TW201739853A - Polyether compounds having epoxy hydroxyl urethane groups and waterborne epoxy resin composition - Google Patents

Abstract

The present invention is to provide polyether compounds having epoxy hydroxyl urethane group as the following formula (I), (II) or (III) shows: and waterborne epoxy resin composition. Using the hydroxyl urethane as emulsifier, the obtained waterborne epoxy resin composition of the present invention has better stability and freeze-thaw durability.

Description

Polyether compound with epoxy hydroxy urethane and waterborne epoxy resin composition

This invention relates to a novel polyether compound having an epoxy hydroxy urethane and an aqueous epoxy resin composition.

Waterborne epoxy resin (WER) refers to a stable dispersion system in which water is the continuous phase and epoxy resin particles or droplets are dispersed. Its important use is in waterborne epoxy resin coatings. The water-based epoxy resin coating is similar to the solvent-based epoxy resin coating. The epoxy resin before coating is a linear structure, and a crosslinking reaction occurs after coating to form a network structure film excellent in performance. Therefore, it is necessary to add a curing agent capable of chemically crosslinking the aqueous epoxy at room temperature before the application. Waterborne epoxy resin coating has many advantages, such as strong adaptability, high adhesion to many substrates, small shrinkage of film after curing, high hardness, good wear resistance, good electrical insulation performance, corrosion resistance and resistance. Good chemical and environmental performance, low volatile organic compound content, no air pollution; good construction operation, curing at room temperature and humid environment, reasonable curing time, and high cross-linking Density, construction tools can be cleaned directly with water.

The epoxy resin itself is insoluble in water and is only soluble in organic solvents such as aromatic hydrocarbons and ketones. The preparation of waterborne epoxy resin is to make the original solvent-based epoxy water-based, usually in the original epoxy resin. The introduction of a hydrophilic molecular segment into the molecular chain or the introduction of a component having an emulsifier function enables the epoxy resin to be dissolved or dispersed in water. According to different ways of water-based, the prepared water-based epoxy resin coating can be divided into a self-emulsified aqueous epoxy resin and an external emulsifier emulsified aqueous epoxy resin.

The method of emulsifying the emulsifier refers to adding a suitable emulsifier, and pulverizing and mixing the epoxy resin, water and emulsifier by mechanical stirring to form an emulsion, which is simple in operation and low in cost; Poor water-based stability results in a large size of the dispersed phase and imperfect film forming properties. Therefore, there is still a need in the industry for a suitable emulsifier to improve the stability and freeze-thaw properties of the epoxy resin emulsion.

In order to solve the above problems, a first object of the present invention is directed to an epoxyhydroxyurethane polyether compound having the following structural formula (I), (II) or (III): Wherein n is 2 to 70; R ₁ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IV): Where m is 0~5 and R ₅ is the following structural formula: R ₂ is C ₂ ～4 alkyl; R ₃ is the following structural formula (V) or (VI): Wherein R ₆ is a C 4-12 alkyl, alkenyl, alkynyl, cycloalkyl or polyether group; and R ₄ is the following structural formula (VII) or (VIII): Wherein R ₇ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IX): , where p is 0~5, and R ₈ is the following structural formula:

In a preferred embodiment, the epoxy hydroxyurethane polyether compound is used as an emulsifier for an epoxy resin.

Another main object of the present invention is to provide an aqueous epoxy resin composition comprising: (a) an epoxy resin, (b) a hydroxyl group-containing carbamate, and (c) water.

In a preferred embodiment, wherein the hydroxyl-containing carbamate is an epoxy hydroxy urethane polyether compound, in a more preferred embodiment, it has the above formula (I), (II) or (III) The structure defined.

In another preferred embodiment, the hydroxyl-containing carbamate has an HLB value between 4 and 17.

In another more preferred embodiment, the hydroxyl-containing carbamate has an HLB value between 12 and 15.

In a preferred embodiment, the aqueous epoxy resin composition further comprises a solvent.

In another more preferred embodiment, the epoxy resin comprises 30 to 65 wt% of the total weight of the aqueous epoxy resin composition; the hydroxyl-containing carbamate accounts for the total weight of the aqueous epoxy resin composition. 3~15wt%; the water accounts for 30~65wt% of the total weight of the aqueous epoxy resin composition; the solvent accounts for 1~20wt% of the total weight of the aqueous epoxy resin composition.

