Methods for manufacturing (meth)acrylate mixtures, methods for manufacturing active energy line-curing compositions, methods for manufacturing active energy line-curing compositions for inks, and methods for manufacturing active energy line-curing compositions for coating agents.

Abstract

This invention provides a manufacturing method in which a desired (meth)acrylate mixture can be obtained from raw materials derived from renewable resources in extremely high yield, with a significant reduction in environmental impact, excellent curability of the obtained mixture, and excellent various physical properties of the cured mixture. A method for manufacturing a (meth)acrylate mixture comprises performing the following steps 1 to 3 sequentially. Step 1: Reacting (meth)acrylic acid with an alcohol having three or more hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution with a specific hydroxyl valence. • Step 2: Perform step 2-1 or step 2-2 below to obtain a product with a specific hydroxyl valence. Step 2-1: Add dicarboxylic acid, diol and (meth)acrylic acid to the reaction solution of Step 1 to obtain the product. Step 2-2: Add dicarboxylic acid and hydroxyalkyl methacrylate to the reaction solution of Step 1 to obtain the product. • Step 3: Neutralization of the reaction solution from Step 2 using an aqueous solution of ammonia and / or an amine compound.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a mixture of (meth)acrylates, a method for manufacturing a mixture of (meth)acrylates derived from renewable resources, and a method for manufacturing a composition comprising the mixture of (meth)acrylates obtained thereby. [Previous Technology]

[0002] Active energy line curing compositions can be cured by irradiation with active energy lines such as ultraviolet light, visible light, and electron beams for a very short time. They are highly productive and widely used in inks, coatings, and photoresist materials. As a component of active energy line curing compositions, (meth)acrylates are used, and polyester (meth)acrylates are known to be among them.

[0003] However, the raw materials used in the manufacture of compounds such as (meth)acrylates are mostly derived from fossil fuels such as petroleum or coal, contributing to environmental pollution. Furthermore, in the manufacture of (meth)acrylates, the final product is obtained through a neutralization-washing step in the purification process of the reaction products. However, this neutralization-washing step generates wastewater, which is mostly treated by incineration, also contributing to environmental pollution. Therefore, there is a need to discover a manufacturing method that uses raw materials derived from renewable resources with low environmental impact to manufacture (meth)acrylates, thereby reducing the amount of wastewater generated after the esterification reaction.

[0004] Against this background, the manufacture of compounds using compounds derived from renewable resources has been studied in recent years, as have polyesters and acrylates. For example, Patent Document 1 discloses a polyester polyol manufactured from (a) recycled and digested polyester, (b) glycol, and (c) lignin or tannin. In Patent Document 1, a raw material for coatings is prepared by urethane esterification of the obtained polyester polyol. However, when manufacturing (meth)acrylates using the polyester polyol obtained in this step, the manufacturing process of the polyester polyol requires complex steps, and there are concerns about high costs. Patent Document 2 describes a radiation-curing coating agent for flooring materials containing compounds derived from renewable resources, such as polyacrylates. However, Patent Document 2 does not describe a refining step for removing catalysts from the product, raising concerns about problems caused by catalysts remaining in the product. Furthermore, since sebacic acid, a vegetable oil derived from renewable resources, is used as the main component, the hardness of the cured product is insufficient for use as a coating agent or similar application. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-508611 [Patent Document 2] Japanese Patent Publication No. 2011-519396 [Summary of the Invention]

[0006] [The problem the invention aims to solve]

[0007] The inventors have conducted extensive research to discover a manufacturing method in which a desired (meth)acrylate mixture can be obtained in high yield using a compound derived from renewable resources as a raw material. The obtained (meth)acrylate mixture is also derived from a compound from renewable resources, resulting in a significant reduction in environmental impact. Furthermore, the obtained (meth)acrylate mixture exhibits excellent curability, and the cured product of the mixture possesses excellent physical properties such as hardness, adhesion, and low curling. [Means for Solving the Problem]

[0008] The inventors have conducted diligent research to solve the aforementioned problem, and as a result, discovered that a method for manufacturing (meth)acrylate mixtures can use raw materials derived from renewable resources, and can convert all reaction raw materials into finished products without discarding (meth)acrylates dissolved in the aqueous phase. This invention was thus completed. The method for manufacturing (meth)acrylate mixtures includes: a step of performing a dehydration esterification reaction of (meth)acrylic acid with an alcohol having three or more hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylates with a specific hydroxyl valence; a step of adding the obtained reaction solution with dicarboxylic acid, diol, and (meth)acrylic acid to obtain a (meth)acrylate mixture with a specific hydroxyl valence; and a step of neutralizing the mixture using a specific method. The invention will now be described in detail. [Effects of the Invention]

[0009] By means of the manufacturing method of the present invention, compounds derived from renewable resources can be used as raw materials to obtain the desired (meth)acrylate mixture in high yield, which can greatly help reduce the environmental impact. The organic phase obtained by the manufacturing method of the present invention and the (meth)acrylate mixture contained in the wastewater after the neutralization and purification step both become raw materials for curable components, exhibiting rapid curing properties, high hardness, excellent adhesion to plastic substrates, and low curling, thus making them suitable for use as inks, coating agents, and photoresist materials. Furthermore, the wastewater after the neutralization and purification step, which is usually treated as wastewater, also becomes a raw material for curable components, thus eliminating the need for wastewater disposal and reducing the environmental impact.

Implementation Method

[0011] This invention relates to a method for manufacturing a mixture of (meth)acrylates, comprising the following steps 1 to 3 in sequence. • Step 1: A dehydration esterification reaction is carried out between (meth)acrylate and (A) an alcohol having three or more hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylates with a hydroxyl valence of 55 mgKOH / g to 175 mgKOH / g. • Step 2: Step 2-1 or Step 2-2 is carried out to obtain a product with a hydroxyl valence of less than 55 mgKOH / g. Step 2-1: (B) dicarboxylic acid, (C) diol, and (meth)acrylate are added to the reaction solution containing hydroxyl-containing (meth)acrylates obtained in Step 1 to obtain a product. Step 2-2: (B) dicarboxylic acid and (D) hydroxyalkyl methacrylate are added to the reaction solution containing hydroxyl-containing (meth)acrylates obtained in Step 1 to obtain a product. • Step 3: Neutralizing the reaction solution obtained in Step 2 using one or more neutralizing agents selected from aqueous solutions of ammonia and aqueous solutions of amine compounds.

[0012] Preferably, in step 2-1, (C) diol is used at a ratio of 1 to 50 moles relative to the total 1 mole of (B) dicarboxylic acid. Preferably, step 2-2 is performed as step 2. Furthermore, it is preferable that at least one of the following compounds—(A) an alcohol having three or more hydroxyl groups, (B) dicarboxylic acid, (C) diol, and (D) (meth)acrylate hydroxyalkyl ester—contains a compound derived from renewable resources.

[0013] The present invention also relates to a method for manufacturing a curable composition, which involves stirring and mixing a (meth)acrylate mixture obtained by sequentially performing steps 1 to 3 with (E) an ethylene unsaturated compound other than the (meth)acrylate mixture [hereinafter referred to as "(E) component"].

[0014] In the method for manufacturing the cured composition, it is preferable that in step 2-1, (C) diol is used at a ratio of 1 to 50 moles relative to 1 mole of the total (B) dicarboxylic acid. Furthermore, it is preferable that step 2-2 is performed as step 2. Additionally, it is preferable that at least one of the following compounds—(A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) diol, and (D) a hydroxyalkyl methacrylate—contains a compound derived from renewable resources. Alternatively, a preferred manufacturing method is to stir and mix the (meth)acrylate mixture obtained by sequentially performing steps 1 to 3, and the components comprising (E-1) a compound having one (meth)acrylic group (hereinafter referred to as "(E-1) component") and (E-2) a compound having two or more (meth)acrylic groups (hereinafter referred to as "(E-2) component") as component (E), in a ratio of 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of component (E-1), and 0 to 40 parts by weight of component (E-2). Furthermore, a preferred manufacturing method is to use the (meth)acrylate mixture obtained in the organic phase and / or the neutralized aqueous phase obtained in step 3 as a formulation component of the cured composition after sequentially performing steps 1 to 3.

