KR100587480B1 - Epoxy modified with alcoxysilane - Google Patents

Abstract

The present invention provides a method for producing a silane-modified epoxy resin composition exhibiting excellent adhesion to inorganic materials such as aluminum and glass, and is a group capable of esterification reaction with an epoxy group in an epoxy resin having two or more epoxy groups in a molecule. It is characterized by de-alcoholizing the hydroxyl group (-OH) and the organic functional group-containing alkoxysilane obtained by the reaction of the compound containing a carboxyl group.

Organic functional group-containing alkoxysilane, epoxy

Description

An organic functional group-containing alkoxysilane-modified epoxy resin composition, and a resin composition for high adhesion thereby. {Epoxy modified with alcoxysilane}

The present invention relates to a method for producing an organofunctional group-containing alkoxysilane-modified epoxy resin composition, and to an alkoxysilane-modified epoxy resin composition prepared thereby, and more particularly, to a group capable of esterification with an epoxy group in an epoxy resin. A method for producing an alkoxysilane-modified epoxy resin composition and alkoxysilane-modified epoxy produced thereby, wherein the hydroxyl group (-OH) obtained by the reaction of an organic polymer containing a phosphorus carboxyl group and an organic functional group-containing alkoxysilane are subjected to a dealcoholization reaction. It relates to a resin composition.

The epoxy resin composition prepared by the present invention exhibits very excellent adhesion to inorganic surfaces such as aluminum and glass as compared to conventional epoxy resins.

Epoxy resins are widely used in various industries such as electricity, construction, ships, and automobiles because of their excellent chemical resistance, mechanical properties, corrosion resistance, electrical properties, and adhesion to metals. In recent years, the use of nonferrous metals such as aluminum or alloys having excellent corrosion resistance, moldability, and excellent electrical and thermal conductivity has been increased for the purpose of high quality and lightweight materials in various industries.

However, the conventional epoxy resin has a problem that the adhesion on the surface of the non-ferrous metal is insufficient. Accordingly, there has been a demand for the development of epoxy resins for the use of adhesives and coatings that exhibit high adhesion to such substrates.

Therefore, alkoxysilanes are widely used as one of methods for improving adhesion to inorganic materials. Alkoxysilanes can be broadly divided into alkoxysilanes containing organic functional groups and alkoxysilanes containing no organic functional groups.Alkoxysilanes containing organic functional groups are organic compounds that chemically bond with alkoxy groups and organic materials that react with inorganic materials in the molecule. It has a functional group that combines organic and inorganic, and reduces the surface energy of organic to improve the wettability (wetting) on the surface of the inorganic to increase the adhesion. In addition, the alkoxysilane containing an organic functional group also plays a role of enhancing the compatibility with other resins. Alkoxysilanes containing such organic functional groups include mercapto-based, glycidoxy, acryl-based, and vinyl-based alkoxysilanes.

Attempts have been made to introduce such alkoxysilanes into resins. For example, Japanese Patent Application Laid-Open No. 2001-59011 (Method for producing an alkoxy-containing silane-modified epoxy resin) shows an organic functional group as a hydroxyl group (-OH) of a bisphenol-type epoxy resin. A method of producing a silane-modified epoxy resin having improved heat resistance by modifying it with an alkoxy silane not containing therein is disclosed.

The present invention introduces a compound containing a carboxyl group in the epoxy resin molecule to increase the number of hydroxyl groups (-OH) to combine the hydroxyl group with an organic functional group-containing alkoxy silane to improve the flowability of the resin, chemical bonds with inorganic materials It is an object of the present invention to provide an epoxy resin composition exhibiting high adhesion to inorganic materials such as nonferrous metals and glass.

An object of the present invention as described above is an intramolecular hydroxyl group (-OH) obtained by esterifying an epoxy resin (A) containing two or more intramolecular epoxy groups and a compound (B) containing two or more intramolecular carboxyl groups. It is achieved by a process for producing an organofunctional group-containing alkoxysilane-modified epoxy resin composition (D), which is prepared by de-alcoholizing an organofunctional group-containing alkoxysilane (C).

In addition, the epoxy resin (A) in the production method of the present invention is a bisphenol (bisphenol) A-type epoxy (epoxy) resin, bisphenol (bisphenol) F-type epoxy (epoxy) resin, hydrogenated bisphenol (Hydrogenated bisphenol) A-type epoxy (epoxy) resin, Bisphenol E type epoxy resin, Cresol novolac type epoxy resin, Phenol novolac type epoxy resin, Brominated epoxy resin, It is characterized in that at least one compound selected from the group consisting of phenoxy (Phenoxy) resin, urethane (urethane) modified epoxy (epoxy) resin and NBR modified epoxy (epoxy) resin.

