KR102586758B1 - An aqueous epoxy resin comprising a gemini-type epoxy emulsifier and a method for preparing the same, and an aqueous epoxy paint comprising the same - Google Patents

Abstract

The present invention relates to an aqueous epoxy resin containing a gemini-type epoxy emulsifier, a method for producing the same, and an aqueous epoxy paint containing the same. More specifically, to an aqueous epoxy resin containing an epoxy resin and a gemini-type epoxy emulsifier represented by the following formula (1): Describe the resin:
[Formula 1]

(However, in Formula 1, PRO is polyalkylene oxide; A is R ¹ -(EO) _n (PO) _m (EO) _r -Z; E is a glycidyl compound bonded to nitrogen ; R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms; EO is ethylene oxide; PO is propylene oxide; n and m are 1 to 100, r is 0 to 100, the ratio of n and m is (n+r) : m = 1 to 8 : 1; Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or is not included)

Description

Water-based epoxy resin comprising a gemini-type epoxy emulsifier and method for producing the same, and water-based epoxy paint comprising the same

The present invention relates to a water-based epoxy resin containing a gemini-type epoxy emulsifier, a method for producing the same, and a water-based epoxy paint containing the same.

In paints, a large amount of volatile organic chemicals (VOCs) is exposed to the air when solvent-based paints are used. In particular, the Special Act on Air Quality Improvement, which has been in effect since 2020, continues to increase the number of regulated substances, and the level of volatile organic compounds is also decreasing.

In particular, epoxy resins have excellent properties such as inherent chemical resistance, water resistance, and abrasion resistance. Therefore, it is used for various purposes, such as preventing damage to the inner wall, outer wall, or floor of building or civil engineering structures, and preventing dust, etc. from being generated from the floor.

However, in the case of conventional epoxy resins, the use of organic solvents has the problem of odor and toxicity, making it difficult to work in closed spaces, and causing human health and environmental problems.

In the case of conventional epoxy paints, volatile organic compounds such as xylene, toluene, benzene, organic phosphorus, and combustion inhibitors are inevitably included as solvents and diluents. Therefore, in line with the strengthening regulations, there is a gradual change to the development of high-solids paints or the use of water-based paints.

In particular, methods for producing water-based epoxy resins and paints include dispersing the epoxy resin through an emulsifier or introducing a hydrophilic substituent into the epoxy resin.

In this regard, according to Republic of Korea Patent No. 10-1870910, an eco-friendly water-soluble paint composition for neutralizing concrete and preventing salt damage, and a construction method using the same, an eco-friendly paint composition made by mixing epoxy resin with a copolymer having a hydrophilic group and a silicone-based surfactant is water-based. A water-soluble paint composition is disclosed.

In addition, according to Republic of Korea Patent No. 10-0938432 water-based epoxy resin, its manufacturing method, water-based epoxy paint composition, and method of forming a coating film using the same, adhesion, gloss, and drying properties are improved by reacting a polyester glycol compound with a bisphenol epoxy compound. A water-based epoxy resin is disclosed.

However, the water-based paint composition prepared by the above method often does not satisfy the practically necessary mechanical properties due to the excessive amount of emulsifier added. Therefore, there is a need to develop a water-based epoxy resin that not only has excellent emulsification performance even when containing a low concentration of surfactant, but also has excellent mechanical properties.

Republic of Korea Patent Publication No. 10-1870910 (2018.06.19.) Republic of Korea Patent Publication No. 10-00938432 (2010.01.15.)

The present invention is intended to solve the above problems, and aims to provide a water-based epoxy resin that can be emulsified in a smaller amount than a conventional surfactant by introducing a gemini-type emulsifier into the water-based epoxy resin, and a method for manufacturing the same.

In addition, another technical problem of the present invention is to provide a water-based epoxy paint manufactured including the water-based epoxy resin.

In order to solve the above technical problem, the present invention,

Provided is an aqueous epoxy resin comprising an epoxy resin and a gemini-type epoxy emulsifier represented by the following formula (1):

[Formula 1]

(However, in Formula 1 above,

The PRO is polyalkylene oxide,

The A is R ¹ -(EO)n(PO)m(EO)rZ,

The E is a glycidyl compound bound to nitrogen,

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

n and m are 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1,

wherein Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or is not included).

Preferably, the polyalkylene oxide is polypropylene oxide.

Also preferably, the epoxy resin includes one or more of bisphenol A-type epoxy, bisphenol F-type epoxy, hydrogenated bisphenol A-type epoxy, and novolak epoxy.

Also preferably, the water-based epoxy resin includes 100 parts by weight of the epoxy resin and 1 to 30 parts by weight of a gemini-type epoxy emulsifier based on 100 parts by weight of the epoxy resin.