In another preferred embodiment, the solvent is one or more selected from the group consisting of alcohols, ethers, and ketones.

In a preferred embodiment, the aqueous epoxy resin composition is used as a coating.

Another main object of the present invention is to provide a method for aqueously modifying an epoxy resin comprising mixing an epoxy resin with a hydroxyl-containing carbamate and adding water for emulsification.

In a preferred embodiment, the epoxy resin is mixed with the hydroxyl-containing carbamate in a solvent.

In a preferred embodiment, the mixture is heated at a temperature of 50 to 80 ° C.

In another preferred embodiment, wherein the water system is added at a rate of from 2 to 10 ml/min.

In another preferred embodiment, the hydroxyl-containing urethane polyether compound has a structure as defined in the above formula (I), (II) or (III).

Epoxy hydroxy urethane polyether compound of the invention

A primary object of the present invention is to provide an epoxy hydroxy urethane polyether compound having the following structural formula (I), (II) or (III): Wherein n is 2 to 70; R ₁ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IV): Where m is 0~5 and R ₅ is the following structural formula: R ₂ is C ₂ ～4 alkyl; R ₃ is the following structural formula (V) or (VI): Wherein R ₆ is a C 4-12 alkyl, alkenyl, alkynyl, cycloalkyl or polyether group; and R ₄ is the following structural formula (VII) or (VIII): Wherein R ₇ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IX): , where p is 0~5, and R ₈ is the following structural formula:

In one aspect, the epoxy hydroxy urethane polyether compound is a modified epoxy functional surfactant, and the modified epoxy functional surfactant is obtained by using a hydroxy urethane polyether. 50 ° C ~ 90 ° C, preferably 60 ~ 70 ° C, more preferably 65 ° C, with AGE reaction 1 ~ 3hr, preferably 2 hours, and then added epoxy resin to 60 ~ 120 ° C, preferably 90 to 110 ° C, more preferably 100 ° C, the reaction is 1 to 3 hours, preferably 2 hr, to obtain an epoxy hydroxy urethane polyether compound, the reaction can simultaneously produce the formula (I), (II) and III) a compound. The above AGE refers to a C ₁₂ -C ₁₄ alkyl glycidyl ether which is a monofunctional epoxy resin.

Waterborne epoxy resin composition of the invention

Another main object of the present invention is to provide an aqueous epoxy resin composition comprising: (a) an epoxy resin, (b) a hydroxyl group-containing carbamate, and (c) water. The aqueous epoxy resin composition referred to herein may also be referred to as an epoxy resin emulsion.

As the epoxy resin used in the present invention, a conventional epoxy resin such as a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, or a linear aliphatic ring can be used. Oxygen resin, alicyclic epoxy resin, epoxy resin obtained with bisphenol A, bisphenol F or bisphenol oxime, phenol novolac resin, polyglycidyl ether of cresol novolac resin, bisphenol A a polyglycidyl ether, adipic acid, decanoic acid of a polyvalent alcohol such as polyglycidyl ether, polypropylene glycol, 1,6-hexanediol, trimethylolpropane or glycerin Polyglycidyl esters and polyepoxypropylamines of polycarboxylic acids such as dimer acids; other epoxy resins also contain glycidyl ethers by making epichlorohydrin with at least 1.5 aromatics The compound of the group hydroxy group is prepared by reacting under basic reaction conditions. In addition to the above epoxy resin, examples of the epoxy resin suitable for use in the present invention also include a monoepoxy resin, a diglycidyl ether of a dihydroxy compound, an epoxy novolac, a cycloaliphatic epoxy resin, and a polycarboxylic acid. Polyglycidyl ester, acrylic resin containing glycidyl methacrylate, and combinations thereof. Further, an epoxy resin in which the above epoxy resin is modified with a polyphenol such as bisphenol A or bisphenol F or a polycarboxylic acid such as adipic acid or sebacic acid may be suitably used. Among these, an epoxy resin obtained from epichlorohydrin and a phenol compound having two hydroxyl groups in the molecule, specifically, an epoxy resin obtained from bisphenol A or bisphenol F and epichlorohydrin can be more suitably used. The epoxy equivalent of the epoxy resins is preferably from 100 to 700 g/eq, such as from 125 to 130 g/eq, from 170 to 180 g/eq, from 490 to 500 g/eq or from 275 to 290 g/eq, and the like.

