KR101887398B1 - Epoxy compound, manufacturing method thereof and adhesive composition using it - Google Patents

Epoxy compound, manufacturing method thereof and adhesive composition using it Download PDF

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KR101887398B1
KR101887398B1 KR1020160062018A KR20160062018A KR101887398B1 KR 101887398 B1 KR101887398 B1 KR 101887398B1 KR 1020160062018 A KR1020160062018 A KR 1020160062018A KR 20160062018 A KR20160062018 A KR 20160062018A KR 101887398 B1 KR101887398 B1 KR 101887398B1
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formula
epoxy
compound represented
epoxy compound
alkylene
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KR1020160062018A
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KR20170130976A (en
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임충선
김현국
김대연
박영일
서봉국
조득희
김동우
김영철
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한국화학연구원
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Priority to PCT/KR2017/005228 priority patent/WO2017200339A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an epoxy compound derived from petroleum by-products and a process for producing the same. Further, the present invention relates to an epoxy composition using an epoxy compound derived from the petroleum by-product.
The epoxy compound according to the present invention has the effect of recycling resources by using dicyclopentadiene, which is a by-product of petroleum, as a starting material.

Description

EPOXY COMPOUND, MANUFACTURING METHOD THEREOF AND ADHESIVE COMPOSITION USING IT BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy compound,

The present invention relates to an epoxy compound derived from petroleum by-products and a process for producing the same. Further, the present invention relates to an epoxy composition using an epoxy compound derived from the petroleum by-product. The epoxy composition may be used as an adhesive or a coating agent.

Bisphenol A, bisphenol F epoxy resin and the like are mainly used as high-performance one-component or two-component adhesives. The bisphenol-based epoxy resin acts as an environmental hormone that disturbs the hormones of the human body, and the use thereof is limited due to the hazard.

Environmental hormones are presumed to be substances that cause ecosystem and human reproductive dysfunction, malformations, growth disorders, cancer and the like, and they are known to affect ecosystems and human hormones, thus prohibiting their use.

The bisphenol-based epoxy compound is a bisphenol-based epoxy compound because it contains a double bond and has brittleness due to strong brittleness after curing and does not contain a volatile organic compound (VOCS). However, , Since a large amount of solvent is required to lower the viscosity, a volatile organic compound may be generated.

Therefore, there is a need for research on an epoxy compound material to replace the bisphenol-based epoxy resin.

It is an object of the present invention to provide an epoxy compound which is free of environmental hormones and which can be widely used in the production of adhesives and coatings using raw materials starting from cheap petroleum by-products.

Another object of the present invention is to provide an epoxy compound which is composed of an aromatic ring and an alkyl chain and can exhibit a high shear strength and an adhesive composition using the same.

Another object of the present invention is to provide an adhesive composition which is flexible after vulcanization and does not contain a volatile organic compound, in order to solve the problem of a strong brittleness after curing in the case of an adhesive using a conventional bisphenol-based epoxy resin.

The present invention relates to an epoxy compound represented by the following general formula (1).

[Chemical Formula 1]

Figure 112016048536119-pat00001

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or

Figure 112016048536119-pat00002
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00003
,
Figure 112016048536119-pat00004
,
Figure 112016048536119-pat00005
,
Figure 112016048536119-pat00006
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen.

The present invention also relates to a process for the production of a compound represented by the following general formula (3), which comprises reacting octahydro-1H-4,7-methanoindene-1,2,5,6- And then reacting the resulting compound with an epoxy compound represented by the following general formula (1).

(3)

Figure 112016048536119-pat00007

[Chemical Formula 4]

Figure 112016048536119-pat00008

Wherein R 11 is alkylene of C 1 to C 10,

Figure 112016048536119-pat00009
,
Figure 112016048536119-pat00010
,
Figure 112016048536119-pat00011
,
Figure 112016048536119-pat00012
.

[Chemical Formula 1]

Figure 112016048536119-pat00013

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or

Figure 112016048536119-pat00014
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00015
,
Figure 112016048536119-pat00016
,
Figure 112016048536119-pat00017
,
Figure 112016048536119-pat00018
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen.

The present invention also relates to an epoxy composition comprising a main component consisting of an epoxy compound represented by the following general formula (1), a curing agent and a curing accelerator.

