JPH0762279A - Coating, ink composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in the flexibility, rigidity and mechanical strength of the coating films therefrom by incorporating a pigment, etc., with a specific zirconium compound, etc., at specified proportions. CONSTITUTION:A composition is first obtained by incorporating (A) a pigment (e.g. carbon black) plus inorganic filler with (B) 0.01-20wt.% of an unsaturated side chain-bearing zirconium or aluminum compound of formula I [M is zirconium or aluminum; X is of formula II (R<2> and R<3> are each 1-30C alkyl, alkenyl or alkoxyl), etc.; Y is of formula III (R<5> and R<6> are each H or CH3; T is O or H2; p is 0-20), etc.; Z is of formula IV (h is the same as p); R<1> is 1-8C alkyl; x is 3; u is 0-2; v is 0-3; w is 0-1]. It is preferable that the objective coating, ink composition comprise (a) 1 pt.wt. of the above composition, (b) 0.15-9 pts.wt. of a resin component such as acrylic resin and (c) 0.15-45 pts.wt. of a solvent component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to paints and inks having high coating strength.

[0002]

2. Description of the Related Art Usually, a dispersant is used in order to improve the dispersibility of a pigment or a filler in a paint. Fatty acid salts, various surfactants, polyester-based oligomers, etc. are typical dispersants, but titanate-based, aluminum-based, zirconium-based, and silane-based surface modifiers have also been used for the same purpose. Of these, titanate-based, aluminum-based, and zirconium-based are mainly viscosity reducing agents, high filling agents,
As a dispersant, silanes are used as a dispersant and a rigidity-imparting agent. Affinities for the fillers differ from each other. Titanate-based and zirconium-based ones have a great effect on TiO ₂ , iron oxide, CaCO _3, etc., but slightly weaker effect on silica, glass, etc., and silane-based ones. , Is known to have the opposite effect. In addition, the aluminum type has a high affinity for carbon black.

On the other hand, one of the important properties of the coating film is the coating strength. This has surface hardness, peel strength, material conformability, etc., and is a physical property related to the flexibility and rigidity of the coating film. The above-mentioned titanate-based, aluminum-based, and zirconium-based are used to impart flexibility to the coating film,
A silane type is used for rigidity. However, flexibility,
There are not many surface treatment agents that give rigidity. Also TiO
_2. Currently, it is difficult to increase the rigidity of coating films containing calcium carbonate. Incidentally, for the purpose of imparting rigidity, there is a titanate compound having a maleic acid skeleton described in JP-A No. 61-204278, but according to the studies by the present inventors, the expected effect can be obtained by using the compound. There wasn't.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a paint and an ink having improved pigment dispersibility, coating film flexibility and rigidity.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, found that a metal compound containing a certain unsaturated side chain can achieve the above object, The present invention has been completed.

The present invention is a paint or ink composition prepared by blending 0.01 to 20% by weight of a zirconium or aluminum compound having an unsaturated side chain represented by the following general formula (I) with a pigment and an inorganic filler. Is.

[0007]

[Chemical 5]

In the above formula, M represents a zirconium or aluminum atom, X represents a group represented by any one of the following general formulas (a) to (ki), and Y represents a general formula (h) to (so) below.
, Z represents a group represented by (ta), and R ¹ represents an alkyl group having 1 to 8 carbon atoms.

[0009]

[Chemical 6]

[0010]

[Chemical 7]

[0011]

[Chemical 8]

In the above groups, R ² and R ³ may be the same or different, but are an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an alkoxyl group, and R ⁴ is an alkyl group having 1 to 30 carbon atoms. R ⁵ and R ^{6, which} may be the same or different, are H or CH ₃ , T is O or H ₂ , and W ^{1 to} W ⁴ may be the same or different, but have 1 to 20 carbon atoms. Alkyl group, H, halogen atom,
Represents a nitro group or an acyl group, p, q, r and h each represent an integer of 0 to 20 (provided that when T is O, p and q are integers of 1 to 20), and A
Represents (ko) or (sa). However, when M is a zirconium atom, x is always 4, but u is 0 to 3
Is an integer of 0, v is an integer of 0 to 4, w is an integer of 0 to 2, and when v = 0, w = 1 to 2, and v =
When 1 to 4, w = 0 to 1 and u + v + 2w ≦ 4 is satisfied (Zr compound), and when M is an aluminum atom, x is always 3, but u is an integer of 0 to 2. , V is an integer from 0 to 3, w is an integer from 0 to 1, and w = 1 when v = 0, w = 0 when v = 1 to 3, and u + v + 2w ≦ 3 is satisfied (Al compound).