The term "HLB value" as used herein refers to the hydrophilic-lipophilic balance value to indicate the hydrophilic or lipophilic properties of the surfactant. The larger the HLB value, the stronger the hydrophilicity, and the smaller the HLB value, the stronger the lipophilicity. The value can be calculated using the empirical formula HLB=7+11.7 logM _W /M _O , where M _W and M _O are the molecular weights of the hydrophilic group and the lipophilic group in the surfactant molecule, respectively. Alternatively, the water solubility method is used to estimate the HLB value, that is, the nature of the HLB value after the test substance is added to water is defined as shown in Table 1:

In a preferred embodiment, the hydroxyl group-containing carbamate of the present invention is an epoxyhydroxyurethane polyether compound and has the structural formula (I), (II) or (III) as defined above. . In another preferred embodiment, the HLB value of the hydroxyl-containing carbamate is estimated by the water solubility method described above. As an emulsifier of the aqueous epoxy resin composition, the HLB value is too small or too large, and no better emulsification function can be obtained; the HLB value of the hydroxyl group-containing carbamate of the present invention can be determined by using the starting material polyetheramine. Adjusted by the content of hydrophilic ethylene oxide (EO), or if the same polyetheramine is used, adjust its [CC]/[NH ₂ ] molar ratio, such as [CC The /[NH ₂ ] molar ratio is controlled from 0.5 to 0.75, such as 0.5, 0.6, 0.66, 0.7 or 0.75. After the experiment, it was found that the hydroxyl group-containing carbamate preferably has an HLB value of 4 to 17, the epoxy resin emulsion stability is preferably between 6 and 16, and the optimum system is between 12 and 15, which can provide an aqueous ring. Stability and freeze-thaw properties of the oxygen resin composition.

In a preferred embodiment of the invention, the aqueous epoxy resin composition further comprises a solvent if necessary. The term "solvent" is used herein to adjust the softening point of the epoxy resin. Therefore, the skilled person can adjust the amount of the solvent according to the characteristics of the hardness of the epoxy resin. If the amount of the solvent is too small, it cannot be The effect of adjusting the softening point of the resin is achieved; if the amount of addition is too large, the volatile organic compound (VOC) in the aqueous epoxy resin composition is too much, and therefore, the amount of the solvent is preferably added to the composition of the aqueous epoxy resin. The total amount of the material is 1 to 20% by weight, preferably 3 to 10% by weight, more preferably 3 to 7% by weight. Of course, if the epoxy resin itself has a suitable softening point, it is also possible to add no solvent.

The solvent to be used in the present invention is not particularly limited as long as it is a solvent which is uniformly dispersed in an epoxy resin and a hydroxyl group-containing urethane, and is inert to the above, and examples thereof include ethyl acetate and 3. Ester of methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, etc.; alcohols such as methanol, ethanol, isopropanol, etc.; , Ethyl citrate, propyl acesulfame, butyl acesulfame, isobutyl acesulfame, tributyl cyanobacteria, etc.; monoethylene glycol dimethyl ether, digan Glyme, such as diglyme, triglyme, etc.; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, A propylene glycol monoalkyl ether such as propylene glycol mono-tert-butyl ether; a ketone such as acetone or methyl ethyl ketone; among these, propylene glycol monoalkyl ether such as propylene glycol methyl ether is preferable.

In another preferred embodiment, the epoxy resin comprises from 30 to 65 wt%, preferably from 40 to 60 wt%, more preferably from 45 to 55 wt%, based on the total weight of the aqueous epoxy resin composition.

In a more preferred embodiment, the hydroxyl group-containing urethane comprises from 3 to 15% by weight, preferably from 3 to 7% by weight, more preferably from 5 to 7% by weight, based on the total weight of the aqueous epoxy resin composition.

