KR100830257B1 - Epoxy resin composition for use of the storage tank of liquefied natural gas line - Google Patents

Abstract

An epoxy resin composition suitable for adhering or sealing the insulating material of the storage tank of a liquefied natural gas carrier is provided to improve the adhesive strength and mechanical strength at low and room temperature. An epoxy resin composition comprises 100 parts by weight of at least one epoxy resin selected from a bisphenol type epoxy resin, a glycidyl ether-based epoxy resin, a glycidyl amine-based epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin and a dimer acid modified epoxy resin; 10-50 parts by weight of an aliphatic modified epoxy resin; 50-100 a polyamide-based curing agent; 10-30 parts by weight of an alicyclic amine-based curing agent; 0.1-20 parts by weight of a silane compound; 0.1-20 parts by weight of a curing catalyst; and 100-400 parts by weight of a pigment.

Description

Epoxy resin composition used for liquefied natural gas storage tank {EPOXY RESIN COMPOSITION FOR USE OF THE STORAGE TANK OF LIQUEFIED NATURAL GAS LINE}

The present invention relates to an epoxy resin composition suitable for use in the adhesion and sealing of heat insulating material of a liquefied natural gas storage tank, and more particularly, to the adhesion and sealing portion of heat insulating material in a structure related to the transport and storage of natural liquefied gas. The present invention relates to an epoxy resin composition which is excellent in adhesive strength and mechanical strength at low and normal temperatures, and excellent in non-flowability before curing, and thus works on vertical walls.

In general, liquefied natural gas is a cryogenic liquid having a boiling point of -162 ° C under atmospheric pressure, and when liquefied, the volume is reduced to 600 times so that the volume ratio can be increased by maintaining the liquid phase during transportation and storage. Therefore, cryogenic storage tanks should be used during transport and storage. In order to insulate such cryogenic storage tanks, an adhesive material is required in the process of installing an insulation material. The material must be able to maintain excellent adhesion to temperature and types of adhesive materials, and has a function of sealing role against liquid pressure. Should be

Adhesives having a bonding function have been used for bonding purposes in many structures. Such bonding applications are applied in various fields, such as automobile and aircraft assembly, in addition to civil engineering. An epoxy resin composition is used as an adhesive for adhesive use in such a structure (hereinafter, "structural adhesive"), and the physical properties required for the epoxy resin composition for structural adhesive use are classified into physical properties before and after curing. The required physical properties before curing include pot life, workability based on fluidity, and the like, and the physical properties required after curing include adhesive strength, watertightness, seawater resistance and durability according to various conditions and materials.

Among these properties, the adhesive strength and mechanical strength, which are commonly required properties of the epoxy resin composition at room temperature and low temperature, are directly linked to the ultimate function of the epoxy resin composition, which is one of the physical properties to be carefully considered in preparing the epoxy resin composition.

It is also known that conventional epoxy resin compositions can be modified by adding butadiene and acrylonitrile copolymers to epoxy resins or by adding adducts of such copolymers and epoxy resins to give low temperature adhesion and flexibility at low temperatures. It is true.

In this regard, European Patent Publication No. 0527706 discloses the use of butadiene acrylonitrile copolymers, polyamides, aliphatic and aromatic amines for high glass transition temperature, elasticity, chemical thixotropic, high temperature resistance and the like. However, this patented technology does not have the mechanical strength enough to be used as a structural adhesive, and has a problem in that the hardness and modulus are low, thereby exhibiting properties close to those of the sealing material rather than the function of the adhesive material, and also excessive amount of butadiene acrylonitrile copolymer rubber. By using an excessive amount of the raw material having a high viscosity, there is a problem in that the viscosity of the material before curing is high and workability is inferior.

In addition, US Patent No. 6,645,341 discloses the inclusion of butadiene acrylonitrile copolymer in the epoxy composition to improve shear adhesion strength, but as a structural adhesive filled to support the adhesion of the insulation panel and the internal load of the tank There is a problem in that the adhesive strength is low to use, and the technology for the adhesive strength at low temperature has not been described.

US Pat. No. 6,572,971 discloses a method of imparting impact and flexibility to an epoxy amine cured product using an acrylonitrile copolymer rubber. However, there is no description of the adhesive strength at low temperature, and the adhesive strength at room temperature is also described. It was found to be unsuitable for use as a structural adhesive.

