WO2016163675A1 - Cashew nut shell extracted oil derivative modified epoxy resin, epoxy resin composition comprising same and production method for same - Google Patents

Abstract

The present invention relates to: a cashew nut shell extracted oil derivative modified epoxy resin which has outstanding anticorrosion properties and resistance to chemicals and is capable of viscosity lowering; a cashew nut shell extracted oil derivative modified epoxy resin composition comprising this cashew nut shell extracted oil derivative modified epoxy resin; and a production method for these.

Description

Cashew nut shell extract oil-modified epoxy resin, epoxy resin composition comprising the same and preparation method thereof

The present invention relates to a cashew nut shell extract oil derivative-modified epoxy resin, a cashew nut shell extract oil derivative-modified epoxy resin comprising the cashew nut shell extract oil derivative-modified epoxy resin, and a preparation method thereof.

More specifically, a cashew nut shell extract oil derivative modified epoxy resin having excellent rust resistance, chemical resistance and low viscosity, and a cashew nut shell extract oil derivative modified epoxy resin composition comprising the cashew nut shell extract oil derivative modified epoxy resin and their It relates to a manufacturing method.

In general, epoxy resins are known to have excellent mechanical and chemical properties compared to other types of resins. Due to the above characteristics, it is applied to ships, civil engineering, construction, electricity, electronic materials, and composite materials, and is widely used as a material for preventing corrosion of steel sheets. For example, the epoxy resin used in the medium method is applied as a coat and top to prevent corrosion of the iron plate excellent in adhesion and water resistance, and the demand is increasing.

However, the problem of high solids and low embrittlement is difficult due to the environmental problems caused by VOCs regulation. In addition, due to poor compatibility with aromatic solvents, the dilution is not good when applied, or a large amount of dilution is required, resulting in problems in appearance and poor workability.

Accordingly, cardanol-modified epoxy resins capable of water repellency and high-solidity by modifying cardanol have been developed and used. (Eg, Korean Patent Publication No. 10-0559055)

However, the existing cardanol-modified epoxy resin has a disadvantage of rust resistance and chemical resistance.

The present invention has been made in view of the above point, and an object of the present invention is to provide an epoxy resin having low viscosity characteristics, overcoming the rust resistance and chemical resistance which is the limitation of the existing cardanol-modified epoxy resin.

Another object of the present invention is to provide an epoxy resin composition comprising the epoxy resin described above.

In order to solve the above problems, the present invention provides a cashew nut shell extract oil derivative-modified epoxy resin represented by the following general formula (1) modified with an aromatic dicarboxylic acid and aliphatic dicarboxylic acid.

(Formula 1)

here,

X is cardanol or epoxide,

Y is phthalic acid (Phthalic aicd), isophthalic acid (Tephthalic acid), terephthalic acid (Diereic acid), aromatic dicarboxylic acid, oxalic acid (Oxalic aicd), malonic acid (Malonic aicd), succinic acid ( succinic acid, glutaric acid, or cadol,

N is an integer of 0 to 30.

In the present invention, Y is particularly phthalic acid, X may be cardanol.

In another aspect, the present invention includes an epoxy resin composition comprising the epoxy resin prepared above. The composition includes 10 to 50% by weight of a solvent capable of diluting it in 50 to 90% by weight of the epoxy resin of Formula 1. Xylene is exemplified as the diluting solvent.

In another aspect, the method for preparing an epoxy resin having excellent rust resistance and chemical resistance and low viscosity may include: i) bisphenol A epoxy, bisphenol F epoxy, bisphenol A epoxy, bisphenol A epoxy, bisphenol M epoxy, phenol novolac epoxy, 20 to 84% by weight of at least one epoxy resin selected from the group consisting of cresol novolac epoxy, BP novolac epoxy, rubber modified epoxy, fatty acid modified epoxy, urethane modified epoxy and silane modified epoxy, cashew nut shell oil (CNSL, cashew nut) shell liquid derivatives 5-30% by weight, aromatic and / or aliphatic dicarboxylic acids 5-30% by weight, and tertiary phosphine, tertiary ammonium salt, tetra ammonium salt And quaternary phosphonium salts. Mixing the falcons with remainder;

ii) heating the mixed composition to 110 to 200 ° C. to form an epoxy resin solution; And

iii) cooling and diluting the resin solution.

The CNSL derivative may be cardol or / and cardanol, preferably cardanol.

In addition, the aromatic dicarboxylic acid may be phthalic acid.