In a more preferred embodiment, the water comprises from 30 to 65 wt%, preferably from 40 to 60 wt%, more preferably from 45 to 50 wt%, based on the total weight of the aqueous epoxy resin composition.

In the aqueous epoxy resin composition of the present invention, a resin component such as another polyester-based aqueous resin or an acrylic-based aqueous resin may be used in combination as needed within a range that does not impair the properties. Further, in the aqueous epoxy resin composition of the present invention, an anti-cissing agent, an anti-sagging agent, a flow-leveling agent, and an elimination can be prepared as needed. Various additives such as a foaming agent, a hardening accelerator, an ultraviolet absorber, and a light stabilizer. The use of the aqueous epoxy resin composition of the present invention is not particularly limited, and examples thereof include a coating material, a binder, a fiber agglomerating agent, and a concrete primer.

The water-based epoxy resin composition of the present invention is widely used for building interior or external water-based paints, water-based paints for inorganic building materials, iron-based rust-proof water-based paints, and automotive repair water-based paints; and automotive paints and beverages. Industrial use such as tanks. Among them, because of excellent properties such as corrosion resistance and dryness to the touch, it is possible to suitably use an iron anti-rust water-based paint which is a multilayer anticorrosive such as a steel structure or a bridge, and is particularly useful as a primer. Iron part of rust-proof water-based paint.

When the aqueous epoxy resin composition of the present invention is used for a coating application, it is preferred to blend various pigments or various additives such as rust preventive pigments, coloring pigments, and externders as needed. Examples of the rust preventive pigment include flaky pigments such as zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, strontium chromate, aluminum chromate, and graphite; and examples of the coloring pigment include Carbon black, titanium oxide, zinc sulfide, oxidation Red iron oxide; the raw material of the substrate may, for example, be barium sulfate, calcium carbonate, talc, kaolin or the like.

The coating method of the aqueous epoxy resin composition of the present invention in the case of coating is not particularly limited, and may be a roll coating, a spray, a brush, a doctor blade, a bar coater, a dip coating, an electrodeposition coating, or the like. get on. After the coating, the treatment method can be carried out at room temperature to heat hardening. The temperature at which the heat is hardened is preferably in the range of 50 to 250 ° C, particularly preferably in the range of 60 to 230 ° C. The heating time is preferably in the range of 2 to 30 minutes, particularly preferably in the range of 5 to 20 minutes.

When the aqueous epoxy resin composition of the present invention is used as a binder, it is not particularly limited, and after being applied to a substrate by spraying, brushing or doctor blade, it can be bonded by bonding the bonding surface of the substrate. The façade forms a strong bonding layer by fixing or pressing around. In the case of the substrate, the steel sheet, the concrete, the mortar, the wood, the resin sheet, and the resin film are suitable, and may be subjected to physical treatment such as polishing, electrical treatment such as corona treatment, chemical conversion treatment, or the like as needed. After various surface treatments of chemical treatment, coating is more appropriate.

Method for watering epoxy resin of the invention

Another main object of the present invention is to provide a method for aqueously modifying an epoxy resin comprising mixing an epoxy resin with a hydroxyl-containing carbamate and adding water for emulsification.

In a preferred embodiment, the epoxy resin is mixed with a hydroxyl-containing carbamate prior to a solvent, and water is added for emulsification.

In the method for water-based epoxy resin, the hydroxyl group-containing urethane is an emulsifier used in an aqueous dispersion of an epoxy resin, and the excellent properties of the aqueous epoxy resin emulsion observed include a preferred resin emulsion. Stability and resin emulsion freeze-thaw properties.

In a preferred embodiment, the mixture is heated to a temperature of 50 to 80 ° C, It is preferably mixed at 60 to 80 °C.

In another preferred embodiment, wherein the water system is added at a rate of 2 to 10 ml/min; if it is added at a rate of less than 2 ml/min, the emulsification takes a long time; and if it is added at a rate of more than 10 ml/min, Will make the emulsification effect worse.

In another preferred embodiment, the hydroxyl group-containing carbamate is an epoxyhydroxyurethane polyether compound and has a structure as defined by the above formula (I), (II) or (III).

