WO2024186169A1 - Acrylate-based resin composition and preparation method therefor - Google Patents

Abstract

The present invention relates to an acrylate-based resin composition and a preparation method therefor and, specifically, to an acrylate-based resin composition and a preparation method therefor, the composition comprising: an acrylate-based resin; and a compound containing a polar group, wherein the composition has a viscosity of 5,000 cps or less at 60℃.

Description

Acrylate resin composition and method for producing the same

This invention claims the benefit of patent application No. 10-2023-0031193 filed with the Korean Intellectual Property Office on March 9, 2023, the entire contents of which are incorporated herein by reference.

The present invention relates to an acrylate resin composition and a method for producing the same, and more particularly, to an acrylate resin composition comprising an acrylate resin and a compound containing a polar group, and having a viscosity of 5,000 cps or less at 60°C, and a method for producing the same.

Among epoxies, bisphenol A (BPA) epoxy, which is economical and has excellent properties, accounts for more than 80% of the entire epoxy family. Bisphenol A epoxy is a general-purpose product used in all industrial fields based on its excellent mechanical and chemical properties, and is widely used as shipbuilding and heavy-duty paints, civil engineering paints, and adhesives.

Epoxy acrylate oligomer is used as an ink or coating material due to its excellent chemical resistance, heat resistance, and durability as well as the advantages of epoxy properties such as flexibility, adhesion, and hardening.

Meanwhile, isosorbide is a 100% biomass material made from corn. It is made by extracting starch from corn and then going through a process to produce glucose, sorbitol, etc.

Plastics made with isosorbide are non-toxic, biodegradable, and have excellent transparency and surface hardness, unlike plastics made from existing petrochemicals.

When manufacturing epoxy acrylate, a hydroxyl group is inevitably generated through the reaction between epoxy and acrylic acid. This hydroxyl group can react with the epoxy, and as the reaction progresses, a large oligomer is formed through the reaction between the epoxy and the hydroxyl group.

Figure 1 briefly illustrates the problem of the prior art, which is the possibility of a side reaction between an epoxy resin and a secondary alcohol. Due to the side reaction as shown in Figure 1, macromolecules are formed, resulting in a relatively high molecular weight and high viscosity. Accordingly, there was a need to develop an epoxy resin that suppresses the side reaction while having a relatively low viscosity.

The present invention provides an acrylate resin composition and a method for producing the same by minimizing the generation of side products of epoxy resin and secondary alcohol in order to solve the problems of the prior art as described above.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

One embodiment of the present invention for achieving the above-described purpose provides an acrylate resin composition comprising an acrylate resin; and a compound including a polar group; and having a viscosity of 5,000 cps or less at 60°C.

According to one embodiment of the present invention, the compound including the polar group may be a primary alcohol compound.

According to one embodiment of the present invention, the compound including the polar group may be a (meth)acrylate compound including a hydroxyl group.

According to one embodiment of the present invention, the compound including the polar group may be one selected from the group consisting of 2-hydroxy ethyl methacrylate (2-HEMA), 2-hydroxy ethyl acrylate (2-HEA), hydroxy propyl acrylate (HPA), hydroxy butyl acrylate (HBA), and combinations thereof.

According to one embodiment of the present invention, the acrylate resin may be a bisphenol-based epoxy (meth)acrylate resin.

According to one embodiment of the present invention, the acrylate resin may be a bio-derived epoxy (meth)acrylate resin.

According to one embodiment of the present invention, the composition may include a compound including the polar group in an amount of less than 1.5 wt% of the total composition.

According to one embodiment of the present invention, the acrylate resin composition may have an intensity peak area corresponding to a RT (Retention Time) of 30 to 33 minutes of a GPC (Gel Permeation Chromatography) graph of less than 5 Area% of the total intensity peak area.

According to one embodiment of the present invention, the acrylate resin may have a structure represented by the following chemical formula 1.

<Chemical Formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , and n is an integer from 0 to 50.

According to one embodiment of the present invention, when measuring the GPC (Gel Permeation Chromatography) of the acrylate resin composition, the intensity peak area corresponding to the n=0 structure of the chemical formula 1 may be 76 Area% or more of the total intensity peak area.

One embodiment of the present invention provides an acrylate-based resin composition, comprising: a first product which is a reaction product of a first compound containing an epoxy group and a second compound which is a (meth)acrylate-based compound containing a polar group; and a second product which is a reaction product of a third compound containing a polar group and the first compound, and having a viscosity of 5,000 cps or less at 60° C.

According to one embodiment of the present invention, the unreacted residual amount of the third compound may be less than 1.5 parts by weight with respect to 100 parts by weight of the acrylate-based resin composition.

According to one embodiment of the present invention, the first product may have a structure represented by the following chemical formula 1.

<Chemical Formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , and n is an integer from 0 to 50.

According to one embodiment of the present invention, the acrylate resin composition may have an area corresponding to the n=0 structure of the chemical formula 1 of 76% or more when measured by GPC (Gel Permeation Chromatography).

One embodiment of the present invention provides a method for producing an acrylate resin composition, comprising reacting a first compound containing an epoxy group; a second compound being a (meth)acrylate compound containing a polar group; and a third compound containing a polar group.