In order to solve the above other technical problems, the present invention,

(1) a first reaction step of reacting a glycidyl ether compound represented by the following formula (2) with a diamine compound represented by the formula (3);

(2) a second reaction step of reacting the compound produced in the first reaction step with a glycidyl compound to prepare a gemini-type epoxy emulsifier represented by the following formula (1);

(3) a mixing step of mixing the prepared gemini-type epoxy emulsifier into an epoxy resin; and

(4) an aqueous emulsion step of emulsifying the mixture by dropwise adding distilled water; providing a method for producing an aqueous epoxy resin comprising:

[Formula 1]

[Formula 2]

[Formula 3]

(However, in Formulas 1 to 3,

The PRO is polyalkylene oxide,

The A is R ¹ -(EO)n(PO)m(EO)rZ,

The E is a glycidyl compound bound to nitrogen,

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

n and m are 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1,

wherein Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or is not included).

Preferably, in the mixing step, when the epoxy resin is in a solid state, alcohol is further included.

In order to solve the above technical problem, the present invention provides a water-based epoxy paint manufactured including the water-based epoxy resin.

The water-based epoxy resin of the present invention as a means of solving the above problem contains a gemini-type surfactant as an emulsifier, and forms micelles even at a lower application concentration compared to conventional single-chain surfactants or block copolymer surfactants, resulting in excellent emulsification performance. There is an effect of having .

In addition, the gemini-type epoxy emulsifier included in the present invention is easy to control the HLB value (Hydrophilic-Lipophile Balance), so not only can it be applied to various epoxy resins, but the epoxy groups remaining in the emulsifier participate in the curing reaction. . Therefore, there is an effect of preventing the problem of deterioration of the physical properties of the epoxy coating film due to elution of the emulsifier, etc.

In addition, by introducing the water-based epoxy resin according to the present invention into the paint, not only can a smooth coating film be created, but also a coating film with excellent mechanical properties can be formed by containing a small amount of emulsifier compared to conventional surfactants. there is.

Figure 1 is a structural formula of a gemini-type epoxy emulsifier according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The terms used in the present invention are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the present application, should not be interpreted in an ideal or excessively formal sense. No.

In one aspect, the present invention relates to an aqueous epoxy resin comprising an epoxy resin and a gemini-type epoxy emulsifier represented by the following formula (1):

[Formula 1]

(In Formula 1 above,

The PRO is polyalkylene oxide,

The A is R ¹ -(EO) _n (PO) _m (EO) _r -Z,

The E is a glycidyl compound bound to nitrogen,

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

n and m are 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1,

Wherein Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or not included)

The gemini-type epoxy emulsifier connects polyalkylene oxide to each amine in Chemical Formula 1. At this time, the amine forms a bond with a bridge containing polyalkylene oxide as a tertiary amine, A, an EO/PO regulator, and E, a glycidyl compound.

Therefore, the gemini-type emulsifier having the above structure has excellent emulsification properties at a lower concentration compared to conventional single-chain emulsifiers or block copolymers.

Meanwhile, it is preferable to use the polyalkylene oxide connecting the amine having the (CH(CH ₃ )CH ₂ O) _i structure. At this time, the i preferably has a value of 1 to 60. If the i value exceeds the range, the ratio of hydrophilic groups in the emulsifier decreases, making it difficult to emulsify the epoxy resin, resulting in the problem of producing a non-emulsified epoxy resin. Therefore, when applying the non-emulsified epoxy resin to a paint, there is difficulty in securing mechanical properties such as lowering hardness when forming a coating film.

Meanwhile, in Formula 1, E is a compound having a glycidyl group bonded to N (nitrogen) in Formula 1, such as polypropylene glycol diglycidyl ether, bisphenol A epoxy resin, bisphenol F epoxy resin, and hydrogen bisphenol A. It may contain one or more of epoxy resin and novolac epoxy resin.

In relation to this, it is preferable to use the glycidyl compound constituting E having a weight average molecular weight of 400 to 1,000. If the molecular weight is less than the above range, there is a problem of deterioration of emulsification performance due to incomplete gemini structure. On the other hand, if the weight average molecular weight exceeds the above range, problems arise such as difficulty in synthesis due to an increase in viscosity when manufacturing the emulsifier and deterioration of emulsification performance due to a decrease in the proportion of hydrophilic groups in the emulsifier.

In addition, E is a polypropylene glycol diglycidyl ether having a propylene glycol repeating unit -[CH ₂ CH(CH ₃ )O] _p -, and p is 1 to 20 repetitions or the weight average of the glycidyl compound. It is desirable to have a p value that satisfies the molecular weight of 400 to 1,000.

