KR100559058B1 - Water-dispersed polymer compositon and method of manufacturing the same - Google Patents

Abstract

A cardanol derivative represented by the following formula is disclosed. Novolac copolymer

It is prepared by the polycondensation reaction of a cardanol derivative, salicylic acid, a phenol compound and an aldehyde compound represented by the above formula. The novolac copolymer has excellent water dispersion stability and excellent physical properties such as storage properties.

Description

Water-dispersed polymer compositon and Method of manufacturing the same

The present invention relates to a copolymer polymerized using a cardanol derivative, a water dispersion resin composition comprising the copolymer, and a method of producing the water dispersion resin composition. More specifically, in the copolymer polymerized using a cardanol derivative having excellent water dispersion stability, the water dispersion resin composition containing the copolymer and improved physical properties such as drying property, and a method for producing the water dispersion resin composition It is about.

Cardanol derivatives are generally derived from cardanol obtained from Cashew Nut Shell Liquid (CNSL). Specifically, it is obtained by the compression extraction method. The composition of CNSL contains about 9: 1 anarchic acid and cardol and a trace amount of 2-methylcardol.

The CNSL can be decarboxylated upon heating in the presence of an acid to obtain cardanol, which is a meta-substituted phenol represented by the following formula (I).

[Formula 1]

In formula (I), x is 0, 1 or 2 and x is dependent on the number of double bonds in the meta-substituted aliphatic side chain.

If not sufficiently purified, the product is represented by the following formula (II). Contains small amounts of cardol.

[Formula 2]

Cardanol represented by the formula (II) has strong hydrophobicity and water resistance and flexibility due to the effect of a long alkyl chain, and its structure is similar to urushiol, which is the main component of lacquer, and thus exhibits properties similar to those of lacquer, particularly excellent in corrosion resistance and water resistance . In addition, there are many attempts to use as a coating material because the production amount is a large amount as a naturally produced material. Most applications have generally been a form in which a polymer is heated to form a certain amount of polymer and then the remaining unsaturated groups are oxidatively polymerized in air using a metal catalyst. In this case, the drying speed is very slow, and the organic solvent contains a large amount of volatile organic compounds. On the other hand, when the resin in the paint is water-ized, the paint is easy to be water-ized, and the content of the organic solvent contained in the water is low so that it is possible to manufacture a more environmentally friendly paint. In addition, it is possible to drastically shorten the drying time by designing the resin in the novolak type and allowing it to be heated and dried using hydrophilic melamine or the like. However, there are few examples of aqueousization with this advantage. Because of the strong hydrophobicity of the long alkyl chains of cardanol, no concrete realization was possible.

The present invention has been made in view of the problems of the prior art as described above, and provides a copolymer polymerized using a cardanol derivative and having excellent water dispersion stability.

It also provides a water-dispersible resin composition comprising the copolymer.

It also provides a method for producing the water dispersion resin composition.

Cardanol derivatives according to one aspect of the present invention are represented by the following formula (3).

[Formula 3]

Copolymer according to an aspect of the present invention is at least one selected from the group consisting of a first repeating unit represented by the following formula (4), a second repeating unit represented by the formula (5) and a third repeating unit represented by the formula (6) The repeating units are irregularly arranged linearly and have a weight average molecular weight of 700 to 12000.

[Formula 4]

[Formula 5]

[Formula 6]

Water dispersion resin composition according to one feature of the invention comprises the copolymer solids, amine compounds and deionized water.

The copolymer is irregularly linear in at least one repeating unit selected from the group consisting of a first repeating unit represented by the following formula (4), a second repeating unit represented by the following formula (5) and a third repeating unit represented by the following formula (6) And the weight average molecular weight is 700 to 12000.

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 4 to 6, l and n are each an integer of 1 to 15, m is an integer of 0 to 15, and R is hydrogen, an alkyl group, benzyl group or phenol group of C _1-4 .