The zirconium compound having an unsaturated side chain and the aluminum compound of the present invention can be generally produced by the following method known per se. That is,
(A) A compound containing at least one compound represented by the following general formula (III) represented by the following general formula (IV) is represented by the following general formula (IV). At least one of the compounds having an unsaturated side chain is subjected to a total t-fold molar reaction (provided that s is 0 to 3, t is 0.1 to 4, and s + t ≦ 4), (b). At least one of the compounds represented by the following general formula (III) is added to the alkoxyzirconium compound represented by the following general formula (II) in a total u-fold mole and a non-representative compound represented by the following general formula (V). At least one of the glycerin derivatives having a saturated side chain is subjected to a total v-fold molar reaction (provided that u is 0 to 3, v is 0.05 to 2,
And u + 2v ≦ 4), (c) the following general formula (II) ′
At least one of the compounds represented by the following general formula (III) with respect to the alkoxyaluminum compound represented by
At least one of the compounds having a total of s times mol and a compound having an unsaturated side chain represented by the following general formula (IV) is reacted at a total t times mol (where s is 0 to 2.5, t
Is 0.1 to 3 and s + t ≦ 3), or (d)
At least one of the compounds represented by the following general formula (III) is represented by the total u-fold mole and the following general formula (V) with respect to the alkoxyaluminum compound represented by the following general formula (II) ′. At least one of the glycerin derivatives having unsaturated side chains is subjected to a total v-fold molar reaction (provided that u is 0 to 2.5, v is 0.05 to 1.5, and u + 2v ≦ 3). It can be manufactured.

[0014]

[Chemical 9]

In the above formula, R ¹ , R ⁵ , R ⁶ , X, Y and T
And h are the same as in the general formula (I).
It should be noted that the amount of each raw material used in the above reaction is not limited as long as the zirconium compound or the aluminum compound according to the present invention is produced, and the amounts described above are merely standard amounts. , But not limited to these amounts. In addition, the above reaction is carried out according to the general formula (IV)
Alternatively, when the reaction is carried out in the presence of a large excess of the unsaturated compound represented by (V) and such an unsaturated compound as a reaction residue is brought together with the target compound into the surface modifier of the pigment or the inorganic filler, The unsaturated compound becomes a diluent and is convenient.

In any case, the reaction can be carried out without a solvent or in a suitable organic solvent such as isopropyl alcohol, toluene, xylene or the like at a temperature from room temperature to about 150 ° C. for several hours to hold the raw material. By reacting in this way, and then removing the by-produced alcohol and the used solvent by distillation or the like, the target substance zirconium compound or aluminum compound is obtained as a highly viscous liquid, wax or powdery substance. . It should be noted that the compounds belonging to the above general formulas can be used in combination of a plurality of types, as can be easily guessed from the above. When the total amount of the raw materials represented by the general formula (IV) (including the combined use) is less than the above range, the content of the zirconium or aluminum compound of the present invention is small, and thus the conventional coupling There is no difference in effect with the agent, on the other hand, when the total amount of the compound represented by the general formula (III) and the compound represented by the general formula (IV) exceeds the above range, a pigment or an inorganic filler Since there are few alkoxyl groups that react with, the reactivity with pigments and inorganic fillers becomes poor.

The general formula (II) which is a raw material of the compound of the present invention
As the alkoxyzirconium compound represented by, for example, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, tetrabutoxyzirconium, and the like, tetrapropoxyzirconium, tetraisopropoxy from the viewpoint of reactivity and economy. Zirconium and tetrabutoxyzirconium are preferred. Examples of the alkoxy aluminum compound represented by the general formula (II) ′ include trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum,
Examples thereof include tributoxyaluminum, and the like, and triisopropoxyaluminum and tributoxyaluminum are preferable from the viewpoint of reactivity and economy.

