KR100511079B1 - Water soluble alkyd resin and paint composition containing same - Google Patents

Abstract

The present invention relates to a water-soluble alkyd resin and a coating composition containing the same. More specifically, in the water-soluble alkyd resin, 1 to 30% by weight of styrene maleic anhydride with respect to the final solid resin, aromatic or aliphatic polyacid 1 To 20% by weight, 10 to 70% by weight of fatty acid or oil, and 7 to 20% by weight of polyhydric alcohol to prepare an alkyd polyol, and then react the alkyd polyol and diisocyanate in an equivalent ratio of 1.3 to 1.7: 0.5 to 1.0. To prepare an alkyd urethane, neutralize the unreacted carboxyl group of the resin end group with an amine, and then add water to prepare an alkyd urethane aqueous product, and then add an emulsifier to the nitro cellulose aqueous product 7-30 weight. The present invention relates to a water-soluble alkyd resin prepared by adding% and a paint composition containing the same.

Description

Water soluble alkyd resin and paint composition containing same

The present invention relates to a water-soluble alkyd resin and a paint composition containing the same, and more particularly, to a water-soluble alkyd resin having a rich carboxyl group and high hardness and fast drying properties and a paint composition containing the same.

Conventional water-soluble alkyd resins are prepared by 1) neutralizing amines with abundant carboxyl groups, 2) hybridizing with acrylic raw materials, or 3) introducing acid and basic metals into the resin end groups, This is disclosed in Korean Patent Publication No. 79-1915 and European Patent No. 0 056 155. In such a prior art, it does not exhibit as fast drying as sufficient usability, and in order to exhibit sufficient fast drying, the viscosity of the resin is high, and there is a disadvantage in that it is difficult to accept. There is a method of denaturing styrene to an alkyd resin to exhibit fast drying, but is limited to solubilization with an aromatic compound, so that the content must be lowered to 15% or less in order to be solubilized, and the effect on drying is insufficient.

Accordingly, an object of the present invention is to prepare a urethane of an alkyd polyol in which the polyhydric acid of an aromatic compound (styrene) is modified, and a nitrocelolose aqueous product containing an emulsifier on the basis of neutralizing the carboxyl group of the resin terminal group with an amine. It is to provide a water-soluble alkyd resin prepared by addition.

Another object of the present invention is to provide a coating composition containing the resin.

The water-soluble alkyd resin of the present invention for achieving the above object is 1 to 30% by weight of styrene maleic anhydride, 1 to 20% by weight of aromatic or aliphatic polyhydric acid, 10 to 70% by weight of fatty acid or oil, And reacting 7 to 20% by weight of a polyhydric alcohol to prepare an alkyd polyol, and then reacting the alkyd polyol and diisocyanate at an equivalent ratio of 1.3 to 1.7: 0.5 to 1.0 to prepare an alkyd urethane, and unreacted of the resin end group. After neutralizing the carboxyl group with an amine, water is added to prepare an alkyd urethane aqueous product, which is then prepared by adding 7-30% by weight of an aqueous nitro cellulose product containing an emulsifier.

The paint composition for achieving the above another object is one or more selected from the group consisting of 90 to 99.9% by weight of the water-soluble alkyd resin, antifreeze agent, desiccant, antifoaming agent, leveling agent, neutralizing agent, drying catalyst, and carbodiimide compound 0.1 to 10% by weight, solvents, water, and pigments.

Looking at the present invention in more detail as follows.

According to the present invention, 1 to 30% by weight of styrene maleic anhydride, 1 to 20% by weight of aromatic or aliphatic polyacid, 10 to 70% by weight of fatty acid or oil, and 7 to 7% of polyhydric alcohol based on the final solid resin 20 wt% is reacted to prepare alkyd polyols.

In the present invention, styrene maleic anhydride having a high hardness superior to other aromatic compounds is essentially used. The amount of the styrene maleic anhydride used is 1 to 30% by weight, preferably 6 to 15% by weight based on the final solid resin, and when less than the amount, the hardness is low, the viscosity is low, and when the amount is greater than the amount, the hardness is High or fragile coating, poor adhesion and easy gelation.