In addition, the carboxyl group-containing compound (B) in the production method of the present invention is characterized in that the dimer acid (dimer aicd), CTBN (Carboxyl terminated butadiene acrylonitrile copolymer) or a mixture thereof.

The present invention also discloses a method for preparing an organofunctional group-containing alkoxysilane-modified epoxy resin composition (D), wherein the organofunctional group-containing alkoxysilane (C) is represented by the following general formula (1).

(Formula 1)

(Wherein n represents an integer of 0 to 4. X represents an alkoxy group, such as a methoxy group or an ethoxy group, and R represents a vinyl group or glycidoxy). (glycidoxy group, acrylic group, or mercapto group.)

The organic functional group-containing alkoxysilane-modified epoxy resin composition (D) produced by the above-described production method of the present invention is preferably 0.5 to 40% by weight of the carboxyl group-containing compound (B) based on 100% by weight of the total composition. When the composition of the carboxyl group (B) is out of the above range, the carboxyl group-containing compound (B) tends to gel due to high viscosity due to the increase in molecular weight during the reaction. In addition, the organofunctional group-containing alkoxysilane (C) needs to be in the range of 0.5 to 9.5% by weight, because it can provide a cured product having excellent adhesiveness as well as curing property.

In the method of the present invention, the esterification reaction of the epoxy resin (A) and the organic polymer (B) having a carboxyl group may be carried out by a conventional esterification reaction method, for example, having the epoxy resin (A) and a carboxyl group. The organic polymer (B) is added to the reaction vessel and proceeds under a catalyst at a reaction temperature of 60-130 ° C., preferably 80-120 ° C., for a total reaction time of 2-6 hours. Examples of catalysts that can be used include tertiary amines, benzyltriethyl ammonium chloride, potassium hydroxide, benzyltrimethyl ammonium hydroxide benzyltrimethyl Ammonium chloride, benzyltrimethyl ammonium chloride, tetramethyl ammonium chloride, and the like.

The production of the organofunctional group-containing alkoxysilane-modified epoxy resin (D) includes, for example, a modified epoxy resin (A + B) and an organofunctional group-containing alkoxysilane (C) obtained by adding an organic polymer having a carboxyl group prepared above. After the addition, it is obtained by advancing the reaction while removing the alcohol produced by heating. The reaction temperature is about 80 to 150 ° C, preferably 100 to 130 ° C, and the total reaction time is about 2 to 10 hours.

In addition, the reaction may be carried out in a solvent, a solvent capable of dissolving silane such as xylene, methyl ethyl ketone, toluene, methyl iso butyl ketone, and the like. It can proceed in, and can dissolve the resin composition as needed.

Examples will be described below.

(Example 1)

745 g of bisphenol F-type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDF-170) and 180 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-18) were added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at a temperature of 120 ° C. for 3 hours. 75 g of mercaptopropyltrimethoxysilane (Dow Corning, Z-6062) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours to obtain an organic functional group-containing alkoxysilane-modified epoxy resin composition (D).

(Example 2)

Bisphenol F type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDF-170) 825 g and CTBN (noveon, brand name Hycar (R))  1300X8) 100g was added and dissolved at 100 ° C. 0.5g of benzyltrimethyl ammonium hydroxide was added as a catalyst, and it was made to react at 120 degreeC for 3 hours. 75 g of mercaptopropyltrimethoxysilane (Dow Corning, Z-6062) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours to obtain an organic functional group-containing alkoxysilane-modified epoxy resin composition (D).

(Example 3)

735 g of hydrogenated bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name ST-3000) and 200 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-4) were added, and it melt | dissolved at 100 degreeC. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 65 g of glycidoxypropyltrimethoxysilane (Dow Corning, Z-6040) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours to obtain an organic functional group-containing alkoxysilane-modified epoxy resin composition (D).

(Example 4)

735 g of hydrogenated bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name ST-3000) and CTBN (noveon, brand name Hycar (R))  1300X13) 200g was added and dissolved at 110 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 65 g of glycidoxypropyltrimethoxysilane (Dow Corning Co., Z-6040) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours to obtain an organic functional group-containing alkoxysilane-modified epoxy resin composition (D).

