AMIDO GROUP-CONTAINING MONOMER COMPOSITION AND METHOD FOR IMPROVING STORAGE STABILITY OF AMIDO GROUP-CONTAINING MONOMER

Abstract

An amido group-containing monomer composition contains 80.00 to 99.99 mass % of an amido group-containing monomer (a) of the following formula (1) and 0.01 to 20.00 mass % of a metal chelate complex (b) having carbonyl group as a ligand:

##STR00001##

wherein R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a hydrocarbon group having a carbon number of 1 to 6, R.sup.3 represents a hydrocarbon group having a carbon number of 1 to 23, and R.sup.4 represents hydrogen or a methyl group.

Claims

1. An amido group-containing monomer composition comprising 80.00 to 99.99 mass % of an amido group-containing monomer (a) represented by the following formula (1) and 0.01 to 20.00 mass % of a metal chelate complex (b) having carbonyl group as a ligand: ##STR00008## in the formula (1), R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a hydrocarbon group having a carbon number of 1 to 6, R.sup.3 represents a hydrocarbon group having a carbon number of 1 to 23, and R.sup.4 represents hydrogen or a methyl group.

2. The amido group-containing monomer composition of claim 1, wherein said metal chelate complex (b) is represented by the following formula (2). ##STR00009## in the formula (2), M represents a transition metal, g represents 1 to 4, h represents 0 to 3, g+h represents a total coordination number of said transition metal, R.sup.5 and R.sup.6 independently represent a hydrocarbon group having a carbon number of 1 to 5 or a phenyl group, respectively, R.sup.7 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 3, and R.sup.8 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 6.

3. A method of improving stability of storage of an amido group-containing monomer, said method comprising adding a metal chelate complex (b) represented by the following formula (2) to an amido group-containing monomer (a) represented by the following formula (1): ##STR00010## in the formula (1), R.sup.1 represents a hydrogen atom or a methyl group, R.sup.2 represents a hydrocarbon group having a carbon number of 1 to 6, R.sup.3 represents a hydrocarbon group having a carbon number of 1 to 23, and R.sup.4 represents hydrogen or a methyl group; ##STR00011## in the formula (2), M represents a transition metal, g represents 1 to 4, h represents 0 to 3, g+h represents a total coordination number of said transition metal, R.sup.5 and R.sup.6 independently represent a hydrocarbon group having a carbon number of 1 to 5 or a phenyl group, respectively, R.sup.7 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 3, and R.sup.8 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 6.

Description

EMBODIMENTS FOR CARRYING OUT THE INVENTION

[0045] Although embodiments of the present invention will be described below, the present invention is not limited to them.

[0046] The composition of the present invention contains 80.00 to 99.99 mass % of an amido group-containing monomer (a) represented by the formula (1) described above and 0.01 to 20.00 mass % of a metal chelate complex (b) having carbonyl group as a ligand. The respective components will be described below.

(Amido Group-Containing Monomer (a))

[0047] The amido group-containing monomer of the present invention is represented by the following formula (1).

##STR00006##

[0048] In the formula (1), R.sup.1 represents hydrogen atom or methyl group.

[0049] R.sup.2 represents a hydrocarbon group having a carbon number of 1 to 6. R.sup.2 may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group or an unsaturated hydrocarbon group. The carbon number of R.sup.2 may more preferably be 1 to 4. R.sup.2 may most preferably be alkylene group. On the viewpoint of availability, methylene group, ethylene group, trimethylene group and tetramethylene group are more preferred.

[0050] R.sup.3 is a hydrocarbon group having a carbon number of 1 to 23. R.sup.3 may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group or an unsaturated hydrocarbon group. The carbon number of R.sup.3 may preferably be 1 to 21 and more preferably be 1 to 18. Preferably, R.sup.3 may be a straight-chain alkyl group or a branched-chain alkyl group, and a readily available straight-chain alkyl group having a carbon number of 1 to 21 is most preferred. For example, methyl group, ethyl group, propyl group, heptyl group, dodecyl group, tetradecyl group, pentadecyl group, heptadecyl group, nonadecyl group and eicosyl group are listed.

[0051] R.sup.4 is hydrogen or methyl group, and hydrogen is more preferred on the viewpoint of availability.

[0052] The amido group-containing monomer (a) may be applied alone or the two or more kinds may be applied in combination.

(Metal Chelate Complex (b) Having Carbonyl Group as a Ligand)

[0053] The metal chelate complex (b) having carbonyl group as a ligand of the present invention is represented by the following formula (2).