In addition, when the epoxide at one end of the glycidyl ether compound or epoxy resin as described above is combined with the nitrogen, it has an open form. Therefore, the gemini-type epoxy emulsifier of the present invention retains a glycidyl group, so that the glycidyl group participates in the curing reaction and the emulsifier adheres to the coating film, thereby minimizing the decrease in water resistance and the decrease in mechanical properties when forming a coating film. there is.

That is, while the conventional emulsifier used a method of dispersing the glycidyl compound using physical force, in the case of the present invention, dispersion can be facilitated by using the reactivity of the glycidyl compound by introducing it into the emulsifier.

On the other hand, A, the EO/PO regulator, includes EO as a repeating unit such as R ¹ -(EO) _n (PO) _m -Z or R ¹ -(EO) _n (PO) _m (EO) _r -Z The ratio of PO can be adjusted. In this regard, (EO) _n (PO) _m or (EO) _n (PO) _m (EO) _r is a copolymer composed of EO and PO, which means a block copolymer. At this time, the (EO) _n (PO) _m (EO) _r is a modified structure in which the reactivity is improved by adding hydrophilic EO to the hydrophobic PO. Additionally, A may have a random copolymer, block copolymer, or alternating copolymer structure. Therefore, as the HLB value is easy to control, it can be applied to various epoxies as an emulsifier.

In relation to this, the ratio of ethylene oxide (EO) and propylene oxide (PO), n:m or (n+r):m, is preferably 1:1 to 8:1. At this time, n and m are preferably 1 to 100, r is preferably 0 to 100, and more preferably m is 1 to 30, n is 24 to 100, and r is 1 to 20.

In relation to the ratio of EO and PO, setting an appropriate HLB value of the compound is important in order to stably emulsify the epoxy resin or maintain the dispersion in a stable state without phase separation, precipitation, or agglomeration after emulsion dispersion. That is, the HLB value is determined according to the ratio of EO and PO, and if the ratio of EO and PO is less than the above range, there is a problem of underhydration of the amine compound. On the other hand, if the above range is exceeded, the dispersibility of the epoxy emulsion prepared with the amine compound decreases as it becomes overhydrophilic, or it becomes difficult to secure the storage stability of the prepared epoxy emulsion.

Meanwhile, R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms and is selected from a methyl group, an ethyl group, a propyl group, and a butyl group.

In this regard, Z is a hydroxyl group having 2 to 5 carbon atoms, which may be hydrocarbyl in the form of a carbon radical with one or more hydrogen atoms removed, hydrocarbyloxy in the form of oxygen bonded to the carbon constituting the hydrocarbyl, or not included. there is. Therefore, the -Z- is -OCH ₂ CH(OH)CH ₂ -, and in this case, A has the form of R1-(EO) _n (PO) _m (EO) _r -OCH ₂ CH(OH)CH ₂ - desirable.

Meanwhile, the epoxy equivalent weight (g/eq) of the gemini-type epoxy emulsifier is preferably 2,000 to 8,000. If the average molecular weight is less than the above range, when emulsifying the solid epoxy resin, the emulsion stability is lowered and precipitation occurs, resulting in storage problems. Additionally, there is a problem that water resistance decreases when forming a coating film. On the other hand, if the average molecular weight exceeds the above range, the viscosity increases during emulsification, making it difficult to proceed with the emulsification process. In addition, even after emulsification, uniform mixing of the base material and hardener becomes difficult due to the high viscosity, so excessive dilution is required, which causes workability problems due to reduced flowability.

In addition, the water-based epoxy resin is 100 parts by weight of the epoxy resin; It is preferable to include 1 to 30 parts by weight of a gemini-type epoxy emulsifier based on 100 parts by weight of the epoxy resin.

This means that when the amount of the gemini-type epoxy emulsifier is less than 1 part by weight, the emulsification performance is poor and water dispersion is difficult. On the other hand, when the gemini-type epoxy emulsifier is included in excess of 30 parts by weight, the mechanical properties of the epoxy resin are reduced due to the excess epoxy emulsifier.

Meanwhile, distilled water is further added to the epoxy resin and the gemini-type epoxy emulsifier to prepare an emulsified water-based epoxy resin. At this time, the distilled water preferably contains 10 to 200 parts by weight. If the distilled water is contained in less than 10 parts by weight, its viscosity is high, making it difficult to handle, such as filtration, when manufacturing water-based epoxy resin. If the distilled water is contained in more than 200 parts by weight, the packaging unit becomes larger based on solid content. Not only is there an unnecessary increase in transportation costs, but sedimentation may occur during long-term storage.