The general formula (I
As R ² and R ³ in the compound represented by II),
_{CH 3, C 2 H 5,} C 3 H 7, C 4 H 9, C 5 H 11, C
₆ H ₁₃ , C ₇ H ₁₅ , C ₈ H ₁₇ , C ₉ H ₁₉ , C ₁₀ H ₂₁ , C
₁₁ H ₂₃ , C ₁₂ H ₂₅ , C ₁₃ H ₂₇ , C ₁₄ H ₂₉ , C ₁₅ H ₃₁ , C
₁₆ H ₃₃ , C ₁₇ H ₃₅ , C ₁₈ H ₃₇ , C ₁₉ H ₃₉ , C ₂₀ H ₄₁ , C
_{H 3 O, C 2 H 5} O, C 3 H 7 O, C 4 H 9 O, C 5 H
₁₁ O, C ₆ H ₁₃ O, C ₇ H ₁₅ O, C ₈ H ₁₇ O, C ₉ H ₁₉
O, C ₁₀ H ₂₁ O, C ₁₁ H ₂₃ O, C ₁₂ H ₂₅ O, C ₁₃ H
₂₇ O, C ₁₄ H ₂₉ O, C ₁₅ H ₃₁ O, C ₁₆ H ₃₁ O, C ₁₆ H ₃₃
O, C ₁₇ H ₃₅ O, C ₁₇ H ₃₃ O, C ₁₈ H ₃₇ O, C ₁₈ H
₃₅ O, C ₁₉ H ₃₉ O, C ₂₀ H ₄₁ O and the like can be mentioned, but from the viewpoint of economy, CH ₃ , C ₂ H ₅ , CH ₃ O, C
₂ H ₅ O, C ₃ H ₇ O, C ₄ H ₉ O, C ₁₀ H ₂₁ O, C ₁₂
H ₂₅ O, C ₁₄ H ₂₉ O, C ₁₆ H ₃₃ O, C ₁₆ H ₃₁ O, C ₁₈ H
₃₇ O and C ₁₈ H ₃₅ O are preferred, and R ⁴ is C
_{H 3, C 2 H 5,} C 3 H 7, C 4 H 9, C 5 H 11, C 6
_{H 13, C 7 H 15,} C 8 H 17, C 9 H 19, C 10 H 21, C 11
_{H 23, C 12 H 25,} C 13 H 27, C 14 H 29, C 15 H 31, C 16
H ₃₁ , C ₁₆ H ₃₃ , C ₁₇ H ₃₅ , C ₁₈ H ₃₅ , C ₁₈ H ₃₇ , C ₁₉
H ₃₉ , C ₂₀ H _{41 and the} like can be mentioned, but from the viewpoint of economic efficiency, C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , C ₁₀ H ₂₁ , C _{12
H 25, C 14 H 29,} C 16 H 31, C 16 H 33, C 18 H 35 and C ₁₈ H ₃₇ are preferable.

Among the compounds represented by the general formula (IV), which are still other starting materials for the compound of the present invention, W ^{1 to} W ⁴ in the phthalic acid derivative having an unsaturated side chain are H, CH ₃ ,
_{C 2 H 5, C 3 H} 7, C 4 H 9, C 5 H 11, C 6 H 13,
_{C 7 H 15, C 8 H} 17, C 9 H 19, C 10 H 21, C 11 H 23,
_{C 12 H 25, C 13 H} 27, C 14 H 29, C 15 H 31, C 16 H 31,
_{C 16 H 33, C 17 H} 35, C 18 H 35, C 18 H 37, C 19 H 39,
C ₂₀ H ₄₁ , Cl, Br, I and the like can be mentioned,
From the viewpoint of economy, H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄
H ₉ , Cl, Br and I are preferred. In addition, W ¹ ~
There is no problem even if W ₄ is another functional group such as a nitro group or an acyl group.