##STR00007##

[0054] In the formula (2), M represents a transition metal, and may preferably be selected from aluminum, chromium, cobalt, vanadium, iron, zinc, zirconium, indium and titanium. On the viewpoint of suppressing self-polymerization upon storage, iron and zirconium are preferred and zirconium is more preferred due to the resistance against coloration. [0055] g represents a coordination number of diketone, g is 1 to 4, h is 0 to 3, and g+h represents a total coordination number of a metal. g is preferably 3 to 4 on the viewpoint of preventing self-polymerization, and g is preferably 1 to 2 on the viewpoint of preventing the reduction of the purity upon storage. [0056] R.sup.5 and R.sup.6 independently represent a hydrocarbon group having a carbon number of 1 to 5 or phenyl group, respectively. The hydrocarbon group may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be alkyl group and preferably be methyl group, ethyl group, normal propyl group, isopropyl group, butyl group or pentyl group, and methyl group is more preferred on the viewpoint of availability. [0057] R.sup.7 represents hydrogen or a hydrocarbon group having a carbon number of 1 to 3. R.sup.7 may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may preferably be alkyl group and more preferably be methyl group, ethyl group, n-propyl group, isopropyl group or the like, and hydrogen is most preferred on the viewpoint of availability. [0058] R.sup.8 is hydrogen or a hydrocarbon group having a carbon number of 1 to 6. R.sup.8 may be a straight-chain hydrocarbon group, a branched-chain hydrocarbon group, a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may preferably be an alkyl group and more preferably be methyl group, ethyl group, normal propyl group, isopropyl group, butyl group, pentyl group or hexyl group, and hydrogen is more preferred on the viewpoint of suppressing the reduction of the purity of a composition.

[0059] The metal chelate complex (b) may be applied alone or the two or more kinds may be applied in combination.

[0060] Provided that the total amount of the amido-group containing monomer (a) and metal chelate complex (b) is defined as 100.00 mass %, the concentration of the amido group-containing monomer (a) is made 80.00 to 99.99 mass %. In the case that the ratio of the amido group-containing monomer (a) is too high, the effect of preventing the self-polymerization cannot be obtained. The ratio is thus made 99.99 mass % or lower, and 99.95 mass % or lower is preferred and 99.90 mass % or lower is more preferred. Further, in the case that the ratio of the amido group-containing monomer (a) is too low, the metal chelate complex (b) may be precipitated. The ratio is thus made 80.00 mass % or higher, and 89.00 mass % or higher is preferred and 90.00 mass % or higher is more preferred.

(Polymerization Inhibitor)

[0061] A polymerization inhibitor may be optionally added to the composition of the present invention. As such component, although it is not limited, known compounds are listed as the polymerization inhibitor.

[0062] For example, polymerization inhibitors such as a phenol-based compound, a nitroso compound or a phenothiazine-based compound are listed.

[0063] The blending ratio of the polymerization inhibitor may preferably be 0 to 1.0 mass % and more preferably be 0.01 to 0.10 mass %, provided that the total amount of the amido group-containing monomer (a) and metal chelate complex (b) is defined as 100 mass %. In the case that the amount of the polymerization inhibitor is low, the effect of preventing the self-polymerization may be insufficient. In the case that the amount of the polymerization inhibitor is high, it may be the cause of the coloration.

(Method of Producing the Composition)

[0064] The method of producing the composition may be performed as follows. [0065] (1) The amido group-containing monomer (a) and metal chelate complex (b) are blended at a predetermined ratio and agitated so that the metal chelate complex is dissolved to produce the composition. [0066] (2) When a (meth) acrylic acid and alkanol amido are subjected to esterification with dehydration under the presence of an acid catalyst to generate the amido group-containing monomer (a), the metal chelate complex (b) is added to the reaction system to produce the composition. [0067] (3) When a (meth)acrylic ester and alkanol amido are subjected to transesterification reaction under the presence of a transesterification catalyst to generate the amido group-containing monomer (a), the metal chelate complex (b) is added to the reaction system to produce the composition. [0068] (4) When acrylic chloride and alkanol amide are reacted to generate the amido group-containing monomer (a), the metal chelate (b) is added to the reaction system to produce the composition.