Meanwhile, in the case where the epoxy resin included in the water-based epoxy resin is in the form of a solid, alcohol may be further included and mixed as necessary. At this time, it is preferable to use an alkoxy alcohol such as methoxypropanol as the alcohol. In addition, the alcohol is preferably contained in an amount of 1 to 50 parts by weight. If the alcohol is less than 1 part by weight, the dissolution of the epoxy resin is not smooth and the emulsification performance is reduced due to an increase in viscosity at the emulsification temperature. On the other hand, when the alcohol content exceeds 50 parts by weight, there is a problem in that the VOCs (volatile organic compounds) content increases due to an increase in the organic solvent content.

In another aspect, the present invention relates to a method for producing a water-based epoxy resin,

(1) a first reaction step of reacting a glycidyl ether compound represented by the following formula (2) with a diamine compound represented by the formula (3); (2) a second reaction step of reacting the compound produced in the first reaction step with a glycidyl compound to prepare a gemini-type epoxy emulsifier represented by the following formula (1); (3) a mixing step of mixing the prepared gemini-type epoxy emulsifier into an epoxy resin; and (4) an emulsion step of emulsifying the mixture by adding distilled water dropwise to the mixture.

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 to 3,

The PRO is polyalkylene oxide,

The A is R ¹ -(EO) _n (PO) _m (EO) _r -Z,

The E is a glycidyl compound bound to nitrogen,

R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,

The EO is ethylene oxide,

The PO is propylene oxide,

n and m are 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1,

Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or is not included.)

Hereinafter, the manufacturing method of the water-based epoxy resin will be described in detail step by step.

First, it is the first reaction step. In this step, the glycidyl ether compound represented by Formula 2 and the diamine compound represented by Formula 3 are reacted.

The glycidyl ether compound represented by Formula 2 is a mono glycidyl ether compound having EO and PO groups, and has a weight average molecular weight of 2,000 to 8,000 and an epoxy equivalent weight (g/eq) of 2,000 to 6,000. It is preferable to use a compound. If the molecular weight of the glycidyl ether compound is less than 2,000, it causes a problem of deterioration of the physical properties of the epoxy resin and paint. On the other hand, when the molecular weight exceeds 8,000, there is a problem in that the reaction to make a water-based epoxy resin does not proceed well due to the high molecular weight.

In addition, the glycidyl ether compound represented by 2 in chemistry has the formula R ¹ -(EO) _n (PO) _m (EO) _r -OH in sodium hydroxide solution and tetrabutyl ammonium bromide (TBAB). It is manufactured by reacting an alcohol compound with epichlorohydrin. At this time, R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms and is selected from a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, n and m are preferably 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1, and more preferably, m is 1 to 100. 30, n is preferably 24 to 100 and r is 1 to 20.

In relation to this, it is preferable that the weight average molecular weight of the diamine compound is 100 to 2,000. If the molecular weight of the compound is less than 100, it is difficult to apply a commercialized product. On the other hand, if the molecular weight of the compound exceeds 2,000, it becomes difficult to emulsify the epoxy resin as the proportion of hydrophilic groups in the emulsifier decreases, and it is difficult to secure mechanical properties as the hardness of the cured film decreases when the product is cured.

As an example, the first reaction step may proceed as shown in Scheme 1 below.

[Scheme 1]

In relation to Scheme 1, in the first reaction step, the glycidyl ether compound represented by Chemical Formula 2 and the diamine compound are mixed to induce a reaction. At this time, the nitrogen of the amine donates electrons to the epoxide, forming an N-C bond as a ring-opening reaction occurs. In addition, since there are two reaction sites as described above per diamine molecule, one mole of diamine reacts with 2 moles of glycidyl compound, resulting in the formation of a bridge connecting the glycidyl compounds.

If a monoamine compound or a triamine compound is included instead of the diamine compound, an additional process including a separate aqueous ammonia solution is required. In other words, if the above additional process is included, variables may occur due to synthesis, which may also cause problems with reproducibility.

Meanwhile, the first reaction step includes 100 parts by weight of the diamine compound; It is preferable to mix 1,000 to 3,000 parts by weight of the glycidyl ether compound represented by Formula 2 with respect to 100 parts by weight of the diamine compound.

At this time, the product produced through the first reaction step is a gemini-type first-step composite, which is characterized by being a secondary amine as shown in the following formula (4).

[Formula 4]

At this time, in relation to Formula 4, PRO is a polyalkylene oxide, A is R ¹ -(EO) _n (PO) _m (EO) _r -Z-, and R ¹ has 1 to 10 carbon atoms. is a saturated or unsaturated alkyl group, wherein EO is ethylene oxide, PO is propylene oxide, m and n are each independently 1 to 100, and r is 0 to 100, The Z is an optionally substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms, or is absent. In relation to this, since Chemical Formula 4 is the same as that described in the above-described Gemini-type epoxy emulsifier, detailed description will be omitted.