(Example 5)

740 g of bisphenol A epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-128) and 90 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-18) were added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 70 g of methacryloxypropyltrimethoxysilane (Dow Corning, Z-6030) was added thereto, demethanated at 130 ° C. for 4 hours, cooled to 80 ° C., and dissolved in 100 g of xylene. An organic functional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Example 6)

710 g of bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-128) and CTBN (noveon, brand name Hycar (R))  1300X13) 120g was added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted for 3 hours at a temperature of 110 ° C. 70 g of methacryloxypropyltrimethoxysilane (Dow Corning Co., Z-6030) was added thereto, demethanated at 130 ° C. for 4 hours, cooled to 70 ° C., and dissolved in 100 g of xylene. An organic functional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Example 7)

740 g of bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-134) and 70 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-2) were added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 90 g of mercaptopropyltrimethoxysilane (Dow Corning Co., Z-6062) was added thereto, demethanated at 130 ° C. for 4 hours, cooled to 80 ° C., and then dissolved in 100 g of xylene. An organofunctional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Example 8)

740 g of bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-134) and CTBN (noveon, brand name Hycar (R))  1300X13) 70g was added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at a temperature of 110 ° C. for 3 hours. 90 g of mercaptopropyltrimethoxysilane (Dow Corning, Z-6062) was added thereto, demethanated at 130 ° C. for 4 hours, cooled to 70 ° C., and then dissolved in 100 g of xylene. An organofunctional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Example 9)

560 g of phenol novolac type epoxy resin (Kukdo Chemical Co., Ltd., trade name YDPN-631) and 250 g of dimer acid (Fujian Liancheng baixin Science & Technology, trade name BX-4) were added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 90 g of glycidoxypropyltrimethoxysilane (Dow Corning, trade name Z-6040) was added thereto, demethanated at 130 ° C. for 4 hours, cooled to 80 ° C., and dissolved in 100 g of xylene. An organic functional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Example 10)

560 g of phenol novolac type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDPN-631) and CTBN (noveon, brand name Hycar (R))  1300 × 8) 250 g were added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. 90 g of glycidoxypropyltrimethoxysilane (Dow Corning Co., Z-6040) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours, cooling to 70 ° C., and then dissolved with 100 g of xylene. An organic functional group-containing alkoxysilane-modified epoxy resin composition (D) was obtained.

(Comparative Example 1)

820 g of bisphenol F type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDF-170) and 180 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-18) were added, and it melt | dissolved at 100 degreeC. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at a temperature of 110 ° C. for 3 hours to obtain an epoxy resin composition.

(Comparative Example 2)

745 g of bisphenol F-type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDF-170) and 180 g of dimer acid (Fujian Liancheng baixin Science & Technology, brand name BX-18) were added and dissolved at 100 ° C. 0.5g of benzyltrimethyl ammonium hydroxide was added as a catalyst, and it was made to react at 110 degreeC for 3 hours. After cooling to 70 ° C., 75 g of mercaptopropyltrimethoxysilane (Dow Corning, trade name Z-6062) was added and mixed to obtain an epoxy resin composition.

(Comparative Example 3)

925 g of bisphenol F-type epoxy resin (Kukdo Chemical Co., Ltd., brand name YDF-170) was added, and it melt | dissolved at 100 degreeC. 75 g of mercaptopropyltrimethoxysilane (Dow Corning, trade name Z-6062) was added thereto, followed by de-methanol reaction at 130 ° C. for 4 hours to obtain an epoxy resin composition.

(Comparative Example 4)

780 g of bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-128) and CTBN (noveon, brand name Hycar (R))  1300X13) 120g was added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. After cooling to 70 ℃ and dissolved in 100 g of xylene (xylene) to obtain an epoxy resin composition.

(Comparative Example 5)

700 g of bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-128) and CTBN (noveon, brand name Hycar (R))  1300X13) 120g was added and dissolved at 100 ° C. 0.5 g of benzyltrimethyl ammonium hydroxide was added as a catalyst and reacted at 110 ° C. for 3 hours. After cooling to 70 ° C., 70 g of methacryloxypropyltrimethoxysilane (Dow Corning Co., Z-6030) was added and mixed, followed by dissolving with 100 g of xylene to obtain an epoxy resin composition.

(Comparative Example 6)

Bisphenol A type epoxy resin (Kukdo Chemical Co., Ltd., brand name YD-134X90)

Experimental Example

In order to evaluate the adhesive strength, the resin composition of Examples 1 to 10 and Comparative Examples 1 to 6 and various curing agents prepared above were applied to aluminum or glass specimens with a thickness of 50 μm, and then to the adhesive test method of ASTM D 3359B. Adhesion test was carried out according to the results are shown in Table 1-4.