[0069] Further, as the metal chelate complex (b) itself of the present invention, having carbonyl group as a ligand, functions as a transesterification catalyst, the metal chelate complex can be applied as the transesterification catalyst in the transesterification reaction of the (meth)acrylic ester and alkanol amido described above. In the case that it is applied for the transesterification reaction, the activity may be increased. It is thus possible to suppress the denaturing of the amido group-containing monomer (a) by denaturing a part of carbonyl group into hydroxy group by adding a small amount of water.

[0070] The amido group-containing monomer (a) of the present invention may be applied by blending it into a paint or coating material as such, for example, or may be applied by polymerization through radical polymerization or the like. As the amido group of the amido group-containing monomer (a) has high aggregating property, it can be adhered to a substrate of a high polarity, so that it is possible to improve the adherence of a paint. Further, according to the polymer containing the amido group-containing monomer (a), it is possible to improve the glass transition temperature of the polymer due to the strong intermolecular interaction derived from the amido group.

[0071] In the case that the self-polymerization of the amido group-containing monomer (a) takes place, the self-polymerization product other than the target product is contained in the polymer produced by applying the amido group-containing monomer (a) as the copolymer, so that the physical property of the product is considerably deteriorated. Further, as the viscosity of the polymerization product of the amido group-containing monomer (a) is relatively high, the viscosity of the product applying the amido group-containing monomer (a) may be increased and precipitation may occur in the product. Thus, it is preferred that the self-polymerization product is not contained. Further, in the case that the amido group-containing monomer is colorized due to the self-polymerization and it is applied in a coating or paint, there is the problem that the coloration derived from the amido group-containing monomer (a) may deteriorate the color phase or design of the product.

[0072] The properties described above (viscosity, precipitation and coloration) due to the self-polymerization of the amido group-containing monomer (a) can be evaluated according to the method described below.

EXAMPLES

Inventive Examples and Comparative Examples

[0073] Although embodiments of the present invention will be described further in detail below referring to the inventive examples and comparative examples, the present invention is not limited to them.

(Evaluation of Ratio of Increase of Viscosity)

[0074] A digital viscometer DV-I Prime manufactured by BROOKFIELD was applied to measure a viscosity (mPa.Math.S) at a melting temperature at 70 C. and a spindle of LV-1. The ratio of the increase of the viscosities before and after the storage test was calculated based on the following formula.

[00001]$\mathrm{Ratio}\mathrm{of}\mathrm{increase}\mathrm{of}\mathrm{viscosity}\left(\%\right)=\left[\left(\mathrm{viscosity}\mathrm{after}\mathrm{storage}-\mathrm{viscosity}\mathrm{before}\mathrm{storage}\right)/\mathrm{viscosity}\mathrm{before}\mathrm{storage}\right]100$

Judgement:

[0075] : less than 20% [0076] x: 20% or more

(Evaluation of Gardner Color Number)

[0077] A sample was adjusted at 70 C. and measured by Gardner color number meter.

Judgement of Gardner Color Number

[0078] : less than 7 [0079] x: 7 or more

(Evaluation of Solubility Test)

[0080] 10 g of DMF was added to 0.5 g of the sample and then agitated at 25 C. for 30 minutes, and the appearance was observed by eyes. [0081] : Turbidity is not observed. [0082] x: Turbidity is observed.

(Evaluation of Ratio of Change of Purity)

[0083] A gas chromatograph (Model: GC-2014 produced by SHIMADZU CORPORATION) and a column DB-1 were applied, and biphenyl was applied as an internal standard substance to measure the purity of the target substance in the sample, so that the ratio of change of purities before and after the long-term storage at 50 C.

[00002]$\mathrm{Ratio}\mathrm{of}\mathrm{change}\mathrm{of}\mathrm{purity}\left(\%\right)=\left[\mathrm{Purity}\left(\%\right)\mathrm{after}\mathrm{storage}/\mathrm{Purity}\left(\%\right)\mathrm{before}\mathrm{storage}\right]100$

Judgement of Ratio of Change of Purity

[0084] : 96% or higher [0085] x: lower than 96%

(Storage Test at 50 C.)

[0086] 100 g of each of the respective compositions of the inventive examples 1 to 12 and comparative examples 1 to 8 was weighed, left to stand at 50 C. for 48 hours, and the ratio of the increase of the viscosity, Gardner color number, solubility test and ratio of the change of purity were measured as described above.

(Long-Term Storage Test at 50 C.)

[0087] 100 g of each of the respective compositions of the inventive examples 1 to 12 and comparative examples 1 to 8 was weighed, left to stand at 50 C. for 240 hours, and the ratio of the increase of the viscosity, Gardner color number, solubility test and ratio of the change of purity were measured as described above.