[0015] In addition, the present invention also relates to a method for manufacturing an active energy line hardening composition, which is a method of stirring and mixing the (meth)acrylate mixture, (E) component, and (F-1) photopolymerization initiator obtained by sequentially performing steps 1 to 3. In the method for manufacturing the active energy line hardening composition, 0.01 to 20 parts by weight of (F-1) photopolymerization initiator are used relative to 100 parts by weight of the total (meth)acrylate mixture and (E) component.

[0016] In the method for manufacturing the active energy line hardening type composition, it is preferable that in step 2-1, (C) diol is used at a ratio of 1 mole to 50 moles relative to the total 1 mole of (B) dicarboxylic acid. Furthermore, it is preferable that step 2-2 is performed as step 2. Furthermore, it is preferable that at least one of the following compounds—(A) an alcohol having three or more hydroxyl groups, (B) dicarboxylic acid, (C) diol, and (D) (meth)acrylate hydroxyalkyl ester—contains a compound derived from renewable resources. Furthermore, it is preferable that the manufacturing method involves stirring and mixing the (meth)acrylate mixture obtained by sequentially performing steps 1 to 3, and the component comprising (E-1) and (E-2) as component (E), at a ratio comprising 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of component (E-1), and 0 to 40 parts by weight of component (E-2). Furthermore, a preferred manufacturing method is one in which, after sequentially performing steps 1 to 3, the (meth)acrylate mixture obtained in step 3 and / or the neutralized aqueous phase is used as a formulation component of the curing composition. Additionally, the preferred manufacturing method is a method for manufacturing an active energy line curing composition for inks or an active energy line curing composition for coating agents. The present invention will now be described in detail.

[0017] 1. Method for manufacturing (meth)acrylate mixture In this invention, the (meth)acrylate mixture obtained by sequentially performing steps 1 to 3 described below is also simply referred to as "(meth)acrylate mixture".

[0018] 1-1. Step 1 Step 1 is the following step: (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups (hereinafter referred to as "compound (A)") are subjected to a dehydration esterification reaction in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylic acid ester with a hydroxyl valence of 55 mgKOH / g to 175 mgKOH / g.

[0019] 1-1-1. Compound (A) Compound (A) is an alcohol having three or more hydroxyl groups, and various compounds may be used. Specific examples of compound (A) include: trivalent or higher polyols such as glycerol, diglycerol, trimethylolpropane, trimethylolethane, pentaerythritol, di-trimethylolpropane, and dipentaerythritol, alkylene oxide adducts of these trivalent or higher polyols, and tris(2-hydroxyethyl)isocyanurate, etc. As compound (A), it is preferred to be a compound derived from renewable resources. Specific examples of this compound include: glycerol, diglycerol, alkylene oxide adducts of glycerol, and alkylene oxide adducts of diglycerol, more preferably alkylene oxide adducts of diglycerol. Furthermore, as examples of the alkylene oxide adducts mentioned above, ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts, etc. Furthermore, in this invention, the term "compound derived from renewable resources" refers to a compound having a renewable resource structure. More specifically, it refers to raw materials derived from biological sources (biomass) and compounds manufactured from raw materials derived from biological sources. Preferably, compounds derived from renewable resources are raw materials derived from plants and compounds manufactured from raw materials derived from plants.

[0020] 1-1-2. Dehydration esterification reaction As a dehydration esterification reaction, it can be carried out by conventional methods, such as heating and stirring (meth)acrylic acid and compound (A) in the presence of an acid catalyst.

[0021] The proportion of (meth)acrylic acid used is preferably 0.05 mol to 20 mol, more preferably 0.05 mol to 5 mol, relative to 1 mol of all hydroxyl groups in compound (A), to form the target (meth)acrylate. The proportion of (meth)acrylic acid used is preferably 0.625 mol to 0.875 mol, more preferably 0.7 mol to 0.8 mol, relative to 1 mol of compound (A).

[0022] Examples of acid catalysts include: inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and fluorinated boric acid; organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and strong acidic cationic ion exchange resins. The preferred ratio of the acid catalyst used is 0.05 mol% to 20 mol% relative to 1 mol of the total number of hydroxyl groups in compound (A).

[0023] The dehydration esterification reaction can be carried out using conventional methods. The reaction temperature can be set appropriately according to the raw materials used and the purpose, but from the viewpoint of preventing shortened polymerization due to reduced reaction time, 65°C to 140°C is preferred, and 75°C to 120°C is even more preferred. By setting the reaction temperature above 65°C, the esterification reaction can be carried out rapidly, and the decrease in yield can be suppressed. On the other hand, by setting the reaction temperature below 140°C, the thermal polymerization of (meth)acrylic acid or the generated (meth)acrylate can be suppressed.

[0024] During the dehydration esterification reaction, it is preferable to promote dehydration by azeotropically mixing the water generated in the dehydration esterification reaction with an organic solvent that has low solubility in water. Preferred organic solvents include, for example, aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; chlorinated hydrocarbons such as trichloroethylene and tetrachloroethylene; and ketones such as methyl ethyl ketone. The amount of organic solvent used is preferably 30% to 60% by weight in the reaction solution, more preferably 40% to 50% by weight.

[0025] In the dehydration esterification reaction, for the purpose of preventing the polymerization of (meth)acrylic acid, it is preferable to use a polymerization inhibitor, and an oxygen-containing gas may be introduced into the reaction solution. Examples of polymerization inhibitors include: organic polymerization inhibitors such as hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, phenanthrene, and N-oxygen compounds; inorganic polymerization inhibitors such as copper chloride and copper sulfate; and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate. The polymerization inhibitor may be used alone or in combination of two or more. The proportion of the polymerization inhibitor in the reaction solution is preferably 5 wtppm to 20,000 wtppm, more preferably 25 wtppm to 3,000 wtppm. Examples of oxygen-containing gases include air, a mixture of oxygen and nitrogen, and a mixture of oxygen and helium.

[0026] In step 1, a reaction solution with a hydroxyl value of 55 mgKOH / g to 175 mgKOH / g is obtained, preferably a reaction solution with a hydroxyl value of 105 mgKOH / g to 115 mgKOH / g. The reaction is then stopped to achieve this hydroxyl value. If the hydroxyl value of the reaction solution exceeds 175 mgKOH / g, a cross-linking (meth)acrylate will be generated in step 2, which may lead to gelation or make stirring difficult. On the other hand, if the hydroxyl value of the reaction solution is less than 55 mgKOH / g, the proportion of the target (meth)acrylate contained in the final product will be significantly reduced. Furthermore, in this invention, the hydroxyl value refers to the value obtained by measurement according to Japanese Industrial Standards (JIS) K 0070.

[0027] 1-2. Step 2 Step 2 is the following step: Performing Step 2-1 or Step 2-2 below to obtain a product with a hydroxyl valence of less than 55 mgKOH / g. Step 2-1: Adding (B) dicarboxylic acid (hereinafter referred to as "Compound (B)"), (C) diol (hereinafter referred to as "Compound (C)"), and (meth)acrylic acid to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in Step 1 to obtain a product. Step 2-2: Adding Compound (B) and (D) hydroxyalkyl methacrylate (hereinafter referred to as "Compound (D)") to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in Step 1 to obtain a product.

[0028] 1-2-1. Step 2-1 In step 2-1, compound (B), compound (C), and (meth)acrylic acid are added to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in step 1 to carry out a dehydration esterification reaction. Hereinafter, compound (B), compound (C), and the reaction method will be described.

[0029] 1-2-1-1. Compound (B) Compound (B) is a dicarboxylic acid, and various compounds may be used. Specific examples of compound (B) include: aliphatic dicarboxylic acids such as itaconic acid, succinic acid, fumaric acid, and adipic acid; aromatic dicarboxylic acids such as terephthalic acid; and dicarboxylic acids with heterocyclic skeletons such as 2,5-furan dicarboxylic acid. Compound (B) is preferably a compound derived from renewable resources. Specific examples of this compound include: itaconic acid, succinic acid, fumaric acid, adipic acid, and 2,5-furan dicarboxylic acid, and itaconic acid is more preferred.