The epoxy resin prepared above is characterized in that the number average molecular weight of 400 to 6,000.

In addition, the epoxy equivalent of the prepared epoxy resin is characterized in that 300 to 3,000.

Epoxy resin composition of the present invention is not only excellent in adhesion, but also excellent in chemical resistance by appropriately introducing aromatic and aliphatic compounds into the molecule compared to the conventional CNSL derivative, typically an epoxy resin compound modified with cardanol. And low viscosity is very easy.

CNSL derivative-modified epoxy resin according to the present invention has improved corrosion resistance and chemical resistance and low viscosity characteristics compared to the conventional cardanol modified epoxy resin, it can be used as the subject of the heavy-duty resin which requires these physical properties.

Hereinafter, the present invention will be described in detail.

The present invention provides a cashew nut shell extract oil derivative-modified epoxy resin represented by the following formula (1).

(Formula 1)

here,

X is cardanol or epoxide,

Y is phthalic acid (Phthalic aicd), isophthalic acid (Tephthalic acid), terephthalic acid (Diereic acid), aromatic dicarboxylic acid, oxalic acid (Oxalic aicd), malonic acid (Malonic aicd), succinic acid ( succinic acid, glutaric acid or cadol,

In Formula 1, n is an integer of 0 to 30.

Cardanol or epoxide may be bonded to both sides of the epoxy resin terminal, or may be bonded to only one side. The structural unit may exist in various forms in the whole resin.

The epoxy resin prepared according to the present invention preferably has an epoxy equivalent of 300 to 3,000 g / eq, more preferably 300 to 2,000 g / eq. If the epoxy equivalent is less than 300 g / eq, the physical performance of the cured coating film is not sufficiently exhibited. If the epoxy equivalent is more than 3,000 g / eq, the viscosity is too high, making it difficult to high-solidize.

On the other hand, the production method of the epoxy resin of the present invention is i) bisphenol A epoxy, bisphenol F epoxy, bisphenol A epoxy, bisphenol A epoxy, bisphenol M epoxy, phenol novolac epoxy, cresol novolac epoxy, BP novolac epoxy, 20 to 84% by weight of at least one epoxy resin selected from the group consisting of rubber-modified epoxy, fatty acid-modified epoxy, urethane-modified epoxy and silane-modified epoxy, 5 to 30% by weight of cashew nut shell liquid (CNSL) derivatives, Mixing step of mixing 5 to 30% by weight of aromatic and / or aliphatic dicarboxylic acid ii) Step of forming the epoxy resin solution having excellent anti-rusting and chemical resistance and low viscosity by heating the mixed composition to 110 to 200 ℃ And iii) cooling and diluting the resin solution. Here, at least one catalyst selected from the group consisting of tertiary phosphine, tertiary ammonium salt, tetra ammonium salt and quaternary phosphonium salt as a catalyst is used. Ethyltriphenylphosphonium Iodide (ETPPI) catalyst, which is a quaternary phosphonium salt, is preferably used.

In one embodiment of the present invention, the epoxy resin is a bisphenol A epoxy resin known to have excellent chemical performance, and phthalic acid is used as the dicarboxylic acid.

Hereinafter, when the CNSL derivative is cardanol, the epoxy resin is BPA, and the dicarboxylic acid is phthalic acid.

In order to manufacture the cardanol derivative epoxy resin of this invention, the bisphenol-A epoxy resin known to be excellent in chemical performance can be used. Such bisphenol A epoxy resin is represented by the following formula (2).

(Formula 2)

Where n is from 0 to 12. Specific examples of the epoxy resins include YD-128, YD-011, YD-014, YD-017, and YD-019 (above, trade names of Kukdo Chemical), and other companies having similar characteristics (Dow, Momentive). The product can also be used and can be easily obtained on the market.

In order to prepare the CNSL derivative-modified epoxy resin according to the present invention, the CNSL derivative must be reacted with the epoxy resin. Representative component of CNSL derivative is cardanol whose structural formula is represented by the following Chemical Formula 3. Cardanol is one of the main components of CNSL (cashew nut shell liquid), which is a phenolic structure containing unsaturated groups and a by-product generated in large quantities during the production and processing of cashew nuts. It basically has a phenolic hydroxyl group, so it is used to react with the epoxy resin.

