KR101717974B1 - Epoxy resin - Google Patents

Abstract

The present invention relates to a Cashew nut husk extract oil derivative modified epoxy resin composition comprising Cashew nut husk extract oil derivative modified epoxy resin excellent in rust resistance and chemical resistance and low in viscosity and having Cashew nut husk extract oil derivative modified epoxy resin, And a manufacturing method thereof.

Description

[0001] Cashew nut husk extract oil derivative modified epoxy resin, epoxy resin composition containing the same,

The present invention relates to a modified Cashew nut skin oil derivative-modified epoxy resin composition comprising Cashew nut shell extract oil derivative-modified epoxy resin, Cashew nut shell extract oil derivative-modified epoxy resin, and a process for producing the same.

More specifically, the present invention relates to a Cashew nut husk extract oil derivative-modified epoxy resin which is excellent in rust-preventive and chemical resistance and can be obtained in a low viscosity, a Cashew nut husk extract oil derivative-modified epoxy resin composition comprising the Cashew nut shell extract oil derivative-modified epoxy resin, And a manufacturing method thereof.

It is generally known that epoxy resins are superior in mechanical and chemical properties to other types of resins. Due to the above characteristics, it is applied to ship, civil engineering, architecture, electricity, electronic material, and composite material field, and is widely used particularly as a material for preventing corrosion of steel plate. For example, the epoxy resin used in the heavy duty type is applied to the undercuts and tops to prevent corrosion of the steel sheet because of its excellent adhesion and water resistance, and its demand is increasing.

However, there is a problem due to the difficulty of high solidification and low embrittlement due to the environmental problems caused by the regulation of VOCs. In addition, the compatibility with aromatic solvents is poor, so dilution may not be performed well, or a large amount of dilution may be required, resulting in problems of appearance and poor workability.

Cadaan-modified epoxy resins capable of water repellency and high solidification by modifying cardanol have been developed and used (for example, Patent Document 10-0559055).

However, existing cadanol-modified epoxy resins have a disadvantage that they are poor in rust resistance and chemical resistance.

Patent Registration No. 10-0559055

The present invention has been made in view of the above points, and an object of the present invention is to provide an epoxy resin which overcomes the rust-preventive and chemical resistance which is the limit of conventional cadanol-modified epoxy resin and has low viscosity.

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

In order to solve the above-described problems, the present invention provides a modified Cashew nut skin oil derivative-modified epoxy resin represented by the following Chemical Formula 1, which is modified with an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid.

(Formula 1)

here,

)이고, X is a cardanol or epoxide (

)ego,

), 아이소프탈산(Isophthalic acid,

), 테레프탈산(Terephthalic acid,

), 디페닉산(Diphenic acid,

)을 포함하는 방향족 디카르복시산, 옥살산(Oxalic aicd), 말론산(Malonic aicd), 숙신산(succinic acid), 글루타르산(glutaric acid), 또는 카돌 이고,Y is phthalic acid (Phthalic acid,

), Isophthalic acid (isophthalic acid,

), Terephthalic acid (Terephthalic acid,

), Diphenic acid (Diphenic acid,

Oxalic acid, malonic acid, succinic acid, glutaric acid, or a chaldehyde, which is an aromatic dicarboxylic acid including oxalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid,

And n is an integer of 0 to 30.

In the present invention, Y may be phthalic acid in particular, and X may be cardanol.

In another aspect, the present invention includes an epoxy resin composition comprising the epoxy resin prepared above. The composition comprises 50 to 90% by weight of the epoxy resin of the formula (1) and 10 to 50% by weight of a solvent capable of diluting the same. As the diluting agent, xylene is exemplified.