According to one embodiment of the present invention, the third compound is present in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total of the first to third compounds. It may be included in the weight.

One embodiment of the present invention provides a photocurable composition comprising the acrylate resin composition; and a polymerization initiator.

One embodiment of the present invention provides a cured film obtained by curing the photocurable composition.

An acrylate resin composition according to one embodiment of the present invention can lower viscosity by suppressing side reactions between an epoxy resin and a secondary alcohol by including a compound containing a polar group.

The method for producing an acrylate resin composition according to one embodiment of the present invention is easy to use because it requires a short preheating time and can use a relatively small amount of diluent, and can produce an acrylate resin composition that can better utilize the properties of an oligomer.

Figure 1 briefly illustrates the possibility of a side reaction between epoxy resin and secondary alcohol, which is a problem of the prior art.

Figure 2 shows GPC (Gel Permeation Chromatography) according to reference examples, examples, and comparative examples.

In this specification, when a part is said to "include" a certain component, this does not mean that other components are excluded, but rather that other components may be included, unless otherwise specifically stated.

In this specification, “A and/or B” means “A and B, or A or B.”

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention provides an acrylate resin composition comprising an acrylate resin; and a compound containing a polar group; and having a viscosity of 5,000 cps or less at 60°C.

An acrylate resin composition according to one embodiment of the present invention can lower viscosity by suppressing side reactions between an epoxy resin and a secondary alcohol by including a third compound containing a polar group.

According to one embodiment of the present invention, the compound including the polar group may be a primary alcohol compound. Specifically, the primary alcohol compound may be a molecule including a primary alcohol moiety having a small molecular weight. By selecting the compound including the polar group as a primary alcohol compound as described above, the production of large molecules generated by a side reaction with the acrylate resin can be minimized.

According to one embodiment of the present invention, the compound including the polar group may be a (meth)acrylate compound including a hydroxyl group. Specifically, the compound including the polar group may be one selected from the group consisting of 2-hydroxy ethyl methacrylate (2-HEMA), 2-hydroxy ethyl acrylate (2-HEA), hydroxy propyl acrylate (HPA), hydroxy butyl acrylate (HBA), and combinations thereof. By selecting the compound including the polar group as hydroxy alkyl acrylate as described above, it is possible to minimize defects in the coating film by participating in a subsequent ultraviolet curing reaction.

According to one embodiment of the present invention, the acrylate resin may be a bisphenol-based epoxy (meth)acrylate resin. By selecting the acrylate resin as described above, the weather resistance and durability of a coating layer formed using the acrylate resin composition can be improved.

According to one embodiment of the present invention, the acrylate resin may be a bio-derived epoxy (meth)acrylate resin. Specifically, an isosorbide-based epoxy resin may be used. By selecting the acrylate resin from the above, the eco-friendliness of the acrylate resin composition can be improved, and the generated pollutants can be minimized, thereby reducing a separate treatment process, thereby reducing the manufacturing cost.

According to one embodiment of the present invention, the composition may include a compound including a polar group in an amount of less than 1.5 wt% of the entire composition. Specifically, the residual amount of the compound including the polar group may be more than 0 part by weight and less than 1.5 parts by weight, 0.1 part by weight or more and 1.4 parts by weight or less, 0.2 part by weight or more and 1.3 parts by weight or less, 0.3 part by weight or more and 1.3 parts by weight or less, 0.4 part by weight or more and 1.3 parts by weight or less, 0.5 part by weight or more and 1.3 parts by weight or less, 0.6 part by weight or more and 1.3 parts by weight or less, 0.7 part by weight or more and 1.3 parts by weight or less, 0.8 part by weight or more and 1.3 parts by weight or less, or 0.9 part by weight or more and 1.3 parts by weight or less. By controlling the residual amount of the compound including the polar group within the above-described range, a low-viscosity and high-purity compound can be implemented.

According to one embodiment of the present invention, the acrylate resin composition may have an intensity peak area corresponding to a RT (Retention Time) of 30 to 33 minutes of a GPC (Gel Permeation Chromatography) graph of less than 5 Area% of the total intensity peak area. By controlling the intensity peak area as described above, a low-viscosity and high-purity compound can be realized.

According to one embodiment of the present invention, the acrylate resin may have a structure represented by the following chemical formula 1.

<Chemical Formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , and n is an integer from 0 to 50.

According to one embodiment of the present invention, when measuring the GPC (Gel Permeation Chromatography) of the acrylate resin composition, the intensity peak area corresponding to the n=0 structure of the chemical formula 1 may be 76 Area% or more of the total intensity peak area. By controlling the intensity peak area as described above, a low viscosity and high purity compound can be realized.

According to one embodiment of the present invention, the acrylate resin may be a first product, and the compound including a polar group may be a third compound. Specifically, one embodiment of the present invention may be an acrylate resin composition including a first product which is an acrylate resin; and a third compound which is a compound including a polar group.