[0030] The proportion of compound (B) used is preferably 0.8 to 50 times the total number of hydroxyl groups in the reaction solution obtained in step 1, and more preferably 0.9 to 1.1 times the total number of hydroxyl groups in 1 mol. If the proportion of compound (B) used is less than 0.8 times the total number of mol, the proportion of (meth)acrylates with polyester units in the (meth)acrylate mixture decreases, the proportion of highly hydrophilic components increases, and these components dissolve in water during the water washing step of the reaction solution, resulting in raw material loss. If the proportion of compound (B) used is greater than 50 times the total number of mol, the acrylate equivalent in the (meth)acrylate mixture decreases, which may sometimes lead to a decrease in the hardness of the hardened composition obtained.

[0031] 1-2-1-2. Compound (C) Compound (C) is a diol, and various compounds may be used. Specific examples of compound (C) include: aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol; diols of cyclic ethers such as 2,5-tetrahydrofurandiethanol; and diols having a heterocyclic skeleton such as 2,5-furandiethanol. Compound (C) is preferably a compound derived from renewable resources. Specific examples of this compound include: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,5-tetrahydrofurandiethanol, and 2,5-furandiethanol.

[0032] The proportion of compound (C) used relative to 1 mole of compound (B) is preferably 1 to 50 moles, more preferably 1.3 to 1.5 moles. If the proportion of compound (C) used is less than 1 mole, the proportion of the target polyester diol decreases, or the proportion of dicarboxylic acid monoester generated as a byproduct increases, and the dicarboxylic acid monoester dissolves in water during the water washing step of the reaction solution, thus sometimes becoming a cause of raw material loss. If the proportion of compound (C) used is greater than 50 moles, the proportion of the target (meth)acrylate decreases, resulting in a decrease in the acrylate equivalent of the reaction product, sometimes leading to a decrease in the hardness of the hardened composition.

[0033] 1-2-1-3. The proportion of (meth)acrylic acid added in step 2-1 as a reaction in step 2-1 is preferably 1.0 to 1.2 times moles relative to compound (C) 1 mole.

[0034] The hydroxyl value of the product from stopping step 2-1 is set to be below 55 mgKOH / g, preferably below 35 mgKOH / g. If the hydroxyl value of the product exceeds 55 mgKOH / g, a large amount of hydrophilic components will remain, and the yield of the target (meth)acrylate will be low.

[0035] In step 2-1, the acid and alcohol dehydration esterification reaction is carried out using the acid catalyst contained in the reaction product of step 1, and various compounds are used for the reaction. The reaction temperature in step 2-1 is preferably 75°C to 110°C, and more preferably 85°C to 100°C.

[0036] Specifically, the dehydration esterification reaction of acid and alcohol in step 2-1 is carried out, including the dehydration esterification reaction of (meth)acrylic acid and alcohol, and the dehydration esterification reaction of compound (B) and compound (C). Examples of the main reactions are listed in (2-1-1) to (2-1-6) below. (2-1-1) By reacting the hydroxyl-containing (meth)acrylate (hereinafter referred to as "hydroxyl-containing (meth)acrylate (1)") obtained in step 1 with (meth)acrylic acid, a (meth)acrylate without hydroxyl groups and a (meth)acrylate containing hydroxyl groups (hereinafter referred to as "hydroxyl-containing (meth)acrylate (2)") are generated. (2-1-2) Polyester diol (hereinafter referred to as polyester diol (2)) is generated by the reaction of compound (B) with compound (C), and polyester (meth)acrylate is generated by the reaction of polyester diol (2) with (meth)acrylic acid. (2-1-3) (meth)acrylate is generated by the reaction of hydroxyl-containing (meth)acrylate (1) or hydroxyl-containing (meth)acrylate (2) with compound (B). (2-1-4) (meth)acrylate is generated by the reaction of polyester diol (2) with compound (B). (2-1-5) (meth)acrylate is generated by the reaction of hydroxyl-containing (meth)acrylate (1), hydroxyl-containing (meth)acrylate (2), and / or polyester diol (2) with compound (B). (2-1-6) (meth)acrylate is generated by the reaction of compound (C) with (meth)acrylic acid.

[0037] In addition, if at least one of compound (A), compound (B) and compound (C) is a compound derived from a renewable resource, the resulting (meth)acrylate mixture is equivalent to a compound derived from a renewable resource.

[0038] 1-2-2. Step 2-2 In step 2-2, compound (B) and compound (D) are added to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in step 1 to carry out a dehydration esterification reaction. Hereinafter, compound (B), compound (D) and the reaction method will be described.

[0039] 1-2-2-1. Compound (B) Compound (B) is a dicarboxylic acid, and various compounds may be used. As specific examples, compounds identical to those described above may be listed. As compound (B), it is preferably a compound derived from renewable resources. As specific examples, compounds identical to those described above may be listed.

[0040] The proportion of compound (B) used is preferably 0.8 to 50 times the total number of hydroxyl groups in the reaction solution obtained in step 1, more preferably 0.9 to 1.1 times the total number of hydroxyl groups in 1 mol. If the proportion of compound (B) used is less than 0.8 times the total number of mol, the proportion of (meth)acrylates with polyester units in the (meth)acrylate mixture decreases, the proportion of highly hydrophilic components increases, and these components dissolve in water during the water washing step of the reaction solution, resulting in raw material loss. If the proportion of compound (B) used is greater than 50 times the total number of mol, the acrylate equivalent in the (meth)acrylate mixture decreases, which may sometimes lead to a decrease in the hardness of the hardened composition obtained.

[0041] 1-2-2-2. Compound (D) Compound (D) is a hydroxyalkyl methacrylate, and various compounds may be used. Specific examples of compound (D) include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, etc. Compound (D) is preferably a compound derived from renewable resources. Specific examples of this compound include: hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, etc., and more preferably hydroxybutyl methacrylate.

[0042] The proportion of compound (D) used relative to the total moles of the remaining (meth)acrylic acid and compound (B) in step 1 is preferably 1.0 to 2.0, more preferably 1.0 to 1.5. If the proportion of compound (D) used is less than 1.0, a large amount of dicarboxylic acid monoester is generated, resulting in deterioration of curability. If the proportion of compound (D) used is greater than 2.0, a large amount of di(meth)acrylate is generated, resulting in deterioration of curability.

[0043] 1-2-2-3. The hydroxyl value of the product in step 2-2 is set to be below 55 mgKOH / g, preferably below 35 mgKOH / g, as a stop factor for the reaction in step 2-2. If the hydroxyl value of the product exceeds 55 mgKOH / g, a large amount of hydrophilic components will remain, and the yield of the target (meth)acrylate will be lower.

[0044] In step 2-2, an acid-alcohol dehydration esterification reaction is carried out using the acid catalyst contained in the reaction product of step 1, and various compounds are used for the reaction. The reaction temperature in step 2-2 is preferably 75°C to 110°C, and more preferably 85°C to 100°C.

[0045] In the dehydration esterification reaction of acid and alcohol in step 2-2, the following (2-2-1) is carried out as a side reaction, and the following (2-2-2) is carried out. (2-2-1) A (meth)acrylate is generated by the reaction of hydroxyl-containing (meth)acrylate (1), compound (B) and compound (D). (2-2-2) A carboxyl-containing (meth)acrylate is generated by the reaction of hydroxyl-containing (meth)acrylate (1) and compound (B).

[0046] In addition, if at least one of compound (A), compound (B) and compound (D) is a compound derived from a renewable resource, the resulting (meth)acrylate mixture is equivalent to a compound derived from a renewable resource.

[0047] In this invention, when step 2-2 is performed as step 2, the obtained (meth)acrylate mixture has excellent curability, and the obtained cured material has excellent physical properties such as hardness, adhesion, and low curling, which is therefore preferred.