Method for producing a water-dispersible resin composition according to one aspect of the present invention comprises the steps of (a) obtaining a cardanol derivative, (b) condensation polymerization step, (c) the step of preparing an aqueous resin solids and (d) deionized water input step Include.

The step of obtaining a cardanol derivative includes a step of maleinating a cardanol and maleic anhydride. The condensation polymerization step includes condensation polymerization of the cardanol derivative, phenolic compound, salicylic acid and aldehyde compound. The deionized water input step includes the step of slowly adding deionized water to the resin solids.

Hereinafter, the present invention will be described in more detail.

The cardanol derivative of the present invention is obtained by mixing cardanol and maleic anhydride in an equivalent ratio of 1: 1, stirring and heating at 190 to 210 ° C. for about 3 to 5 hours, and then removing the unreacted acid by vacuum distillation. As described above, maleinization starts to occur at about 140 ° C. in the presence of conjugated unsaturated groups, but in the case of cardanol having a large number of non-conjugated unsaturated groups, active methylene groups must be formed to promote the reaction. As it starts to occur in the vicinity, a corresponding reaction temperature is required. Therefore, the reaction temperature range of 190-210 degreeC is preferable, More preferably, it is 195-205 degreeC. The cardanol derivative prepared as above has an acid value of about 101 per equivalent. The derived cardanol derivative has the structure of Formula 3 below.

[Formula 3]

The cardanol derivative obtained by the above method forms a novolak-based copolymer through a polycondensation reaction with a phenol compound, salicylic acid and an aldehyde compound.

As the phenolic compound, p-tertiarybutyl phenol, octyl phenol, nonyl phenol and the like may be used. P-tert-butyl phenol is preferably used.

In addition, as salicylic acid which gives an acid value to disperse the copolymer, o-oxybenzoic acid, m-oxybenzoic acid or p-oxybenzoic acid may be used.

As the aldehyde compound, formaldehyde, butylaldehyde, hepaldehyde, hexaaldehyde, acetaldehyde, propionaldehyde, p-formaldehyde, benzaldehyde, salicylicaldehyde can be used. Preferably p-formaldehyde is used.

The total equivalents of the cardanol derivatives, the phenol compounds, and the salicylic acid and the equivalents of the aldehyde compounds preferably have an equivalent ratio of 1.1-1.3: 1. If it is out of the said range, it cannot function as a novolak resin.

In addition, the cardanol derivatives, phenolic compounds, salicylic acid and aldehyde compounds are preferably polycondensed at a weight ratio of 1: 0.3-0.5: 0.08-0.15: 0.1-0.15, respectively.

When the condensation polymerization reaction is completed, water is condensation-polymerized and removed from the aldehyde compound, so that 100 parts by weight of the third repeating unit represented by the following Chemical Formula 6 and the first repeating unit represented by the following Chemical Formula 8 to 8 are actually synthesized. 15 parts by weight and 30 to 50 parts by weight of the second repeating unit represented by Formula 5 are included. The first repeating unit is a unit combined with an aldehyde compound condensed with salicylic acid to remove water. The second repeating unit is a unit in which an aldehyde compound condensed with a phenol compound and water is removed. The third repeating unit is a unit combined with an aldehyde compound condensed with a cardanol derivative to remove water. When the content ratio of salicylic acid is less than 8 parts by weight, in order to maintain the required acid value, a large amount of cardanol derivatives are included to relatively reduce the coating film hardness of the resulting coating film. It is preferable that 8 to 15 parts by weight is included because there are less danol derivatives, which may cause problems of deterioration in water dispersibility and storage stability. The content ratio of the salicylic acid is more preferably 10 to 13 parts by weight. The aldehyde compound is relatively added in the condensation reaction so that the equivalent ratio of the total phenolic compound and the equivalent of the aldehyde compound is 1: 1.1-1.3.

