours, to disperse the small spheres And by rotating, a dispersion liquid in which the powder is uniformly dispersed can be prepared.

Examples of the dispersion medium include alcohols, ketones, esters, ethers and the like. Examples of alcohols include ethanol, methanol, and diacetone alcohol (hereinafter, referred to as DAA). Examples of ketones include MEK, 2-pentanone, 4-heptanone, cyclohexanone, and the like. PGME as esters
A, acetate, butyl acetate and the like are exemplified. Examples of ethers include 2-ethoxyethanol (hereinafter, referred to as E / C), 2-methoxyethanol, and the like. Examples of the powder include oxide powder and metal powder. Examples of the oxide powder include alumina (Al ₂ O ₃ ) and titania (Ti
O ₂ ), tin-indium composite oxide (ITO), antimony-tin composite oxide (ATO), zinc oxide (ZnO), ruthenium oxide (RuO), and the like.
Pd, Ru, Au and the like are exemplified. Further, low-order titanium oxide (titanium black, hereinafter, referred to as TB), carbon black (hereinafter, referred to as CB) and the like are exemplified.

By using the polypropylene glycol compound of the present invention as a dispersant, it is possible to prepare a dispersion in which powder is uniformly dispersed regardless of the type of dispersion medium such as alcohols, ketones and esters. . Further, even when this dispersion is heated, the dispersion does not cause aggregation.

[0025]

Next, embodiments of the present invention will be described. <Example 1> The compound shown in FIG.
It is called Compound A. ), TB in powder, MEK in dispersion medium
Were prepared respectively. First, a dispersant is added to the powder at a ratio of 20% by weight to 100% by weight of the powder, and a dispersion medium is further added so that the concentration of the powder contained in the dispersion becomes 40% by weight to obtain a mixed solution. Was. Next, this mixed solution was charged into a container of a wet attritor device together with the small spheres, and the impeller was rotated for about 2 hours to disperse and rotate the small spheres, thereby preparing a dispersion in which the powder was uniformly dispersed.

Example 2 A dispersion was prepared in the same manner as in Example 1 except that the compound shown in FIG. 1B (hereinafter, referred to as compound B) was used as a dispersant. <Example 3> The compound shown in FIG.
It is called Compound C. A dispersion liquid was prepared in the same manner as in Example 1 except that (1) was used. <Example 4> The compound shown in FIG.
It is called Compound D. A dispersion liquid was prepared in the same manner as in Example 1 except that (1) was used. <Example 5> The compound shown in FIG.
It is called Compound E. A dispersion liquid was prepared in the same manner as in Example 1 except that (1) was used. <Example 6> The compound shown in FIG.
It is called Compound F. A dispersion liquid was prepared in the same manner as in Example 1 except that (1) was used. <Example 7> The compound shown in FIG.
It is called Compound G. A dispersion liquid was prepared in the same manner as in Example 1 except that (1) was used.

Example 8 A dispersion was prepared in the same manner as in Example 1 except that the dispersant was added at a ratio of 1% by weight to 100% by weight of the powder. <Example 9> A dispersion was prepared in the same manner as in Example 1 except that the dispersant was added at a ratio of 70% by weight with respect to 100% by weight of the powder. Example 10 A dispersion was prepared in the same manner as in Example 1 except that ethanol was used as a dispersion medium. Example 11 A dispersion was prepared in the same manner as in Example 1 except that PGMEA was used as the dispersion medium. <Example 12> Example 1 except that DAA was used as the dispersion medium.
A dispersion was prepared in the same manner as described above. Example 13 Example 1 except that E / C was used as the dispersion medium.
A dispersion was prepared in the same manner as described above.

<Examples 14 to 19> Dispersions were prepared in the same manner as in Examples 8 to 13 except that Compound B was used as a dispersant. <Examples 20 to 25> Dispersions were respectively prepared in the same manner as in Examples 8 to 13 except that Compound C was used as a dispersant. <Examples 26 to 31> Dispersions were prepared in the same manner as in Examples 8 to 13, except that Compound D was used as a dispersant. <Examples 32 to 37> Dispersions were prepared in the same manner as in Examples 8 to 13 except that Compound E was used as a dispersant. <Examples 38 to 43> Dispersions were respectively prepared in the same manner as in Examples 8 to 13 except that Compound F was used as a dispersant. <Examples 44 to 49> Dispersions were respectively prepared in the same manner as in Examples 8 to 13 except that Compound G was used as a dispersant.

