KR20050025302A - A high molecule urethane rebirth acrylic paint dispersing agant - Google Patents

Abstract

An acrylic dispersing agent modified with urethane is provided to improve qualities of paint such as wettability, dispersibility, water and solvent resistance, hardening property, leveling of the paint surface, glossiness and color, and also workability and productivity. The acrylic dispersing agent modified with urethane is produced by conducting solution polymerization, as a main component, an aliphatic vinyl ester obtained from esterification of a compound having a carboxyl group and a compound having a hydroxyl group among compounds having C10-24, and a compound obtained from esterification of each compound having a carboxyl group or a hydroxyl group with a monomer such as acrylic acid or methacrylic acid and C1-8 compounds having a hydroxyl group, with a (meth)acrylic alkyl ester monomer with a side chain having C1-4, such as epsilon-caprolactam derivatives such as methylmethacrylate, butylacrylate, ethylacrylate, 2-hydroxyethylmethacrylate, methacrylic acid and acrylic acid or a specific monomer where E.O. is added to (meth)acrylic alkyl esters by alternate, random, block polymerization, and with a glycidyl acryl monomer through a radical reaction by a pyrolysis initiator; substituting the resulted copolymer with amines; and reacting thereto diisocyanate.

Description

A high molecule urethane rebirth acrylic paint dispersing agant}

The present invention relates to a polymer urethane-modified acrylic pigment dispersant, and more particularly, to a dispersant necessary for increasing wettability and gloss of paint and improving paint dispersion, and in particular, an acrylic polymer copolymer copolymerized using solution polymerization using monomers. To provide a type dispersant.

Existing paint dispersants are ester-type low molecular weight and surfactant dispersants using fatty acids, etc., but they have good dispersibility, but they are less wettable and contain more thixotropy. Narrowness has the disadvantage.

Accordingly, the present invention is to provide a polymer urethane-modified acrylic pigment dispersant that can eliminate all the problems of the conventional paint dispersant,

The present invention particularly provides a dispersant necessary for increasing wettability and gloss of paint and improving paint dispersion. The present invention has been completed to provide a polymer pigment dispersant copolymer of acrylic type copolymerized using solution polymerization using monomers. will be.

To this end, the polymeric urethane-modified acrylic pigment dispersant provided in the present invention is a vinyl fatty acid ester material and a carboxyl or hydroxyl group obtained by esterifying a substance having a carboxyl group or a hydroxyl group among organic materials between C ₁₀ and C ₂₄ . Each substance having an alkyl acrylate or an alkyl methacrylate mainly composed of a monomer such as acrylic acid or methacrylic acid, a substance obtained by esterifying a C ₃ to C ₂₄ hydroxyl group material (such as vinyl alcohol) and a fatty acid In the esters, monomers having C ₃ to C ₂₄ carbon atoms in the side chains are methyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxy ethyl methacrylate, methacrylic acid, acrylic acid and ε-caprolactam derivatives. Acrylate) or methacrylic acid The copolymerized compound was finally polymerized by solution polymerization of an alkyl ester or an acrylic acid alkyl ester by a radical reaction using a thermal decomposition initiator with a glycidyl acryl monomer and a special monomer impregnated with PO and EO by alternating, random or block polymerization. Substitution is carried out using amines and the diisocyanate is reacted.

The resultant acrylic type thus obtained provides a method for producing an acrylic resin, which has good wettability and dispersibility of the paint, good solvent resistance, curability of the paint, and leveling property of the coating film surface.

Among the monomers used in the present invention, a composition of 10 to 30% by weight of butyl methacrylate and 20 to 30% by weight of 2-hydroxyethyl methacrylate in the monomer of C ₁ to C ₄ in the methacrylic acid alkyl ester or the acrylic acid esters , ε-caprolactam derivative is 20 to 30% by weight, the monomer having impregnated PO and EO to the methacrylic acid alkyl ester or acrylic acid alkyl ester is 20 to 50% by weight, a substance having a carboxyl or hydroxyl group of C ₁₀ ~ C ₂₄ The ester polymer of or the polymer esterified by acid, alcohol, etc. is applied by the composition in 30 to 50 weight% and 10 to 20 weight% of glycidyl acrylic monomers.