The polymerization reaction for synthesizing the novolac copolymer is preferably carried out in at least one acid atmosphere of hydrochloric acid, sulfuric acid, oxalic acid, p-toluene sulfonic acid. It is particularly preferable to proceed under sulfuric acid atmosphere. The polymerization reaction is carried out at a temperature range of about 80 to 90 ℃ and the reaction is performed for about 5 to 7 hours. Whether or not the reaction is completed can be determined by whether the equivalent of the condensation water, which is the product of the condensation polymerization reaction, corresponds to the equivalent number of the added aldehyde compound. After the reaction is completed, unreacted acid and trace condensate are removed by vacuum distillation.

The synthesized novolac copolymer has a first repeating unit represented by the following formula (4), a second repeating unit represented by the following formula (5) and a third repeating unit represented by the following formula (6) are irregularly arranged linearly and It has a weight average molecular weight.

 [Formula 4]

··· (I)

(I)

[Formula 5]

··· (II)

(II)

[Formula 6]

··· (III)

(III)

In Chemical Formulas 4 to 6, l, m, and n are each an integer of 1 to 15, and R is hydrogen, an alkyl group, benzyl group, or phenol group of C _1-4 .

Using the copolymer solids synthesized as described above to prepare a water-dispersible resin composition according to one feature of the present invention.

The water dispersion novolak resin composition which concerns on this invention contains (i) novolak copolymer solid content, an amine compound, and deionized water. The novolac copolymer solids and deionized water are preferably included in a weight ratio of 1: 1-3. If the ratio of deionized water is less than 1, deionized water is dispersed in the novolak copolymer, which is not preferable. On the other hand, if the ratio of deionized water exceeds 3, the relative content of the novolak copolymer as an active ingredient is too small. Not preferred. More preferably, the novolak copolymer solids and deionized water are included in a weight ratio of 1: 1.5-2.

Obtained as described above, the novolak copolymer solids from which unreacted acid and condensed water have been removed are cooled to about 50-70 ° C. Thereafter, the acid value obtained by adding the acid value of the used cardanol derivative and the salicylic acid is neutralized by adding an amine compound.

Then, deionized water is gradually added to the neutralized novolak copolymer solid to prepare a water dispersion resin composition.

As the amine compound, at least one of triethylamine, ammonia water, hexamine, and dimethyl ethanol amine can be used.

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

Cardanol derivatives

Synthesis Example

1200 g of cardanol and 192 g of maleic anhydride were added to the 2 L flask, and the mixture was gradually heated to a temperature of about 5 ° C. for 5 hours. Thereafter, the viscosity was checked using a Gardner bubble viscometer, and when the viscosity was at least W, the resulting product was cooled and filtered to obtain a cardanol derivative having an acid value of about 101 per equivalent.

Water dispersion resin composition

Example 1

153 g of cardanol derivative (acid value 40), 59 g of p-tert-butyl butyl, 15.5 g of p-oxybenzoic acid (25 value of acid) and 26 g of p-formaldehyde (91%) obtained in the synthesis example were removed. It was added to a 2L flask equipped with a water separator which can be stirred, and diluted with 2.5 g of concentrated sulfuric acid in 50 g of deionized water. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C., and slowly added 29.7 g of triethylamine, followed by stirring for 10 minutes. Then, 330 g of deionized water was slowly added with vigorous stirring to prepare an aqueous dispersion resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Example 2

203 g of cardanol derivative obtained in the synthesis example (acid value 60), p-oxybenzoic acid 7.2 g (acid value 13), and 16.7 g of p-formaldehyde (91%) were each equipped with a water separator capable of removing the reaction condensation water. After the flask was stirred, 2.5 g of concentrated sulfuric acid was diluted with 50 g of deionized water and added. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C, slowly added 29.5 g of triethylamine, and stirred for 10 minutes. Then, 340 g of deionized water was slowly added with vigorous stirring to prepare an aqueous dispersion resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Example 3