Further, a group in a compound having an unsaturated side chain represented by the general formula (IV), which is another raw material of the compound of the present invention, and which has any of the groups (co) to (so) (Ko) or (sa) and (ko) or (sa) is A
As the groups (si) to (so) having as, R ⁵ is H, R
⁶ is CH ₃ , T is O, and r is 0-20,
R ⁵ is H, R ⁶ is H, T is O, and r is 0 to 12, R ⁵ is H, R ⁶ is CH ₃ , T is H ₂ , and r
Is 0 to 20, R ⁵ is H, R ⁶ is H, and T is H.
₂ , and r is 0 to 20, R ⁵ is CH ₃ , R
⁶ is CH ₃ , T is O, and r is 0-20,
R ⁵ is CH ₃ , R ⁶ is H, T is O, and r is 0 to 20.
Where R ⁵ is CH ₃ , R ⁶ is CH ₃ , T is H ₂ ,
And r is 0 to 20, and R ⁵ is CH ₃ ,
R ⁶ is H, T is H _2, and r can be mentioned those 0-20. These compounds represented by the general formula (IV) have the same effect regardless of whether R ⁵ is H or CH ₃ .

As the glycerin derivative having an unsaturated side chain represented by the general formula (V), which is another raw material of the compound of the present invention, R ⁵ is H, R ⁶ is CH ₃ , T is O, and h Is 0 to 20, R ⁵ is H, R ⁶ is H, T is O, and h is 0 to 20, R ⁵ is H, R ⁶ is CH ₃ , T is H ₂ , and h Is 0 to 20, R
⁵ is H, R ⁶ is H, T is H ₂ , and h is 0 to 20, R ⁵ is CH ₃ , R ⁶ is CH ₃ , T is O, and h is 0 to 20, R ⁵ is CH ₃ , R ⁶ is H, T
Is O and h is 0 to 20, R ⁵ is CH ₃ ,
R ⁶ is CH _3, T is H _2, and what h is 0 to 20, and R ⁵ may include those CH _3, R ⁶ is 0 to 20 H, T is H _2, and h is You can

In producing the metal compound having an unsaturated side chain of the present invention, hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,6-t-butyl-p-cresol, 2 , 3-
It goes without saying that a radical polymerization inhibitor such as dimethyl-6-t-butylphenol, anthraquinone, phenothiazine and tocophenol may be added.

The pigment and the inorganic filler in the present invention are carbon black, acetylene black, pine smoke, graphite, ivory black, bone black, pine black, titanium oxide, iron oxide black, manganese black, ilmenite black, yellow lead, cadmium. Yellow, zinc yellow, cyanamide lead, Naples yellow, ultramarine yellow, male yellow, vermilion, cadmium red, antimony red, red iron oxide, ultramarine red, ultramarine violet, cobalt violet, manganese violet, Prussian blue, cobalt blue, chromium oxide green , Guinea green, chrome green, zinc green, green soil, patina, flower patina, iron oxide yellow, ocher, sheena, amber, chalk, calcium carbonate, rice, barite powder, barium sulphate, clay, and powder, ground Powder, talc, silica, glass powder, silica powder, diaper Soil, alumina, gypsum, Hansa Yellow, Toluidine Red, Litol Red, Phthalocyanine Blue, Phthalocyanine Green, Quinacridone Red, Aluminum powder, Bronze powder, Red lead, Cyanamide lead, Lead chromate, Lead sulfate, Zinc dust, Lead suboxide, MO / F
Ferrite magnetic powder samarium cobalt, neodymium iron cobalt, zirconium cobalt, or the like made of e ₂ O ₃ (M is one or more of Ba, Sr, Ca, Mg, Zn, and Pb) can be used. In particular, carbon, metal hydroxide, metal oxide, carbonate, sulfate, chromate, silicate, organic pigment, magnetic powder and the like are effective. The shape is not limited at all.