In another aspect of the present invention, there is provided a method for producing an epoxy resin having excellent rust resistance and chemical resistance and low viscosity, which comprises: (1) 20 to 84% by weight of at least one epoxy resin selected from the group consisting of cresol novolac epoxy, bifionone novolac epoxy, rubber modified epoxy, fatty acid modified epoxy, urethane modified epoxy and silane modified epoxy, cashew nutshell oil (CNSL, cashew nut 5 to 30% by weight of an aromatic and / or shell liquid derivative, 5 to 30% by weight of an aromatic and / or aliphatic dicarboxylic acid, and at least one of tertiary phosphine, tertiary ammonium salt, tetra ammonium salt, And a quaternary phosphonium salt. ≪ RTI ID = 0.0 > Mixing the glass-sheet portion;

Ii) reacting the mixed composition at 110 to 200 DEG C to form an epoxy resin solution; And

And iii) cooling and diluting the resin solution.

In the above, the CNSL derivative may be cardol or / and cardanol, preferably a cardanol.

Also, the aromatic dicarboxylic acid may be phthalic acid.

The epoxy resin prepared above has a number average molecular weight of 400 to 6,000.

The epoxy equivalent of the epoxy resin is 300 to 3,000.

The epoxy resin composition of the present invention is superior in adhesiveness to conventional CNSL derivatives, typically, cardanol-modified epoxy resin compounds, as well as aromatic compounds and aliphatic compounds suitably introduced into the molecule to provide excellent chemical resistance, And low viscosity is very easy.

The CNSL derivative-modified epoxy resin according to the present invention has improved rust resistance, chemical resistance and low viscosity as compared with the conventional cadanol-modified epoxy resin, and can be used as a subject of a heavy-duty edible resin requiring such properties.

Hereinafter, the present invention will be described in detail.

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

(Formula 1)

here,

)이고, X is a cardanol or epoxide (

)ego,

), 아이소프탈산(Isophthalic acid,

), 테레프탈산(Terephthalic acid,

), 디페닉산(Diphenic acid,

)을 포함하는 방향족 디카르복시산, 옥살산(Oxalic aicd), 말론산(Malonic aicd), 숙신산(succinic acid), 글루타르산(glutaric acid) 또는 카돌 이고,Y is phthalic acid (Phthalic acid,

), Isophthalic acid (isophthalic acid,

), Terephthalic acid (Terephthalic acid,

), Diphenic acid (Diphenic acid,

Oxalic acid, malonic acid, succinic acid, glutaric acid or chalcone, and the like.

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

The terminal of the epoxy resin may have either a caranol or an epoxide on both sides or may be bonded to either side only. The structural unit may exist in various forms in the entire resin.

The epoxy resin prepared according to the present invention preferably has an epoxy equivalent of 300 to 3,000 g / eq and 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 becomes too high, making it difficult to achieve high solids.

On the other hand, the process for producing an epoxy resin of the present invention comprises the steps of: (i) mixing a mixture of a bisphenol A epoxy, a bisphenol A epoxy, a bisphenol A epoxy, a bisphenol A epoxy, a bisphenol M epoxy, a phenol novolac epoxy, a cresol novolac epoxy, 20 to 84% by weight of one or more epoxy resins 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 derivative (CNSL) And 5 to 30% by weight of an aromatic and / or aliphatic dicarboxylic acid; ii) heating the mixed composition at 110 to 200 ° C to form an epoxy resin solution having excellent rustproofing and chemical resistance and low viscosity , And iii) cooling and diluting the resin solution. Wherein the catalyst comprises at least one catalyst selected from the group consisting of tertiary phosphine, tertiary ammonium salt, tetra ammonium salt and quaternary phosphonium salt, And preferably an ETPPI (Ethyltriphenylphosphonium iodide) catalyst, which is a quaternary phosphonium salt.

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

Hereinafter, when the CNSL derivative is cardanol, the epoxy resin is BPA and the dicarboxylic acid is phthalic acid, the process for producing the epoxy resin of the present invention will be described as an example,

In order to produce the cardanol derivative epoxy resin of the present invention, it is possible to use a bisphenol A type epoxy resin which is known to have excellent chemical performance. The bisphenol A type epoxy resin is represented by the following general formula (2).

(2)

Wherein n is from 0 to 12. Specific examples of the above epoxy resin include YD-128, YD-011, YD-014, YD-017 and YD-019 Etc.) are also available and are easily available on the market.