148 g of cardanol derivative obtained in the synthesis example (acid value 41), 70 g of p-tert-butyl butyl, 6.1 g of p-oxybenzoic acid (acid value 10), and 26 g of p-formaldehyde (91%) were used to remove the reaction condensed water. It was added to a 2L flask equipped with a water separator which can be stirred, and diluted with 2.5 g of concentrated sulfuric acid in 50 g of deionized water. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C, and slowly added 22.5 g of triethylamine, followed by stirring for 10 minutes. Then, 375 g of deionized water was slowly added with vigorous stirring to prepare an aqueous dispersion resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Example 4

160 g of cardanol derivatives obtained in the synthesis example (acid value 41), 48 g of p-tert-butyl butyl, 22 g of p-oxybenzoic acid (acid value 35), and 26 g of p-formaldehyde (91%) were used to remove the reaction condensed water. It was added to a 2L flask equipped with a water separator which can be stirred, and diluted with 2.5 g of concentrated sulfuric acid in 50 g of deionized water. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C, slowly added 35 g of triethylamine, and stirred for 10 minutes. Then, 384 g of deionized water was slowly added with vigorous stirring to prepare an aqueous dispersion resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Comparative Example 1

160 g of cardanol, 63.5 g of p-tertiarybutyl, 49 g of p-oxybenzoic acid (acid value 65) and 38.2 g of p-formaldehyde (91%) were added to a 2 L flask equipped with a water separator to remove the reaction condensate. After stirring, 2.5 g of concentrated sulfuric acid was added to 50 g of deionized water. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C, slowly added 36.4 g of triethylamine, and stirred for 10 minutes. Then, 465 g of deionized water was slowly added with vigorous stirring to prepare a water-dispersed novolak resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Comparative Example 2

350 g of cardanol derivative (acid value 65) obtained in the synthesis example, 26.2 g of p-tert-butyl and 26.2 g of p-formaldehyde (91%) were added to a 2 L flask equipped with a water separator capable of removing the reaction condensed water. After stirring, 4.1 g of concentrated sulfuric acid was diluted with 70 g of deionized water and added. After the addition, the temperature was increased and maintained at 90 ° C. for 5 hours to prepare a novolac copolymer. The novolak copolymer prepared above was vacuum distilled to remove unreacted material and trace amount of condensed water, cooled to 50 ° C, slowly added 35 g of triethylamine, and stirred for 10 minutes. Then, 44 g of deionized water was slowly added with vigorous stirring to prepare a water-soluble novolak resin composition having a phenol compound equivalent / paraformaldehyde equivalent weight of 1.13.

Using water-dispersible resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 2, 10% by weight of melamine resin of resin was added to each resin composition as a curing agent (CYMEL-303, manufactured by CYTEC) to form an aqueous transparent clearer. The paints were compared relative to the physical properties after preparation (Preparation Examples 1 to 4, Comparative Preparation Examples 1 and 2, respectively). The compounding composition of each manufacture example and a comparative manufacture example is shown in Table 1.

Item Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Production Example 1 Comparative Production Example 2 Deionized Water (DIW) 12 12 12 12 12 12 Water dispersion resin 80 80 80 80 80 80 CYMEL-303 8 8 8 8 8 8 Sum 100 100 100 100 100 100

Experimental Example 1

The physical properties of the paints were measured in the following manners with respect to the appearance, viscosity and non-volatile content of the respective water-dispersible aqueous clear paints prepared in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2. The results are shown in Table 2.

Experimental Method

(1) Appearance / Color: Observed

(2) Viscosity (KU): The paint was kept at 25 ° C and measured with a Krebs-Stormer viscometer.

(3) Non-volatile content (%): 1 g of the paint was measured by heating at 105 ° C. for 3 hours.

(4) Room Temperature Storage Stability (ΔKU): Stored at 60 ° C. for 7 days, and the difference from the initial KU viscosity was measured.