The invention is illustrated by the following examples and examples, which are intended to be illustrative only and not to limit the scope of the invention. The raw materials used in the following preparations and examples are defined as follows: BDGE125: Polyglycidyl ether of 1,4 butanediol produced by the Changchun Synthetic Resin Factory, having an epoxy equivalent of from 125 to 130 g/eq.

BE180: Polyglycidyl ether of bisphenol A produced by Changchun Synthetic Resin Factory, having an epoxy equivalent of 170 to 180 g/eq.

BE501: Polyglycidyl ether of bisphenol A produced by Changchun Synthetic Resin Factory, having an epoxy equivalent of 490 to 500 g/eq.

AGE: C ₁₂ ~C ₁₄ alkyl glycidyl ether produced by Changchun Synthetic Resin Factory with an epoxy equivalent of 275 to 290 g/eq.

Jeffamine D230: Produced by Huntsman.

Jeffamine D400: Produced by Huntsman.

Jeffamine D2000: Produced by Huntsman.

Jeffamine ED2003: Produced by Huntsman.

Preparation example

Preparation Example 1-1: BDGE125 cyclic carbonate synthesis:

100 g of BDGE125 epoxy resin and 0.1 to 5% of the quaternary ammonium salt were placed in the reaction vessel, stirred and heated to 150 ° C, passed through CO ₂ , and reacted at a pressure of 5 kg/cm ² for 4 hr to obtain BDGE 125 ring carbonic acid. ester. The CO ₂ consumption was calculated to give a conversion of 95%.

Preparation Example 1-2: Synthesis of BE180 cyclic carbonate:

100g BE180 epoxy resin, 0.1~5% quaternary ammonium salt was placed in the reaction kettle, stirred and heated to 150 ° C, passed through CO ₂ , and reacted at a pressure of 5 kg / cm ² for 4 hr to obtain BE180 ring carbonic acid. ester. The conversion of CO _{2 was} calculated to give a conversion of 93%.

Preparation Example 2: Hydroxyurethane polyether synthesis:

The BDGE125 cyclic carbonate of Preparation Example 1-1 and the BE180 cyclic carbonate of Preparation Example 1-2 were separately reacted with a different type of polyetheramine shown in Table 2 below at 160 ° C for 7 hr to obtain a hydroxycarbamic acid. The ester polyether, the test formula is shown in Table 2 below:

Note: [CC]/[NH ₂ ] is the molar ratio of the cyclic carbonate group/amine group.

Preparation Example 3: Hydroxycarbamate Polyether Synthesis Containing Epoxy Functional Groups:

The synthesized sample No. S01~S12 hydroxyurethane polyether was reacted with a specific amount of AGE at 65 ° C for 2 hr, and then heated to a temperature of 100 ° C for 2 hr by adding BE180 epoxy resin to obtain an epoxy functional group. Hydroxy urethane polyether (sample No. S13~S24; wherein: S13~S18 are compounds corresponding to formula (I), (II) and (III) of the present invention, R ₁ is a butane group; R ₂ is ethane And a propane group; R ₃ is a group derived from AGE, R ₄ is derived from a BE180 group; S19 to S24 correspond to the compounds of the formula (I), (II) and (III) in the present case, and R ₁ is derived from BE 180 The group; R ₂ is an ethane and propane group; R ₃ is a group derived from AGE, and R ₄ is a group derived from BE 180, and the test formulations are as shown in Tables 3 and 4 below. The HLB value is estimated using a water solubility method.

Note 1: [AHEW] is the amine hydrogen equivalent weight.

Note 2: The gelation of HLB value means that the molecular weight of the product is too large to produce a gel during the reaction.

Example

Epoxy resin aqueous test using epoxy functional epoxy-containing urethane polyether: A certain proportion of BE501 epoxy resin, epoxy functional hydroxy urethane polyether (sample No. S13~S24) as emulsifier, propylene glycol methyl ether as solvent, and AGE as diluent to adjust system viscosity, put Into a 100 ml glass reactor, the temperature is raised to 70 ° C, and the above materials are stirred and mixed, and a specific ratio of pure water is added at a rate of 2 to 10 ml / min to emulsify, thereby obtaining an aqueous epoxy resin composition (sample No. S25~S36).

The obtained epoxy resin composition was tested for stability by centrifugal sedimentation. The test conditions were centrifugal force = 1600 G * 5 min, and the stability was compared.