[Chemical Formula 1]

Figure 112016048536119-pat00019

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or

Figure 112016048536119-pat00020
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00021
,
Figure 112016048536119-pat00022
,
Figure 112016048536119-pat00023
,
Figure 112016048536119-pat00024
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen.

The epoxy compound according to the present invention has the effect of recycling resources by using dicyclopentadiene, which is a by-product of petroleum, as a starting material.

In addition, the epoxy compound according to the present invention can be applied as a liquid molding resin, and can form a high shear strength because it is composed of an aromatic ring and an alkyl chain. And thus can be suitably used in adhesives or coating fields requiring high shear strength. Further, when applied to an adhesive material, it has an effect of suppressing decomposition due to a photoreaction.

In addition, the epoxy compound according to the present invention can reduce the harmfulness of the human body unlike an epoxy resin such as bisphenol A or bisphenol F, which is known to disturb the human environmental hormone.

The epoxy compound of the present invention is a resin having improved hardness and improved brittleness because the cured polymer is soft and flexible as compared with conventional bisphenol-based epoxy compounds.

In addition, since it is easy to control the structure from a single molecule to a polymer by controlling the reaction ratio, it is advantageous to manufacture it for various purposes.

The adhesive composition comprising the epoxy compound according to the present invention can be applied to automotive adhesives, building exterior wall adhesives, coatings, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing the flexibility of a specimen made from an epoxy compound according to Example 1 of the present invention. FIG.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described more fully hereinafter with reference to the accompanying drawings, It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Among the existing oil byproducts, dicyclopentadiene (DCPD) is one of the most common oil byproducts and production is increasing for use as a liquid molding resin. Existing DCPD has been studied with interest in the application of liquid molding resin, and studies have been conducted to epoxidize two double bonds in DCPD and then introduce a hydroxyl group into the epoxy ring.

The inventors of the present invention have found that an epoxy resin derived from dicyclopentadiene having an epoxy functional group can be prepared by reacting diglycidyl ether using a substance having a hydroxyl group introduced into the above epoxy ring, .

The epoxy resin thus produced has a high shear strength and is composed of a cyclic ring and an alkyl chain, and can be used for a variety of purposes such as exterior walls of a building, electronic products, structural adhesives, and coatings due to the absence of light- In addition, the cured polymer is more soft than the conventional bisphenol-based resin and can be used as a resin having improved rigidity.

One embodiment of the present invention is an epoxy compound represented by the following formula (1).

[Chemical Formula 1]

Figure 112016048536119-pat00025

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or

Figure 112016048536119-pat00026
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00027
,
Figure 112016048536119-pat00028
,
Figure 112016048536119-pat00029
,
Figure 112016048536119-pat00030
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen.

In one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by Formula 2, but is not limited thereto.

(2)

Figure 112016048536119-pat00031

Wherein R 11 is alkylene of C 1 to C 10.

More specifically, in Formula 2, R 11 may be C 4 to C 6 alkylene, but is not limited thereto. It is possible to provide a ductile epoxy excellent in flexibility and excellent in mechanical properties such as tensile strength and flexural strength within a range in which the number of carbon atoms satisfies the above range.

In one embodiment of the present invention, the epoxy compound of Formula 1 is obtained by reacting octahydro-1H-4,7-methanoindene-1,2,5,6-tetraol represented by Formula 3 with And then reacting it with a diglycidyl ether compound.

(3)

Figure 112016048536119-pat00032

[Chemical Formula 4]

Figure 112016048536119-pat00033

Wherein R 11 is alkylene of C 1 to C 10,

Figure 112016048536119-pat00034
,
Figure 112016048536119-pat00035
,
Figure 112016048536119-pat00036
,
Figure 112016048536119-pat00037
.

At this time, the following compounds can be prepared by controlling the molar ratio of the reaction, and the reaction is not limited thereto.