(Formula 3)

In general, the reaction of the epoxide with the phenolic hydroxy group can be partially reacted at a high temperature, but the catalyst is used for commercially efficient production. The reaction temperature is run at approximately 110 to 200 ℃. Due to the unsaturated group such as cardanol and PtBP, it is easy to lower the viscosity, so that a special solvent is not used, but if necessary, an aromatic solvent such as xylene can be used to more easily decrease the viscosity.

The reaction between the epoxy resin and cardanol is preferably performed for about 2 to 6 hours. The content of the epoxy resin added during the reaction is preferably 20 to 84% by weight. More preferably, it is 70 to 80 weight%.

If the content of the epoxy resin in the reaction is less than 20% by weight, the chemical resistance is not sufficient, whereas if the content of the epoxy resin exceeds 84% by weight, the adhesion, water repellency is lowered, and the high solidification and low embrittlement action becomes difficult.

The content of phthalic acid added during the reaction is preferably 5 to 30% by weight. If the content of phthalic acid is less than 5% by weight, the chemical resistance is not sufficient, whereas if the content of the phthalic acid is more than 30% by weight, a phenomenon of increasing the viscosity of the resin occurs, making it difficult to lower the viscosity and high solidification of the epoxy resin.

The cardanol-modified epoxy resin produced by the reaction has a structural formula represented by the following formula (4).

(Formula 4)

here,

X is cardanol or epoxide,

Y is phthalic acid (Phthalic aicd),

In Formula 1, n is an integer of 0 to 30.

Cardanol may be bonded to both sides of the epoxy resin terminal, or may be bonded to only one side. The structural unit may exist in various forms in the whole resin.

The epoxy resin prepared according to the present invention preferably has an epoxy equivalent of 300 to 3,000 g / eq, more preferably 300 to 2,000 g / eq. If the epoxy equivalent is less than 300 g / eq, the physical performance of the cured coating film is not sufficiently exhibited. If the epoxy equivalent is more than 3,000 g / eq, the viscosity is too high, making it difficult to high-solidize.

The prepared number average molecular weight of Formula 1 has 400 to 6,000. If the number average molecular weight of the resin is less than 400, the defect of the cured coating film appears. If the number average molecular weight of the resin is 6,000 or more, the hardness is high and the adhesion is poor and the content of the epoxy resin is high, so that high solidification and low embrittlement are difficult.

On the other hand, the cardanol-modified epoxy resin composition is prepared by diluting the cardanol-modified epoxy resin with a diluting solvent. Xylene is preferred as the diluent solvent.

The cardanol-modified epoxy resin composition includes 50 to 90% by weight of the cardanol-modified epoxy resin and 10 to 50% by weight of the dilution solvent.

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

Example 1

Into a flask equipped with a thermometer, a stirrer, and a cooler, 2,880 g of bis-phenol A epoxy resin (YD-128 equivalent: 187), cardanol 540 g, and phthalic acid 180 g of Kukdo Chemical were charged. 2000 ppm of ETPPI catalyst cardanol and 1000 ppm BTMAc to phthalic acid were dissolved in the mixture at 90 to 110 ° C. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of viscosity (25 degreeC) 611 CPS, epoxy equivalent 322 g / eq was obtained.

Example 2

Into the flask equipped with a thermometer, a stirrer, and a cooler, 2520 g of bis-phenol A epoxy resin (YD-128 equivalent: 187) from Kukdo Chemical, 540 g of cardanol, and 540 g of phthalic acid were charged. The mixture was dissolved in a catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) at 90 to 110 ℃ to 2000 ppm compared to cardanol, BTMAc (Benzyltrimethylammonium Chloride, yakuri pure chemical) 1000 ppm to phthalic acid. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of the viscosity (25 degreeC) 88,000 CPS and epoxy equivalent 829 g / eq was obtained.

Example 3

Into a flask equipped with a thermometer, a stirrer, and a cooler, 2700 g of bis-phenol A epoxy resin (YD-128 equivalent: 187) from Kukdo Chemical, 540 g of cardanol, and 360 g of phthalic acid were charged. The mixture was dissolved in a catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) at 90 to 110 ℃ to 2000 ppm compared to cardanol, BTMAc (Benzyltrimethylammonium Chloride, yakuri pure chemical) 1000 ppm to phthalic acid. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. Thus, the epoxy resin of this invention which has the characteristic value of viscosity (25 degreeC) 4409 CPS and epoxy equivalent 453 g / eq was obtained.