Item Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Production Example 1 Comparative Production Example 2 (1) appearance / color Orange liquid Orange liquid Orange liquid Orange liquid Orange liquid Orange liquid (2) viscosity (KU) 70 69 72 60 74 65 (3) Non-volatile matter 39.7 38.7 38.2 38.2 38.2 39.5 Storage stability (4) normal temperature +1 KU +1 KU +2 KU +1 KU Separation +1 KU (5) 60 ℃ +2 KU +3 KU +6 KU +1 KU Separation +2 KU

As a result of the experiment of Experimental Example 1, the paint of Preparation Example 4 having the highest acid value had the lowest viscosity, and Preparation Examples 1 to 3 having an acid value of about 65 showed similar viscosity. In the case of non-volatile content and appearance, there was no significant difference, but in case of storage stability, Comparative Preparation Example 1 using only salicylic acid occurred at room temperature, and in case of 60 ° C. storage stability, the coating material of Preparation Example 5 having an acid value of 50 was further added. Separation occurred. In addition, the acid value of 63 and the small value of the acid value of the cardanol derivative 40 was a slight increase in viscosity when stored at 60 ℃. Experimental Example 2 was carried out with the paints prepared in Preparation Example and Comparative Preparation Example except for the paints of Preparation Example 3 and Comparative Preparation Example 2 in which the layer separation occurred.

Experimental Example 2

Each of the Cree paints prepared in Preparation Examples 1, 2 and 4, and Comparative Preparation Example 2 was coated on a 0.8T hot-dip galvanized steel sheet with an airless spray to a thickness of about 20 μm of a dry film, and then dried at 140 ° C. for 5 minutes. Baked in oven for 30 minutes. Water resistance was inspected for about one week after half of the coated specimen was immersed in water after the edges were treated with take. Corrosion resistance is treated by taking a corner part after take-drying and then cutting it over X in front of the coated specimen and then maintaining it for 16 hours after spraying 5% salt water for 8 hours. The extent of erosion was determined by expressing in mm. In the case of hardness, the surface of the dry coating film was measured by measuring the pencil hardness using Mitsubishi-Uni pencil. The results are shown in Table 3 below.

Item Preparation Example 1 Preparation Example 2 Preparation Example 4 Comparative Production Example 2 Hardness F B H 2B Water resistance Good Fine blister Fine blister Good Corrosion resistance 0.8 mm 1 mm 1.4 mm 1.2 mm

Referring to Table 3 shown in Experimental Example 2, in the case of hardness, the paint dry coating film of Preparation Example 4 having a large content of salicylic acid was the best, and the paint drying coating film of Comparative Preparation Example 2 using only a cardanol derivative had the lowest hardness. In the case of water resistance, dry blisters of paints prepared in Preparation Examples 2 and 4 having an acid value of 70 or more generated fine blisters on the surface of the coating film. Indicated. In case of corrosion resistance, the degree of erosion of the dry coating films of Preparation Examples 2 and 4, which was weak in water resistance, was severe and was proportional to the difference in acid value.

According to the above results, it can be seen that the storage stability is ensured when the acid value of the water-dispersed resin composition is at least 50, and even if it is 50 or more, the acid value of m-oxybenzoic acid can be used without using maleated cardanol derivatives. When preparing the dispersion resin composition it can be seen that the storage stability is not secured due to the high hydrophobicity of the cardanol itself. It was found that the use of maleated cardanol derivatives is essential. In case of using acidic cardanol derivatives with an acid value of 50 or more, when the acid value was 70 or more, the physical properties were weak to water resistance, and the corrosion resistance was similar when the water resistance was weak. When acid value is assigned using only maleized cardanol without m-oxybenzoic acid, there is no problem in water storage stability and water resistance. It can be seen that the efficient parallel use of is required.

The water-dispersible resin composition according to the present invention has excellent storage stability and excellent physical properties of its own coating film. In addition, there is an advantage that the water stability of the cardanol derivative in the manufacturing process can be secured.