In order to add the cationic property to the resin thus synthesized, amines are added in the same ratio as the glycidyl acrylic monomers, followed by substitution reaction at 80 to 100 ° C.

In the third reaction, the diisocyanate is used after calculating the appropriate amount in consideration of the equivalent of the hydroxyl group contained in the resin.

Methacrylic acid alkyl esters or acrylic acid alkyl esters have good viscosity increase, solvent resistance, and chemical resistance when used in many cases. However, an appropriate amount of methacrylic acid alkyl esters or acrylic acid alkyl esters may be used.

When using 2-hydroxyethyl methacrylate or ε-caprolactam derivatives, problems such as water resistance, chemical resistance, and durability occur, so that they are properly controlled and EO or PO imides on alkyl esters, or esters of C ₁₀ to C ₂₄ It is effective to use an appropriate amount because the compound is at risk of gelation during synthesis.

It can be copolymerized by the solution polymerization method in the presence of a peroxide using the above vinyl-based monomer.

The polymerization catalyst may be BPO, TBPO, AIBN, DTBP, TBPB and the like.

Selection of the polymerization initiator is appropriately selected according to the reaction temperature, and the appropriate amount of the polymerization initiator may be used because the amount of the polymerization initiator can greatly affect the molecular weight. Usually, the amount of polymerization initiator used in solution polymerization is about 1 to 2% by weight based on the vinyl monomer.

Hydrocarbons, alcohols, esters, ketones, ethylene glycol derivatives and the like can be used as the solvent used in the solution polymerization, and the solvent is selected in consideration of the reaction temperature, molecular weight and the like.

Since the reaction temperature of the solution polymerization is related to the molecular weight, it is usually reacted at 80 ~ 140 ℃, depending on the type of solvent is carried out under the appropriate temperature.

A polymerization initiator, a solvent, and the like are appropriately calculated for the vinyl monomer, and the reaction is controlled so that an unreacted monomer does not exist by a solution polymerization method, thereby producing an acrylic resin most suitable for wettability and dispersion of a pigment.

Conventional paint dispersant is an ester type low molecular weight and high molecular weight wet dispersant using fatty acid, but the dispersibility is good, but the wettability is somewhat low and it contains thixotropy. This narrowness has the disadvantage.

On the other hand, the polymer wetting dispersant of the acrylic resin type of the present invention dispersibility is similar to or better than the conventional type dispersing agent, and because the wettability and the thixotropy are less, the control range for the amount of pigment used in the coating work is superior to that of the conventional dispersing agent and chromaticity. Is also good.

Hereinafter, the present invention will be described in detail with reference to Examples.

(Example 1)

After placing xylene and butyl acetate in the flask, the temperature was raised to 120-130 ° C., and then, 100 g of the acrylic monomer mixture shown in Table 1 below was homogeneously mixed and added dropwise over 2 to 3 hours while maintaining the temperature of the solution.

After reacting for 2 hours, 0.5 g of peroxide was dissolved in xylene to further polymerize the unreacted monomer, and then dropwise added in a fixed amount over 30 minutes. After the completion of the holding reaction for 2 hours, the reaction is terminated by adding an appropriate amount of isocyanate.

It synthesize | combined in this way and obtained the slightly yellow viscous acrylic dispersion resin solution.

(Example 2)

In the same manner as in Example 1, the acrylic monomer mixture of Table 1 was solution polymerized as a homogeneous mixture.

Thus synthesized, a yellow viscous acrylic resin was obtained.

(Example 3)

In the same manner as in Example 1, the acrylic monomer mixture of Table 1 was solution polymerized as a homogeneous mixture.