The method of introducing the styrene maleic anhydride into the coating component may use an esterification step such as reacting a polyacid of an aromatic compound of a general alkyd resin. The styrene maleic anhydride is a kind of oligomer and is composed of a copolymer of styrene and maleic anhydride. The styrene maleic anhydride has an anhydride group at its terminal and can be used as a polyacid. The styrene portion of this oligomer shows high hardness. The hardness and glass transition temperature and the number of anhydride groups in the terminal group change according to the ratio of styrene and maleic anhydride in the oligomer. The higher the content of the maleic anhydride, the more the number of anhydrides in the terminal group. . Therefore, the higher the content of maleic anhydride is, the higher the hardness is, and tends to gel when reacted. The oligomer is currently commercialized and its introduction is from 1978. The styrene maleic anhydride is rarely used for coating, and has been studied as an emulsifier by forming a salt at the terminal group.

Otherwise, a process for preparing microcapsules using partial ester salts of styrene maleic anhydride for pharmaceutical use is disclosed in US Pat. No. 5,310,721.

In addition, the styrene maleic anhydride is disclosed in U.S. Patent No. 4,923,917 for a flame retardant plastic material for processing plastics, and U.S. Patent No. 5,162,416 for a polymer mixture for improving impact resistance to crystalline polymer materials. Published. It is also disclosed in US Pat. No. 5,001,004 for stain prevention for textile purposes, and in many other patents for use in various molded parts for special purposes.

Looking at the other resin component, polyester can be regarded as an ester feature condensate of a polyacid and a polyhydric alcohol. Alkyd resins can be understood as polyesters modified with fatty acids and oils. Alkyd and Polyester are defined as in 1966, STUTTGART, FRANCKH'SHE, 1, S, 202, ROMPP'S Chemical Dictionary, and the Ulmans Chemical Encyclopedia. (S), the organic coating film formation of (ULLMANNS ENCYCLOPIDIA TECHINICAL CHEMI AND DH SOLOMON). 75-101, Robert Lee. It is a kind of condensation described by Krieger Publishing Co., Ltd. (ROBERT E. KRIEGER PUB. Co., NEW YORK 1977).

In the present invention, polyhydric alcohols (eg, aliphatic and cycloaliphatic alcohols) for the production of alkyds and polyesters are used at 7 to 20% by weight, preferably 12 to 16% by weight, relative to the final solids resin, If it is less than the amount, the flexibility is low, the viscosity is high, and it is easy to gelate during the reaction. If it is more than the amount, the hardness is low, the viscosity is low, and drying is slow. Examples of the polyhydric alcohol include ethylene glycol, 1,3 or 1,2-propanediol, 1,4, 1,3 or 1,2-butanediol, 2-ethylpropanediol-1,3, 2-ethylhexanediol- Such as 1,3, neopentylglycol, 1,6-hexanediol, 1,4 or 1,2-cyclohexanediol, 1,4-bis-hydroxymethyl-cyclohexane, or adipic acid-bis-ethylene glycol ester Alcohols having 1 to 15 carbon atoms, particularly 2 to 6 carbon atoms and 1 to 6 carbon atoms.

For the hydroxyl groups used, di (di-) having an aromatic ratio of 1-4 per molecule and ether alcohols such as triethylene glycol and dipropylene glycol were used, and oxethyllierte and perhydric bisphenol were used. (perhydrierte bisphenol), 1,2,4-butanetriol, 1,2,6, -hexanetriol, trimethylolethane, trimethylolpropane, glycerine, pentaerythritol, pipeentaerythrol, mannitol ), Sorbitol, propanol, butanol, cyclohexanol, and benzyl alcohol, and monovalent alcohols having 1 to 6 carbon atoms in the chain are used.

Typical alcohols are glycerin, pentaerythritol, neopentylglycol, or trimethylolpropane.

Aromatic or aliphatic polyacids in the synthesis of polyesters and alkyds are in particular di-, tri-, tetratanic, aliphatic, aromatic, saturated alicyclic, unsaturated carboxylic acids, having 2 to 14, 4 to 12 carbon atoms, Esterizable derivatives such as phthalic hydride (PhAn), isophthalic acid (IPA), terephthalic acid (TPA), tetrahydro- and hexahydrophthalic hydride (HHPHAn), endomethylene tetrahydrophthalan Hydride (EETH), phthalic acid, succinic acid, adipic acid, sebacic acid, trimellitic acid, trimellitic anhydride (TMAn), pyromellitic hydride (PMAn), maleic acid, etc. Anhydride (PhAn) is a conventional acid. The other aromatic or aliphatic polyacid is 1 to 20% by weight, preferably 3 to 8% by weight relative to the final solid resin, the hardness is less than the amount, the viscosity is low, if the amount is more than the amount is slightly higher It tends to gel during the reaction.