As described above, although described with reference to the preferred embodiment of the present invention, those skilled in the art will be variously modified without departing from the spirit and scope of the invention described in the claims below. And can be changed.

Claims (14)

At least one repeating unit selected from the group consisting of a first repeating unit represented by the following formula (I), a second repeating unit represented by the following formula (II), and a third repeating unit represented by the following formula (III) is irregularly arranged in a line, Copolymers having a weight average molecular weight of 700 to 12000.

(I)

(II)

(III) (In the formulas (I) to (III), l and n are each an integer of 1 to 15, m is an integer of 0 to 15, and R is hydrogen, an alkyl group of C _1-4 , a benzyl group, or a phenol group) The method of claim 2, wherein m is not 0, and the first repeating unit is 8 to 15 parts by weight and the second repeating unit is 30 to 100 parts by weight of the third repeating unit, 100 parts by weight of the third repeating unit. To 50 parts by weight of the copolymer, characterized in that arranged. (i) at least one repeating unit selected from the group consisting of a first repeating unit represented by the following formula (I), a second repeating unit represented by the following formula (II) and a third repeating unit represented by the following formula (III) is irregularly linearly A water dispersion resin composition comprising a novolak copolymer solid having a weight average molecular weight of 700 to 12000 arranged, (ii) an amine compound and (iii) deionized water.

(I)

(II)

(III) (L and n of Formulas I to III are each an integer of 1 to 15, m is an integer of 0 to 15, and R is hydrogen, an alkyl group, benzyl group or phenol group of C _1-4 ) The water dispersion resin composition according to claim 3, wherein the weight ratio of the novolac copolymer solid content and the deionized water is 1: 1-3. The water-dispersible resin composition according to claim 3, wherein the amine compound is included to have an equivalent ratio equal to the sum of acid values of the novolac copolymer. The water-dispersible resin composition of claim 3, wherein the amine compound comprises at least one compound selected from the group consisting of triethylamine, ammonia water, hexamine, and dimethylethinol amine. (a) maleinization of cardanol and maleic anhydride to obtain a cardanol derivative to obtain a cardanol derivative; (b) a condensation polymerization step of condensation polymerization of the cardanol derivatives, phenol compounds, salicylic acid and aldehyde compounds; (c) preparing an aqueous resin solid by removing the condensed water produced in the condensation polymerization step; (D) method of producing a water-dispersible resin composition comprising the step of slowly adding deionized water to the resin solids. The method of claim 7, wherein the step (a) comprises the step of raising the temperature to a temperature of 190 to 210 ℃ for the maleinization reaction. 8. The method according to claim 7, wherein in step (b), the cardanol derivative, the phenol compound, the salicylic acid, and the aldehyde compound are each polycondensed at a weight ratio of 1: 0.3-0.5: 0.08-0.15: 0.1-0.15. Method for producing a dispersed resin composition. According to claim 7, wherein the step (b) is a method of producing a water dispersion resin composition, characterized in that the polymerization reaction for 5 to 7 hours at a temperature of 80 to 90 ℃. 8. The method of claim 7, wherein the step (c) comprises vacuum distillation of the condensation product in order to remove condensation water. The method of claim 7, wherein the step (c) further comprises the step of cooling to a temperature of 50 to 70 ℃ after removing the condensed water. 8. The method of claim 7, wherein the step (d) further comprises the step of adding and stirring the amine compound before adding deionized water to the resin solids. According to claim 7, wherein the aqueous resin of the step (c) is the first repeating unit represented by the formula (I), the second repeating unit represented by the formula (II) and the third repeating unit represented by the formula (III) A method for producing a water-dispersible resin composition, which is irregularly arranged and is a copolymer having a weight average molecular weight of 700 to 12000.

(I)

(II)

(III) (In Formulas I to III, l, m, n are each an integer of 1 to 15, wherein R is hydrogen, an alkyl group, benzyl group or phenol group of C _1-4 )