[0048] 1-3. Step 3 Step 3 is as follows: In the reaction solution obtained in step 2, the acidic components in the reaction solution are neutralized by one or more neutralizing agents selected from aqueous solutions of ammonia and aqueous solutions of amine compounds.

[0049] The reaction solution obtained in step 2 contains not only the (meth)acrylate mixture as a product, but also unreacted (meth)acrylic acid and acidic components such as acid catalysts. The neutralization treatment in step 3 is performed to remove unreacted (meth)acrylic acid and acid catalysts from the reaction solution. The neutralization treatment is carried out by contacting the reaction solution with a neutralizing agent, which is an alkaline aqueous solution. Specifically, it can be performed using conventional methods, such as adding a neutralizing agent to the reaction solution and stirring and mixing. Examples of amine compounds used as neutralizing agents include ethylamine, ethylenediamine, diethylamine, pyrrolidine, piperidine, triethylamine, and pyridine. In this invention, an aqueous solution of ammonia and / or an aqueous solution of an amine compound are used as neutralizing agents. In this invention, alkali metal salts such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkaline earth metal salts such as calcium hydroxide are not used as neutralizing agents, thus forming a so-called metal-free product that does not contain metal compounds in the final product or wastewater.

[0050] In step 3, it is preferable to use an aqueous solution of ammonia and an aqueous solution of an ammonium salt, or an aqueous solution of an amine compound and an aqueous solution of an ammonium salt. Here, ammonium sulfate and the like can be listed as examples of ammonium salts.

[0051] The concentration of the aqueous solution of ammonia and the aqueous solution of the amine compound can be set appropriately according to the purpose, preferably 1% to 50% by weight, more preferably 10% to 20% by weight. The proportion of the neutralizing agent used is preferably adjusted to 1 to 1.5 times the acid value of the organic phase and preferably the acid value of the organic phase after pre-washing.

[0052] When performing step 3 as a neutralization step, it is preferable to add an organic solvent to the reaction solution obtained in step 2 for dilution or to perform pre-washing before performing step 3.

[0053] The organic solvent used for dilution is preferably the same compound as the organic solvent used in steps 1 and 2. The dilution ratio of the organic solvent is preferably adjusted so that the total concentration of the diluted organic solvent and organic solvent is 50% to 70% by weight.

[0054] Distilled water and purified water are preferred as the washing agent used in the pre-washing process. The washing process may be performed only once or multiple times.

[0055] As a washing agent, to impart a specific gravity difference, an aqueous solution of ammonium salt or sodium salt may be used as needed. Specifically, examples include ammonium sulfate, sodium ammonium sulfate, and sodium chloride, etc. For the purpose of being metal-free, ammonium sulfate is preferred. The washing treatment may be performed once or multiple times, depending on the purpose.

[0056] The neutralized liquid is separated into two layers: an organic phase and an aqueous phase. Since the specific gravity of the organic phase is lower than that of the aqueous phase, it is separated into an organic phase on top and an aqueous phase on the bottom. The aqueous phase is extracted and separated from the organic phase. The method of using the separated organic phase can be selected according to the appropriate content of the organic phase. Examples of methods for using the separated organic phase include using it directly as a raw material for a curable composition, or using it as a raw material for a curable composition after removing the organic solvent by distillation. The method of using the extracted aqueous phase can be selected according to the appropriate content of the aqueous phase. Examples of methods for using the extracted aqueous phase include: using it directly as a raw material for a curable composition, using it as a raw material for a curable composition after removing water by distillation, or disposing of it as waste.

[0057] 1-4. Method of using (meth)acrylate mixtures The (meth)acrylate mixtures obtained by the manufacturing method of the present invention can also be used in the organic phase (meth)acrylate mixtures obtained in the neutralization step of step 3, or in the aqueous phase (meth)acrylate mixtures.

[0058] Examples of (meth)acrylate mixtures contained in the organic phase after step 2-1 and step 3 include (O-1-1) to (O-1-5). (O-1-1) The hydroxyl-free (meth)acrylate obtained in step 1, the hydroxyl-free (meth)acrylate obtained in step 2, (O-1-2) the hydroxyl-free polyester di(meth)acrylate obtained by reacting polyester diol (2) with (meth)acrylic acid, (O-1-3) the hydroxyl-free (meth)acrylate obtained by reacting hydroxyl-containing (meth)acrylate (1) and / or hydroxyl-containing (meth)acrylate (2) with compound (B), (O-1-4) the hydroxyl-free (meth)acrylate obtained by reacting hydroxyl-containing (meth)acrylate (1), hydroxyl-containing (meth)acrylate (2), and / or polyester diol (2) with compound (B), (O-1-5) the hydroxyl-free di(meth)acrylate obtained by reacting compound (C) with (meth)acrylic acid.

[0059] The (meth)acrylate mixture contained in the aqueous phase after step 2-1 and step 3 is a compound having hydroxyl and (meth)acrylic groups, or a compound having carboxyl and (meth)acrylic groups, etc. Examples of such compounds include (W-1-1) to (W-1-5). Furthermore, compounds having carboxyl and (meth)acrylic groups exist in the aqueous phase as ammonium salts or salts of amine compounds. (W-1-1) Hydroxyl-containing (meth)acrylate (1), hydroxyl-containing (meth)acrylate (2) (W-1-2) Hydroxyl-containing polyester mono(meth)acrylate obtained by reaction of polyester diol (2) with (meth)acrylate (W-1-3) Hydroxyl-containing mono(meth)acrylate obtained by reaction of compound (B) with (meth)acrylate (W-1-4) Carboxyl-containing mono(meth)acrylate obtained by reaction of hydroxyl-containing (meth)acrylate (1) or hydroxyl-containing (meth)acrylate (2) with compound (B) (W-1-5) Unreacted (meth)acrylate

[0060] Examples of (meth)acrylate mixtures contained in the organic phase after step 2-2 and step 3 include (O-2-1) and (O-2-2). (O-2-1) The (meth)acrylate without hydroxyl groups obtained in step 1. (O-2-2) The (meth)acrylate obtained by reacting a (meth)acrylate containing hydroxyl groups (1), compound (B), and compound (D).

[0061] The (meth)acrylate mixture contained in the aqueous phase after step 2-2 and step 3 is a compound having hydroxyl and (meth)acrylic groups, and a compound having carboxyl and (meth)acrylic groups, etc. Examples of such compounds include (W-2-1) to (W-2-4). Furthermore, compounds having carboxyl and (meth)acrylic groups exist in the aqueous phase as ammonium salts or salts of amine compounds. (W-2-1) Hydroxyl-containing (meth)acrylate (1) (W-2-2) Carboxyl-containing (meth)acrylate obtained by reacting hydroxyl-containing (meth)acrylate (1) with compound (B) (W-2-3) Carboxyl-containing mono(meth)acrylate obtained by reacting compound (B) with compound (C) (W-2-4) Unreacted (meth)acrylate

[0062] In this case, the organic phase or aqueous phase containing the (meth)acrylate mixture can be used directly, or the (meth)acrylate mixture after removing the organic phase or aqueous phase from the organic solvent or water can be used.

[0063] 2. Curing Composition The (meth)acrylate mixture obtained by the manufacturing method of the present invention can be used in various applications where (meth)acrylates have been previously used. For example, it can be used as a main component, crosslinking component, or reactive diluent component in coatings, inks, adhesives, resists, fillers, and molding materials, and is preferably used in various industrial applications. As a molding material, it can also be processed into the shape of films and sheets, and as films and sheets, it can be used for optical applications such as optical lenses. The (meth)acrylate mixture obtained by the manufacturing method of the present invention is preferably used as a component of a curing composition, and is more preferably used as a coating agent and ink.

[0064] The (meth)acrylate mixture obtained by the manufacturing method of the present invention can also be used as a component of the organic phase obtained in the neutralization step of step 3, or as a component of the aqueous phase. In this case, the organic phase or aqueous phase containing the (meth)acrylate mixture can also be used directly, or the (meth)acrylate mixture after evaporating the organic solvent or water from the organic phase or aqueous phase can also be used.