US Patent Nos. 3,842,037 and US Pat. No. 4,465,722 describe methods for producing high molecular weight polyepoxy resins by reacting low molecular weight epoxy compounds in the presence of a catalyst in the presence of a catalyst, US Pat. No. 3,655,818, US Pat. 4,708,996 and U.S. Patent No. 4,789,712 are prepared by mixing a rubber-modified acrylic butadiene copolymer or a rubber-modified carboxyterminated butadiene acrylonitrile in order to increase impact resistance and flexibility to a high molecular weight epoxy resin prepared through the preparation method. Use is disclosed. However, these methods have a problem that it is difficult to use as a structural adhesive to support the load because the glass transition temperature of the rubber itself is too low.

Korean Patent Laid-Open Publication No. 1988-0000111 refers to a composition containing an epoxy resin modified with butadiene acrylonitrile copolymer rubber in order to increase the cutting property by a knife after curing, but this improves the flexibility when applied but the adhesive strength There is a problem falling.

Butadiene acrylonitrile copolymer rubber, which has been conventionally applied to solve the rigidity of an epoxy resin, has a bad smell and a disadvantage in terms of workability due to its high viscosity. In addition, when an aliphatic epoxy resin is used alone, it has inferior disadvantages such as flowability, storage stability, and reactivity.

The purpose of the present invention is to solve the problems as described above, when applied to the adhesion and sealing of the insulating material is excellent in the adhesive strength and mechanical strength at low temperature and room temperature, liquefaction that can work on the vertical wall with excellent non-flowability before curing It is to provide an epoxy resin composition suitable for application to the heat insulating material of the natural gas line storage tank.

The epoxy resin composition of this invention is 10-50 weight part of aliphatic modified epoxy resins, 50-100 weight part of polyamide-type hardeners, 10-30 weight part of alicyclic amine-type hardeners, and a silane compound 0.1 with respect to 100 weight part of epoxy resins. To 20 parts by weight, a curing catalyst 0.1 to 20 parts by weight, and pigments, characterized in that it comprises 100 to 400 parts by weight.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(1) epoxy resin

The epoxy resin used in the present invention is a main component of the composition used for the purpose of maintaining excellent adhesion and improving the durability of the material, etc., and has at least two or more epoxy groups in one molecule and an epoxy equivalent of 100 to 500 g / eq. It is more preferable that it is 150-300 g / eq.

As said epoxy resin, bisphenol-type epoxy resins, such as bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, bisphenol H, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, phenol novolak-type An epoxy resin, a cresol novolak-type epoxy resin, a dimer acid modified epoxy resin, etc. are mentioned, These can be used individually or in mixture of 2 or more types. There is no restriction | limiting in particular in the mixing ratio at the time of mixed use, For example, when mixing bisphenol A and bisphenol F, the mixing ratio is preferably 99.9-50: 0.1-50 in weight ratio, and the content ratio of bisphenol F with respect to bisphenol A is used. If it is less than 0.1, the low temperature mechanical properties of the composition is poor, and if it exceeds 50, a problem occurs that the compressive strength of the mechanical strength of the composition is lowered.

(2) aliphatic modified epoxy resin

The aliphatic modified epoxy resin used in the present invention is a component for imparting excellent impact resistance, heat resistance and good mechanical properties at low temperature (-170 ° C), which is a low molecular weight bisphenol type epoxy resin or a mixture of this and a novolac epoxy resin. It can manufacture by making a polyhydric phenol compound or a mixture of this and an aliphatic epoxy resin react in presence of a catalyst.

As the low molecular weight bisphenol type epoxy resin used in the reaction for producing the aliphatic modified epoxy resin, the weight average molecular weight is 200 ~ 3,000, epoxy equivalent is preferably 100 ~ 1000g / eq, bisphenol A epoxy resin, Bisphenol F type epoxy resin, polyepoxide diglycidyl ether, etc. can be used, For example, KCC R-8815, R-8816, R-8827, R-8828, R-8829, N8010, N8020, N8030 and the like.

The aliphatic epoxy resin that can be used in the reaction is preferably an epoxy equivalent of 200 ~ 1000g / eq, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol poly Glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentylglycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl It can be selected and used among ether etc. and these derivatives, As an example, EX Siri by Nagase Chemical Co., Ltd. can be used. In, EX-611, EX-612, EX-512, EX-521, EX-411, EX-421, EX-301, EX-313, EX-314, EX-321, EX-211, EX-212, EX-252, EX-821, EX-830, EX-831, EX-841, EX-920, EX-921, EX-931 and the like, and EPODIL 748 and EPODIL 750 from AIR PRODUCT.