Example 4

Into a flask equipped with a thermometer, a stirrer, and a cooler, 2700 g of bis-phenol A epoxy resin (YD-128 equivalent: 187) from Kukdo Chemical, 720 g of cardanol, and 180 g of phthalic acid were charged. The mixture was dissolved in a catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) at 90 to 110 ℃ to 2000 ppm compared to cardanol, BTMAc (Benzyltrimethylammonium Chloride, yakuri pure chemical) 1000 ppm to phthalic acid. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of viscosity (25 degreeC) 730 CPS, epoxy equivalent 375 g / eq was obtained.

Example 5

Into a flask equipped with a thermometer, a stirrer, and a cooler, 3442.5 g of bis-phenol A epoxy resin (YD-128 equivalent: 187) manufactured by Kukdo Chemical, 202.5 g of PtBP, and 405 g of Isophthalic acid were added. The mixture was dissolved in an amount of 3000 ppm of ETPPBr (Ethyltriphenylphosphonium Bromide, dow chemical) compared to cardanol and 1500 ppm of TMAc (Trimethylammonium Chloride, yakuri pure chemical) compared to phthalic acid at 90 to 110 ° C. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of viscosity (25 degreeC) 12,300 CPS and epoxy equivalent 350.8 g / eq was obtained.

Example 6

3442.5 g of bis-phenol F-type epoxy resin (YDF-170 equivalent: 170), cardanol 405 g, and phthalic acid 202.5 g were added to a flask equipped with a thermometer, a stirrer, and a cooler. The mixture was dissolved in a catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) at 90 to 110 ℃ to 2000 ppm compared to cardanol, BTMAc (Benzyltrimethylammonium Chloride, yakuri pure chemical) 1000 ppm to phthalic acid. The mixture was added with the catalyst was reacted at 110 to 200 ℃ and after 3 hours the acid value was measured to complete the reaction when the 0.1 or less. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of the viscosity (25 degreeC) 2,070 CPS and epoxy equivalent 288.1 g / eq was obtained.

Comparative Example 1

1785.6 g of bis-phenol A epoxy resin (YD-128 equivalents: 187) and cardanol 1814.4 g were charged to a flask equipped with a thermometer, a stirrer, and a cooler. The mixture was dissolved by adding 2000 ppm of catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) to cardanol at 90 to 110 ° C. The mixture was reacted at 110 to 200 ° C. and terminated after the reaction for 3 hours. After the reaction was completed, the mixture was diluted with xylene. In this way, the epoxy resin of this invention which has the characteristic value of the viscosity (25 degreeC) 2945 CPS and epoxy equivalent 1286 g / eq was obtained.

Comparative Example 2

2340 g of bis-phenol A epoxy resin (YD-128 equivalents: 187) and cardanol 1260 g of Kukdo Chemical were charged into a flask equipped with a thermometer, a stirrer, and a cooler. The mixture was dissolved by adding 2000 ppm of catalyst ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) to cardanol at 90 to 110 ° C. The mixture was reacted at 110 to 200 ° C. and terminated after the reaction for 3 hours. After the reaction was completed, the mixture was diluted with xylene. Thus, the epoxy resin of this invention which has the characteristic value of viscosity (25 degreeC) 1350 CPS, epoxy equivalent 464 g / eq was obtained.

The epoxy resins of the present invention prepared in Examples and Comparative Examples are shown in Table 1 below.

Manufactured epoxy resin

	Example 1	Example 2	Example 3	Example 4	Comparative Example 1	Comparative Example 2
Epoxy equivalent weight (g / eq)	322	829	453	375	1286	464
Viscosity (cps @ 25 ° C )	611	88000	4409	730	2945	1350

After mixing the epoxy resin of the present invention and the conventional bisphenol A-type epoxy resin (Kukdo Chemical YD-011X75, YD-136X80) using a curing agent G-5022X70 in an equivalence ratio of 1: 1 and then using an applicator on an iron specimen It was shown in Tables 2 and 3 by comparing the physical properties of the coating film to the thickness.

Coating property evaluation

	Example 4	YD-011X75	YD-136X80
Hardener, G-5022X70 (Topic: curing agent ratio)	1: 1	1: 1	1: 1
Flex resistance (Erichsen Test, mm)	9.54	10.11	9.42
Impact resistance (Dupont Test, 0.5Kg)	900F	500F	1000F
Drying time (Touch / cure, 25 ℃, hr)	7.7 / 10.9	4 / 7.3	6.7 / 10.3

G-5022X70: Kukdo Chemical Polyamide Curing Agent

Water resistance and corrosion resistance evaluation

	Example 4	YD-011X75	YD-136X80
Blister	◎	○	○
Corrosion and Peeling	◎	○	○

Evaluation criteria-◎: Very good, ○: Good, △: Normal, X: Poor

The impact resistance test results of Table 2 were evaluated based on ASTM D 2794, and the improved impact resistance was confirmed as compared with the existing bisphenol A type epoxy resin (YD-011X75 manufactured by Kukdo Chemical). In addition, the flex resistance test results were evaluated based on ISO 1520, and improved flex resistance results were obtained compared to the existing bisphenol A-type epoxy resin (YD-136X80 manufactured by Kukdo Chemical).

