JP2002293917A - Polyalkylene glycol ester containing amino group and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an amino group-containing polyglycol ester compound that is useful as a dispersant shows excellent fluidity and dispersion stability of fine particles of pigments in an organic solvent, and gives excellent gloss for a dried film. SOLUTION: The objective amino group containing polyalkylene glycol ester is represented by the following general formula (1) (wherein X is a polyalkylenepolyamine at least number (a) of active hydrogen atoms or a residue after removing number (a) of active hydrogen atoms from the polyalkyleneimine; R1 is H, methyl; R2 is a 2-4C alkylene; R3 is H, a 1-9C alkyl group or phenyl which may be substituted; n is an integer of 2-50; a is an integer of 1-200).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention contains an amino group which is useful as a dispersant which is excellent in fluidity and dispersion stability when a fine pigment is dispersed in an organic solvent and gloss when a dry film is formed. It relates to a polyalkylene glycol ester compound.

[0002]

2. Description of the Related Art In printing inks, paints and the like, pigments are dispersed in a fine state so that printed materials or coated products have a suitable color tone and glossiness. Also,
By dispersing the pigment in a stable state, not only the flowability of the printing ink or paint is improved and the printability is improved, but also the labor and energy required for manufacturing the printing ink or paint can be significantly reduced. Further, a dispersion in a stable state generally has excellent storage stability.

[0003] However, pigments used in printing inks and paints often have a fine particle size in order to realize a clearer color tone, which increases the cohesive force between the pigment particles and has the above-mentioned suitability. It is often difficult to get them to.

Various pigment dispersants have been disclosed to solve such problems. For example, Japanese Patent Publication No. 41-246
No. 6-334, and the pigment derivatives disclosed in Japanese Patent Publication No. 54-340.
No. 09, JP-B-63-30057 and the like have a certain effect as a pigment dispersant, but when a finer pigment is used in order to obtain a higher-quality printing ink and paint, The effect was not enough. In addition, due to the increasing interest in environmental issues in recent years, organic solvents used in printing inks and coatings have been increasing from those based on aromatics such as toluene to those based on esters or alcohols. This is extremely disadvantageous for dispersing pigments.
In such printing inks and paints, the effects of the above-described pigment dispersants cannot be said to be satisfactory, and many of them have no effect at all.

Japanese Unexamined Patent Publication (Kokai) No. 2-126928 discloses a compound obtained by adding ethylene oxide or propylene oxide to a polyamine compound, and shows its effectiveness in polar solvents such as alcohols. Ethylene oxide and propylene oxide are added to all of them, and there has been a problem that the adsorptivity to the pigment specific to the amine component is impaired and the effect is insufficient.

[0006]

The problem to be solved by the present invention is to provide a pigment having excellent fluidity and dispersion stability when a fine pigment is dispersed in an organic solvent, and excellent gloss and the like when formed into a dry film. An object of the present invention is to provide an amino group-containing polyalkylene glycol ester compound useful as an agent.

[0007]

The amino group-containing polyalkylene glycol ester compound represented by the following general formula (1) has excellent fluidity, dispersion stability, and dryness when a fine pigment is dispersed in an organic solvent. The present invention was found to be useful as a dispersant having excellent gloss and the like in the case where the present invention was performed, and the present invention was completed. General formula (1)

[0008]

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(Wherein X is a polyalkylenepolyamine compound having at least a active hydrogens or a residue obtained by removing a active hydrogens from a polyalkyleneimine compound;
R ₁ is a hydrogen atom or a methyl group; R ₂ is an alkylene group having 2 to 4 carbon atoms; R ₃ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a phenyl group which may have a substituent; ~ 5
Integer of 0 and a represent an integer of 1 to 200. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the general formula (1) of the present invention, X is a polyalkylenepolyamine compound or a polyalkyleneimine compound having at least a active hydrogen as a starting material. And X is a residue starting from a polyalkylenepolyamine compound or a polyalkyleneimine compound having b active hydrogens, the relationship between a and b is 1 ≦ b−
It is preferable that a ≦ 10. If ba is a negative value, it is unreasonable in chemical structure. If it is 0, the effect when used as a dispersant is significantly weakened. Affinity with a solvent or a vehicle as a medium is deteriorated, which may cause a problem in suitability.