The aliphatic epoxy resin used in the reaction is preferably used in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the low molecular weight bisphenol-type epoxy resin, but when it is less than 10 parts by weight, the mechanical properties at low temperature are inferior, which is not preferable. When it exceeds 50 weight part, hardness becomes low and it is unpreferable.

Examples of the polyhydric phenol compound used to prepare the aliphatic modified epoxy resin include 2,2-bis (p-hydroxyphenyl) propane, (2,4-dihydroxyphenyl) methane and bis (2-hydroxyphenyl). Methane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy Phenyl) ethane, 1,3-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxy-2,6-dimethyl-3-methoxy) phenyl, 2,2-bis (4- Hydroxyphenyl) propane, 4,4-dihydroxyphenyl, bis (4-hydroxy-3-chloronaphthyl) ether, bis (4-hydroxy-3-bromophenyl) ether, 1,1-bis (4-hydroxyphenol) -2-phenylethane, 2,4-bis (P-hydroxyphenyl) -4-methylpentane, bisphenol A, 2,2-bisphenol A, etc. are mentioned. It is preferable that the usage-amount of a polyhydric phenol compound is 0.1-2.0 mol with respect to 1 mol of the said low molecular weight bisphenol-type epoxy resins.

As a catalyst used to prepare the aliphatic modified epoxy resin, basic amines such as sodium hydroxide, sodium hydrogen sulfate, lithium chloride, lithium oxide, tin chloride, zinc chloride, BF3-ether compound, BF3-composite compound, and quaternary ammonium salts (Lewis base); Ammonium halide salt compounds such as phenyltrimethylammonium chloride salt, tetramethylammonium salt, benzyltrimethylammonium chloride salt, dodecyltrimethylammonium chloride salt and tetraalkylammonium halogen; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2, Imidazoles such as 4-dimethylimidazole and 2-phenyl-4-methylimidazole; And butyl triphenyl phosphonium bromide, tri-allyl phosphine, butyl allyl phosphine, triphenyl phosphine, butyl triphenyl phosphate formate, butyl triphenyl phosphate oxalate, ethyl triphenyl phosphate succinate, ethyl triphenyl phospho Phosphonium salts, such as a nium salt compound, its derivatives, etc. can be used.

The addition amount of the catalyst is preferably 0.01 to 0.5 parts by weight based on 100 parts by weight of the low molecular weight bisphenol-type epoxy resin to be used. When the addition amount is less than 0.01 parts by weight, the reaction rate is lowered and is not preferable. Side reactions occur and are undesirable.

The catalyst may be used by dissolving in solvents (ketone alcohols) for the diffusion effect.

In consideration of the effect on color during the reaction to prepare the aliphatic modified epoxy resin, an inert gas may be injected for the purpose of oxidation prevention, and a solvent may be added to adjust the reaction rate resulting from the bulk reaction. Ketone alcohol can be used as a main solvent. In addition, better results can be obtained by dividing the addition of the catalyst into primary and secondary reactions in order to control the reaction rate and excessive reaction.

When explaining the manufacturing process of the aliphatic modified epoxy resin used in the present invention in detail as follows.

A low molecular weight bisphenol-type epoxy resin alone or a novolak epoxy resin is melted and a polyhydric phenol compound alone or a mixture of this and an aliphatic epoxy resin is added to carry out a polymerization reaction at a reaction temperature of 150 to 200 ° C. It is not preferable because the physical properties of the product are lowered due to the remaining of the reactants, and the gelation due to the rapid activation of the catalyst and the polymerization of heterogeneous polymers are observed above 200 ° C.

It is preferable that the epoxy equivalent of the aliphatic modified epoxy resin obtained through the said reaction is 200-2000 g / eq.

When the aliphatic modified epoxy resin is used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the epoxy resin, when it is less than 10 parts by weight, the mechanical strength at low temperature tends to be lowered, and when it exceeds 50 parts by weight. Tends to have low hardness and high elongation.