Example 50 A dispersion was prepared in the same manner as in Example 11, except that a mixture of Compound A and Compound B in a weight ratio of 1: 1 was used as a dispersant. <Example 51> Example 1 was repeated except that a mixture of compound A and compound C at a weight ratio of 1: 1 was used as a dispersant.
A dispersion was prepared in the same manner as in Example 1. Example 52 Example 1 was repeated except that a mixture of Compound A and Compound D at a weight ratio of 1: 1 was used as a dispersant.
A dispersion was prepared in the same manner as in Example 1. <Example 53> Example 1 was repeated except that a mixture of compound A and compound E at a weight ratio of 1: 1 was used as a dispersant.
A dispersion was prepared in the same manner as in Example 1.

Example 54 A dispersion was prepared in the same manner as in Example 11, except that a mixture of Compound B and Compound C in a weight ratio of 1: 1 was used as a dispersant. <Example 55> 30 dispersants were added to 100% by weight of powder.
% By weight, and the dispersion was prepared in the same manner as in Example 18 except that the concentration of the powder contained in the dispersant solution was 35% by weight. <Example 56> 30 parts of dispersant was added to 100% by weight of powder.
% By weight, and the dispersion was prepared in the same manner as in Example 24 except that the concentration of the powder contained in the dispersant solution was 35% by weight.

<Example 57> TB and CB were mixed with powder at a weight ratio of 6: 4, and compound A and compound B were mixed with a dispersant at a weight ratio of 1: 1. A dispersion liquid was prepared in the same manner as in Example 1 except that the above-mentioned compound was used and a dispersant was added at a ratio of 25% by weight with respect to 100% by weight of the powder. Except using Al ₂ O ₃ to <Example 58> Powder Example 2
A dispersion was prepared in the same manner as in Example 2. <Example 59> A dispersion liquid was prepared in the same manner as in Example 10, except that TiO ₂ was used as the powder, and that a mixture of Compound A and Compound B at a weight ratio of 1: 1 was used as the dispersant. . <Example 60> A dispersion was prepared in the same manner as in Example 59, except that ATO was used as the powder and the concentration of the powder contained in the dispersant solution was 50% by weight. <Example 61> Example 59 except that ITO was used for the powder.
A dispersion was prepared in the same manner as described above.

Comparative Example 1 A dispersion was prepared in the same manner as in Example 10 except that the compound shown in FIG. 2 (H) (polyoxyalkylene alkyl ether phosphate, compound H hereinafter) was used as the dispersant. Prepared. <Comparative Example 2> Example 1 except that Compound H was used as a dispersant.
A dispersion was prepared in the same manner as in Example 1. Comparative Example 3 A dispersion was prepared in the same manner as in Example 10 except that the compound (fatty acid diethanolamide, hereinafter, referred to as compound I) shown in FIG. 2 (I) was used as a dispersant. Comparative Example 4 Example 1 except that Compound I was used as a dispersant.
A dispersion was prepared in the same manner as in Example 1.

<Comparative Evaluation> Examples 1 to 61 and Comparative Example 1
The dispersion particle diameter of the dispersion liquid prepared in each of Nos. To 4 was measured using a submicron particle size distribution analyzer (COULTER N4 Plus, manufactured by COULTER). The dispersion was divided into two, and one was allowed to stand at a temperature of 20 ° C. for one week, and the other was heated at a temperature of 80 ° C. for 2 hours. The dispersion particle size in these dispersions was also measured using the above-mentioned submicron particle size distribution analyzer. Examples 1 to 25 are shown in Table 1, Examples 26 to 50 are shown in Table 2, and Examples 51 to 61 and Comparative Examples 1 to 4 are shown in Table 3.
The changes over time in Tables 1 to 3 indicate the dispersion particle diameters of the liquid which was left standing at a temperature of 20 ° C. for one week, and the changes after heating the liquid heated at a temperature of 80 ° C. for 2 hours.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