In some polyester and alkyd resin productions saturated, unsaturated alicyclic, aliphatic primary and benzoic acid, para-tertiary-butylbenzoic acid (PTBBA), tolyic acid (TOLY ACID), hexahydrobenzoic acid (HH BENZOIC ACID) Aliphatic primary carbonic acid with 3 to 24 carbon atoms per molecule, such as ABIETIC ACID and lactic acid.

The resin thus prepared has a constant molecular weight of 2,000 to 10,000, and suitable alkyd resins have an oil content of 5 to 70% in solids, a hydroxyl value of 30 to 140 and an acid value of 0 to 60 mg. KOH / g. In general, the final product can be obtained by reaching the desired acid value while removing water during the condensation reaction under inert gas, ie nitrogen gas, at 140-250 ° C. Polyester and alkyd resins are generally non-neutralized. The oil length of the alkyd resins of suitable dispersion systems is defined as triglycerides, defined as 5-50, in particular 20-40% by weight.

The oils or dry or non-dry fatty acids used in the present invention generally contain 6 to 24 carbon atoms in the form of previous glycerin esters (triglycerides). Fats and fatty acids, such as vegetable and animal oils, coconut, ricinus, tung, olive, soybeans, cottonseed, saflower, dihydrate carbon (DCO) oil, It can be produced from synthetic fatty acids made from a combination of isomers from pig oil, tallow, trane, deoiled fatty acids (tofa) and naturally-unsaturated oils. Commonly used saturated fatty acids are coconut fatty acids, such as 1-ethylhexanoic acid and isononan acid (3,4,4, -trimethylolhexanoic acid), and palmitic acid. ), Stearic acid and synthetic saturated fatty acids. The amount of the fatty acid or oil is 10 to 70% by weight, preferably 20 to 50% by weight based on the final solid resin, less than the amount is less flexible, higher viscosity, easier to gelate the reaction, than the amount The more, the lower the hardness, the lower the viscosity, and the slower the drying.

Thus, the urethane resin is prepared by adding diisocyanate to the alkyd polyol made of the aromatic compound. At this time, the polyol and the isocyanate group are all reacted according to the required physical properties, or the isocyanate group is left to react with amines to form urea bonds. In the present invention, the aqueous dispersion resin is prepared by neutralizing with an amine leaving a carboxyl group. That is, the alkyd polyol and the diisocyanate are reacted at an equivalent ratio of 1.3 to 1.7: 0.5 to 1.0, preferably 1.5: 0.6, to prepare alkyd urethane, and after neutralizing the unreacted carboxyl group of the resin end group with amine Water is added to prepare alkyd urethane water dispersions. The less isocyanate in the reaction, the lower the flexibility, the higher the viscosity, the easier gelation during the reaction, the higher the isocyanate, the lower the viscosity, and the slower the drying. As the diisocyanate used in the present invention, hexamethylene diisocyananeite, or toluene diisocyanate may be used.

Then, to the alkyd urethane aqueous product, 7 to 30% by weight, preferably 15 to 21% by weight of nitro cellulose aqueous product containing an emulsifier is added. Nitro cellulose aqueous product containing the emulsifier is added to exhibit fast drying. The preparation of such dispersions is described in detail in EP 0 056 155 (A1, BAYER). The dispersion is composed of 5 to 35 parts by weight of nitro cellulose, 5 to 30 parts by weight of alkyd resin, 4 to 40 parts by weight of amino resin, 30 to 300 parts by weight of water, 0.5 to 10 parts by weight of emulsifier, wherein the emulsifier Are easy to disperse, 1) polyvinyl acetate having a hydrosis degree of 70 to 87%, 2) poly-vinylpyrrolidin, and 3) hardened vinyl acetate / vinyl. It consists of a pinolidine-copolymer. If the amount of the nitro cellulose aqueous dispersion containing the emulsifier is less than the amount, the drying is slow. If the amount is more than the amount, the water resistance is poor and the internal drying is poor.