(3) polyamide curing agent

The polyamide curing agent used in the present invention is used as a curing agent of the epoxy resin, and specific examples thereof include diethyltriamine (DETA), ethylenediamine (EDA), triethylenetetraamine (TETA), and tetraethylenepentaamine (TEPA). ), Aliphatic amines such as diethylaminopropylamine (DEAPA), methanediamine (MDA), N-aminoethylpiperidine (N-AEP), m-xylenediamine (m-XDA), and 1,3-bisamino Aromatic amines, such as methyl cyclohexane (1, 3-BAC), and polyamides, etc. are mentioned, These can be used individually or 2 types or more. When the epoxy resin is cured using the polyamide-based curing agent, a cured product having a main chain crosslinked skeleton as shown in Chemical Formula 1 is obtained.

[Formula 1]

　　　　　　　　　　

　　

(Wherein R ₅ is ethylene, C _{1 to} C ₈ aliphatic, aromatic polyamine or polyamide.)

In the epoxy resin composition of the present invention, it is preferable that the polyamide curing agent is used in an amount of 50 to 100 parts by weight based on 100 parts by weight of the epoxy resin (1). There exists a tendency to fall, and when it exceeds 100 weight part, a crosslinking density becomes high and there exists a tendency for the mechanical strength in low temperature to fall.

(4) alicyclic amine curing agent

The cycloaliphatic amine curing agent used in the present invention is mainly used for the purpose of imparting the hardness and mechanical strength of the cured product, and specific examples thereof include isophorone diamine, diaminocyclohexane, 4,4-bisparaaminocyclohexylmethane, and the like. Can be mentioned.

The alicyclic amine curing agent is preferably used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the epoxy resin (1). When the alicyclic amine curing agent is less than 10 parts by weight, the hardness of the cured product is low, and the mechanical strength and hardness decrease. If the part is oversized, the flexibility at low temperatures is deteriorated and the mechanical strength is poor.

(5) silane compound

The silane compound used in the present invention is used to improve the adhesion with the epoxy resin, it may be used an alkoxy silane compound represented by the formula (2).

[Formula 2]

(Wherein R ₁ and R ₂ are each an alkyl group having 1 to 4 carbon atoms, X is an alkyl group containing a functional group, and a and b each represent an integer of 0 to 2).

Specific examples of the silane compound include β-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyl Silane coupling agents such as trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane; And alkoxysilanes such as dimethylmethoxysilane, methyltrimethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane. .

The amount of the silane compound used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin (1). If the amount of the silane compound is out of this range, poor adhesion to the substrate may occur, which is not preferable.

(6) curing catalyst

The curing catalyst used in the present invention is used to control the curing rate of the composition, and specific examples include diethylenetriamine, triethylenetriamine, isophoronediamine, xylenediamine, 2,4,6-tris (dimethylaminomethyl ) Phenols and the like.

It is preferable that the curing catalyst is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin (1). In this case, the pot life is shortened, which adversely affects workability.

(7) pigment

Pigments used in the present invention are used to control the flowability of the composition.

The amount of the pigment is preferably 100 to 400 parts by weight with respect to 100 parts by weight of the epoxy resin (1), but less than 100 parts by weight is poor in flowability and a problem in workability, viscosity exceeds 400 parts by weight Becomes high, and the fall of spreadability comes.

Specific examples of the pigment include titanium dioxide (TiO ₂ ), barium sulfate (BaS0 ₄ ), calcium carbonate (CaC0 ₃ ), silica (SiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), and the like.

In addition, the epoxy resin composition of the present invention may further include conventional additives such as adhesion promoters, dispersants, thixotropic agents, etc., as necessary, within the scope of not impairing the object of the present invention.

The epoxy resin composition of the present invention can be prepared by using a mixing stirrer to separate each of the components into a prescribed amount of the main ingredient and the curing agent and sufficiently stirring each, and then mixing the stirred main ingredient and the curing agent using an automatic mixing device at room temperature. It should be used within the pot life after mixing the topic and hardener. When mixing a large amount of the subject and hardener, the pot life will be shortened. In addition, since mixing of bubbles causes a decrease in strength of the cured resin, it is necessary to remove a portion where bubbles are mixed.