Next, the second reaction step is a step of preparing a gemini-type epoxy emulsifier by reacting a glycidyl compound with the composition produced by the reaction in the first step. At this time, in the second reaction step, the reaction is induced by mixing the compound of Chemical Formula 4 with the glycidyl compound, and similarly to the first reaction step, the nitrogen of the amine provides electrons to the epoxide of the glycidyl compound to initiate a ring opening reaction. As this happens, an N-C bond is formed. In addition, since there are two reaction sites as described above per molecule of the compound of Formula 4, 2 moles of glycidyl compound per 1 mole compound reacts, and through this, the final product is a gemini type of tertiary amine having a gemini structure. It becomes an epoxy emulsifier.

In relation to this, the glycidyl compound, which is a reactant in the secondary reaction step, is a compound having 1 or 2 or more glycidyl functional groups and is a diglycidyl compound or an epoxy resin. More specifically, it is selected from the group consisting of polypropylene glycol diglycidyl ether, bisphenol A-type epoxy, bisphenol F-type epoxy, hydrogenated bisphenol A-type epoxy, and novolac epoxy, and mixtures thereof.

Meanwhile, the weight average molecular weight of the glycidyl compound in the secondary reaction step is preferably 400 to 1,000. If the molecular weight is less than 400, emulsification performance deteriorates due to incomplete gemini structure. On the other hand, if the molecular weight exceeds 1,000, synthesis is difficult due to an increase in viscosity when preparing the emulsifier, and the ratio of hydrophilic groups in the emulsifier decreases, causing problems that deteriorate emulsification performance.

In relation to this, the second reaction step includes 100 parts by weight of the diamine compound; It is preferable to mix 100 to 500 parts by weight of the glycidyl compound with respect to 100 parts by weight of the diamine compound.

As an example, in the secondary reaction step, a gemini-type epoxy emulsifier is prepared as shown in Scheme 2 below.

[Scheme 2]

Next is a mixing step in which the prepared gemini-type epoxy emulsifier is added to the epoxy resin and the compounds are mixed.

At this time, the epoxy resin is preferably selected from the group consisting of bisphenol A-type epoxy, bisphenol F-type epoxy, hydrogenated bisphenol A-type epoxy, novolac epoxy, and mixtures thereof.

Additionally, the water-based epoxy resin includes 100 parts by weight of the epoxy resin and 1 to 30 parts by weight of a Gemini-type epoxy emulsifier based on 100 parts by weight of the epoxy resin.

At this time, in the mixing step, if the epoxy resin is a solid epoxy resin, 1 to 50 parts by weight of alcohol may be optionally further mixed. Hereinafter, detailed descriptions are omitted since they are the same as those described above.

Lastly, there is an emulsion step in which distilled water is added dropwise to the mixed compounds to emulsify the compounds.

At this time, as described above, the distilled water preferably contains 10 to 200 parts by weight based on 100 parts by weight of the epoxy resin.

Meanwhile, the viscosity of the water-based epoxy resin prepared by the above method is preferably 50 to 1.000 cps, and the epoxy equivalent weight (g/eq) is preferably 200 to 600. In addition, the non-volatile content of the water-based epoxy resin is preferably 50 to 62%, and the average particle diameter is preferably 300 to 800 nm.

Meanwhile, in another aspect, the present invention has a technical feature of providing a water-based paint containing a water-based epoxy resin. At this time, the water-based paint preferably contains 35 to 65 parts by weight of the water-based epoxy resin based on the total weight of the paint. If the water-based epoxy resin is included in less than 35 parts by weight, the mechanical and chemical properties of the coating film are low due to the low resin content. On the other hand, if the water-based epoxy resin is included in more than 65 parts by weight, it may affect the flowability, hardness, and long-term storage of the paint.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. Examples of the present invention are provided to more completely explain the present invention to those with average knowledge in the art.

<Test Example 1> Glycityl ether production and synthesis results confirmation

To confirm the molecular weight and epoxy equivalent value of the gemini-type emulsifier according to the EO/PO ratio of the glycidyl ether compound, glycidyl ether was prepared as follows.

(1-1) Preparation Example 1: Preparation of glycityl ether (1)

Glycidyl ether compound (H ₃ C(OCH ₂ CH ₂ ) _n (OCH(CH ₃ )CH ₂ ) _m OH, MEP-4075, MW:4000 g/mol, EO:PO=4:1) 200g (0.05 mol) was completely dissolved at 65°C and stirred.

Next, 1.612 g (0.005 mol) of tetrabutyl ammonium bromide (TBAB) was added as a catalyst, and 40 g (0.5 mol) of NaOH (50 w/v%) was added.