Specific examples of the polyalkylene polyamine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and tripropylenetetramine. Examples of the polyalkyleneimine compound include polyethyleneimine, And polypropyleneimine. The polyalkylenimine may be linear or branched, and preferably has a molecular weight of 300 to 10,000.

In the general formula (1) of the present invention, R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkylene group having 2 to 4 carbon atoms. The polyalkyleneoxy group may be composed of different types of alkylene groups having different chain lengths, and the sequence thereof may be one in which different types of alkyleneoxy groups are bonded in a block shape or are randomly bonded. Is also good.

In the general formula (1) of the present invention, R ₃ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a phenyl group which may have a substituent, and the alkyl group is linear or branched. Preferred examples of the substituent of the phenyl group which may be in a cyclic or cyclic form include an alkyl group having 1 to 9 carbon atoms, a halogen group,
Examples include a nitro group, a cyano group, a hydroxyl group, and an alkoxy group having 1 to 4 carbon atoms.

In the general formula (1) of the present invention, n is an integer of 2 to 50, a is an integer of 1 to 200, and n is a polyalkylene glycol chain of the amino group-containing polyalkylene glycol ester compound of the present invention. Is a number that determines the number of polyalkylene glycol chains, respectively.
Therefore, by appropriately combining n and a, the weight average molecular weight of the amino group-containing polyalkylene glycol ester compound of the present invention can be selected. The preferred range of the weight average molecular weight of the amino group-containing polyalkylene glycol ester compound of the present invention is from 500 to 50,000, and the more preferred range is from 1,000 to 10,000.

The amino group-containing polyalkylene glycol ester compound of the present invention comprises: A: a polyalkylene polyamine compound or a polyalkylene imine compound; and B: a polyalkylene glycol ester compound represented by the following general formula (2):

[0016]

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Is used as a starting material. As a specific example of the production method, a method of mixing and reacting the raw materials A and B is the simplest, and an alcohol such as methanol or an ether such as tetrahydrofuran or dioxane may be used as a synthesis solvent. There is no problem if the reaction temperature is in the range of 0 to 200 ° C, but 10 to 80 ° C is more preferable. The chemical reaction applied to this production method is a widely known chemical reaction for adding a primary or secondary amine to a double bond of acrylate or methacrylate, and is, for example, ORGANIC SYNTHESES Collective Volume III,
258. In general, acrylates are more reactive and easier to produce.

The amino group-containing polyalkylene glycol ester compound of the present invention is useful as a dispersant for dispersing a fine pigment in an organic solvent to obtain a high-quality printing ink or paint.

When the amino group-containing polyalkylene glycol ester compound of the present invention is used as a dispersant, examples of the organic solvent include aromatic hydrocarbons such as toluene, petroleum hydrocarbons such as mineral spirits, halogenated hydrocarbons such as chlorobenzene, and the like. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
Esters such as ethyl acetate, butyl acetate, amyl acetate, and 2-ethoxyethyl acetate; alcohols such as methanol, ethanol, propanol and butanol; cellosolves such as ethyl cellosolve and butyl cellosolve; and ketones are particularly preferable. , Alcohols, cellosolves, esters and the like. Of course, the organic solvent may be a mixture of two or more.

When used in printing inks or paints, the dispersion medium may contain known printing ink vehicles or paint vehicles. Examples of these vehicles include nitrocellulose and cellulose acetate. ,
Ethyl cellulose, urethane resin, polyamide resin, polyvinyl butyral resin, acrylic resin, polyester resin, alkyd resin, lime rosin, tall oil rosin,
Wood rosin, rosin ester, rosin modified phenol resin, petroleum resin, linseed oil, tung oil, soybean oil, maleic resin, vinyl resin, cyclized rubber, chlorinated rubber, ethylene-vinyl acetate resin, gilsonite, dammar, shellac, epoxy resin, chloride There are vinyl, silicone resin, melamine resin, urea resin, benzoguanamine resin and the like.