The present invention is explained in more detail by the following examples and comparative examples. The following examples are merely examples for illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example  And Comparative example

<Aliphatic modified epoxy resin Production Example  >

Production Example  One

In step 1, 600 g of a polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was added to a flask and heated to 120 to 130 ° C. In step 2, bisphenol A 239 g and ethyltriphenylphosphonium bromide 1.2 as polyhydric phenol compounds were added. After adding g (10% methanol dilution) and dissolving, 114 g of an aliphatic epoxy resin (manufactured by Nagase Chemical Co., Ltd., EX931) was added and reacted at 160 to 170 ° C. for about 5 hours until the phenolic OH group was completely consumed. A modified epoxy resin was obtained. Physical properties of the resin are as follows.

Epoxy equivalent: 350g / eq, Melt viscosity: G (Butylcalbitol NV = 40%),

Production Example  2

In step 1, 600 g of a polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was added to a flask, and the temperature was raised to 120 to 130 ° C. In step 2, 269.3 g of 2,2-bisphenol A and a novolak-type epoxy resin N 86 g of -8470 (equivalent to 207 g / eq, manufactured by KCC) and 1.34 g of ethyltriphenylphosphonium bromide (10% methanol dilution) were added, and after dissolution, 119 g of an aliphatic epoxy resin (EPODIL 748 from AIR PRODUCT) was added and 160 to After reacting at 170 degreeC for about 5 hours, the aliphatic modified epoxy resin was obtained. Physical properties of the resin are as follows.

Epoxy equivalent: 810g / eq, Melt viscosity: V (Butylcarbitol NV = 40%)

Example  And Comparative example

After mixing each component in the compounding ratio (weight ratio) shown in following Table 1 (Example) and Table 2 (comparative example), the epoxy resin composition was manufactured, and the physical property evaluation test was done by the following method.

Evaluation

1) housework time

After mixing the master and the curing agent, the temperature change over time was measured. A curing exotherm curve of time-temperature was obtained. In this curve, 70% of the time when the temperature rise suddenly occurred (however, if the time could not be clearly identified, 60% of the time to the maximum heat generation temperature) was set as the pot life.

2) Shear and adhesive strength at 20 ~ -170 ℃

Five samples at 20 ° C., five samples at −100 ° C. and five samples at −170 ° C. were tested by the ISO 4587 method, respectively. The sample is usually a metal connected by an aluminum plate.

At each temperature the shear bond strength should be at least 12 MPa.

3) Shear tensile strength by material at 20 ~ -170 ℃

Five samples were run at each temperature. Tensile curve shows the maximum tensile strength when the sample breaks and the state of the fracture surface when the sample breaks. In case of breakage, breakage of adhesive material should occur. If interfacial peeling occurs during fracture, this is a bad condition.

Adhesive material

1) Plywood / RPUF (Reinforced polyurethane form) / RSB (Rigid secondary barrier)

2) Flexible secondary barrier (FSB) / Rigid secondary barrier (RSB)

3) STEEL / RSB (Rigid secondary barrier)

Measuring conditions

Crosshead Speed: 1 ~ 1.3mm / min

Curing condition: 25 ℃ × 14 days curing

Temperature: 20 ℃, -100 ℃, -170 ℃

The results of the above test are shown in Table 3 (Example) and Table 4 (Comparative Example).

TABLE 1

                                   (Unit: weight part)

Example One 2 subject Bisphenol A type epoxy resin ¹⁾ R8828 100 70 Bisphenol F type epoxy resin ²⁾ Epiclonal 830 0 30 Aliphatic modified epoxy resin Preparation Example 1 10 Preparation Example 2 20 Silane compound ³⁾ epoxy silane One 0.1 Hardener Polyamide ⁴⁾ Ｒ９９００ 50 10 ⁵⁾ Sunmide 350 0 50 Cycloaliphatic amine ⁶⁾ PAC 10 10 Silane compound ⁷⁾ aminosilane 5 10 Curing catalyst ⁸⁾ DMP30 20 20 Pigment Calcium carbonate ⁹⁾ CCR 200 250

1) R8828: bisphenol A epoxy resin (manufactured by KCC Corporation)

2) epiclone 830: bisphenol F type epoxy resin (manufactured by DOW Corporation)

3) epoxy silane: γ-glycidoxypropyltrimethoxysilane

4) R9930: polyamide resin (manufactured by KCC Corporation)

5) sunamide 305: polyamide resin (made by AIR PRODUCT)

6) PACM: bis- (p-aminocyclohexyl) methane (product of AIR PRODUCT company)