TABLE 1

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 aluminum 100 100 100 100 46 89 24 Glass 100 100 100 100 20 64 3

Curing condition: 80 ℃ heating for 2 hours

Curing Agent: G-640 (Kukdo Chemical Co., Ltd., Polyamide Type)

TABLE 2

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 aluminum 100 100 100 100 0 0 0

Curing condition: room temperature 3 days curing

Curing agent: KH-816 (Kukdo Chemical Co., Ltd., modified alicyclic amine type)

TABLE 3

Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 4 Comparative Example 5 Comparative Example 6 aluminum 100 100 100 100 100 100 82 92 61 Water resistance experiment 100 100 100 100 100 100 14 15 8

Curing condition: Curing at 80 ℃ for 1 hour after curing at room temperature for 5 days

Curing Agent: G-640 (Kukdo Chemical Co., Ltd., Polyamide Type)

Water resistance test: Adhesion test was performed after standing in water for 2 days.

TABLE 4

Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 4 Comparative Example 5 Comparative Example 6 aluminum 100 100 100 100 100 100 56 69 12

Curing condition: Curing at 80 ℃ for 1 hour after curing at room temperature for 5 days

Curing Agent: Phenalkamine (cardolite NC541X90)

In the above table, the epoxy resin (Comparative Example 6) and the resin composition in which the epoxy resin was modified with an organic functional group-containing alkoxysilane (Comparative Example 3) show insufficient adhesion to aluminum or glass. In addition, in the case of the resin composition (comparative example 4) obtained by esterification of an epoxy resin and a carboxyl group-containing compound, and the resin composition (comparative example 5) which mixed the organic functional group containing alkoxysilane here, the comparative example 6 and the comparative example 3 Although the adhesiveness is improved than the resin composition of, it can be seen that the adhesion to water resistance is insufficient. On the other hand, it can be seen that the resin composition according to the present invention of Examples 1 to 10 provides excellent adhesion to aluminum or glass regardless of the adhesion of the curing agent.

The organic functional group-containing alkoxysilane-modified epoxy resin composition of the present invention is useful as an adhesive and a coating agent exhibiting high adhesion to inorganic materials in which existing epoxy resins exhibit insufficient adhesiveness.

Claims (5)

After esterifying the epoxy resin (A) containing two or more intramolecular epoxy groups and the compound (B) containing two or more intramolecular carboxyl groups, the alkoxysilane (C) containing an organofunctional group is dealcoholized. A process for producing an organofunctional group-containing alkoxysilane-modified epoxy resin composition (D), which is prepared by According to claim 1, wherein the epoxy resin (A) is bisphenol (bisphenol) type epoxy (epoxy) resin, bisphenol (bisphenol) type epoxy (epoxy) resin, hydrogenated bisphenol (Hydrogenated bisphenol) type epoxy (epoxy) resin, bisphenol (bisphenol) S-type epoxy resin, Cresol novolac type epoxy resin, phenol novolac type epoxy resin, brominated epoxy resin, phenoxy The organic functional group-containing alkoxysilane-modified epoxy resin composition (D), which is at least one compound selected from the group consisting of a phenoxy resin, a urethane modified epoxy resin, and an NBR modified epoxy resin. Manufacturing method. The organic functional group-containing alkoxysilane-modified epoxy resin composition (D) according to claim 1, wherein the carboxyl group-containing compound (B) is a dimer acid, a carboxyl terminated butadiene acrylonitrile copolymer (CTBN), or a mixture thereof. Manufacturing method. According to claim 1, wherein the organofunctional group-containing alkoxysilane (C) is a method for producing an organic functional group-containing alkoxysilane-modified epoxy resin composition (D), characterized in that the general formula is represented by the following formula (1). (Formula 1)

(Wherein n represents an integer of 0 to 4. X represents an alkoxy group, such as a methoxy group or an ethoxy group, and R represents a vinyl group or glycidoxy). (glycidoxy group, acrylic group, or mercapto group.) The organic functional group-containing alkoxysilane-modified epoxy resin composition (D) produced by the method according to any one of claims 1 to 4, wherein the carboxyl group-containing compound (B) is used based on 100% by weight of the modified epoxy resin composition (D). ) Is 0.5 to 40% by weight, the organofunctional group-containing alkoxysilane (C) is an organic functional group-containing alkoxysilane-modified epoxy resin composition (D), characterized in that 0.5 to 9.5% by weight.