According to one embodiment of the present invention, the acrylate-based resin composition may include a first product which is a reaction product of a first compound including an epoxy group and a second compound which is a (meth)acrylate-based compound including a polar group. Specifically, the first product may be produced by a main reaction in which the first compound and the second compound react. As described above, the first product which is a desired product can be obtained in an excess amount by the reaction of the first compound including an epoxy group and the second compound which is a (meth)acrylate-based compound including a polar group, and a product having excellent mechanical properties can be implemented. The first product may be an oligomer.

According to one embodiment of the present invention, a first product which is a reaction product of a first compound including an epoxy group and a second compound which is a (meth)acrylate-based compound including a polar group; a third compound including a polar group and a second product which is a reaction product of the first compound; and may have a viscosity of 5,000 cps or less at 60° C. As described above, by including a first product which is a reaction product of a first compound including an epoxy group and a second compound which is a (meth)acrylate-based compound including a polar group; and a second product which is a reaction product of a third compound including a polar group and the first compound, and having a viscosity of 5,000 cps or less at 60° C., the viscosity can be lowered by suppressing a side reaction between the epoxy resin and the secondary alcohol.

According to one embodiment of the present invention, the acrylate-based resin composition may include a third compound including a polar group and a second product which is a reaction product of the first compound. As described above, the acrylate-based resin composition may include a third compound including a polar group and a second product which is a reaction product of the first compound, thereby realizing a lower viscosity than when only the first product is produced. The second product may be an oligomer.

According to one embodiment of the present invention, the viscosity of the acrylate resin composition may be 5,000 cps or less at 60°C. Specifically, the viscosity of the acrylate resin composition at 60°C is more than 0 cps and less than 5,000 cps, more than 0 cps and less than 4,000 cps, more than 100 cps and less than 4,900 cps, more than 200 cps and less than 4,800 cps, more than 300 cps and less than 4,700 cps, more than 400 cps and less than 4,600 cps, more than 500 cps and less than 4,500 cps, more than 600 cps and less than 4,400 cps, more than 700 cps and less than 4,300 cps, more than 800 cps and less than 4,200 cps, more than 900 cps and less than 4,100 cps, more than 1,000 cps and less than 4,000 cps, more than 1,100 cps and less than 3,900 cps, and more than 1,200 cps or more but less than 3,800 cps, 1,300 cps or more but less than 3,700 cps, 1,400 cps or more but less than 3,600 cps, 1,500 cps or more but less than 3,500 cps, 1,600 cps or more but less than 3,400 cps, 1,700 cps or more but less than 3,300 cps, 1,800 cps or more but less than 3,200 cps, 1,900 cps or more but less than 3,100 cps, 2,000 cps or more but less than 3,000 cps, 2,100 cps or more but less than 2,900 cps, 2,200 cps or more but less than 2,800 cps, 2,300 cps or more but less than 2,700 cps, 2,400 cps or more but less than 2,600 cps or It can be 2,400 cps or more and 2,500 cps or less. By controlling the viscosity of the acrylate resin composition within the above-described range, the preheating time is shortened in the process of preparing the acrylate resin composition, the viscosity is low, so that less diluent can be used, making it easy to use, and the characteristics of the first product, the oligomer, can be more utilized.

According to one embodiment of the present invention, the acrylate-based resin composition includes the third compound, and the third compound may be a substance that remains during the reaction process of the second product. Specifically, the third compound prevents the secondary alcohol moiety of the first product from reacting with the epoxy group included in the first compound, so that the polar group included in the third compound may first react with the first compound to form a low-molecular-weight, low-viscosity compound. Furthermore, the third compound may react with the first compound and remain. As described above, by implementing the acrylate-based resin composition including the third compound, and the third compound being a substance that remains during the reaction process of the second product, the generation of large molecules with a high molecular weight can be prevented, and the viscosity can be implemented to be low, thereby improving the convenience of use when applying the product.

According to one embodiment of the present invention, the unreacted residual amount of the third compound may be less than 1.5 parts by weight with respect to 100 parts by weight of the acrylate-based resin composition. Specifically, the residual amount of the third compound may be more than 0 parts by weight and less than 1.5 parts by weight, 0.1 parts by weight or more and 1.4 parts by weight or less, 0.2 parts by weight or more and 1.3 parts by weight or less, 0.3 parts by weight or more and 1.3 parts by weight or less, 0.4 parts by weight or more and 1.3 parts by weight or less, 0.5 parts by weight or more and 1.3 parts by weight or less, 0.6 parts by weight or more and 1.3 parts by weight or less, 0.7 parts by weight or more and 1.3 parts by weight or less, 0.8 parts by weight or more and 1.3 parts by weight or less, or 0.9 parts by weight or more and 1.3 parts by weight or less with respect to 100 parts by weight of the acrylate-based resin composition. By controlling the residual amount of the third compound within the above-described range, foreign substances can be minimized and defects in the coating film can be prevented when the acrylate resin composition is applied to a product.

In this specification, the residual amount of the third compound may be confirmed through GPC (Gel Permeation Chromatography).

According to one embodiment of the present invention, the first product may have a structure represented by the following chemical formula 1.

<Chemical Formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , and n is an integer from 0 to 50.