Figure 112016048536119-pat00038

Figure 112016048536119-pat00039

Figure 112016048536119-pat00040

Figure 112016048536119-pat00041

Figure 112016048536119-pat00042

Figure 112016048536119-pat00043

Figure 112016048536119-pat00044

Figure 112016048536119-pat00045

Figure 112016048536119-pat00046

In the compounds 1 to 13 R 11 is alkylene of C 1 to C 10,

Figure 112016048536119-pat00047
,
Figure 112016048536119-pat00048
,
Figure 112016048536119-pat00049
,
Figure 112016048536119-pat00050
. ≪ / RTI >

In one embodiment of the present invention, in the production of the epoxy compound of Formula 1, the octahydro-1H-4,7-methanoindene-1,2,5,6-tetraol represented by Formula 3, Tetraethylammonium iodide is added to a mixture of diglycidyl ether compounds represented by the general formula (4), and the reaction is carried out at 150 to 170 ° C for 1 to 6 hours, but the present invention is not limited thereto.

In one embodiment of the present invention, the epoxy compound of Formula 1 may be a liquid at room temperature.

In one embodiment of the present invention, the compound represented by Formula 3 is prepared by epoxidizing a dicyclopentadiene of Formula 5 to prepare a dicyclopentadiene diepoxide of Formula 6, .

[Chemical Formula 5]

Figure 112016048536119-pat00051

[Chemical Formula 6]

Figure 112016048536119-pat00052

Another embodiment of the present invention is an epoxy composition comprising a main component comprising an epoxy compound represented by the following general formula (1), a curing agent and a curing accelerator.

[Chemical Formula 1]

Figure 112016048536119-pat00053

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or

Figure 112016048536119-pat00054
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00055
,
Figure 112016048536119-pat00056
,
Figure 112016048536119-pat00057
,
Figure 112016048536119-pat00058
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen.

In one embodiment of the adhesive composition of the present invention, the curing agent may be an acid anhydride-based curing agent, a phenol-based curing agent, or an amine-based curing agent, but is not limited thereto.

Examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadonic acid anhydride, glutaric acid anhydride, Hydroxycarboxylic anhydride, hydrophthalic anhydride, and methyltetrahydrophthalic anhydride. More specifically, it may be, for example, methylhexahydrophthalic acid, but is not limited thereto.

Examples of the phenolic curing agent include phenol resins such as formaldehyde condensation type resol-type phenol resin, non formaldehyde condensation type phenol resin, novolac-type phenol resin, novolac-type phenol formaldehyde resin and polyhydroxystyrene resin; Resol type phenol resins such as aniline-modified resole resin and melamine-modified resol resin; Novolac-type phenolic resins such as phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolak resins and naphthol novolak resins; Special phenolic resins such as dicyclopentadiene-modified phenolic resins, terpene-modified phenolic resins, triphenolmethane-type resins, phenol aralkyl resins having phenylene skeleton or diphenylene skeleton, and naphthol aralkyl resins; And polyhydroxystyrene resins such as poly (p-hydroxystyrene).

Examples of the amine-based curing agent include aliphatic amines, modified aromatic amines, and mixtures thereof. The modified aliphatic amines include dicyandiamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, mentantiamine, N -Aminoethylpiperazine, m-xylylene diamine and isophorone diamine group, and the modified aromatic amine is a mixture of 4,4-diaminodiphenylmethane, m-phenylenediamine and diaminodiphenylsulfone Or a mixture of two or more thereof.

In one embodiment of the epoxy composition of the present invention, the cure accelerator is selected from the group consisting of 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, Imidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2-undecylimidazole, 3-heptadecylimidazole, 2-phenylimidazole, 2-phenylimidazoline, Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and 1-cyanoethyl-2-undecylimidazole and 1-cyanoethyl- Like imidazole; N, N-dimethylcyclohexylamine, N, N-dimethylaminobenzene, N, N-dimethylaminopentylamine, N, Tertiary amines such as N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7, and 1,5-diazabicyclo [4.3.0] nonene-5; And phosphorus compounds such as triphenylphosphine, tribenzylphosphine, and tributylphosphine, and the like can be used. In addition, onium salts and metal salts of the above-mentioned imidazole, tertiary amine, and phosphorus compounds and derivatives thereof may be used. These may be used alone or in a mixture of two or more. Of these curing accelerators, imidazole can be preferably used.

In one embodiment of the epoxy composition of the present invention, inorganic fillers such as silica, talc, aluminum hydroxide, and calcium carbonate may be further added, if necessary. These fillers may be used alone or in admixture of two or more.