[0065] When an organic phase containing a mixture of (meth)acrylates is used directly, it becomes a component of an organic solvent system; when an aqueous phase containing a mixture of (meth)acrylates is used directly, it becomes a component of an aqueous system.

[0066] When using the (meth)acrylate mixture obtained by the manufacturing method of the present invention as a component of a curing composition, various components used in the curing composition can be formulated. As specific examples, examples include vinyl unsaturated compounds (hereinafter referred to as "(E) component") other than the (meth)acrylate mixture obtained by the manufacturing method of the present invention, and polymerization initiators (hereinafter referred to as "(F) component"), etc.

[0067] 2-1. (E) Component As (E) component, examples include compounds having one (meth)acrylic group (hereinafter referred to as "(E-1) component") and compounds having two or more (meth)acrylic groups (hereinafter referred to as "(E-2) component").

[0068] 2-1-1. (E-1) Ingredient (E-1) Ingredient (E-1) is a compound having one (meth)acrylic group in one molecule. Specific examples of (E-1) ingredient include (meth)acrylates having one (meth)acrylic group (hereinafter referred to as "monofunctional (meth)acrylates") and (meth)acrylamine compounds having one (meth)acrylic group (hereinafter referred to as "monofunctional (meth)acrylamines").

[0069] Specific examples of monofunctional (meth)acrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate, stearyl methacrylate, and other alkyl methacrylates; cyclohexyl methacrylate, menthyl methacrylate, isobornyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and other monofunctional (meth)acrylates having alicyclic groups; Monofunctional (meth)acrylates with cyclic ether groups, including glycidyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate (2-methyl-2-ethyl-1,3-dioxacyclopentan-4-yl), cyclohexanespiro-2-(1,3-dioxacyclopentan-4-yl), and methyl methacrylate (3-ethyl-3-oxetanebutyl methacrylate); aromatic monofunctional (meth)acrylates such as benzyl acrylate, phenoxyethyl acrylate, o-phenylphenoxy acrylate, and p-cumylphenol ethyl acrylate; monofunctional (meth)acrylates with maleimide groups, such as methacryloxyethyl hexahydrophthalimide; and methacrylylmorpholine. Monofunctional (meth)acrylates containing alkoxyalkyl groups, such as ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, and alkyl carbitol (meth)acrylate; and monofunctional (meth)acrylates containing alkoxy groups, such as oxypropyl methyldimethoxysilane, oxypropyl trimethoxysilane, oxypropyl methylethoxysilane, and oxypropyl triethoxysilane.

[0070] Specific examples of monofunctional (meth)acrylamide compounds include: N-methyl (meth)acrylamide, N-n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-dibutyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-n-hexyl (meth)acrylamide, and other N-alkyl (meth)acrylamides; N-hydroxyethyl (meth)acrylamide, and other N-hydroxyalkyl ( Methyl (meth)acrylamide; and N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-di-n-propyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di-n-butyl (meth)acrylamide and N,N-dihexyl (meth)acrylamide, etc., and N,N-dialkyl (meth)acrylamide, etc.

[0071] As component (E-1), it is preferably a compound derived from renewable resources and manufactured from raw materials derived from renewable resources. Specific examples of such compounds include: octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, menthyl acrylate, and isobornyl (meth)acrylate. The content ratio of component (E-1) can be appropriately set according to the purpose, and it is preferably 0 to 20 parts by weight in the total amount of curing components.

[0072] 2-1-2. (E-2) component (E-2) component is a compound having two or more (meth)acrylic groups. Among the components (E-2), compounds having two (meth)acrylic groups include: di(meth)acrylates of aliphatic diols such as ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, nonanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; di(meth)acrylates of polyalkylene glycols such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; and di(meth)acrylates of polyols such as glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, di-trimethylolpropane di(meth)acrylate, and dipentaerythritol di(meth)acrylate. Di(meth)acrylates of polyol epoxide adducts, such as glycerol epoxide adducts, pentaerythritol epoxide adducts, di(meth)acrylates of 2-trimethylolpropane epoxide adducts, and di(meth)acrylates of dipentaerythritol epoxide adducts; di(meth)acrylates of isocyanuric acid epoxide adducts; urethane (meth)acrylates of pentaerythritol di(meth)acrylate and organic polyisocyanates; di(meth)acrylates of alicyclic diols, such as tricyclodecane dimethylol di(meth)acrylate; di(meth)acrylates of bisphenol A epoxide adducts and di(meth)acrylates of bisphenol F epoxide adducts, etc. Furthermore, examples of the alkyl oxide adducts mentioned above include: ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts, etc.

[0073] As compounds having three or more (meth)acrylic groups, examples include: glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate or tetra(meth)acrylate, di-trimethylolpropane tri(meth)acrylate or tetra(meth)acrylate, and dipentaerythritol tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate or hexa(meth)acrylate, etc., polyol poly(meth)acrylates; Poly(meth)acrylates derived from polyol epoxide adducts, including tri(meth)acrylates, pentaerythritol epoxide adducts, di-trimethylolpropane epoxide adducts, diglycerol epoxide adducts, dipentaerythritol epoxide adducts, penta(meth)acrylates, and hexa(meth)acrylates; tri(meth)acrylates derived from isocyanate epoxide adducts; and poly(meth)acrylates derived from pentaerythritol epoxide adducts, which are compounds with hydroxyl groups and three or more (meth)acrylic acid groups, react with organic polyisocyanates to produce urethane (meth)acrylates. Examples of the alkyl oxide adducts mentioned above include: ethylene oxide adducts, propylene oxide adducts, and adducts of ethylene oxide and propylene oxide. Additionally, examples of the organic polyisocyanates mentioned above include: toluene diisocyanate, 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated toluene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, terephthalic diisocyanate, toluene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate inter-adducts, 4,4'-dicyclohexylmethane diisocyanate, trimethylolpropane tris(toluene diisocyanate) adduct, and isophorone diisocyanate.

[0074] Oligomers may also be used as (E-2) components, such as: reaction products of glycols, organic polyisocyanates and hydroxyl-containing (meth)acrylates, namely urethane (meth)acrylates and epoxy (meth)acrylates.

[0075] As component (E-2), it is preferably a compound derived from renewable resources and manufactured from raw materials derived from renewable resources. Specific examples of such compounds include: ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol epoxy alkyl adduct di(meth)acrylate, glycerol tri(meth)acrylate, and diglycerol epoxy alkyl adduct tetra(meth)acrylate, etc. The content ratio of component (E-2) can be set appropriately according to the purpose, and it is preferably 0 to 40 parts by weight in the total amount of the (meth)acrylate mixture and component (E) (hereinafter, the (meth)acrylate mixture and component (E) are collectively referred to as "curing components").

[0076] 2-2. (F) Component (F) is a polymerization initiator. When the curing composition is used as an active energy beam curing composition, especially when producing a visible light or ultraviolet light curing composition, a photopolymerization initiator (hereinafter referred to as "(F-1) component") is incorporated into the composition. Furthermore, when producing an electron beam curing composition, it is not necessary to incorporate a photopolymerization initiator. The (F-1) component is a compound that generates free radicals by irradiation with an active energy beam, initiating the polymerization of a compound having vinyl unsaturated groups.

[0077] Specific examples of the (F-1) component include: benzoin dimethyl ketal, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-hydroxy-2-methyl)phenyl]acetone, etc. Aromatic ketone compounds such as [2-methyl-2-methylpropoxy]benzyl]phenyl]-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)]phenyl-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one, 3,6-bis(2-methyl-2-morpholinylpropoxy)-9-n-octylcarbazole, methyl phenylglyoxylate, ethyl anthraquinone, and phenanthrenequinone; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylthio)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propane-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone and other benzophenone compounds; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphonite, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc., are phosphine oxide compounds; Thioxanthones, 2-chlorothioxanthones, 2,4-diethylthioxanthones, isopropylthioxanthones, 1-chloro-4-propylthioxanthones, 3-[3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride, and fluorothioxanthones, etc., are thioxanthone compounds.