The obtained aqueous epoxy resin composition was placed in a freezer at -18 ° C for 17 hr, taken out at room temperature for 7 hr, and allowed to return to temperature, and the above test was repeated 5 times to observe whether emulsification had layer hardening.

The experimental results are shown in the following table 5:

Note 1: The emulsion stability is based on whether the emulsion produces delamination or resin aggregation. If there is no delamination or resin aggregation, it is recorded as OK, and if there is delamination or resin aggregation, it is recorded as NG.

Note 2: ○: The emulsion did not change after 5 times of freezing and rewarming test; △: the emulsion did not change after 3 times of freezing and rewarming test; ×: After freezing and returning to temperature, emulsification delamination or resin aggregation occurred.

According to the above results, when the hydroxy carbamate is used as an emulsifier, the epoxy resin composition can be made water-based; and when the HLB of the hydroxy carbamate is between 4 and 17, an epoxy resin emulsion having better stability can be obtained. When the HLB of the hydroxy carbamate is between 12 and 15, an epoxy resin emulsion with better stability and freeze-thaw properties can be obtained.

The aqueous epoxy resin composition of the present invention contains an hydroxy urethane as an emulsifier, thereby making the epoxy resin composition water-based, and further obtaining an epoxy resin emulsion having better stability and freeze-thaw property.

Claims (13)

An aqueous epoxy resin composition comprising: (a) an epoxy resin, (b) a hydroxyl-containing carbamate, and (c) water. The aqueous epoxy resin composition of claim 1, wherein the hydroxyl group-containing carbamate is an epoxy hydroxy urethane polyether compound and has the following structural formula (I), (II) or (III) : Wherein n is 2 to 70; R ₁ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IV): Where m is 0~5 and R ₅ is the following structural formula: R ₂ is C ₂ ～4 alkyl; R ₃ is the following structural formula (V) or (VI): Wherein R ₆ is a C 4-12 alkyl, alkenyl, alkynyl, cycloalkyl or polyether group; and R ₄ is the following structural formula (VII) or (VIII): Wherein R ₇ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IX): , where p is 0~5, and R ₈ is the following structural formula: The aqueous epoxy resin composition of claim 1 or 2, wherein the hydroxyl-containing carbamate has an HLB value of from 4 to 17. The aqueous epoxy resin composition of claim 3, wherein the hydroxyl group-containing carbamate has an HLB value of from 12 to 15. The aqueous epoxy resin composition of claim 1 or 2, which further comprises a solvent. The aqueous epoxy resin composition of claim 1 or 2, wherein the epoxy resin comprises from 30 to 65 wt% of the total weight of the aqueous epoxy resin composition. The aqueous epoxy resin composition of claim 1 or 2, wherein the hydroxyl group-containing urethane comprises from 3 to 15% by weight based on the total weight of the aqueous epoxy resin composition. The aqueous epoxy resin composition of claim 1 or 2, wherein the water comprises from 30 to 65 wt% of the total weight of the aqueous epoxy resin composition. The aqueous epoxy resin composition of claim 5, wherein the solvent comprises from 1 to 20% by weight based on the total weight of the aqueous epoxy resin composition. The aqueous epoxy resin composition of claim 5, wherein the solvent is one or more selected from the group consisting of alcohols, ethers, and ketones. The aqueous epoxy resin composition of claim 1 or 2, which is used as a coating. An epoxy hydroxy urethane polyether compound having the following structural formula (I), (II) or (III): Wherein n is 2 to 70; R ₁ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IV): Where m is 0~5 and R ₅ is the following structural formula: R ₂ is C ₂ ～4 alkyl; R ₃ is the following structural formula (V) or (VI): Wherein R ₆ is a C 4-12 alkyl, alkenyl, alkynyl, cycloalkyl or polyether group; and R ₄ is the following structural formula (VII) or (VIII): Wherein R ₇ is a C4-12 alkyl, alkenyl, alkynyl, cycloalkyl, polyether group or the following structural formula (IX): , where p is 0~5, and R ₈ is the following structural formula: The epoxy hydroxy urethane polyether compound of claim 12 which is an emulsifier for an epoxy resin.