Next, 46.26 g (0.5 mol) of epichlorohydrin was added and reacted for 24 hours.

After the reaction was over, water and epichlorohydrin were removed, dissolved in the solvent dichloromethane (DCM), and then diatomaceous earth was added and mixed. The solution was filtered and the internal solvent was removed to prepare glycidyl ether.

(1-2) Preparation Example 2: Preparation of glycityl ether (2)

Prepared in the same manner as Preparation Example 1, except that glycidyl ether compound (H ₃ C (OCH ₂ CH ₂ ) _n (OCH (CH ₃ ) CH ₂ ) _m OH, MEP-4080, MW: 4000 g/mol, EO :PO=5:1) was applied.

(1-3) Preparation Example 3: Preparation of glycityl ether (3)

Prepared in the same manner as Preparation Example 1, except that the glycidyl ether compound (H ₃ C (OCH ₂ CH ₂ ) _n (OCH (CH ₃ ) CH ₂ ) _m (OCH ₂ CH ₂ ) _r OH, MEP-4750, MW :4000 g/mol, EO:PO=4:1, n=63, m=17, r=5) were applied.

(1-4) GPC analysis of glycidyl ether

GPC analysis was performed to confirm the molecular weight of the glycidyl ether prepared in Preparation Examples 1 to 3. The GPC analysis result values are shown in Table 1 below.

Manufacturing Example 1 Production example 2 Production example 3 M _n ^One) 3,338 3,206 3,651 M _w ²⁾ 3,992 3,590 3,753 M _z ³⁾ 4,151 3,878 3,849 D ⁴⁾ 1.0498 1.1199 1.0281 1) number average molecular weight
2) weight average molecular weight
3) z average molecular weight
4) polydispersity (Mw/Mn)

According to Table 1 above, when the ratio of EO increased, the molecular weight tended to increase slightly, but it was confirmed that the polydispersity value converged to a value close to 1. That is, it was confirmed that glycidyl ether was synthesized uniformly through the molecular weight of the synthesized glycidyl ether compound.

(1-5) Epoxy equivalent value analysis of glycidyl ether

In order to check the epoxy equivalent value of the glycidyl ethers prepared in Preparation Examples 1 to 3, they were dissolved in salt ginseng-dioxane solution and back-titrated with an aqueous sodium hydroxide solution to confirm the presence or absence of epoxy. The equivalent value of each epoxy is shown in Table 2 below.

Epoxy equivalent weight (EEW, g/eq) Manufacturing Example 1 4,118.22 Production example 2 4,219,80 Production example 3 4,051.27

According to Table 2 above, the epoxy equivalent value was around 4,000 to 4,200. Considering that the epoxy equivalent value obtained through this process is generally 4,000 at 100% reaction, it can be confirmed that the results of Preparation Examples 1 to 3 are close to the target value.

<Test Example 2> Manufacturing of Gemini emulsifier, manufacturing of water-based epoxy resin using it, and confirmation of basic physical properties of the resin

(2-1) Preparation Example 4: Preparation of Gemini emulsifier

To prepare Gemini emulsifier, 10,424 g of glycidyl ether (MW: 5,212) prepared in Preparation Example 1, 447 g of polypropylene oxide diamine (Jeffamine D-400, MW: 447), and 5,212 g of deionized water were placed in a separate container. After mixing, the mixture was reacted at 85°C for 6.5 hours to obtain the first-stage Gemini composite.

Next, 1,280 g of polypropylene glycol diglycidyl ether (DE-208, MW: 640) was mixed with the first-stage composite, heated to 90°C, and reacted for 7.5 hours to prepare Gemini emulsifier, a Gemini second-step composite.

(2-2) Water-based epoxy resin production

A water-based epoxy resin was prepared according to Table 3 below. At this time, in the water-based epoxy resin production method, the epoxy resin and solvent were added to a high-speed stirring device and the temperature was raised to 90°C to completely dissolve. Next, the prepared gemini-type epoxy emulsifier or general emulsifier was added and dissolved, and then distilled water was added dropwise for 4 hours while stirring at high speed at the same temperature to prepare an emulsified water-based epoxy resin.

(Unit: g) Example 1 Example 2 Comparative Example 1 Comparative Example 2 epoxy resin YD-011 100 - 100 - YD-128 - 100 - 100 solvent methoxy propanol 10 - 10 - emulsifier Gemini type 10 8 - - non-ion - - 10 8 Distilled water 80 69.4 80 69.4

(2-3) Confirmation of basic properties of water-based epoxy resin

The average particle size, non-volatile matter content, epoxy equivalent weight, and viscosity of the water-based epoxy resins prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 4 below.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Average particle size (nm) 550 580 610 630 Non-volatile content (%) 55.1 60.3 55.3 60.5 Epoxy equivalent (q/eq) 522 200 475 185 Viscosity (cps) 125 592 358 668

As shown in Table 4, the water-based epoxy resins of Examples 1 and 2 according to the present invention contained a gemini-type emulsifier and were confirmed to have lower viscosity compared to existing water-based epoxy resins.