Examples of pigments used when the amino group-containing polyalkylene glycol ester compound of the present invention is used as a dispersant include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, and perylene pigments. , Organic pigments such as perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, carbon black, oxidation There are inorganic pigments such as titanium, graphite, cadmium yellow, cadmium red, red iron oxide, iron black, zinc white, navy blue and ultramarine blue.

Other than pigments used when the amino group-containing polyalkylene glycol ester compound of the present invention is used as a dispersant, there are coal, graphite, magnetic powder, cement and the like.

The dispersing machine used when the amino group-containing polyalkylene glycol ester compound of the present invention is used as a dispersing agent may be any dispersing machine usually used for producing printing inks or paints. And a dissolver, a high-speed mixer, a homomixer, a kneader, a flasher, a roll mill, a sand mill, an attritor, and the like.

[0024]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

Example 1 Polypropylene glycol ester of acrylic acid having a molecular weight of about 400 (Blenmer AP400 manufactured by NOF Corporation) 4
00 parts and ethylenediamine 60 parts were mixed and stirred at room temperature for 4 hours. The obtained resin was subjected to IR analysis.
The absorption from the heavy bonds 810 cm ^-1, 1410 cm ^-1
And the peak at 1620 cm ^-1 completely disappeared, confirming the formation of an adduct of acrylic acid polypropylene glycol ester to diethylenetriamine, which is the target substance.

Examples 2 to 8 Table 1 shows compounds synthesized by the method according to Example 1. Structural confirmation also confirmed that all the compounds were target substances by the same method.

[0027]

[Table 1]

Example 9 Copper phthalocyanine pigment (CI Pigment Bl)
ue15: 4) 20 parts, varnish for gravure ink (composed of 17% nitrocellulose, 12% ethyl acetate, 6% isopropyl alcohol, 62% ethanol, 3% plasticizer), 80 parts, 2 parts of compound A and 300 parts of 2 mm steel balls And mixed with a paint conditioner for 60 minutes to prepare a gravure ink. Similarly, gravure inks were prepared using compounds B to K instead of compound A. Table 2 shows the results of measuring the viscosity of the prepared ink with a B-type viscometer (6 rpm).

Comparative Example Copper phthalocyanine pigment (CI Pigment Bl)
ue15: 4) 20 parts, 80 parts of a gravure ink varnish and 300 parts of a 2 mm steel ball were mixed and dispersed by a paint conditioner for 60 minutes to prepare a gravure ink. Measure the viscosity of the prepared ink with a B-type viscometer (6 rpm).
Table 2 shows the results measured in m).

[0030]

[Table 2]

[0031]

According to the present invention, an amino group-containing polyalkylene glycol ester compound useful as a dispersant can be provided.

Continued on the front page F-term (reference) 4D077 AB03 AB05 AC05 BA02 DC02Z DC32Z DC42Z DC47Z DD04X DD05X DD38X DD43X DE02X DE04X DE07X DE08X DE09X DE17X DE24X DE26X DE34X 4H006 AA01 AB68 AC21 BN10 BT12 BU32 A04 AE04

Claims (4)

[Claims] 1. An amino group-containing polyalkylene glycol ester compound represented by the following general formula (1). General formula (1) (Wherein X is a polyalkylenepolyamine compound or a polyalkyleneimine compound having at least a active hydrogens and a residue obtained by removing a active hydrogens, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a carbon atom having 2 carbon atoms. To 4 alkylene groups, R ₃ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms or a phenyl group which may have a substituent, n represents an integer of 2 to 50, and a represents an integer of 1 to 200. ) 2. The compound according to claim 1, which has a weight average molecular weight of 500 to 50,000. 3. X is a residue obtained by removing a number of active hydrogens from a polyalkylenepolyamine compound or a polyalkyleneimine compound having b number of active hydrogens, wherein the relationship between a and b is 1 ≦ ba ≦ The compound according to claim 1, wherein the compound is 10. 4. A dispersant comprising the compound according to claim 1.