When coating the coating composition of the present invention as a base, one or more selected from the group consisting of known drying agents, defoamers, leveling agents, neutralizing agents, drying catalysts, and carbodiimide compounds in 90 to 99.9% by weight of the water-soluble alkyd resin 0.1 to 10% by weight of an additive, a solvent, water, and a pigment are mixed and used in a conventional manner. Water-soluble solvents such as methylpinolidone, ethylene glycol monobutyl ether and water are used as the solvent, and organic acid metal salts such as cobalt naphthenate, zinc naphthenate and manganese naphthenate are used as a drier, and zincated and methylhoic acid are used as fillers. Barium and zinc phosphate. As an antifoamer, a silicone emulsion is preferable and triethylamine, dimethylethylamine, etc. are used as a neutralizing agent. Water and a coloring pigment are added and used for this suitably. In addition, a carbodiimide compound is used to aid drying. Such carbodiimide compounds are mentioned in US Pat. No. 4,612,054.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Examples 1 and 2

Table 1 shows the material components and weights of Examples 1 and 2.

matter Weight ratio Example 1 Example 2 DCO Fatty Acid 400 400 Trimethylolpropane 270 270 Isophthalic acid 100 - Styrene Maleic Anhydride 236.8 473.9 Benzoic acid 150 150 Trimellitic anhydride 100 100 Methylpinolidone 100 150 Acetone 600 600 Sum 1956.8 2143.9 Hexamethylene diisocyanate 40.7 81.4 Dimethylolpropionic acid 26.8 26.8 Dibutyltinlaurate 1.0 1.0 Triethylamine 150.7 150.7 water 987.6 1028.9 Nitro Cellulose / Alkyd Dispersion 743.6 743.6

To the heatable 5 L reactor is added DCO fatty acid, trimethylolpropane, isophthalic acid, styrene maleic anhydride, benzoic acid among these materials. The temperature of the reactor to which the above materials are added is maintained at 220 to 250 ° C., and the mixture is stirred and injected with nitrogen gas. After titrating with 0.1N KOH based on KSM 5000, the acid value is measured. When the acid value is 3 or less, cooling starts. After cooling, if the temperature of the reactor drops below 140 ° C., trimellitic anhydride is added. Thereafter, the temperature of the reactor is maintained at 160 to 180 ° C, and the mixture is stirred while injecting nitrogen gas. The acid value is measured by the same method as described above and cooled again when the acid value is about 50 to 35. When the reactor temperature is lower than 100 ℃ dilution with methylpynolidone, acetone. The physical properties of the resin thus prepared were 62 ± 1 for 30 minutes in a 150 ° C. oven, 360-980 cps and 980-1700 cps with a Brookfield viscometer, with an acid value of 50-35. And the color is transparent. To this composition, hexamethylene diisocyanate, dimethylol propionic acid, dibutyltin laurate are added. Cool when Encio Pro (NOC%) is 0 Pro while maintaining the reaction temperature at 100 ° C. When reaction temperature reaches 60 degreeC, triethylamine is added and water is added. Remove acetone by vacuum. At this time, the resin physical properties measured by the same method as described above, the non-volatile content is 50 ± 1, the viscosity is measured by the Brookfield viscometer, the viscosity is 400 ~ 500cps and 900 ~ 1000cps, it has an apparent milky shape . To this, nitrocellulose / alkyd dispersion is added, but the nitrocellulose / alkyd dispersion to be added is prepared in advance.

Comparative Example 1

To prepare a resin composition by mixing the materials shown in Table 2 in the following weight ratio.

matter Weight ratio DCO Fatty Acid 400 Trimethylol propane 150 Pentaerythritol 120 Isophthalic acid 200 Benzoic acid 150 Trimellitic anhydride 100 Isopropyl Alcohol 700 Sum 2370

DCO fatty acid, trimethylolpropane, pentaerythritol, isophthalic acid and benzoic acid are added to a heatable 5 L reactor and synthesized at a reaction temperature of 200 to 250 ° C. It measures by the same method as the acid value measurement in the said Example, and if it is 20-7, it cools. After that trimellitic anhydride was added and synthesized at a reaction temperature of 160 ~ 190 ℃. If the acid value is about 40 to 60, cool it. When the reaction temperature is less than 100 ℃ add isopropyl alcohol. As a result of measuring by the same method as the said physical property measuring method, a non volatile matter is 55 +/- 1, a viscosity is G-K (G-K), an acid value is 40-60, and a color is transparent.

Comparative Example 2

To prepare a resin composition by mixing the materials shown in Table 3 in the following weight ratio.

matter Weight ratio Comparative Example 1 Composition 2370 Methacrylic acid 70 Azobisisobutylonitrile (initiator) 3.5 Sum 2443.5

70 g of methacrylic acid and an initiator were added to the composition prepared in Comparative Example 1 for 30 minutes, the reactor was heated to 80 ° C. while injecting nitrogen gas, and the reactor was kept at 80 ° C. while stirring, for 1 hour. Stirring is continued, and a coating composition is obtained.