[0088] Table 1 indicates the structure (R.sup.1, R.sup.2, R.sup.3 and R.sup.4 in the formula (1)) of the amido group-containing monomer (a) and abbreviations.

[0089] Table 2 shows the structure (R.sup.5, R.sup.6, R.sup.7, R.sup.8, g and h in the formula (2)) of the metal chelate complex (b) or (b) and abbreviations.

[0090] Further, table 3 shows the polymerization inhibitors and abbreviations.

TABLE-US-00001 TABLE 1 Table 1, Amido group-containing monomer (a) R.sup.1 R.sup.2 R.sup.3 R.sup.4 (a)-1 H CH.sub.2CH.sub.2 CH.sub.3 (methyl group) H (a)-2 H CH.sub.2CH.sub.2 (CH2).sub.6CH.sub.3 (heptyl group) H (a)-3 H CH.sub.2CH.sub.2 (CH.sub.2).sub.16CH.sub.3 (heptadecyl group) H (a)-4 CH.sub.3 CH.sub.2CH.sub.2 CH.sub.3 (methyl group) H (a)-5 H CH.sub.2CH.sub.2CH.sub.2CH.sub.2 CH.sub.3 (methyl group) H (a)-6 H CH.sub.2CH.sub.2 CH.sub.3 (methyl group) CH.sub.3

TABLE-US-00002 TABLE 2 Table 2 Metal chelate complex (b) or (b) M R.sup.5 R.sup.6 R.sup.7 R.sup.8 g h (b)-1 Zr CH.sub.3 CH.sub.3 H H 4 0 (b)-2 Zr CH.sub.3 CH.sub.3 H H 1 3 (b)-3 Fe CH.sub.3 CH.sub.3 H H 3 0 (b)-1 Zr CH.sub.3 CH.sub.3 H H 0 4

TABLE-US-00003 TABLE 3 Table 3, Polymerization inhibitor (c) Polymerization inhibitor Name (c)-1 Tertially butyl hydroquinone (c)-2 hydroquinone (c)-3 Phenothiazine

Inventive Examples 1 to 12 and Comparative Examples 1 to 8

[0091] As shown in table 4, table 5, table 6 and table 7, the amido group-containing monomer (a), metal chelate complex (b) and polymerization inhibitor (c) were selected, blended and mixed according to the respective blending ratios to obtain the respective compositions.

[0092] Further, as the component (b-2), zirconium isopropoxide was applied.

TABLE-US-00004 TABLE 4 Inv. Ex. 1 Inv. Ex. 2 Inv. Ex. 3 Inv. Ex. 4 Inv. Ex. 5 Inv. Ex. 6 Monomer Amido group-containing (a)-1 95 composition monomer (a) (weight parts) (a)-2 95 (a)-3 95 (a)-4 95 (a)-5 95 (a)-6 95 Metal chelate complex(b) (b)-1 5 5 5 5 5 5 (weight parts) (b)-2 (b)-3 Polymerization (c)-1 Inhibitor (c) (c)-2 (weight parts) (c)-3 Evaluation Storage test at 50 C. Ratio of increase of (2) (1) (0) (2) (1) (2) viscosity % Gardner color number (4) (4) (4) (4) (4) (4) Solubility test (No (No (No (No (No (No turbidity) turbidity) turbidity) turbidity) turbidity) turbidity) Long term storage test Ratio of increase of (5) (3) (1) (4) (2) (4) at 50 C. viscosity % Gardner color number (4) (5) (4) (4) (4) (4) Solubility test (No (No (No (No (No (No turbidity) turbidity) turbidity) turbidity) turbidity) turbidity) Ratio of change of (98) (98) (100) (98) (98) (98) purity %

TABLE-US-00005 TABLE 5 Inv. Ex. 7 Inv. Ex. 8 Inv. Ex. 9 Inv. Ex. 10 Inv. Ex. 11 Inv. Ex. 12 Monomer Amido group-containing (a)-1 47.5 composition monomer (a) (weight parts) (a)-2 90 99.5 95 95 47.5 95 (a)-3 (a)-4 (a)-5 (a)-6 Metal chelate complex(b) (b)-1 10 0.5 2.5 5 (weight parts) (b)-2 5 2.5 (b)-3 5 Polymerization (c)-1 0.05 Inhibitor (c) (c)-2 (weight parts) (c)-3 Evaluation Storage test at 50 C. Ratio of increase of (0) (6) (8) (4) (2) (0) viscosity % Gardner color number (4) (4) (4) (7) (4) (5) Solubility test (No (No (No (No (No (No turbidity) turbidity) turbidity) turbidity) turbidity) turbidity) Long term storage test Ratio of increase of (0) (8) (12) (6) (4) (0) at 50 C. viscosity % Gardner color number (4) (4) (4) (7) (4) (6) Solubility test (No (No (No (No (No (No turbidity) turbidity) turbidity) turbidity) turbidity) turbidity) Ratio of change of (97) (99) (99) (98) (98) (98) purity %