[0078] When the component in the organic phase obtained in the neutralization step of step 3 is used as a (meth)acrylate obtained by the manufacturing method of the present invention, as component (F-1), α-hydroxyphenyl ketones have good and better surface hardening properties even when they are thin film coatings under atmospheric conditions. Specifically, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propane-1-one are preferred.

[0079] When the component used in the neutralization step of step 3 is a (meth)acrylate obtained by the manufacturing method of the present invention, the component (F-1) is preferably 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, or methyl phenylglyoxylate, in terms of its excellent compatibility with water.

[0080] When using a curing composition as a thermosetting composition, a thermopolymerization initiator (hereinafter referred to as "(F-2) component") is incorporated into the composition. Various compounds can be used as (F-2) component, such as organic peroxides and azo compounds.

[0081] 3. Method for manufacturing a curable composition The present invention also relates to a method for manufacturing a curable composition. That is, a method for manufacturing a curable composition in which a mixture of (meth)acrylates is stirred and mixed with component (E).

[0082] In addition, the present invention also relates to a method for manufacturing an active energy line curing composition. That is, the method for manufacturing an active energy line curing composition is a method of stirring and mixing a mixture of (meth)acrylate, component (E), and component (F-1), wherein 0.01 to 20 parts by weight of component (F) are used relative to 100 parts by weight of the total curing components.

[0083] In the method for manufacturing the composition, it is preferable that in step 2-1, compound (C) is used at a ratio of 1 to 50 moles relative to the total 1 mole of compound (B). Furthermore, when step 2-2 is performed as step 2, the resulting (meth)acrylate mixture exhibits excellent curing properties, and the resulting cured product possesses excellent hardness, adhesion, and low curling properties, which is therefore preferable. Additionally, it is preferable that at least one of compounds (A), (B), (C), and (D) comprises a compound derived from renewable resources.

[0084] Furthermore, as a method for manufacturing the aforementioned composition, it is preferable to stir and mix the (meth)acrylate mixture with component (E) in the proportions shown below. The mixture comprises 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of component (E-1) as component (E), and 0 to 40 parts by weight of component (E-2).

[0085] Furthermore, a preferred method for manufacturing the composition is as follows: after sequentially performing steps 1 to 3, the mixture of (meth)acrylates in the organic phase and / or the neutralized aqueous phase obtained in step 3 is used as a formulation component of the cured composition. [Example]

[0086] Hereinafter, embodiments and comparative examples will be shown to describe the present invention in more detail. Furthermore, the present invention is not limited to these embodiments. In addition, unless otherwise specified, "parts" refers to parts by weight, and "%" refers to percentages by weight.

[0087] In this manufacturing example, 1H NMR was measured under the following conditions.

[0088] <1H NMR Measurement Conditions> Apparatus: AVANCE III (manufactured by Bruker) Measurement Mode: Single Mode Solvent: CDCl3 Pulse Angle: 45 degrees Sample Concentration: 4 wt%~6 wt% Concentration Cycles: 16 times

[0089] 1. Example [Method for manufacturing acrylate mixture] 1-1. Example 1-1 1) Step 1 In a 1 L four-necked flask with a side tube and equipped with a reflux tube, 196 g of diglycerol ethylene oxide adduct (manufactured by Kao Corporation, Emalgen G2E-4, hereinafter referred to as "G2E4"), 119 g of acrylic acid (0.76 moles relative to 1 mole of all hydroxyl groups in the alcohol), 8.3 g of 70% methanesulfonic acid (hereinafter referred to as "MSA"), 0.6 g of copper chloride, and 240 g of toluene were added. While blowing oxygen-containing gas (5% oxygen, 95% nitrogen) into the flask, the mixture was heated and stirred at a reaction temperature of 85°C to 95°C. As the reaction proceeded, the generated water was removed from the system using a Dean-Stark tube, and a dehydration esterification reaction was carried out for 11 hours. The hydroxyl valence of the obtained reaction product was 61 mgKOH / g.

[0090] 2) Step 2 After completing Step 1, after restoring atmospheric pressure once more, add 71 g of itaconic acid (hereinafter referred to as "ITA") as compound (B), 70 g of 1,4-butanediol (hereinafter referred to as "BDOH") as compound (C), 56 g of acrylic acid (hereinafter referred to as "AA"), and 67 g of toluene. While blowing oxygen-containing gas into the flask, heat and stir at a reaction temperature of 85°C to 95°C. As the reaction proceeds, remove the generated water from the system using a Dean-Stark tube, and carry out a dehydration esterification reaction for 13 hours.

[0091] 3) Step 3 After the reaction in Step 2 is completed, 389 g of toluene is added for dilution. Then, 106 g of distilled water is added and stirred, and the aqueous phase as the lower layer is removed after standing. Next, 53 g of 10% ammonia water and 53 g of 4% ammonium sulfate water are added under stirring and stirred thoroughly, and the lower phase of 380 g is recovered after standing. Then, 178 g of 4% ammonium sulfate water is added to the organic phase under stirring and stirred, and the aqueous phase as the lower layer is removed after standing. The upper organic phase is heated under reduced pressure and distilled to remove toluene. The obtained acrylate mixture is 248 g (yield 60%). The results of APHA, hydroxyl value, acid value, and viscosity are shown in Table 2. The 1H NMR spectrum of the obtained organic phase acrylate is shown in Figure 1, and the 1H NMR spectrum of the obtained aqueous phase acrylate is shown in Figure 2.

[0092] 1-2. Examples 1-2 to 1-7 In Example 1, the raw materials and proportions shown in Tables 1 and 2 were used, except that steps 1 and 2 were performed using the same methods as in Example 1. Similar to Example 1, step 3 was performed, including dilution with toluene, washing with distilled water, neutralization with 10% ammonia and 4% ammonium sulfate solution, recovery of the lower phase, washing with 4% ammonium sulfate solution, and solvent removal. The amount of aqueous phase recovered during neutralization was shown in Table 2. The yield, APHA, acid value, and viscosity of the obtained acrylate mixture are shown in Table 2.

[0093] 1-3. Comparative Example 1-1 In Example 1, the raw materials and proportions shown in Tables 1 and 2 were used, except that steps 1 and 2 were performed using the same method as in Example 1. After step 2, 389 g of toluene was added and diluted. Then, 106 g of distilled water was added and stirred, and after standing, the aqueous phase as the lower layer was removed. Next, 126 g of a 20% sodium hydroxide aqueous solution was added under stirring and stirred thoroughly, and after standing, 243 g of the lower phase was recovered. Subsequently, 207 g of 4% ammonium sulfate solution was added to the organic phase under stirring and stirred, and after standing, the aqueous phase as the lower layer was removed. The upper organic phase was heated under reduced pressure and distilled to remove toluene. The obtained acrylate mixture was 340 g (yield 82%).

[0094] 1-4. Comparative Example 1-2 In a 1 L four-necked flask with a side tube and a reflux duct, 117 g of G2E4, 42 g of itaconic acid (0.5 mol relative to 1 mol of all hydroxyl groups in the alcohol), 13.5 g of 70% MSA, 0.6 g of copper chloride, and 381 g of toluene were added. While oxygen-containing gas was blown into the flask, the mixture was heated and stirred at a reaction temperature of 85°C–95°C. During the reaction, the generated water was removed from the system using a Dean-Stark tube, and a dehydration esterification reaction was carried out for 6 hours. However, a gel insoluble in toluene was formed, which became entangled with the stir bar, making stirring difficult; therefore, the synthesis was stopped. The reaction rate, calculated based on the amount of water distilled, was 30%.