According to one embodiment of the present invention, the composition may further include a third product which is a reaction product of the first compound and the first product. Specifically, the third product may be generated by a side reaction in which an epoxy group included in the first compound and a secondary alcohol moiety included in the first product react. More specifically, the third product is generated by competitively reacting each of the secondary alcohol moiety included in the first product and the primary alcohol moiety included in the third compound with the first product, and the primary alcohol moiety included in the third compound has a higher reactivity than the secondary alcohol moiety included in the first product, thereby minimizing a side reaction. Furthermore, the lower the content of the third product in the acrylate-based resin composition, the more preferable it is. As described above, by further including the third product which is a reaction product of the first compound and the first product, an appropriate viscosity of the acrylate-based resin composition can be implemented.

According to one embodiment of the present invention, the goal is to suppress the third product, which is a product of the side reaction. As described above, by suppressing the third product, which is a product of the side reaction, the acrylate resin composition obtains a relatively low molecular weight and low viscosity.

According to one embodiment of the present invention, the third product may be a reaction product of the first compound and one or more first products. Furthermore, the third product may be a reaction product of the first compound and two or more or more first products.

According to one embodiment of the present invention, the first compound containing the epoxy group may be any conventional epoxy resin having two or more epoxy groups in the molecule. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, styrene type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol S type epoxy resin, bisthioether type epoxy resin, resorcinol type epoxy resin, biphenylaralkylphenol type epoxy resin, naphthalenediol type epoxy resin, phenol novolac type epoxy resin, aromatic modified phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, bisphenol novolac type epoxy resin, binaphthol type epoxy resin, naphthol novolac type epoxy resin, β-naphtholaralkyl type epoxy resin, dinaphtholaralkyl type epoxy resin, α-naphtholaralkyl type epoxy resin, trisphenylmethane type epoxy resin, etc., trifunctional epoxy resin, tetrakisphenylethane type epoxy Polyhydric alcohol polyglycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylol ethane polyglycidyl ether, and pentaerythritol polyglycidyl ether, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, aliphatic cyclic epoxy resins such as cyclohexane dimethanol diglycidyl ether, glycidyl esters such as dimer acid polyglycidyl ester, glycidylamine type epoxy resins such as phenyl diglycidyl amine, tolyl diglycidyl amine, diaminodiphenylmethane tetraglycidyl amine, and aminophenol type epoxy resins, alicyclic epoxy resins such as cellulose 2021P (a product of Daicel Corporation), phosphorus-containing epoxy resins, and bromine-containing epoxy Resin, urethane-modified epoxy resin, and oxazolidone ring-containing epoxy resin are listed, but are not limited to these. In addition, these epoxy resins may be used alone or in combination of two or more types.

According to one embodiment of the present invention, the first compound including an epoxy group may be a bisphenol-based compound. Specifically, the bisphenol-based compound may be one selected from the group consisting of bisphenol A-based compounds, bisphenol F-based compounds, bisphenol S-based compounds, and combinations thereof. Preferably, the bisphenol-based compound may be a bisphenol A epoxy resin. By selecting the first compound including an epoxy group within the above-described range, the physical properties can be improved, and excellent chemical resistance, heat resistance, and durability can be realized as a coating material.

According to one embodiment of the present invention, the first compound including the epoxy group may be a bio-epoxy resin. Specifically, an isosorbide-based epoxy resin may be used. By selecting the first compound including the epoxy group from the above, the eco-friendliness of the acrylate-based resin composition can be improved, and the generated pollutants can be minimized, thereby reducing a separate treatment process, thereby reducing the manufacturing cost.

Among bio-epoxy resins, isosorbide-based epoxy resins are BPA-free and environmentally friendly compared to existing bisphenol A (BPA)-based epoxy resins. In addition, isosorbide-based bio-epoxy resins not only have non-yellowing characteristics, but also have excellent physical properties such as mechanical strength and thermal properties.

According to one embodiment of the present invention, the isosorbide-based epoxy resin can be manufactured by reacting diglycidyl ether isosorbide (DGEI) with epihalohydrin.

According to one embodiment of the present invention, the first product, which is a reaction product of the isosorbide-based epoxy resin and the second compound, which is a (meth)acrylate-based compound containing a polar group, may be an isosorbide-based epoxy acrylate resin.

According to one embodiment of the present invention, the polar group included in each of the second compound and the third compound may be a hydroxyl group or an amine group.

According to one embodiment of the present invention, the second compound, which is a (meth)acrylate compound including the polar group, reacts with the first compound to produce a first product.

According to one embodiment of the present invention, the second compound, which is a (meth)acrylate-based compound including the polar group, may have a higher reactivity toward the first compound than the third compound. As described above, by selecting the second compound, which is a (meth)acrylate-based compound including the polar group, to have a higher reactivity toward the first compound than the third compound, the yield of the first product can be improved.

According to one embodiment of the present invention, the second compound, which is a (meth)acrylate compound including the polar group, may include at least one of acrylic acid, methacrylic acid, cyanoacrylic acid, crotonic acid, alpha-phenylacrylic acid, methoxyacrylic acid, alpha-4-phenylphenylacrylic acid, monomethyl ester of maleic acid, monomethyl ester of fumaric acid, hydroxy ethyl acrylate (HEA), and hydroxy propyl acrylate (HPA).