The various coating agents shown in following Table 4 were added to resin obtained by the above Example and the comparative example, and each coating material was manufactured.

Mixed Paint Paint A (Example 1) Paint B (Example 2) Comparative Paint A (Comparative Example 1) Comparative Paint B (Comparative Example 2) Resin composition Preparation Example 1 Preparation Example 2 Comparative Production Example 1 Comparative Production Example 2 347 347 315 315 Ethylene glycol 15 15 15 15 ammonia 10 10 10 10 Titanium dioxide 60 60 60 60 Triethylamine 15 15 15 7 Deionized water - - 20 20 Cobalt Naphthanate (6%) 2 2 2 2 Manganese Naphthanate (6%) 2 2 2 2 Calcium Naphthanate (6%) 2 2 2 2 Active-8 One One One One Carbodiimide 15.8 - - -

The units of all materials listed in Table 4 above are g.

Results according to the physical properties of the paint obtained as a result are shown in Table 5 below.

          Paint property Example 1 Paint A Example 2 Paint B Comparative Example 1 Comparative Paint A Comparative Example 2 Comparative Paint B Nonvolatile matter * 60.0 60.0 61.8 61.8 viscosity* 86 114 94 81 pH 8.5 8.5 8.5 8.7 dry Dry touch 1H 1H 4H 3H Solidification 2H 1H 7H 4H Curing drying 6H 4H 18H 16H Polish 93 87 91 90 Storage stability * Good Good Good Good Water resistance Good Good Bad Bad smell weakness weakness Severe Severe Pencil hardness HB 2H 4B 3B

* Non-volatile content: Baking 3 hours in an oven at 105 ± 2 ℃.

* Viscosity: 25 ℃ KU Viscometer measurement.

Storage stability: Storage test at 60 ° C. for 7 days.

* Glossiness is 60 °, measured 7 days after drying.

* Corrosion resistance is detected after 24 hours of drying and immersion in water at 40 ℃ for 24 hours.

* Pencil hardness is measured after 11 days of drying.

As can be seen in Comparative Examples 1 and 2, resins which increase the crosslinking density by the maximum possible value as the water solubility is increased in the existing technology have a lower crosslinking density than the resin of the present invention, and the drying is slow due to the poor crystallinity. , Water resistance and hardness are poor.

As a result of comparing and analyzing the physical properties of the resin composition prepared according to the present invention and the paint prepared using the same, the paint of the present invention can obtain a paint superior to the paint using the conventional composition in various physical properties of the paint.

The resins of the present invention are characterized by the composition of styrene maleic anhydride having high crystallinity and the fast-drying polyurethane and nitro cellulose composition even though the carboxyl group required for solubilization is located at the terminal group and thus the crosslinking density is not increased, such as its usefulness. The result can satisfy both water solubility and quick drying. In addition, the composition of the styrene maleic anhydride having high crystallinity shows much superior hardness with less crosslinking density than the usability, and the durability is also improved by decreasing the permeability of water due to the crystalline structure.

Claims (3)

In the water-soluble alkyd resin, 1 to 30% by weight of styrene maleic anhydride, 1 to 20% by weight of aromatic or aliphatic polyhydric acid, 10 to 70% by weight of fatty acid or oil, and 7 to 20% of polyhydric alcohol, based on the final solid resin After reacting% to prepare an alkyd polyol, the alkyd polyol and diisocyanate are reacted in an equivalent ratio of 1.3 to 1.7: 0.5 to 1.0 to prepare an alkyd urethane, and the unreacted carboxyl group of the resin end group is neutralized with amine. A water-soluble alkyd resin, which is prepared by adding water to prepare an alkyd urethane water dispersion, and then adding 7 to 30% by weight of a nitro cellulose water dispersion containing an emulsifier. The alkyd resin has a molecular weight of 2,000 to 10,000, an oil content of 5 to 70% in solid content, a hydroxyl value of 30 to 140, and an acid value of 0 to 60 mg. Water-soluble alkyd resin, characterized in that KOH / g. 90 to 99.9% by weight of the water-soluble alkyd resin according to claim 1, 0.1 to 10% by weight of one or more other additives selected from the group consisting of a drying agent, an antifoaming agent, a leveling agent, a neutralizing agent, a drying catalyst, and a carbodiimide compound, a solvent, A paint composition containing a water-soluble alkyd resin, comprising water and a pigment.