7) aminosilane: γ-aminopropyltriethoxysilane

8) DMP30: 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by AIR PRODUCT)

9) CCR: CALCITE (manufactured by HAKUENKA)

TABLE 2

                                                         (Unit: parts by weight)

Comparative example One 2 3 4 5 6 subject Bisphenol A type epoxy resin ¹⁾ R8828 70 70 70 70 70 70 Bisphenol F type epoxy resin ²⁾ Epiclonal 830 30 30 30 30 30 30 Aliphatic modified epoxy resin Preparation Example 1 0 0 50 100 30 30 Aliphatic epoxy resin ³⁾ EX-931 0 0 0 0 0 30 Silane compound ⁴⁾ epoxy silane 10 0 0 0 5 5 Hardener Polyamide ⁵⁾ RW30 50 10 50 50 2 20 ⁶⁾ Sunmide 350 70 70 70 70 0 0 Cycloaliphatic amine ⁷⁾ PAC 30 30 30 30 30 0 Aliphatic amines ⁸⁾ ANCAMINE2071 0 0 0 0 0 20 Aromatic amines ⁹⁾ MXDA 10 0 10 0 0 0 Butadiene Copolymer ¹⁰⁾ ATN 20 0 0 0 0 0 Silane compound ¹¹⁾ aminosilane 10 10 10 10 0 0 Curing catalyst ¹²⁾ DMP30 20 20 20 20 10 10 Pigment Calcium carbonate ¹³⁾ CCR 300 300 300 300 100 100

1) R8828: bisphenol A epoxy resin (manufactured by KCC Corporation)

2) epiclone 830: bisphenol F type epoxy resin (manufactured by DOW Corporation)

3) EX9310: aliphatic epoxy resin (made by Nagase Chemical Co., Ltd.)

4) epoxy silane: γ-glycidoxypropyltrimethoxysilane

5) R9930: polyamide resin (manufactured by KCC Corporation)

6) sunamide 305: polyamide resin (manufactured by AIR PRODUCT)

7) PACM: bis- (p-aminocyclohexyl) methane (product of AIR PRODUCT company)

8) ANCAMINE2071: triethylene tetraamine (product of AIR PRODUCT company)

9) MXDA: m-xylenediamine (manufactured by Kukdo Chemical Co., Ltd.)

10) ATBN: Butadiene acrylonitrile (made by NOVEON)

11) aminosilane: γ-aminopropyltriethoxysilane

12) DMP30: 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by AIR PRODUCT)

13) CCR: CALCITE (product of HAKUENKA company)

TABLE 3

Example One 2 Pot life (minutes) 73 70 Workability smell Good Good Flow Good Good Shear Adhesion Strength MPa 20 ℃ 17 16 -100 ℃ 17 18 -170 ℃ 17 17 Shear Tensile Strength (Plywood / RPUF / RSB) MPa 20 ℃ Material destruction Material destruction -10 ℃ Material destruction Material destruction -170 degrees Celsius Material destruction Material destruction Shear Tensile Strength (FSB / RSB) MPa 20 ℃ Material destruction Material destruction -10 ℃ Material destruction Material destruction -170 ℃ Material destruction Material destruction Shear Tensile Strength (STEEL / RSB) MPa 20 ℃ Material destruction Material destruction -10 ℃ Material destruction Material destruction -170 ℃ Material destruction Material destruction

TABLE 4

Comparative example One 2 3 4 5 6 Pot life (minutes) 72 79 75 71 75 73 Workability smell Bad Good Good Good Good Good Flow Good Good Bad Bad Good Bad Shear Adhesion Strength MPa 20 ℃ 13 16 9 5 15 16 -100 ℃ 13 5 11 8 15 8 -170 ℃ 11 4 15 11 11 9 Shear Tensile Strength (Plywood / RPUF / RSB) MPa 20 ℃ Material destruction Material destruction Material destruction Material destruction Material destruction Material destruction -10 ℃ Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation -170 degrees Celsius Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Shear Tensile Strength (FSB / RSB) MPa 20 ℃ Interfacial separation Interfacial separation Material destruction Interfacial separation Interfacial separation Interfacial separation -10 ℃ Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation -170 ℃ Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Shear Tensile Strength (STEEL / RSB) MPa 20 ℃ Material destruction Interfacial separation Interfacial separation Material destruction Interfacial separation Interfacial separation -10 ℃ Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation -170 ℃ Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation Interfacial separation

According to the present invention, there is little shrinkage at the time of curing, maintains the appropriate pot life, viscosity, and flowability, and is excellent in workability and mechanical strength at low and normal temperatures. It is possible to provide an epoxy resin composition that can be used for attaching a heat insulation panel to a liquefied natural gas storage tank.