(2-4) Production of water-based epoxy paint and confirmation of basic properties of the paint

In order to confirm the basic properties of the water-based epoxy resin, a water-based epoxy paint was prepared using the water-based epoxy resin prepared above.

The detailed mixing and basic physical property results of the paint are shown in Table 5 and Table 6 below.

Each test method was tested according to ASTM test standards.

1) Topic section Paint formulation
(Unit: parts by weight) Example 4-1 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 Mercury
epoxy
profit Example 1 50.0 30.0 70.0 - - Comparative Example 1 - - 50.0 - Comparative Example 2 - - - - 50.0 colored pigments 13.5 13.5 13.5 13.5 13.5 constitution pigment 15.0 15.0 15.0 15.0 15.0 anti-rust pigment 7.0 7.0 7.0 7.0 7.0 Distilled water - 20.0 - - - additive dispersant 0.5 0.5 0.5 0.5 0.5 defoamer 0.2 0.2 0.2 0.2 0.2 leveling agent 0.3 0.3 0.3 0.3 0.3 thickener 1.3 1.3 1.5 1.3 1.3 Adhesion enhancer 0..5 0.5 0.5 0..5 0..5 2) Hardener section hardener resin
(Kukdo Chemical, KH-700) 85.0 85.0 85.0 85.0 85.0 solvent 15.0 15.0 15.0 15.0 15.0 ※ Mixing ratio (weight ratio) = subject: hardener = 10: 1

Test result Example 4-1 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 Viscosity (KU) 79.8 75.4 68.1 105.2 112.4 importance 1.405 1.374 1.341 1.410 1.398 SVR (%) 51.88 37.69 51.83 52.71 51.95

According to the viscosity test results, the paint compositions of Example 4-1 and Comparative Examples 4-1 and 4-2, which had a desirable resin viscosity, showed excellent viscosity of 68 to 80 KU. On the other hand, the paint compositions of Comparative Examples 4-3 and 4-4, which were high viscosity resins, showed a viscosity of 100 KU or more.

As a result, it was confirmed that the higher the initial viscosity of the water-based epoxy resin, the more it affected the viscosity of the paint, and this was confirmed to be influenced by the selection of the initial emulsifier.

(2-5) Confirmation of water-based epoxy paint workability

In order to confirm the workability of the water-based epoxy paint using a water-based epoxy resin, the flowability and degree of film formation of the paints prepared in Example 4-1 and Comparative Examples 4-1 to 4-4 were confirmed.

In relation to this, the flowability of the paint was tested based on ASTM standards, and the degree of film formation was determined by forming a dry film of 100㎛ on 5 sheets of each 60mm × 150mm (2T thick) specimen.

At this time, the degree of formation of the coating film was confirmed by the degree of shrinkage of the formed coating film, and the presence/absence of dust spray generation during the process of forming the coating film was confirmed.

The dilution ratio, flowability, and film formation results for the above test are shown in Table 7 below.

Test result Example 4-1 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 Water dilution ratio compared to paint
(weight%) 5 - - 15 20 flowability
(based on 100㎛) Great commonly bad bad bad film formation
(based on 100㎛) Great commonly commonly bad bad

According to the table above, the dilution of the paint is diluted in a small amount in the case of the paint compositions of Example 4-1 and Comparative Example 4-1 and Comparative Example 4-2 without dilution, where the water dilution ratio is 5% by weight relative to the total weight of the paint. Even so, it was possible to form a coating film of an appropriate level.

On the other hand, in the case of the paint compositions of Comparative Examples 4-3 and 4-4, a coating film could be formed only when excessively diluted due to dust spray generation.

Meanwhile, according to the results of flowability based on 100㎛ based on the diluted paint, Comparative Examples 4-2 to 4-4, excluding Comparative Example 4-1, confirmed the phenomenon of coating film flowing. In addition, in the case of Comparative Example 4-1, the coating film slightly flowed, and in the case of Example 4-1, the coating film maintained excellent flowability.

According to the film formation results, all five specimens of Example 4-1 showed good results, and in the case of Comparative Examples 4-1 and 4-2, it was confirmed that a film thickness that was relatively lower than theoretical was formed. In addition, in Comparative Examples 4-3 and 4-4, it was confirmed that there was difficulty in forming a smooth surface as some dust spray occurred despite dilution of water by 15 to 20% by weight.