According to one embodiment of the present invention, the third compound may be a primary alcohol compound. Specifically, the primary alcohol compound may be a molecule including a primary alcohol moiety having a small molecular weight. By selecting the third compound as a primary alcohol compound as described above, the production of the third product, which is a reaction product of the first product and the first compound, can be minimized. That is, the molecule including the primary alcohol moiety is less reactive than the second compound and more reactive than the secondary alcohol moiety included in the first product. Therefore, the side reaction due to the reaction of the secondary alcohol moiety can be minimized without significantly affecting the production of the main product according to the main reaction.

According to one embodiment of the present invention, the third compound may be a hydroxyl alkyl acrylate. Specifically, the third compound may be one selected from the group consisting of 2-hydroxy ethyl methacrylate (2-HEMA), 2-hydroxy ethyl acrylate (2-HEA), hydroxy propyl acrylate (HPA), hydroxy butyl acrylate (HBA), and combinations thereof. By selecting the third compound as a hydroxyl alkyl acrylate as described above, it is possible to minimize defects in the coating film by participating in a subsequent ultraviolet curing reaction.

According to one embodiment of the present invention, the acrylate resin composition may have an area corresponding to the n=0 structure of the chemical formula 1 of 76% or more when measured by GPC (Gel Permeation Chromatography). As described above, the acrylate resin composition can implement a high-purity and low-viscosity compound by controlling the area when measured by GPC (Gel Permeation Chromatography).

According to one embodiment of the present invention, the acrylate resin composition may have a peak area of 20% or less that appears at 32 minutes or more and 34 minutes or less when measuring GPC. By controlling the peak area of the acrylate resin composition within the above-described range, the viscosity of the epoxy acrylate composition can be implemented low, and the convenience of work when applying the epoxy acrylate composition to a product can be improved.

In this specification, the “GPC” measurement conditions may mean measurements made using the following conditions and equipment.

1. Device-GPC system [SHIMADZU]/RI detector (differential refractometer)

-Dissolution conditions: 1mL/Min

-Column: Shodex LF-804, KF-802.5 (30cm)

-Column temperature: 40℃

-Guard Column: KF-G4A

2. 25㎕ Syringe

3. Filter paper - PVDF syringe filter (13mm 0.45㎛. Whatman)

4. THF (Tetrahydrofuran, HPLC grade reagent, eluent)

5. Polystyrene compound

(MW = 162, 266, 377, 725, 953, 1880, 5110, 8900, 17300, 34000, 62500, 125000, 271000, 554000, 1170000, 2460000)

One embodiment of the present invention provides a method for producing an acrylate-based resin composition comprising: a first compound including an epoxy group; a second compound being a (meth)acrylate-based compound including a polar group; and a third compound including a polar group.

The method for producing an acrylate resin composition according to one embodiment of the present invention is easy to use because it requires a short preheating time and can use a relatively small amount of diluent, and can produce an acrylate resin composition that can better utilize the properties of an oligomer.

According to one embodiment of the present invention, the third compound may be reacted by mixing it with the first compound and the second compound simultaneously. As described above, by mixing the third compound with the first compound and the second compound simultaneously and reacting it, the production of the third product by side reaction can be minimized.

According to one embodiment of the present invention, the third compound may be added during the reaction between the first compound and the second compound. As described above, by adding the third compound during the reaction between the first compound and the second compound, the production of the third product due to a side reaction can be minimized.

According to one embodiment of the present invention, the third compound may be added simultaneously with or in the middle of the first compound and the second compound, but if it is added after the reaction of the first compound and the second compound is completed, the effect of lowering the viscosity may be minimal.

According to one embodiment of the present invention, the third compound is present in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total of the first to third compounds. It may be included in weight parts. Preferably, it may be included in weight parts of 1.5 to 2.5 parts, more preferably, in weight parts of 1.7 to 2.3 parts, or in weight parts of 2 parts. When the amount of the third compound added is adjusted within the above-described range, the side reaction can be suppressed to implement an appropriate viscosity.

According to one embodiment of the present invention, the third compound may be included in an amount of 0.02 equivalents or more and 0.06 equivalents or less relative to 1 equivalent of the first compound. Preferably, it may be 0.03 equivalents or more and 0.05 equivalents or less, and more preferably 0.04 equivalents. When the amount of the third compound added is adjusted within the above-described range, the side reaction can be suppressed to implement an appropriate viscosity.

According to one embodiment of the present invention, the reaction temperature may be 80° C. or more and less than 105° C. Preferably, it may be 85° C. or more and 105° C. or less, 85° C. or more and 100° C. or less, 85° C. or more and 95° C. or less, and more preferably 90° C. By controlling the reaction temperature within the above-described range, the side reaction can be suppressed to implement an appropriate viscosity, and if the temperature range is exceeded, there is a problem that the side reaction increases.