In one embodiment of the epoxy composition of the present invention, the blending ratio of the subject (constituent component A) composed of the epoxy compound represented by the formula (1) to the curing agent (constituent component B) is preferably an activating group reactive with an epoxy group in the curing agent, Group or a hydroxyl group is used in a proportion of 0.5 to 1.5 equivalents, more preferably 0.7 to 1.2 equivalents based on 1 equivalent of an epoxy group in the epoxy resin. In this range, the curing rate is appropriate, and the excellent properties of the shear strength can be exhibited.

In one embodiment of the epoxy composition of the present invention, the compounding ratio of the curing accelerator (component (C)) may be 0.001 to 8 parts by weight based on 100 parts by weight of the subject (component (A)), 0.1 to 3 parts by weight. Sufficient curing acceleration effect can be exhibited within the above range, and discoloration may not occur.

In one embodiment of the epoxy composition of the present invention, the subject is composed of an epoxy compound of the following formula (2), and when the acid anhydride-based curing agent is used as the curing agent, the physical properties of a shear strength of 10 MPa or more and a shear strength of 10 to 30 MPa And when the amine-based curing agent is used as a curing agent, the T-peel strength can be satisfied to a physical property of 30 N / 25 mm or more, more preferably 50 N / 25 mm or more, specifically 30 to 100 N / 25 mm.

(2)

Figure 112016048536119-pat00059

Wherein R 11 is alkylene of C 1 to C 10.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The following physical properties were measured by the following methods.

1. Shear Strength

The measurement was made in accordance with ASTM D 1002.

The epoxy composition was applied in such a manner that two metal specimens of 25 mm X 100 mm X 1.6 mm were overlapped by 12.7 mm and cured at 140 ° C for 2 hours to prepare test pieces. A universal testing machine (Instron) was used and the test speed was 1.3 mm / min.

2. T-peel strength

ASTM D 1876.

Two metal specimens of 25 mm X 150 mm X 0.8 mm were bent in a line shape and then an epoxy composition was applied in an overlapping amount of 80 mm and cured at 140 DEG C for 2 hours to prepare test specimens. A universal testing machine (Instron) was used and the test speed was 254 mm / min.

3. Epoxy equivalent weight

The epoxy equivalent weight was measured according to the ASTM D1652-04 standard.

[Example 1]

1) Synthesis of epoxy compound

15 g of octahydro-1H-4,7-methanoindene-1,2,5,6-tetraol of the following formula 3 was placed in a beaker and 1,6-hexanediol diglycidyl ether) were added and mixed.

(3)

Figure 112016048536119-pat00060

1.4 g of tetraethylammonium iodide was added to the mixed solution, and after heating at 60 ° C for 4 hours, the reaction was started at an epoxy equivalent weight (EEW, epoxy equivalent weight) of 188 g / eq, and the reaction was stopped when 310 g / eq . The theoretical equivalent weight was 280 g / eq, indicating that the unreacted 1,6-hexanediol diglycidyl ether was further reacted with the epoxy resin.

As a result, the following compounds were prepared. According to the result of elemental analysis, it was found that a difference of theoretical value and measured value was 5.8% or less and an epoxy resin having a purity of 94% was produced. C 58 H 104 O 20 (1120), (H 2 O) 0.25 (1124.5), and the measured values were C = 58.3 (61.89) and H = 8.9 (9.29). The above moisture was further calculated by the fact that about 0.5% of the moisture was contained in the epoxy resin, and the moisture content was measured by 870 KF titrino plus.

The error was calculated as follows.

C: (61.89-58.3) /61.89 = 5.8%

H: (9.29-8.9) /9.29 = 4.2%

Figure 112016048536119-pat00061

2) Preparation of epoxy composition

An epoxy composition was prepared by mixing 4 g of the epoxy compound prepared in 1), 2.4 g of methylhexahydrophthalic anhydride as a curing agent, and 0.065 g of 1,2-dimethylimidazole as a curing accelerator, And the results are shown in Table 1 below.

[Example 2]

An epoxy composition was prepared by mixing 10 g of the epoxy compound prepared in 1) of Example 1, 0.68 g of dicyandiamide as a curing agent and 0.1 g of 1,2-dimethylimidazole as a curing accelerator, And the physical properties were measured. The results are shown in Table 1 below.