As a result, it was confirmed that the higher the initial viscosity of the water-based epoxy resin, the higher the dilution ratio of the paint must be, which causes problems with reduced flowability and makes it difficult to form a smooth coating film due to dust spray.

(2-6) Confirmation of mechanical and chemical properties of water-based epoxy paints

To confirm the physical properties of a water-based epoxy paint using a water-based epoxy resin, a specimen was manufactured in the same manner as the workability confirmation above.

Water resistance, adhesion, salt water resistance, and hardness were confirmed as physical property confirmation items, and the specific confirmation method was conducted based on the ASTM and ISO standards in Table 8 below.

Test result Example 4-1 Comparative Example 4-1 Comparative Example 4-2 Comparative Example 4-3 Comparative Example 4-4 water resistance
(ASTM D870) 30 days
clear 12th
parts sound 14 days
parts sound 21st
wrinkles, swelling 18th
wrinkles, swelling Adhesion
(ASTM D3359) 5B 4B 4B 5B 5B salt water
(ASTM B117) More than 48 hours 24 hours
swelling occurs 36 hours
swelling occurs Swelling occurs in 48 hours Swelling occurs in 48 hours Hardness
(ISO 15184) H F HB F F

According to the water resistance test results, in Example 1, there was no problem with the coating film even after more than 30 days, and in Comparative Examples 4-1 to 4-4, the coating film was damaged after 12 days, 14 days, 21 days, and 18 days, respectively. It was confirmed that some wrinkles and swelling occurred.

Next, according to the adhesion results, Example 4-1 and Comparative Examples 4-3 and 4-4 showed excellent adhesion results of 5B, and Comparative Examples 1 and 2 with a small resin content showed slightly poor adhesion strength. was able to confirm.

Next, according to the salt-resistant water results, in the case of Example 4-1, there was no abnormality in the coating film even after 48 hours or more, and in Comparative Examples 4-1 to 4-4, it was confirmed that swelling of the coating film occurred within 48 hours. there was.

Finally, according to the results of the hardness test of the coating film using pencil hardness, Example 4-1 showed a result value of H, and Comparative Example 4-2, which had a large resin content, showed a coating film hardness value of HB, and the remaining Comparative Example 4 In the case of -1, 4-3, and 4-4, the result value was F.

As a result, it was confirmed that when the water-based epoxy resin of the present invention was below or exceeded the appropriate range, the mechanical and chemical properties tended to decrease, and Example 1 using the Gemini emulsifier was better than Comparative Example 3 and Comparative Example 4 using a conventional emulsifier. I was able to confirm its excellence.

Therefore, as confirmed from the above results, it was confirmed that the water-based epoxy resin according to the present invention is easy to mix with the base material and the curing agent, so there is no need to dilute the water by more than 10% by weight. In addition, paints manufactured using the above resins are expected to be widely used in related industries due to their excellent workability, mechanical properties, and chemical properties.

The above description is merely an illustrative explanation of the technical idea of the present invention, and those skilled in the art will be able to make various modifications and variations without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but are for explanation, and the scope of the technical idea of the present invention is not limited by these examples. The scope of protection of the present invention should be interpreted in accordance with the scope of the patent claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of rights of the present invention.

Claims (7)

A main part consisting of 35 to 65 parts by weight of an aqueous epoxy resin, 35.5 parts by weight of a pigment consisting of a colored pigment, an extender pigment, and a rust preventive pigment, and 2.8 parts by weight of an additive; and
It consists of a hardener part consisting of a hardener resin and a solvent,
The main part and the hardener part are mixed in a ratio of 10:1,
The water-based epoxy resin is characterized in that it contains an epoxy resin and a gemini-type epoxy emulsifier represented by the following formula (1) in a weight ratio of 100: 1 to 30,
Water-based epoxy paint:
[Formula 1]

(However, in Formula 1 above,
The PRO is polyalkylene oxide,
The A is R ¹ -(EO) _n (PO) _m (EO) _r -Z,
The E is a glycidyl compound bound to nitrogen,
R ¹ is a saturated or unsaturated alkyl group having 1 to 10 carbon atoms,
The EO is ethylene oxide,
The PO is propylene oxide,
n and m are 1 to 100, r is 0 to 100, and the ratio of n and m is (n + r): m = 1 to 8: 1,
wherein Z is substituted hydrocarbyl or hydrocarbyloxy having 2 to 5 carbon atoms or is not included). According to claim 1,
A water-based epoxy paint, characterized in that the polyalkylene oxide is polypropylene oxide. According to claim 1,
A water-based epoxy paint, characterized in that the epoxy resin includes one or more of bisphenol A-type epoxy, bisphenol F-type epoxy, hydrogenated bisphenol A-type epoxy, and novolac epoxy. delete delete delete delete