According to one embodiment of the present invention, the reaction may further include a reaction catalyst. Specifically, it may include at least one selected from the group consisting of triethylamine (TEA), trimethylamine (TMA), triethanolamine (TEOA), tetramethylammonium chloride (TMAC), tetramethylammonium bromide (TMAB), tetraethylammonium chloride (TEAC), benzyltriethylammonium chloride (BTEAC), tetraethylammonium bromide (TEAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), triphenylphosphine (TPP), sodium hydroxide (NaOH), and potassium hydroxide (KOH).

According to one embodiment of the present invention, additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, etc. can be blended as needed. Among these, as the curing accelerator, for example, a known compound known as a curing accelerator, a curing catalyst, a latent curing agent, etc. commonly applied to an epoxy resin can be used, and includes tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, etc. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether (MEHQ), pyrogallol, t-butylcatechol, phenothiazine, hindered phenol compounds, phosphorus stabilizers, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fibers, silica, mica, alumina, and the like. In addition, examples of antifoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

According to one embodiment of the present invention, the acrylate-based resin composition can be a curable resin composition since it includes a compound having an average of two or more polymerizable unsaturated groups.

In one embodiment of the present invention, the acrylate resin composition includes a photocurable composition further comprising a polymerization initiator.

According to one embodiment of the present invention, the acrylate-based resin composition may contain a photopolymerization initiator or a radical polymerization initiator as an initiator, and may contain other multifunctional acrylates, etc. The acrylate-based resin composition may contain a resin component in the composition, that is, a first product (epoxy acrylate resin and a component that becomes a resin after curing, and does not include a solvent) in an amount of 70 wt% or more and less than 100 wt%.

According to one embodiment of the present invention, various known photopolymerization initiators can be used as the photopolymerization initiator. For example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and pt-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl))biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole; Biimidazole compounds such as 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, halomethylthiazole compounds such as 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, Halomethyl-s-triazine compounds such as 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 1,2-octanedione, O-acyl oxime compounds such as 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-o-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-o-acetate, 1-(4-methylsulfanylphenyl)butane-1-one oxime-o-acetate, sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc. Examples thereof include organic peroxides such as anthraquinones, azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; and tertiary amines such as triethanolamine and triethylamine. In addition, these photopolymerization initiators may be used alone or in combination of two or more.

According to one embodiment of the present invention, one or more of the photopolymerization initiator and a known photosensitizer can be used simultaneously. Examples of the photosensitizer include Michler's ketone, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine, etc. The amount of the photosensitizer to be used is preferably more than 0 parts by weight and less than or equal to 20 parts by weight with respect to 100 parts by weight of the acrylate resin composition.

According to one embodiment of the present invention, in order to carry out thermal polymerization, it is preferable to mix a radical polymerization initiator, but in order to carry out only photocuring, mixing is not necessary. Preferred radical polymerization initiators include, for example, known peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and t-butyl peroxypivalate; and azo compounds such as 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-(methylisobutyrate), α,α-azobis-(isobutyronitrile), and 4,4'-azobis-(4-cyanovaleric acid).

According to one embodiment of the present invention, the amount of the polymerization initiator used is preferably 0.01 parts by weight or more and 100 parts by weight with respect to 100 parts by weight of the acrylate resin composition.

According to one embodiment of the present invention, the thermal polymerization initiator and the photopolymerization initiator may be used simultaneously, or only one of them may be used.

According to one embodiment of the present invention, the amount of the photopolymerization initiator used may be 0.01 parts by weight or more and 100 parts by weight or less, with respect to 100 parts by weight of the acrylate resin composition.

According to one embodiment of the present invention, the amount of the thermal polymerization initiator used is preferably 0.01 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the acrylate resin composition.

According to one embodiment of the present invention, as light irradiated for photopolymerization, for example, visible light, ultraviolet rays, ultraviolet rays, electron rays, g-rays, i-rays, X-rays, etc. can be used, and the wavelength range is preferably 250 nm or more and 450 nm or less.

The acrylate resin composition of the present invention can be used for surface coating of wood and the like.

One embodiment of the present invention includes a cured film obtained by curing the photocurable composition.

Hereinafter, the present invention will be described in detail by way of examples in order to specifically explain the present invention. However, the embodiments according to the present invention can be modified in various different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to a person having average knowledge in the art.

<Example 1>

The first compound, bisphenol A epoxy (DGEBA, Bisphenol A epoxy. Kukdo Chemical, YD-128), the second compound, acrylic acid (LG Chemical, acrylic acid), and the third compound, 2-hydroxyethyl methacrylate (Nippon Shokubai, 2-HEMA), were mixed in a weight ratio of 69.5:26.8:2 (the remaining 1.7% is the reaction catalyst BTEAC and the polymerization inhibitor MEHQ). Then, the mixture was reacted at 90°C to produce the first product, bisphenol A epoxy diacrylate, and the third product, the reaction product of the first compound and the first product, to form an epoxy acrylate composition.

<Example 2>

An epoxy acrylate composition was formed in the same manner as in Example 1, except that 2-hydroxyethyl acrylate (2-HEA) was used as the third compound in Example 1.