[0095] [Table 1] Example Comparative example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-1 1-2 Step 1 AA 119 119 119 119 119 119 119 141 Compound (A) G2E4 196 196 196 196 196 196 117 DGLY 91 PET 88 Compound (B) ITA 42 acid catalyst MSA 8.3 8.3 8.3 8.3 8.3 8.3 8.3 8.3 13.5 Polymer inhibitors CuCl2 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 organic solvents TOL 240 240 240 240 240 240 240 284 381 Hydroxyl valence of the product (mgKOH / g) 61 77 61 61 61 61 61 61 35

[0096] In Table 1, the numbers refer to the weight parts contained, and the abbreviations refer to those described below. ･AA: Acrylic acid ◆ Compound (A) ･G2E4: Diglycerol ethylene oxide modified alcohol, Emalgen G2E-4 manufactured by Kao Corporation (containing a diglycerol backbone as a raw material derived from renewable resources) ･DGLY: Diglycerol ･PET: Pentaerythritol ◆ Compound (B) ･ITA: Itaconic acid (manufactured by Itaconix Corporation, a raw material derived from renewable resources) ◆ Acid catalyst ･MSA: 70% methanesulfonic acid aqueous solution ◆ Polymerization inhibitor ･CuCl 2: Copper chloride ◆ Organic solvent ･TOL: Toluene

[0097] [Table 2] Example Comparative example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-1 Step 2 AA 61 61 61 61 61 61 61 Compound (B) ITA 72 72 72 SUC 65 65 FDC 86 ADI 81 81 Compound (C) BDOH 70 70 70 PDOH 59 FDM 100 EG 48 TFM 103 Compound (D) HBA 96 organic solvents TOL 67 67 67 67 67 67 67 67 Step 3 neutralization Aqueous phase 387 650 391 385 422 363 385 243 Desolventization Collection 248 (60) 144 (46) 241 (61) 255 (60) 236 (57) 266 (60) 247 (60) 340 (82) APHA 94 80 96 102 113 134 92 90 Hydroxyl valence (mgKOH / g) 35 35 18 18 18 17 35 26 Acid value (mgKOH / g) 0.86 0.98 0.92 0.88 0.97 1.32 0.87 1.73 Viscosity (mPa·s) 149 120 133 187 174 303 110 283

[0098] In Table 2, numbers refer to the number of weight portions included, and abbreviations refer to those described below. The numbers in parentheses in the "Amount" row refer to the yield (%). ◆Compound (B) ･SUC: Succinic acid (manufactured by Roquette, derived from renewable resources) ･FDC: 2,5-Furandicarboxylic acid (manufactured by Avantium, derived from renewable resources) ･ADI: Adipic acid (derived from renewable resources) ◆Compound (C) ･BDOH: 1,4-Butanediol (manufactured by BASF, derived from renewable resources) ･PDOH: 1,3-Propanediol (manufactured by DuPont Tate & Lyle, derived from renewable resources) ･FDM: 2,5-Furandimethylethanol (manufactured by OG (shares), derived from renewable resources) ･EG: Ethylene glycol (manufactured by Grenncol Taiwan, derived from renewable resources) ･TFM: 2,5-Tetrahydrofurandimethylethanol (manufactured by OG (shares), derived from renewable resources) ◆Compound (D) ･HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemicals Co., Ltd.)

[0099] Liquidity Evaluation: • APHA: Determined according to JIS K 0071-1:2017. • Hydroxyl value: Determined according to JIS K 0070. • Acid value: Determined according to JIS K 0070. • Viscosity: Determined at 25°C using an E-type viscometer (TV-22 type viscometer manufactured by Toki Industries, Ltd., cone-plate type).

[0100] 1-5. Evaluation Results Compared with Examples 1-1 to 1-7, the reaction product generated in Comparative Example 1-1 contained cross-linking material in a certain proportion, and the product had high hydrophilicity. As a result, a gel insoluble in toluene was generated in the reaction solution, making further reaction difficult.

[0101] 2. Example [Preparation of active energy line hardening type composition] 2-1. Example 2-1 100 parts by weight of acrylate mixture obtained after solvent removal from organic phase prepared in Example 1-1 were mixed with 1-hydroxy-cyclohexyl-phenyl ketone (Omnirad 184 manufactured by IGM Resins, hereinafter referred to as "Omn184") as component (E-1), and stirred and mixed at 60°C for 3 hours to obtain the composition.

[0102] 2-2. Examples 2-2 to 2-7 [Preparation of active energy line hardening solvent-free composition] The composition was prepared using the acrylate mixture obtained after solvent removal from the organic phase as prepared in Examples 1-2 to 1-7, except that the composition was prepared using the same method as in Example 2-1.

[0103] 2-3. Comparative Example 2-1 [Preparation of active energy line hardening solvent-free composition] The composition was prepared using the acrylate mixture obtained after solvent removal as prepared in Comparative Example 1-1, except that the composition was prepared using the same method as in Example 2-1.

[0104] 2-4. Example 3-1 [Preparation of an Active Energy Line Hardening Type Aqueous Dispersion Composition] 5 parts of methyl benzoylformate (Omnirad MBF manufactured by IGM Resins, hereinafter referred to as "MBF") as component (E-1) were added relative to 100 parts of the solid component in the aqueous phase separated in Example 1-1. The mixture was stirred and mixed at 60°C for 3 hours to obtain an aqueous dispersion composition.

[0105] 2-5. Examples 3-2 to 3-7 [Preparation of active energy line hardening type aqueous dispersion composition] The composition was prepared using the aqueous phase separated in Examples 1-2 to 1-7, except that the method was the same as in Example 3-1.

[0106] 2-6. Comparative Example 3-1 [Preparation of an active energy line hardening type aqueous dispersion] 5 parts of MBF as component (E-1) were added to 100 parts of the solid component separated from the water in Comparative Example 1-1, and the mixture was stirred and mixed at 60°C for 3 hours to obtain an aqueous dispersion.

[0107] 3. Evaluation method of hardened material (1) Manufacturing of test specimens Using the obtained composition, a 10 cm square piece of easy-adhesive PET film manufactured by Toyobo (Cosmoshine Co., Ltd.) [Cosmoshine (registered trademark) A4360, film thickness: 100 μm. Hereinafter referred to as "A4360"] was coated with a film thickness of 10 μm using a bar coater. Using the obtained composition, ultraviolet light was irradiated using a high-pressure mercury lamp (Eye Graphics Co., Ltd. H06-L41) including a conveyor belt, under the conditions of UV-A lamp output illuminance of 80 W / cm, irradiation intensity of 290 mW / cm2 per pass, and irradiation energy of 400 mJ / cm2.

[0108] (2) Hardening property is evaluated by touch and using the following evaluation criteria for the hardened material obtained after one pass. ○: No stickiness on the surface. △: Slight stickiness on the surface. ×: Stickiness on the surface.

[0109] (3) Appearance of the hardened material The hardened material of the obtained test specimens shall be evaluated by visual inspection and using the following evaluation criteria. ○: Colorless and transparent. △: Slight white turbidity is visible. ×: White turbidity is visible.

[0110] (4)The pencil hardness was evaluated according to JIS K 5600-5-4 with a load of 750 g.

[0111] (5) Adhesion Test: A 1 mm longitudinal and transverse slit was cut into the test specimen using a cutting tool to form 25 squares of 1 mm × 1 mm size. #405 cellophane tape manufactured by Nichiban (stock) was then applied to the checkerboard pattern and forcefully peeled off. The number of residual films after peeling was evaluated. A higher number of residual films indicates better adhesion.

[0112] (6)The average height of the four vertices of the hardened material obtained by the curling test is measured. Preferably, it is less than 1.0 mm.

[0113] 4. Evaluation Results The evaluation results are shown in Table 3 and Table 4.