As a result, the same acrylic resin as in Example 1 was obtained.

compound Example 1 Example 2 Example 3 Glycidyl acrylate 10 10 10  ε-caprolactam derivatives 20 20 20 C ₁₀ ~ C ₂₄ ester compound 39 29 39 2-hydroxy ethyl methacrylate - 10 - n-butyl methacrylate 10 20 - E.O Part Alkyl Esters 20 10 30 Initiator One One One system 100 100 100

(Test example)

In order to test the performance of each synthesized resin, paints were prepared using the composition shown in Table 2, and general properties were compared.

Example 1 Example 2 Example 3 Synthetic resin 100 100 100 Carbon black 8 8 8 excited 30 30 30 Dispersion additive 1.15 1.15 1.15 Ceramic Beads (Balls) 90 90 90 system 229.15 229.15 229.15

(Comparative Example)

Existing Dispersant Example 1 Example 2 Example 3 Polish △ ○ ○ ◎ Blackdo △ ○ ○ ◎ Wettability △ △ ○ ○

The results from the above test examples were summarized in a table and compared.

Classification: ◎ Excellent, ○ Good, △ Normal, Ｘ Poor

(Example 4)

After placing xylene and butyl acerate in the flask, the temperature was raised to 110-120 ° C., and then 100 g of the acrylic monomer mixture of Table 4 was added to the mixture homogeneously while maintaining the temperature of the solution. After reacting for 2 hours, 0.5 g of peroxide was dissolved in xylene to further polymerize the unreacted monomer, and then dropwise added in a fixed amount over 30 minutes.

After the completion of the holding reaction for 2 hours, the reaction is terminated by adding an appropriate amount of isocyanate. Thus synthesized to obtain a slightly yellow viscous acrylic resin solution.

(Example 5)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture. In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 6)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture. However, the last isocyanate reaction is excluded here.

In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 7)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture.

In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 8)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture.

In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 9)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture.

In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 10)

In the same manner as in Example 4, the acrylic monomer mixture of Table 4 was solution polymerized as a homogeneous mixture.

In this manner, a pale yellow viscous acrylic resin was obtained.

compound Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Glycidyl methacrylate 20 15 20 15 10 10 20  ε-caprolactam acrylate 50 50 60 - - - - Ester modified acrylate of C ₁₀ ~ C ₂₄ - - - 50 29 29 - 2-hydroxy ethyl methacrylate - - 19 - 30 40 40 n-butyl methacrylate 10 10 - 34 - 10 20 E.O department alkyl ester modified acrylate 19 24 - - 30 10 19 Initiator (catalyst) One One One One One One One system 100 100 100 100 100 100 100

(Test example)

In order to test the performance of each synthesized resin, paints were prepared using the composition of Table 5, and general properties were compared.

Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Synthetic resin 100 100 100 100 100 100 100 Carbon black 8 8 8 8 8 8 8 excited 30 30 30 30 30 30 30 Dispersion additive 1.15 1.15 1.15 1.15 1.15 1.15 1.15 Ball (ceramic bead) 90 90 90 90 90 90 90 system 229.15 229.15 229.15 229.15 229.15 229.15 229.15

(Comparative Example)

The results from the above test example are summarized in Table 6 and compared.

Existing Dispersant Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Polish △ ○ △ △ ○ ○ △ △ Blackdo △ ○ ○ ◎ ○ ○ △ △ Wettability △ ○ ○ △ ○ △ ○ ○

Classification: ◎ Excellent, ○ Good, △ Normal, Ｘ Poor

(Example 11)

In the same manner as in Example 4, the acrylic monomer mixture of Table 7 was solution polymerized as a homogeneous mixture.

In this manner, a pale yellow viscous acrylic resin was obtained.

(Example 12)

In the same manner as in Example 4, the acrylic monomer mixture of Table 7 was solution polymerized as a homogeneous mixture.