Claims (11)

One or two or more epoxy resins selected from bisphenol type epoxy resins, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, and dimer acid modified epoxy resins. 10 to 50 parts by weight of an aliphatic modified epoxy resin, 50 to 100 parts by weight of a polyamide curing agent, 10 to 30 parts by weight of an alicyclic amine compound, 0.1 to 20 parts by weight of a silane compound, and a curing catalyst of 0.1 to 20 parts by weight. An epoxy resin composition comprising a weight part and 100 to 400 parts by weight of a pigment. The method of claim 1, wherein the aliphatic modified epoxy resin is a low molecular weight bisphenol-type epoxy resin or a mixture of a low molecular weight bisphenol-type epoxy resin and a novolak epoxy resin in the presence of a catalyst of a polyhydric compound or a mixture of a polyhydric phenol compound and an aliphatic epoxy resin Epoxy resin composition, characterized in that it is prepared by reacting under. The bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyepoxide D according to claim 2, wherein the low molecular weight bisphenol type epoxy resin has a weight average molecular weight of 200 to 3,000 and an epoxy equivalent of 100 to 1000 g / eq. Epoxy resin composition, characterized in that selected from glycidyl ether. The method of claim 2, wherein the aliphatic epoxy resin is sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydride) Oxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A Epoxy which is selected from diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and derivatives thereof Resin composition. The epoxy resin composition according to claim 2, wherein the aliphatic epoxy resin is used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the low molecular weight bisphenol type epoxy resin. The compound according to claim 2, wherein the polyhydric phenol compound is 2,2-bis (p-hydroxyphenyl) propane, (2,4-dihydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, 2,2 -Bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1 , 3-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxy-2,6-dimethyl-3-methoxy) phenyl, 2,2-bis (4-hydroxyphenyl) propane , 4,4-dihydroxyphenyl, bis (4-hydroxy-3-chloronaphthyl) ether, bis (4-hydroxy-3-bromophenyl) ether, 1,1-bis (4-hydroxy Epoxy resin composition selected from phenol) -2-phenylethane, 2,4-bis (P-hydroxyphenyl) -4-methylpentane, bisphenol A and 2,2-bisphenol A. The catalyst according to claim 2, wherein the catalyst is sodium hydroxide, sodium hydrogen sulfate, lithium chloride, lithium oxide, tin chloride, zinc chloride, BF3-ether compound, BF3-composite compound, quaternary ammonium salt, phenyltrimethylammonium chloride, tetramethylammonium salt , Benzyltrimethylammonium chloride salt, dodecyltrimethylammonium chloride salt, tetraalkylammonium halogen, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole and butyltriphenylphosphonium bromide, tri-allylphosphine, butylallyl Epoxy resin bath, characterized in that selected from phosphine, triphenylphosphine, butyltriphenylphosphate formate, butyltriphenylphosphate oxalate, ethyltriphenylphosphate succinate, ethyltriphenylphosphonium salt compound and derivatives thereof Relic. The method of claim 1, wherein the polyamide curing agent is diethyltriamine, ethylenediamine, triethylenetetraamine, tetraethylenepentaamine, diethylaminopropylamine, methanediamine, N-aminoethylpiperidine, m-xylene Epoxy resin composition characterized by the 1 type (s) or 2 or more types chosen from diamine, 1, 3-bisamino methyl cyclohexane, and polyamides. The epoxy resin composition according to claim 1, wherein the cycloaliphatic amine-based curing agent is selected from isophorone diamine, diaminocyclohexane, and 4,4-bisparaaminocyclohexylmethane. The silane compound according to claim 1, wherein the silane compound is β-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, dimethylmethoxysilane, methyltrimethoxysilane, tetramethoxy Epoxy resin composition, characterized in that it is selected from silane, dimethyl diethoxysilane, methyl triethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane. The epoxy resin composition of claim 1, wherein the curing catalyst is selected from diethylenetriamine, triethylenetriamine, isophoronediamine, xylenediamine, and 2,4,6-tris (dimethylaminomethyl) phenol. .