The resin component is not particularly limited either, but rosin,
In addition to natural resins such as shellac and gilsonite, acrylic resins, phenolic resins, amino resins such as butyl urea and melamine resins, alkyd resins, polyester resins such as unsaturated polyester, polyamide resins, epoxy resin resins, vinyl chloride, vinyl acetate, etc. The vinyl resin type, the cellulose resin type such as nitrocellulose resin, the urethane resin type, the petroleum resin type, the fluorine resin and the like can be mentioned, but the acrylic type and the unsaturated polyester type are particularly effective. The addition amount is 0.15 to 9 parts by weight with respect to 1 part by weight of the pigment and the inorganic filler, but in the case of a magnetic paint, it is generally 0.15 to 0.6 part by weight with respect to 1 part by weight of magnetic powder. . If it is more than the above range, the fluidity of the coating material is deteriorated, and if it is less than the above range, it causes problems such as sagging and the strength of the coating film. The curing agent usually used in each paint system is not particularly limited.

The solvent system is not particularly limited as long as it dissolves the resin, and it may be used in combination with vegetable oil or drying oil.
The addition amount is 0.15 with respect to 1 part by weight of the pigment and the inorganic filler.
Although the amount is up to 45 parts by weight, if the amount is more than 45 parts by weight, dripping, pigment settling and the like will be hindered, and if it is less than this, the fluidity will be poor.

The surface modification method of the pigment and the inorganic filler is carried out by directly adding 0.1 to 20% by weight, preferably 0.5 to 5% by weight of the surface modifier to the pigment and the inorganic filler, and applying the Henschel mixer. And the like, and a wet method in which the solvent is removed after the pigment and the inorganic filler are dipped in the solution. In addition, an effect which is often used in the preparation of paints, such as an integral method in which a surface modifier is added at the time of kneading with a vehicle and various additives, can sufficiently exert the effect. It should be noted that even if the addition amount is large, at least the effect is small.

Further, a thickening agent within a range that does not impair the characteristics,
The use of commonly used paint ink additives such as anti-settling agents, antifouling agents, antistatic agents, etc. is all right.

The effects of the present invention are exhibited by the following mechanism.
The zirconium or aluminum compound having an unsaturated side chain in the present invention has an affinity for many pigments and inorganic fillers, and is rapidly adsorbed on the surface in paint. In addition, since the metal compound in the present invention has a relatively long side chain, good wettability with an organic matrix such as a resin or a solvent results in dispersibility of a pigment or an inorganic filler and flexibility of a coating film. Is improved. Further, since the terminal has a double bond capable of reacting with the resin and the solvent component, the rigidity of the coating film is also improved.

Next, the contents of the present invention will be described in detail with reference to examples. It should be noted that the following examples do not limit the scope of the present invention, but are intended to more clearly illustrate the characteristics of the present invention.

Synthesis Examples 1 and 2 100 g (675 mmol) of phthalic anhydride and 88 g (677 mmo) of ethylene glycol monomethacrylate.
l) and p-methoxyphenol 1 g (8 mmol) 8
Mixing at 0 ° C. for 3 hours, 188 g of phthalic acid monoester was synthesized, and 17 g (61 mmol) of this ester was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate.
23 g of metal compound Z-1 was prepared by reacting at 40 ° C. for 2 hours while distilling off the low-boiling alcohol produced as a by-product. In addition, 1.86 g of isostearic acid (6.5 mmo)
l) was added dropwise to 5 g of Z-1 (6.5 mmol) at 40 ° C.
The reaction was carried out for 2 hours while distilling off the alcohol to prepare 6.4 g of metal compound Z-2.

Synthesis Examples 3 to 8 Phthalic anhydride 100 g (675 mmol), polyoxyethylene monomethacrylate (polymerization degree of polyoxyethylene 4) 177 g (675 mmol), and p-methoxyphenol 1 g (8 mmol) were mixed at 80 ° C. for 3 hours. , Phthalic acid monoester 277g was synthesized.
1.2 g (61 mmol) was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate, and the reaction was carried out at 40 ° C. for 2 hours while distilling off the low boiling alcohol produced as a by-product to prepare 47 g of the metal compound Z-3. Similarly, 75.3 g (91.5 mmol) of the phthalic acid ester was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate.
While distilling alcohol off, the reaction was carried out at 40 ° C. for 2 hours to prepare 79 g of metal compound Z-4. Also Z-3, Z-4
Mix 10 g each with 5 g of the above phthalate ester to give Z
-5 and Z-6. Similarly, Z-3 and Z-4 are each 1
0 g was mixed with 5 g of polyoxyethylene dimethacrylate (degree of polymerization: 4) to give Z-7 and Z-8.