Thus synthesized, a slightly yellow viscous acrylic resin was obtained.

compound Example 4 Example 5 Glycidyl acrylate 10 10  ε-caprolactam derivatives 30 20 C ₁₀ ~ C ₂₄ ester compound 30 20 P.O Part Alkyl Esters 20 30 n-butyl methacrylate - - E.O Part Alkyl Esters 10 20 Initiator One One system 100 100

(Test example)

In order to test the performance of each synthesized resin, paints were prepared using the composition shown in Table 8, and general properties were compared.

Example 11 Example 12 Synthetic resin 100 100 Carbon black 8 8 excited 30 30 Dispersion additive 1.15 1.15 ball 90 90 system 229.15 229.15

(Comparative Example)

The results from the above test example were summarized in Table 9 and compared.

Existing Dispersant Example 11 Example 12 Polish △ △ ○ Blackdo △ ○ ○ Wettability △ ○ ○

Classification: ◎ Excellent, ○ Good, △ Normal, Ｘ Poor

As described in detail above, the polymeric urethane-modified acrylic pigment dispersant provided in the present invention has good compatibility with other resins in which the acrylic type product has good wettability and dispersibility of paints, and has good water resistance, solvent resistance and curability of paints, Good leveling property of coating surface, excellent gloss and color of paint, and excellent wettability. The control range is better than conventional dispersant and good chromaticity compared to conventional dispersant. It can be provided with a number of effects such as improvement and quality improvement of the paint.

Claims (7)

Among the substances between C ₁₀ and C ₂₄ , a substance obtained by esterifying a substance having a carboxyl group or a hydroxyl group with each other, and each of the substances having a carboxyl group or a hydroxyl group are selected from monomers such as acrylic acid or methacrylic acid, and C ₁ to C _8. methyl hydro as a main component and the reaction is obtained by screen material and the ester having a hydroxyl group with the carbon number of the side chain in the acrylic acid alkyl ester or methacrylic acid alkyl esters, C ₁ ~ C ₄ monomer between methacrylate, butyl acrylate, Ε-caprolactam derivatives such as ethyl acrylate, 2-hydroxy ethyl methacrylate, methacrylic acid, acrylic acid, or methacrylic acid alkyl esters or acrylic acid alkyl esters. Pyrolysis Initiator with Glycidyl Acrylic Monomer The polymer urethane-modified acrylic pigment dispersant obtained by solution polymerization by radical reaction by and substituting the copolymerized compound using amines and making diisocyanate react. The method of claim 1; It is characterized by consisting of 10-30% by weight of butyl methacrylate and 20-30% by weight of 2-hydroxyethyl methacrylate in the C ₁ to C ₄ monomer in the methacrylic acid alkyl ester or acrylic acid esters in the monomer. Polymer urethane modified acrylic pigment dispersant. The method of claim 1; The ε-caprolactam derivative is a polymeric urethane-modified acrylic pigment dispersant, characterized in that consisting of 20 to 30% by weight of the composition. The method of claim 1; The polymer urethane-modified acrylic pigment dispersant, wherein the monomer to which E.O is added to the methacrylic acid alkyl ester or the acrylic acid alkyl ester is composed of 20 to 50% by weight. The method of claim 1; The ester polymer of the substance having a C ₁₀ to C ₂₄ carboxyl group or a hydroxyl group or a polymer esterified with an acid or an alcohol is composed of 30 to 50% by weight and a composition within 10 to 20% by weight of a glycidyl acrylic monomer. Polymer urethane modified acrylic pigment dispersant. The method of claim 1; In the dispersant, amines were added in the same ratio as the glycidyl acrylic monomer, and the substitution reaction was carried out at 80 to 100 ° C. Polymer urethane modified acrylic pigment dispersant. The method of claim 1; The solvent used in the solution polymerization is a polymeric urethane-modified acrylic pigment dispersant, characterized in that one of a hydrocarbon, alcohol, ester, ketone, ethylene glycol derivatives.