In order to prepare the CNSL derivative-modified epoxy resin according to the present invention, the CNSL derivative should be reacted with the epoxy resin. A representative component of the CNSL derivative is cardanol, which has the structural formula shown below. Cadanol is a phenolic structure containing unsaturated groups and is one of the major components of cashew nut shell liquid (CNSL), a by-product that occurs in large quantities during the production of cashew nuts. It has basically a phenolic hydroxy group, so it is used to react with epoxy resin.

(Formula 3)

In general, the reaction of the epoxide with the phenolic hydroxyl group is catalyzed for commercial efficient production although some reactions are possible at high temperatures. The reaction temperature is maintained at about 110 to 200 ° C. It is not easy to lower the viscosity because of unsaturated groups such as cardanol and PtBP, so that a special solvent is not used. However, if necessary, the use of an aromatic solvent such as xylene makes it easier to lower the viscosity.

The reaction between the epoxy resin and the cardanol preferably proceeds 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% by weight.

If the content of the epoxy resin is less than 20% by weight, the chemical resistance is insufficient. On the other hand, if the content of the epoxy resin exceeds 84% by weight, the adhesiveness and water repellency are lowered, and high solids and low embrittling action become 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. On the other hand, when the content of the phthalic acid exceeds 30% by weight, the viscosity of the resin increases and low viscosity and high solidification of the epoxy resin become difficult.

The cadanol-modified epoxy resin produced by the above reaction has the structural formula shown in the following Chemical Formula 4.

(Formula 4)

here,

)이고,X is a cardanol or epoxide (

)ego,

)이고,Y is phthalic acid (Phthalic acid,

)ego,

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

The terminal of the epoxy resin may be bonded to either side of the cardanol or may be bonded to either side of the epoxy resin. The structural unit may exist in various forms in the entire resin.

The epoxy resin prepared according to the present invention preferably has an epoxy equivalent of 300 to 3,000 g / eq and 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 becomes too high, making it difficult to achieve high solids.

The number average molecular weight of the prepared Formula 1 is 400 to 6,000. If the number-average molecular weight of the resin is less than 400, defective cured coatings appear. If the number average molecular weight of the resin is 6,000 or more, the hardness is high and the adhesion failure and the content of the epoxy resin are high.

On the other hand, the cadanol-modified epoxy resin composition is prepared by diluting the cadanol-modified epoxy resin with a diluting solvent. The diluting agent is preferably xylene.

The cadanol-modified epoxy resin composition comprises 50 to 90% by weight of the cadanol-modified epoxy resin and 10 to 50% by weight of the diluting 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

A flask equipped with a thermometer, a stirrer and a condenser was charged with 2,880 g of bis-phenol A type epoxy resin (YD-128 equivalent: 187), Kanto Chemical Co., 540 g of cardanol and 180 g of phthalic acid. To the mixture was added 2000 ppm of catalytic ETPPI and 1000 ppm of BTMAc to phthalic acid at 90 to 110 ° C. The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 611 CPS and an epoxy equivalent of 322 g / eq was obtained.

Example 2

A flask equipped with a thermometer, a stirrer and a condenser was charged with 2520 g of Bis-phenol A type epoxy resin (YD-128 equivalent: 187), 540 g of cardanol and 540 g of phthalic acid. The mixture was dissolved in 2000 ppm of catalan ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) and 1000 ppm of BTUMc (Benzyltrimethylammonium Chloride, yakuri pure chemical) relative to phthalic acid at 90-110 ° C. The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 88,000 CPS and an epoxy equivalent of 829 g / eq was obtained.

Example 3

2700 g of bisphenol A type epoxy resin (YD-128 equivalent: 187) of Kukdo Chemical, 540 g of cardanol and 360 g of phthalic acid were added to a flask equipped with a thermometer, a stirrer and a condenser. The mixture was dissolved in 2000 ppm of catalan ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) and 1000 ppm of BTUMc (Benzyltrimethylammonium Chloride, yakuri pure chemical) relative to phthalic acid at 90-110 ° C. The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 4409 CPS and an epoxy equivalent of 453 g / eq was obtained.