<Example 3>

An epoxy acrylate composition was formed in the same manner as in Example 1, except that hydroxypropyl acrylate (HPA) was used as the third compound in Example 1.

<Reference Example 1>

An epoxy acrylate composition was formed in the same manner as in Example 1, except that 2-ethylhexanol (2-EH) was used as the third compound.

<Reference Example 2>

An epoxy acrylate composition was formed in the same manner as in Example 1, except that the content of the third compound was used at 5 wt%.

<Comparative Example 1>

An epoxy acrylate composition was formed in the same manner as in Example 1, except that the third compound was not included.

<Experimental Example 1: GPC Measurement>

GPC was measured for the above examples, comparative examples, and reference examples.

1. Device-GPC system [SHIMADZU]/RI detector (differential refractometer)

-Dissolution conditions: 1mL/Min

-Column: Shodex LF-804, KF-802.5 (30cm)

-Column temperature: 40℃

-Guard Column: KF-G4A

2. 25㎕ Syringe

3. Filter paper - PVDF syringe filter (13mm 0.45㎛. Whatman)

4. THF (Tetrahydrofuran, HPLC grade reagent, eluent)

5. Polystyrene compound

(MW = 162, 266, 377, 725, 953, 1880, 5110, 8900, 17300, 34000, 62500, 125000, 271000, 554000, 1170000, 2460000)

Figure 2 shows GPC (Gel Permeation Chromatography) according to reference examples, examples, and comparative examples.

Referring to (a) of the above Figure 2, it was analyzed that Comparative Example 1, which does not include the third compound, the primary alcohol compound, has a high molecular weight as a third product, which is a macromolecular molecule, is generated by the reaction of the first compound, which is the side reaction, and the first product, and the area percentage of the main peak is less than 76%.

With reference to FIGS. 2 (b) to (e) above, the examples and reference examples included the third compound, thereby minimizing the generation of macromolecules due to the side reaction, thereby reducing the area percentage of the peak indicating a high molecular weight compared to the prior art, and it was analyzed that the area percentage of the main peak was 76% or more.

The intensity peak area corresponding to the RT (Retention Time) of 30 to 33 minutes corresponding to the macromolecule resulting from the side reaction was approximately 6 to 7 Area% in Comparative Example 1.

It can be seen that Examples 1 to 3 all show less than 5 area %, which shows that the production of macromolecules due to side reactions can be suppressed by using primary alcohol.

<Experimental Example 2: GC Measurement>

For the above examples, comparative examples, and reference examples, the content of residual third compounds (compounds containing polar groups) was measured through gas chromatography (GC).

<Measurement Conditions>

1) Equipment name: SHIMADZU GC-2010plus

2) SPL2 (Injector)

　 　i) Temperature: 220℃

　 　ii) Injection mode: Split mode

　 　iii) Injection volume: 1㎕

3) Column: BP5 (SGE / 25m x 0.22mm x 0.25㎛)

　 　i) Column Oven

Rate
(Unit: ml/min) temperature
(Unit:℃) Hold time
(Unit: minutes) 0 - 40.0 3.00 1 5.00 85.0 0.00 2 40.00 280.0 30.0

4) Detector (FID)

i) Detector temperature: 280℃

5) Gas flow

i) Makeup Gas : He

　 ii) Makeup flow: 30.0ml/min

　 iii) H2 flow: 40.0ml/min

　 iv) Air flow: 400.0ml/min

- Carrier gas: He

Comparative Example 1 Example 1 Example 2 Example 3 Reference Example 1 Reference example 2 Residual amount of compounds containing polar groups (wt%) - 1.1 1.3 0.9 1.4 2.1

As shown in Table 2 above, Reference Example 2, in which an excessive amount of a polar group-containing compound was used, was found to have a residual amount exceeding 1.5 wt%, and Examples 1 to 3 and Reference Example 1, since 2 wt% was used during synthesis, the residual amount was also measured to be less than 1.5 wt%.

Comparative Example 1, in which no polar group-containing compound was used, was not detected.

<Experimental Example 3: Measurement of viscosity and mechanical properties>

In order to measure the viscosity and mechanical properties of the above Examples, Comparative Examples, and Reference Examples as shown in Table 3 below, a photocurable composition was prepared by mixing 5 parts by weight of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide as an initiator with respect to 100 parts by weight of the compositions of the above Examples, Comparative Examples, and Reference Examples, and this was coated on a glass substrate and photocured. The measurement methods for each property are as follows.

<Coating and photocuring conditions>

1) Coating thickness: 150~250μm

2) Width: 1.5cm

3) Exposure: 1,000~2,000mJ/ ^cm2 (high pressure mercury lamp)

<Viscosity>: Measured according to ASTM D4402.

<Pencil hardness>: Measured according to ASTM D3363.

<Molecular weight>: Measured from GPC analysis of Experimental Example 1.

<Tensile strength, elongation and Young's modulus>: Measured using a universal materials testing machine from LLOYD, under the conditions of a speed of 50 mm/min and a gauge of 10 cm.

<Chemical resistance>: After soaking the coating in acetone, methyl ethyl ketone, isopropyl alcohol, and toluene, the coating was rubbed 500 times each and visually observed for damage to the coating film.