[Example 3]

An epoxy composition was prepared by mixing 10 g of the epoxy compound prepared in 1), 1.6 g of diaminodiphenylmethane as a curing agent, and 0.1 g of 1,2-dimethylimidazole as a curing accelerator, And physical properties were measured. The results are shown in Table 1 below.

[Example 4]

An epoxy compound was prepared in the same manner as in Example 1 except that 1,4-butanediol diglycidyl ether was used instead of 1,6-hexanediol diglycidyl ether in Example 1, and 10 g of the prepared epoxy compound, 0.68 g of dicyandiamide as a curing agent and 0.1 g of 1,2-dimethylimidazole as a curing accelerator were mixed to prepare an epoxy composition. The epoxy composition was cured at 170 캜 and its physical properties were measured.

Shear strength (MPa) T-peel strength (N / 25 mm) Example 1 11.2 32.7 Example 2 2 90 Example 3 0.5 198 Example 4 10.5 30.5

As shown in Table 1, the adhesive composition using the epoxy compound according to the present invention exhibited a shear strength of 10 MPa or more when an acid anhydride-based curing agent was used as a curing agent, and an amine-based curing agent was used as a curing agent It was found that the T-peel strength was greatly improved to 90 N / 25 mm or more.

Further, as shown in FIG. 1, it was confirmed that a specimen manufactured using the epoxy compound of Example 1 can be made into a flexibly curved material.

Claims (9)

1. An epoxy compound represented by the following formula (1).
[Chemical Formula 1]
Figure 112016048536119-pat00062

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or
Figure 112016048536119-pat00063
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00064
,
Figure 112016048536119-pat00065
,
Figure 112016048536119-pat00066
,
Figure 112016048536119-pat00067
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen. The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound represented by Formula 2 below.
(2)
Figure 112016048536119-pat00068

Wherein R 11 is alkylene of C 1 to C 10. The method according to claim 1,
Wherein the epoxy resin is represented by the following general formula (3): wherein R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
(3)
Figure 112018029453837-pat00091
 Tetrahydro-1H-4,7-methanedene-1,2,5,6-tetraol represented by the following formula (3) and a diglycidyl ether compound represented by the following formula (4) A process for producing an epoxy compound represented by the following formula (1).
(3)
Figure 112016048536119-pat00069

[Chemical Formula 4]
Figure 112016048536119-pat00070

Wherein R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00071
,
Figure 112016048536119-pat00072
,
Figure 112016048536119-pat00073
,
Figure 112016048536119-pat00074
.
[Chemical Formula 1]
Figure 112016048536119-pat00075

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or
Figure 112016048536119-pat00076
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00077
,
Figure 112016048536119-pat00078
,
Figure 112016048536119-pat00079
,
Figure 112016048536119-pat00080
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen. 5. The method of claim 4,
Wherein the compound represented by Formula 3 is prepared by epoxidizing a dicyclopentadiene of Formula 5 to prepare a dicyclopentadiene diepoxide of Formula 6 and then performing a ring opening reaction.
[Chemical Formula 5]
Figure 112016048536119-pat00081

[Chemical Formula 6]
Figure 112016048536119-pat00082
 5. The method of claim 4,
Wherein the compound represented by Formula 1 is a compound represented by Formula 2 below.
(2)
Figure 112016048536119-pat00083

Wherein R 11 is alkylene of C 1 to C 10. 1. An epoxy composition comprising a base comprising an epoxy compound represented by the following formula (1), a curing agent and a curing accelerator.
[Chemical Formula 1]
Figure 112016048536119-pat00084

In Formula 1, R 1 , R 2 , R 3, and R 4 are each independently hydrogen or
Figure 112016048536119-pat00085
Is selected from the R 11 is alkylene of C 1 to C 10,
Figure 112016048536119-pat00086
,
Figure 112016048536119-pat00087
,
Figure 112016048536119-pat00088
,
Figure 112016048536119-pat00089
, Except that R 1 , R 2 , R 3 and R 4 are all hydrogen. 8. The method of claim 7,
Wherein the curing agent is an acid anhydride-based curing agent. 9. The method of claim 8,
Wherein the epoxy composition has a shear strength of 10 MPa or more, or a T-peel strength of 30 N / 25 mm or more.
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