Example 4

2700 g of bisphenol A type epoxy resin (YD-128 equivalent: 187) of Kukdo Chemical Co., 720 g of cardanol and 180 g of phthalic acid were added to a flask equipped with a thermometer, a stirrer and a condenser. The mixture was dissolved in 2000 ppm of catalan ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) and 1000 ppm of BTUMc (Benzyltrimethylammonium Chloride, yakuri pure chemical) relative to phthalic acid at 90 to 110 ° C. The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 730 CPS and an epoxy equivalent of 375 g / eq was obtained.

Example 5

3442.5 g of Bis-phenol A type epoxy resin (YD-128 equivalent: 187) of Kukdo Chemical Co., 202.5 g of PtBP and 405 g of isophthalic acid were added to a flask equipped with a thermometer, a stirrer and a condenser. The mixture was dissolved at a temperature of 90 to 110 ° C by adding 3000 ppm of catalytic ETPPBr (dit chemical) to cardanol and 1500 ppm of phthalic acid (trimethylammonium chloride, yakuri pure chemical). The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 12,300 CPS and an epoxy equivalent of 350.8 g / eq was obtained.

Example 6

3442.5 g of bisphenol F type epoxy resin (YDF-170 equivalent: 170) manufactured by Kukdo Chemical Co., 405 g of cardanol and 202.5 g of phthalic acid were added to a flask equipped with a thermometer, a stirrer and a condenser. The mixture was dissolved in 2000 ppm of catalan ETPPI (Ethyltriphenylphosphonium Iodide, dow chemical) and 1000 ppm of BTUMc (Benzyltrimethylammonium Chloride, yakuri pure chemical) relative to phthalic acid at 90-110 ° C. The mixture in which the catalyst was added was reacted at 110 to 200 ° C, and after 3 hours, the acid value was measured to be 0.1 or less, and the reaction was terminated. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 2,070 CPS and an epoxy equivalent of 288.1 g / eq was obtained.

Comparative Example 1

In a flask equipped with a thermometer, a stirrer and a condenser, 1785.6 g of Bis-phenol A type epoxy resin (YD-128 equivalent: 187) and 1814.4 g of cardanol were added. The mixture was dissolved at a temperature of 90 to 110 DEG C by adding 2000 ppm of catalytic ETPPI (Ethyltriphenylphosphonium iodide, dow chemical) to cardanol. The mixture was reacted at 110 to 200 ° C, and the reaction was terminated after 3 hours of reaction. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 2945 CPS and an epoxy equivalent of 1286 g / eq was obtained.

Comparative Example 2

A flask equipped with a thermometer, a stirrer and a condenser was charged with 2340 g of Bis-phenol A type epoxy resin (YD-128 equivalent: 187) and 1260 g of cardanol. The mixture was dissolved at a temperature of 90 to 110 DEG C by adding 2000 ppm of catalytic ETPPI (Ethyltriphenylphosphonium iodide, dow chemical) to cardanol. The mixture was reacted at 110 to 200 ° C, and the reaction was terminated after 3 hours of reaction. After completion of the reaction, the reaction solution was diluted with xylene. Thus, an epoxy resin of the present invention having a viscosity (25 DEG C) of 1350 CPS and an epoxy equivalent of 464 g / eq was obtained.

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

The prepared epoxy resin Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Epoxy equivalent
(g / eq) 322 829 453 375 1286 464 Viscosity
(cps @ 25 & lt ; 0 & gt ; C ) 611 88000 4409 730 2945 1350

An epoxy resin of the present invention prepared above and a conventional bisphenol-type epoxy resin (YD-011X75, YD-136X80 made by Kokudo Chemical Co., Ltd.) were mixed at an equivalent ratio of 1: 1 using a curing agent G-5022X70, And the physical properties thereof were compared and shown in Tables 2 and 3 below.