As apparent from Table 3, Comparative Examples 1 and 2
The dispersion prepared in the above can uniformly disperse the powder added in the dispersion medium composed of esters, but cannot be dispersed in the dispersion medium composed of alcohols. Conversely, the dispersions prepared in Comparative Examples 3 and 4 are alcohols The added powder can be uniformly dispersed in the dispersion medium composed of esters, but not in the dispersion medium composed of esters. Further, in the dispersions of Comparative Examples 2 and 3 in which the powder was able to be dispersed in the dispersion medium, the dispersed particle diameter after being allowed to stand at 20 ° C. for one week was larger than the particle diameter immediately after dispersion. On the other hand, as is clear from Tables 1 to 3, in Examples 1 to 61, the added powder could be dispersed using any type of dispersion medium. Further, the dispersion which was allowed to stand at a temperature of 20 ° C. for 1 week and the dispersion which had been heated at a temperature of 80 ° C. for 2 hours each showed a particle diameter almost the same as the particle diameter in the dispersion immediately after dispersion. It can be seen that a dispersion having excellent aging and heat resistance can be prepared by using the compound as a dispersant.

[0038]

As described above, the polypropylene glycol compound of the present invention is a compound having propylene oxide as a main skeleton, and the above formulas (1) and (2) in which an amino group and a hydroxyl group are added to propylene oxide. ) And the compound represented by the formula (5). This compound has heat resistance and does not cause aggregation. When this compound is used as a dispersant, a dispersion having excellent dispersing effect can be prepared without selecting a dispersant depending on the type of dispersion medium.

[Brief description of the drawings]

FIG. 1 is a chemical formula showing a compound used as a dispersant in Examples.

FIG. 2 is a chemical formula showing a compound used as a dispersant in a comparative example.

Claims (5)

[Claims] 1. A polypropylene glycol-based compound represented by the following formula (1), wherein propylene oxide is a main skeleton, wherein said propylene oxide is added with an amino group and a hydroxyl group. Embedded image Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen, an alkyl group or a phenyl group having 1 to 20 carbon atoms, and W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, and phenoxide. Group, hydrogen, an alkyl group having 1 to 20 carbon atoms or a phenyl group, p is 0 to 10
, Q is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, and t is an integer of 0 to 10. 2. A polypropylene glycol-based compound represented by the following formula (2), wherein propylene oxide is a main skeleton, wherein the propylene oxide is added with an amino group and a hydroxyl group. Embedded image Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen, an alkyl group or a phenyl group having 1 to 20 carbon atoms, and W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, and phenoxide. Group, hydrogen, an alkyl group having 1 to 20 carbon atoms or a phenyl group, p is 0 to 10
, Q is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, t is an integer of 0 to 10,
Is a functional group represented by the following formula (3) and formula (4).
Z _{1 to} Z ₄ are hydrogen or an alkyl group having 1 to 20 carbon atoms, i is an integer of 1 to 10, and j is an integer of 1 to 10. Embedded image Embedded image 3. A polypropylene glycol-based compound represented by the following formula (5), which is a compound having propylene oxide as a main skeleton, wherein said propylene oxide is added with an amino group and a hydroxyl group. Embedded image Wherein X is an alkoxide group having 1 to 10 carbon atoms, a halogen or phenoxide group, Y is hydrogen, an alkyl group or a phenyl group having 1 to 20 carbon atoms, and W and U are alkoxide groups having 1 to 10 carbon atoms, halogen, and phenoxide. Group, hydrogen, an alkyl group having 1 to 20 carbon atoms or a phenyl group, p is 0 to 10
, Q is an integer of 5 to 400, r is an integer of 2 to 100, s is an integer of 1 to 3, and t is an integer of 0 to 10. 4. The polypropylene glycol-based compound according to claim 1, which has a molecular weight of 900 to 20,000. 5. A dispersant using the polypropylene glycol compound according to claim 1.