<Light resistance>: After leaving it for 500 hours under a UV tester (UV-B wavelength, Coretech Korea) at room temperature, the occurrence of damage was visually observed.

Comparative Example 1 Example 1 Example 2 Example 3 Reference Example 1 Reference example 2 Compound containing polar group - 2-HEMA 2-HEA 2-HPA 2-EH 2-HEMA Viscosity (@60℃) 5,500 3,500 4,000 3,600 3,800 3,100 Pencil hardness HB HB HB HB HB HB Molecular weight (Mw) 790 728 810 781 792 713 tensile strength 7,000~8,000 7,000~8,000 8,000~9,000 7,000~8,000 7,000~8,000 7,000~8,000 Elongation rate < 2% < 2% < 2% < 2% < 2% < 2% Young's modulus 450,000~
500,000 450,000~
500,000 500,000~
600,000 450,000~
500,000 450,000~
500,000 450,000~
500,000 Chemical resistance Pass Pass Pass Pass Minor damage occurs Minor damage occurs Light resistance Pass Pass Pass Pass Occurrence of micro cracks Occurrence of micro cracks

According to Table 3 above, Comparative Example 1, which does not include the third compound, the primary alcohol compound, was analyzed to have a high molecular weight and a viscosity of 5,000 cps or more at 60°C, as the third product, which is a macromolecular molecule, is generated by the reaction between the first compound, which is the side reaction, and the first product.

In addition, the above examples and reference examples were analyzed to have a viscosity of 5,000 cps or less at 60°C by minimizing the formation of macromolecules due to the side reaction by including the third compound.

However, in the case of the above Reference Example 1, when 2-ethylhexanol (2-EH) without an acrylate group was used as the third compound, microcracks occurred after UV curing, and in the case of Reference Example 2, where an excessive amount of primary alcohol was used, it was found that while an even lower viscosity could be exhibited if the residual amount was excessive, some physical properties were deteriorated.

Claims (18)

An acrylate resin composition comprising an acrylate resin and a compound containing a polar group, and having a viscosity of 5,000 cps or less at 60°C. In claim 1, An acrylate resin composition, wherein the compound containing the above polar group is a primary alcohol compound. In claim 1, An acrylate resin composition, wherein the compound containing the polar group is a (meth)acrylate compound containing a hydroxyl group. In claim 1, An acrylate resin composition, wherein the compound containing the polar group is one selected from the group consisting of 2-hydroxy ethyl methacrylate (2-HEMA), 2-hydroxy ethyl acrylate (2-HEA), hydroxy propyl acrylate (HPA), hydroxy butyl acrylate (HBA), and combinations thereof. In claim 1, An acrylate resin composition, wherein the above acrylate resin is a bisphenol-based epoxy (meth)acrylate resin. In claim 1, An acrylate resin composition, wherein the above acrylate resin is a bio-derived epoxy (meth)acrylate resin. In claim 1, An acrylate resin composition comprising a compound including the polar group in an amount of less than 1.5 wt% of the total composition. In claim 1, The above acrylate resin composition is an acrylate resin composition, wherein an intensity peak area corresponding to a RT (Retention Time) of 30 to 33 minutes in a GPC (Gel Permeation Chromatography) graph is less than 5 Area% of the total intensity peak area. In claim 1, An acrylate resin composition, wherein the acrylate resin has a structure represented by the following chemical formula 1. <Chemical formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , n is an integer from 0 to 50. In claim 9, An acrylate resin composition, wherein, when measuring the GPC (Gel Permeation Chromatography) of the above acrylate resin composition, the intensity peak area corresponding to the n=0 structure of the above chemical formula 1 is 76 Area% or more of the total intensity peak area. A first product which is a reaction product of a first compound containing an epoxy group and a second compound which is a (meth)acrylate compound containing a polar group; A third compound including a polar group; and a second product which is a reaction product of the first compound; An acrylate resin composition having a viscosity of 5,000 cps or less at 60°C. In claim 11, An acrylate resin composition, wherein the unreacted residual amount of the third compound is less than 1.5 parts by weight per 100 parts by weight of the acrylate resin composition. In claim 11, An acrylate resin composition, wherein the first product has a structure represented by the following chemical formula 1. <Chemical Formula 1>

In the above chemical formula 1, R is a residue derived from epoxy resin, R1 is hydrogen or CH ₃ , n is an integer from 0 to 50. In claim 13, The above acrylate resin composition is an acrylate resin composition, wherein an area corresponding to the n=0 structure of the chemical formula 1 is 76% or more when measured by GPC (Gel Permeation Chromatography). A first compound comprising an epoxy group; A second compound which is a (meth)acrylate compound containing a polar group; and A method for producing an acrylate resin composition, comprising reacting a third compound containing a polar group. In claim 15, The third compound is present in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total of the first to third compounds. A method for producing an acrylate resin composition, the composition being included by weight. An acrylate resin composition according to any one of claims 1 to 10; and A photocurable composition comprising a polymerization initiator. A cured film obtained by curing the photocurable composition of Article 17.

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