Synthesis Examples 9 to 12 Phthalic anhydride 100 g (675 mmol), polyoxyethylene monoacrylate (polyoxyethylene polymerization degree 9) 316.5 g (675 mmol), p-methoxyphenol 2 g (16 mmol) at 80 ° C. Time-mixed, 416 g of phthalic acid monoester was synthesized, 18.8 g (30.5 mmol) of this ester was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate, and the by-produced low boiling point alcohol was distilled off at 40 ° C. for 2 hours. By reacting for a period of time, 26 g of a metal compound Z-9 was prepared. Further, 10.5 g (22.6 mmol) of ditridecyl phosphate was added dropwise to 10 g of Z-9 (11.3 mmol),
While distilling alcohol off, the reaction was carried out at 40 ° C. for 2 hours to prepare 19 g of metal compound Z-10. Also Z-9, Z-
10 g of each was mixed with 5 g of 2-ethylhexyl methacrylate to give Z-11 and Z-12.

Synthesis Examples 13 to 16 Maleic anhydride 100 g (1.02 mol), polyoxyethylene monomethacrylate (polyoxyethylene polymerization degree 4) 689 g (1.02 mol), p-methoxyphenol 2 g (16 mmol) were added at 80 ° C. Mixing for 3 hours, synthesize maleic acid monoester 788 g, add 23.6 g (30.5 mmol) of this ester to 10 g (30.5 mmol) of tetrapropyl zirconate, and distill off the low boiling point alcohol by-produced at 40 ° C. And reacted for 2 hours to prepare 31 g of the metal compound Z-13. Similarly, the maleic acid ester 47.2 g (61.1 mmo)
10 g of tetrapropyl zirconate (30.5 m)
(mol) to prepare 53 g of the metal compound Z-14. Also, Z-13 and Z-14 each 10g, styrene 5
g was mixed to obtain Z-15 and Z-16.

Synthesis Examples 17 and 18 100 g (1.02 mol) of maleic anhydride, 148 g (1.02 mol) of polyoxyethylene monoallyl (degree of polymerization of polyoxyethylene 2), and 1 g (8 mmol) of p-methoxyphenol were added at 80 ° C. Mixed for 3 hours to synthesize maleic acid monoether (148 g).
8 g (60.9 mol) was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate, and the reaction was carried out at 40 ° C. for 2 hours while distilling off the low boiling alcohol produced as a by-product to prepare 21 g of a metal compound Z-17. Similarly, 22.2 g (91.4 mmol) of the above ether was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate to prepare 26 g of the metal compound Z-18.

Synthesis Examples 19 to 22 Diketene 50 g (595 mmol), polyoxyethylene monomethacrylate (polyoxyethylene polymerization degree 4) 401 g (594 mmol), p-methoxyphenol 2 g (16 mmol), 4-dimethylaminopyridine 100 mg (0 .8 mmol) was mixed at 80 ° C. for 3 hours to synthesize 450 g of acetoacetic acid ester, 46.3 g (61 mmol) of this ester was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate, and low-boiling alcohol by-produced was distilled off. While reacting at 40 ° C. for 2 hours, 52 g of metal compound Z-19 was prepared. Similarly, 69.5 g (91.6 mmol) of the acetoacetic acid ester was added dropwise to 10 g (30.5 mmol) of tetrapropyl zirconate to prepare 74 g of the metal compound Z-20. Also Z
-19 and Z-20 each mixed with 5 g of polyoxyethylene dimethacrylate (degree of polymerization 4), Z-21, Z
It was set to -22.