Table 3 was evaluated based on the ASTM D 714 test method, the result of confirming the water resistance and corrosion resistance after 14 days immersed in a 70 ℃ autoclave specimen. Compared with the existing bisphenol A type epoxy resin (YD-011X75, YD-136X80 manufactured by Kukdo Chemical Co., Ltd.), water resistance and corrosion resistance were improved.

Chemical resistance evaluation

Curing agent: G-5022X70	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	YD-128	YD-011X75
Methyl Ethyl Ketone	200 times	200 times	200 times	5th	5th	200 times	200 times
Methanol	200 times	200 times	200 times	20 times	20 times	200 times	200 times
Xylene	200 times	200 times	200 times	15th	Episode 13	200 times	200 times

The chemical resistance of Table 4 was evaluated based on ASTM D 4752, and the experiment was performed after curing for 1 hour at 80 ° C. after curing for 1 day at room temperature. Compared with the existing cardanol-modified epoxy resin Comparative Example 1 and Comparative Example 2, it was confirmed that the cardanol phthalic acid-modified epoxy resin Example 1, Example 2, Example 3 is excellent.

Chemical resistance evaluation

Curing agent: G-5022X70	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	YD-128	YD-011X75
Methyl Ethyl Ketone	200 times	200 times	200 times	1 time	20 times	200 times	200 times
Methanol	200 times	200 times	200 times	1 time	80 times	200 times	200 times
Xylene	200 times	200 times	200 times	Episode 2	100 times	200 times	200 times

Table 5 chemical resistance was evaluated based on ASTM D 4752 and the experiment was carried out after 7 days of curing at room temperature. Compared with the existing cardanol-modified epoxy resin Comparative Example 1 and Comparative Example 2, it was confirmed that the cardanol phthalic acid-modified epoxy resin Example 1, Example 2, Example 3 is excellent.

Claims (5)

1. Cashew nut shell extract oil derivative modified epoxy resin represented by the formula (1).

   

   (Formula 1)

   here,

   X is cardanol or epoxide,

   Y is phthalic acid (Phthalic aicd), isophthalic acid (Tephthalic acid), terephthalic acid (Diereic acid), aromatic dicarboxylic acid, oxalic acid (Oxalic aicd), malonic acid (Malonic aicd), succinic acid ( succinic acid, glutaric acid or cadol,

   In Formula 1, n is an integer of 0 to 30.
2. The method of claim 1, wherein the epoxy resin has a number average molecular weight of 400 to 6,000 cashew nut shell extract oil derivative modified epoxy resin
3. 2. The cashew nut shell extract oil-modified epoxy resin according to claim 1, wherein the epoxy equivalent of the epoxy resin is 300 to 3,000.
4. Cashew nut shell extract oil derivative-modified epoxy resin composition comprising 50 to 90% by weight of the epoxy resin of claim 1 and 10 to 50% by weight of a volatile solvent.
5. i) bisphenol A epoxy, bisphenol F epoxy, bisphenol A epoxy, bisphenol A epoxy, bisphenol M epoxy, phenol novolac epoxy, cresol novolac epoxy, BP novolac epoxy, rubber modified epoxy, fatty acid modified epoxy, urethane modified epoxy and 20 to 84% by weight of at least one epoxy resin selected from the group consisting of an epoxy resin which is at least one selected from silane-modified epoxy, 5 to 30% by weight of cashew nut shell liquid (CNSL) derivatives, aromatic and / or aliphatic 5-30% by weight of dicarboxylic acid and tertiary phosphine, tertiary ammonium salt, tetra ammonium salt and quaternary phosphonium salt Mixing at least one catalyst selected from the residues.

   ii) heating the mixed composition to 110 to 200 ° C. to form an epoxy resin solution; And

   iii) a method of preparing a cashew nut shell extract oil-modified epoxy resin composition, comprising the step of cooling and diluting the resin solution.