TABLE-US-00006 TABLE 6 Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Mono- Amido group- (a)-2 100 100 100 mer containing compo- monomer (a) sition (weight parts) Metal chelate (b)-1 complex(b) (b)-1 5 (weight parts) (b)-2 5 Polymerization (c)-1 Inhibitor (c) (c)-2 (weight parts) (c)-3 Evalu- Storage test at Ratio of increase x(825) x(725) x(795) ation 50 C. of viscosity % Gardner color (5) (6) (6) number Solubility test x(turbidity found) x(turbidity found) x(turbidity found) Long term Ratio of increase x(Unmeasurable)*1 x(Unmeasurable)*1 x(Unmeasurable)*1 storage test of viscosity % at 50 C. Gardner color x(17) x(18) x(18) number Solubility test x(turbidity found) x(turbidity found) x(turbidity found) Ratio of change x(Unmeasurable) x(Unmeasurable) x(Unmeasurable) of purity %

TABLE-US-00007 TABLE 7 Com. Ex. 4 Com. Ex. 5 Com. Ex. 6 Com. Ex. 7 Com. Ex. 8 Monomer Amido group- (a)-2 99.9 99.9 99.9 99.5 75 composition containing monomer (a) (weight parts) Metal chelate (b)-1 25 complex(b) (b)-1 (weight parts) (b)-2 Polymerization (c)-1 0.1 0.5 Inhibitor (c) (c)-2 0.1 (weight parts) (c)-3 0.1 Evaluation Storage test at Storage test at x(205) x(265) x(235) (5) (0) 50 C. 50 C. Gardner color x(8) x(10) x(11) x(15) (5) number Solubility test x(turbidity x(turbidity x(turbidity (no (no found) found) found) turbidity) turbidity) Long term storage Long term storage x(unmeasurable)*1 x(unmeasurable)*1 x(unmeasurable)*1 (9) (0) test at 50 C. test at 50 C. Gardner color x(>18)*2 x(>18)*2 x(>18)*2 x(17) (5) number Solubility test x(turbidity x(turbidity x(turbidity (no (no found) found) found) turbidity) turbidity) Ratio of change of x(unmeasurable) x(unmeasurable) x(unmeasurable) (98) x(95) purity % [0093] 1: The measurement could not be performed due to the gelation and high viscosity. [0094] 2: The limit of Gardner color number is 18. Due to the gelation and solidification, light from a back light of a Gardner system is not transmitted and blocked, so that the color is thickened and the Gardner color number is increased.

[0095] As can be seen from the results shown in table 4 and table 5, according to the inventive examples 1 to 12, the amido group-containing monomer compositions each having good ratio of increase of viscosity, Gardner color number, solubility test and ratio of change of purity were obtained. Particularly good results were obtained, in the inventive examples 1 to 8, 11 and 12 with zirconium acetylacetonate applied and in the inventive example 9 with the partial hydroxide of zirconium acetylacetonate applied.

[0096] On the other hand, according to the comparative examples 1 to 3, as the metal chelate complex (b) of the formula (2) was not added, self-polymerization occurred during the storage test at 50 C. and long-term storage test at 50 C. of the amido group-containing monomer composition, resulting in deterioration of the results of the ratio of increase of viscosity and solubility test.

[0097] Further, as to the comparative examples 4 to 7 in which the metal chelate complex (b) of the formula (2) was not added and instead the polymerization inhibitor was applied, self-polymerization and coloration occurred and the ratio of increase of viscosity, Gardner color number and solubility test were not good according to the comparative examples 4 to 6 in which the amount of the polymerization inhibitor was small. Further, according to the comparative example 7 in which the amount of the polymerization inhibitor is large, the coloration occurred and Gadner color number was not good.

[0098] Further, according to the comparative example 8 in which the added amount of the metal chelate complex (b) was excessive, the reduction of the purity was observed.