Synthesis Examples 23 to 26 100 g (675 mmol) of phthalic anhydride, 177 g (675 mmol) of polyoxyethylene monomethacrylate (polymerization degree of polyoxyethylene 4) and 1 g (8 mmol) of p-methoxyphenol were mixed at 80 ° C. for 3 hours. , Phthalic acid monoester 277g was synthesized.
0.3 g (49 mmol) was added dropwise to 10 g (49 mmol) of triisopropoxyaluminum, and the reaction was carried out at 40 ° C. for 2 hours while distilling off the low boiling point alcohol produced as a by-product to prepare 47 g of the metal compound A-1. Similarly, 80.6 g (98 mmol) of the phthalic acid ester was added dropwise to 10 g (49 mmol) of triisopropoxyaluminum and reacted at 40 ° C. for 2 hours while distilling alcohol to prepare 84 g of metal compound A-2. Further, 5 g of polyoxyethylene dimethacrylate (polymerization degree: 9) was mixed with 10 g of each of A-1 and A-2 to give A-3 and A-4.

Synthesis Examples 27 to 30 Diketene 50 g (595 mmol), polyoxyethylene monomethacrylate (polyoxyethylene polymerization degree 4) 401 g (594 mmol), p-methoxyphenol 2 g (16 mmol), 4-dimethylaminopyridine 100 mg (0 0.8 gm) was mixed at 80 ° C. for 3 hours, 450 g of acetoacetic acid ester was synthesized, 37.2 g (49 mmol) of this ester was added dropwise to 10 g (49 mmol) of triisopropoxyaluminum, and 40% while distilling low-boiling alcohol by-produced. 44.2g of metal compound A-5 was prepared by reacting at 0 ° C for 2 hours. Further, oleyl acetoacetate 7.8 g (22.
1 mmol) was added dropwise to prepare 26 g of the metal compound A-6. Further, 10 g each of A-5 and A-6 was mixed with 5 g of phthalic acid ester of polyoxyethylene monomethacrylate used in Synthesis Example 23 to obtain A-7 and A-8.

Synthesis Example 31 The following is a synthesis example for a comparative example. To 10 g (35.2 mmol) of tetrapropyl titanate, 16.5 g (105 mmol) of monoallyl maleate and 0.1 g (0.8 mmol) of p-methoxyphenol were added, and the low boiling point alcohol by-produced was distilled off at 40 ° C. After reacting for 2 hours, 20 g of a metal compound compound T-1 was prepared. To 10 g (35.2 mmol) of tetrapropyl titanate,
Monooleyl maleate 25.8 g (70.5 mmo
l), 0.1 g of p-methoxyphenol (0.8 mmo
1) was added, and the reaction was carried out at 40 ° C. for 2 hours while distilling off the low-boiling-point alcohol produced as a by-product to give the metal compound compound T-2 to 3
1 g was prepared.

Examples 1 to 30 and Comparative Examples 1 to 8 100 parts by weight of unsaturated polyester (Polymer 9305Z manufactured by Takeda Pharmaceutical Co., Ltd.), 10 parts by weight of titanium oxide (TCR-10, TOKEM PRODUCTS Co., Ltd.) , Calcium carbonate (Sankyo Flour Milling Co., Ltd., Escalon 100) 20 parts by weight, curing catalyst (NOF Corporation, Perbutyl O)
0.7 parts by weight and 0.6 parts by weight of one of the treating agents Z-1 to 22 and A-1 to 8 were mixed in a paint shaker for 30 minutes to prepare a paint. Mild steel plate (0.8 x 70 x 150 mm) obtained by degreasing this paint with xylene and acetone
Was coated using a 40 bar coater and heat-cured at 130 ° C. for 30 minutes to form a coating film test piece. The adhesion of this coating film test piece was measured by 100 cross cut (10 mm × 10 m
m, 1 square 1 mm × 1 mm) tape peeling test (n = 2 average). Further, the pencil hardness and the material conformability by an Erichsen tester (manufactured by Ueshima Seisakusho Co., Ltd.) were examined. For comparison, a titanate-based coupling agent (manufactured by Ajinomoto Co., Inc., Planeact KR TT) was used instead of the above treatment agent.
S, KR 38S), silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A-171, A-174), unsaturated acid ester-based dispersant (manufactured by Big Chemie Japan Co., Ltd., B)
Ykumen), T-1, T-2 and tests without additives were carried out. The results are shown in Table 1.