Evaluation of Physical Properties of Coating Film Example 4 YD-011X75 YD-136X80 Hardener, G-5022 X70
(Subject: compounding ratio of hardener) 1: 1 1: 1 1: 1 Flexibility
( Erichsen Test , mm ) 9.54 10.11 9.42 Impact resistance
(Dupont Test, 0.5 Kg) 900F 500F 1000F Drying time
(Touch / cure, 25 ° C, hr) 7.7 / 10.9 4 / 7.3 6.7 / 10.3

G-5022X70: Route Chemistry Polyamide hardener

Water resistance and corrosion resistance evaluation Example 4 YD-011X75 YD-136X80 Blister ◎ ○ ○ Corrosion and exfoliation ◎ ○ ○

Evaluation criteria -?: Very good,?: Good,?: Fair, X: poor

The results of the impact resistance test in Table 2 were evaluated based on ASTM D 2794, and the improved impact resistance was confirmed as compared with that of the existing bisphenol-type epoxy resin (YD-011X75 manufactured by Kukdo Chemical Co., Ltd.). Also, the flexural strength test results were evaluated on the basis of ISO 1520, and the flexural resistance was improved as compared with the conventional bisphenol-type epoxy resin (YD-136X80 made by Kukdo Chemical Co., Ltd.).

Table 3 above was evaluated based on the ASTM D 714 test method, and it was confirmed that the water resistance and corrosion resistance after immersing the specimen in an autoclave at 70 ° C for 14 days. Compared with the conventional bisphenol-type epoxy resin (YD-011X75, YD-136X80, National Highway Chemicals), the water resistance and corrosion resistance were improved.

Chemical resistance evaluation Hardener: G-5022X70 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 YD-128 YD-011
X75 Methyl Ethyl Ketone 200 times 200 times 200 times 5 times 5 times 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 15 times 13 times 200 times 200 times

The chemical resistance evaluation of Table 4 was based on ASTM D 4752, and the curing was carried out at room temperature for 1 day and then at 80 ° C for 4 hours. It was confirmed that the cadanolphthalic acid-modified epoxy resin of Example 1, Example 2, and Example 3 were far superior to the existing cadanol-modified epoxy resin of Comparative Example 1 and Comparative Example 2.

Chemical resistance evaluation Hardener: G-5022X70 Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 YD-128 YD-011
X75 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 evaluation was made according to ASTM D 4752, and the test was conducted after curing at room temperature for 7 days. It was confirmed that the cadanolphthalic acid-modified epoxy resin of Example 1, Example 2, and Example 3 were far superior to the existing cadanol-modified epoxy resin of Comparative Example 1 and Comparative Example 2.

Claims (5)

A cashew nut skin oil derivative modified epoxy resin represented by the following formula (1).

(Formula 1)

here,
X is a cardanol or epoxide (

)ego,
Y is phthalic acid (Phthalic acid,

), Isophthalic acid (isophthalic acid,

), Terephthalic acid (Terephthalic acid,

) Or diphenic acid (Diphenic acid,

Oxalic acid, malonic acid, succinic acid, or glutaric acid, which is an aromatic dicarboxylic acid,
In the general formula (1), n is an integer of 1 to 30. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin has a number average molecular weight of 400 to 6,000. 2. The modified epoxy resin according to claim 1, wherein the epoxy equivalent of the epoxy resin is 300 to 3,000. A vulcanized husk shell oil extraction oil-modified epoxy resin composition comprising 50 to 90% by weight of an epoxy resin as claimed in claim 1 and 10 to 50% by weight of a volatile solvent. The epoxy resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of (i) bisphenol epoxy epoxy resin, bisphenol epoxy epoxy resin, bisphenol epoxy epoxy resin, bisphenol epoxy epoxy resin, bisphenol epoxy epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bipyinnovolak epoxy resin, rubber modified epoxy resin, 20 to 84% by weight of at least one epoxy resin selected from the group consisting of epoxy resins selected from the group consisting of epoxy resins and silane-modified epoxy resins, 5 to 30% by weight of cashew nut shell liquid derivatives (CNSL) 5 to 30% by weight of dicarboxylic acid, and a mixture of tertiary phosphine, tertiary ammonium salt, tetra ammonium salt and quaternary phosphonium salt. By weight of at least one catalyst selected from the group consisting of:
Ii) reacting the mixed composition at 110 to 200 DEG C to form an epoxy resin solution; And
And iii) cooling and diluting the resin solution. ≪ RTI ID = 0.0 > 18. < / RTI >