[0040]

[Table 1]

Examples 31 to 60, Comparative Examples 9 to 16 100 parts by weight of acrylic resin MMA solution (Acrysilap SY-430 manufactured by Mitsubishi Rayon Co., Ltd.), 10 parts by weight of red iron oxide (manufactured by Bayer, 110M), water Aluminum oxide (Showa Light Metal Co., Ltd., Heidilite H-32)
20 parts by weight, 0.7 parts by weight of curing catalyst (Perbutyl O produced by NOF CORPORATION) and treating agents Z-1 to 22 and A-1 to 8
From 1 type, 0.4 parts by weight was mixed with a paint shaker for 30 minutes to prepare a paint. Mild steel plate (0.8 × 70 × 150 m) degreased with xylene and acetone
m) is applied using a 40 bar coater, and at 130 ° C for 3
A coating film test piece was formed by heat curing for 0 minutes. The adhesion of this coating film test piece was measured by 100 cross cut (10 mm × 10
mm, 1 square 1 mm × 1 mm) was peeled off and tested (average of n = 2). Further, the pencil hardness and the material conformability by an Erichsen tester (manufactured by Ueshima Seisakusho Co., Ltd.) were examined. For comparison, a titanate-based coupling agent (manufactured by Ajinomoto Co., Inc., Planeact KR TT) was used instead of the above treatment agent.
S, KR 38S), silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A-171, A-174), unsaturated acid ester-based dispersant (manufactured by Big Chemie Japan Co., Ltd., B)
Ykumen), T-1, T-2 and tests without additives were carried out. The results are shown in Table 2.

[0042]

[Table 2]

[0043]

As described above, it can be seen that the coating material and ink of the present invention have improved peeling strength, coating film hardness and material conformability.

Claims (4)

[Claims] 1. A coating material or an ink composition, which comprises 0.01 to 20% by weight of a zirconium or aluminum compound having an unsaturated side chain represented by the following general formula (I) with respect to a pigment and an inorganic filler. [Chemical 1] In the above formula, M represents a zirconium or aluminum atom, X represents a group represented by any one of the following general formulas (a) to (ki), and Y represents any one of the following general formulas (h) to (so). And Z is a group represented by (ta), and R ¹
Represents an alkyl group having 1 to 8 carbon atoms. [Chemical 2] [Chemical 3] [Chemical 4] In the above groups, R ² and R ³ may be the same or different, but are an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an alkoxyl group, and R ⁴ is an alkyl group having 1 to 30 carbon atoms; ⁵ and R ⁶ may be the same or different but are H or CH ₃ , T is O or H ₂ , W ¹
~ W ⁴ may be the same or different, but have 1 carbon atom
~ 20 represents an alkyl group, H, a halogen atom, a nitro group or an acyl group, and p, q, r and h are each 0 to.
Represents an integer of 20 (provided that T is O, p and q are integers of 1 to 20), and A represents (co) or (sa). However, when M is a zirconium atom, x is always 4, but u is an integer of 0 to 3, v is an integer of 0 to 4, w is an integer of 0 to 2, and When v = 0, w = 1 to 2, when v = 1 to 4, w = 0 to 1 and u + v + 2w ≦ 4 is satisfied (Zr compound), and when M is an aluminum atom, x Is always 3, but u is an integer from 0 to 2,
v is an integer of 0 to 3, w is an integer of 0 to 1, and w = 1 when v = 0, and w = when v = 1 to 3.
0 and satisfy u + v + 2w ≦ 3 (Al compound). 2. 1 part by weight of a pigment and an inorganic filler surface-treated with 0.01 to 20% by weight of a zirconium or aluminum compound having an unsaturated side chain according to claim 1.
Resin component 0.15 to 9 parts by weight and solvent component 0.15 to 4
A paint or ink composition prepared by mixing 5 parts by weight. 3. The paint or ink according to claim 1, wherein the pigment or filler is carbon, metal hydroxide, metal oxide, carbonate, sulfate, chromate, silicate, organic pigment or magnetic powder. Composition. 4. The paint and ink composition according to claim 1, wherein the resin component is an acrylic type or an unsaturated polyester type.