[0114] [Table 3] Example Comparative example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-1 hardening ○ ○ ○ ○ ○ ○ ○ △ Appearance ○ ○ ○ ○ ○ ○ ○ △ Pencil hardness 2H 2H H H 2H H 3H H

[0115] [Table 4] Example Comparative example 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-1 hardening ○ ○ ○ ○ ○ ○ ○ × Appearance ○ ○ ○ ○ ○ ○ ○ × Pencil hardness H H F F H F 2H - Tightness twenty four twenty three twenty two twenty three twenty four twenty three 25 - curly 0.1 mm 0.1 mm 0.2 mm 0.3 mm 0.2 mm 0.3 mm 0 mm -

[0116] The compositions of Examples 2-1 to 2-7 exhibit excellent curing properties, with superior appearance and pencil hardness of the cured products. Furthermore, the aqueous dispersion compositions of Examples 3-1 to 3-7 also exhibit excellent curing properties, with good appearance, pencil hardness, adhesion, and curling of the cured products. On the other hand, the aqueous dispersion composition of Comparative Example 3-1, due to the presence of sodium salt, suffers from deteriorated curing properties, resulting in a worse appearance of the cured product, making it impossible to evaluate pencil hardness, adhesion, and curling. Based on the above results, it is clear that in Examples 1-1 to 1-7, all the reactants can be converted into raw materials for the curable composition. This invention prevents the generation of highly environmentally unfriendly neutralized wastewater and can be established as an industrially effective manufacturing method. [Industrial Applicability]

[0117] The manufacturing method of the present invention can obtain the desired (meth)acrylate mixture in high yield using compounds derived from renewable resources as raw materials. The obtained (meth)acrylate mixture is equivalent to compounds derived from renewable resources, which can greatly help reduce the environmental impact. The organic phase obtained by the manufacturing method of the present invention and the (meth)acrylate mixture contained in the wastewater after the neutralization and purification step can both be used as raw materials for hardened compositions, etc. The hardened compositions can be preferably used as inks, coating agents, resists, fillers and molding materials, etc., and can be even more preferably used as coating agents and inks. [Simplified Explanation of the Diagram]

[0010] Figure 1 shows the 1H NMR spectrum of the organic phase acrylate obtained in Example 1-1. Figure 2 shows the 1H NMR spectrum of the aqueous phase acrylate obtained in Example 1-1.

Claims

1. A method for manufacturing a mixture of (meth)acrylates, comprising the following steps 1 to 3 in sequence: • Step 1: A dehydration esterification reaction is carried out between (meth)acrylate and (A) an alcohol having three or more hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylates with a hydroxyl valence of 55 mgKOH / g to 175 mgKOH / g. • Step 2: Step 2-1 or Step 2-2 is carried out to obtain a product with a hydroxyl valence of less than 55 mgKOH / g. Step 2-1: (B) dicarboxylic acid, (C) diol, and (meth)acrylate are added to the reaction solution containing hydroxyl-containing (meth)acrylates obtained in Step 1 to obtain a product. Step 2-2: (B) dicarboxylic acid and (D) hydroxyalkyl methacrylate are added to the reaction solution containing hydroxyl-containing (meth)acrylates obtained in Step 1 to obtain a product. • Step 3: The reaction solution obtained in Step 2 is neutralized using one or more neutralizing agents selected from aqueous solutions of ammonia and aqueous solutions of amine compounds.

2. The method for producing the (meth)acrylate mixture as claimed in claim 1, wherein in step 2-1, (C) diol is used in a ratio of 1 to 50 moles relative to a total of 1 mole of (B) dicarboxylic acid.

3. A method for manufacturing a mixture of (meth)acrylates as claimed in claim 1, wherein step 2-2 is performed as step 2.

4. A method for producing a mixture of (meth)acrylates as claimed in any one of claims 1 to 3, wherein at least one of the following compounds comprises a compound derived from a renewable resource: (A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl methacrylate.

5. A method for manufacturing a curable composition, comprising: stirring and mixing a (meth)acrylate mixture obtained by sequentially performing steps 1 to 3 below with an ethylene unsaturated compound other than the (meth)acrylate mixture (E) [hereinafter referred to as "component (E)"]; • Step 1: performing a dehydration esterification reaction of (meth)acrylate with (A) an alcohol having three or more hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylate with a hydroxyl valence of 55 mgKOH / g to 175 mgKOH / g; • Step 2: performing step 2-1 or step 2-2 below to obtain a product with a hydroxyl valence of less than 55 mgKOH / g; Step 2-1: adding (B) dicarboxylic acid, (C) diol and (meth)acrylate to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in step 1 to obtain a product; Step 2-2: adding (B) dicarboxylic acid and (D) hydroxyalkyl methacrylate to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in step 1 to obtain a product; • Step 3: Neutralizing the reaction solution obtained in Step 2 with one or more neutralizing agents selected from aqueous solutions of ammonia and aqueous solutions of amine compounds.

6. A method for manufacturing a hardened composition as claimed in claim 5, wherein in step 2-1, (C) diol is used in a ratio of 1 to 50 moles relative to a total of 1 mole of (B) dicarboxylic acid.

7. A method for manufacturing a hardened composition as claimed in claim 5, wherein step 2-2 is performed as step 2.

8. A method for manufacturing a hardened composition as claimed in any one of claims 5 to 7, wherein at least one of the following compounds: (A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl methacrylate comprises a compound derived from a renewable resource.

9. A method for manufacturing a hardened composition as claimed in any one of claims 5 to 7, wherein the (meth)acrylate mixture obtained by sequentially performing steps 1 to 3, and the components comprising (E-1) having one (meth)acrylic group (hereinafter referred to as "(E-1) component") and (E-2) having two or more (meth)acrylic groups (hereinafter referred to as "(E-2) component"), are stirred and mixed in a ratio comprising 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of (E-1) component, and 0 to 40 parts by weight of (E-2) component.

10. A method for manufacturing a hardened composition as claimed in any one of claims 5 to 7, wherein after performing steps 1 to 3 in sequence, the mixture of (meth)acrylates in the organic phase obtained in step 3 and / or the neutralized aqueous phase is used as a formulation component of the hardened composition.

11. A method for manufacturing an active energy line hardening composition, comprising stirring and mixing a (meth)acrylate mixture, component (E), and a (F-1) photopolymerization initiator obtained by sequentially performing steps 1 to 3 below, wherein in the method for manufacturing the active energy line hardening composition, 0.01 to 20 parts by weight of (F-1) photopolymerization initiator are used relative to 100 parts by weight of the total (meth)acrylate mixture and component (E). • Step 1: Dehydrating and esterifying (meth)acrylate with an alcohol having three or more hydroxyl groups (A) in the presence of an acid catalyst to obtain a reaction solution containing hydroxyl-containing (meth)acrylate with a hydroxyl valence of 55 mgKOH / g to 175 mgKOH / g. • Step 2: Performing step 2-1 or step 2-2 below to obtain a hydroxyl valence of 55 mgKOH / g. Step 2-1: Add (B) dicarboxylic acid, (C) diol and (meth)acrylic acid to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in Step 1 to obtain the product; Step 2-2: Add (B) dicarboxylic acid and (D) hydroxyalkyl methacrylate to the reaction solution containing hydroxyl-containing (meth)acrylate obtained in Step 1 to obtain the product; Step 3: Neutralize the reaction solution obtained in Step 2 with one or more neutralizing agents selected from aqueous solutions of ammonia and aqueous solutions of amine compounds.

12. A method for manufacturing an active energy line hardening composition as claimed in claim 11, wherein in step 2-1, (C) diol is used at a ratio of 1 mole to 50 moles relative to a total of 1 mole of (B) dicarboxylic acid.

13. A method for manufacturing an active energy line hardening composition as claimed in claim 11, wherein step 2-2 is performed as step 2.

14. A method for manufacturing an active energy line hardening composition as claimed in any one of claims 11 to 13, wherein at least one of the following compounds—(A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl methacrylate—contains a compound derived from a renewable resource.

15. A method for manufacturing an active energy line hardening composition as claimed in any one of claims 11 to 13, wherein the (meth)acrylate mixture obtained by sequentially performing steps 1 to 3, and the component comprising component (E-1) and component (E-2) as component (E), are stirred and mixed in a ratio comprising 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of component (E-1), and 0 to 40 parts by weight of component (E-2).

16. A method for manufacturing an active energy line hardening composition as claimed in any one of claims 11 to 13, wherein after performing steps 1 to 3 in sequence, the mixture of (meth)acrylates in the organic phase and / or the neutralized aqueous phase obtained in step 3 is used as a formulation component of the hardening composition.

17. A method for manufacturing an active energy line-curable composition for ink, comprising a method for manufacturing an active energy line-curable composition as described in any one of claims 11 to 16.

18. A method for manufacturing an active energy line curable composition for a coating agent, comprising a method for manufacturing an active energy line curable composition as described in any one of claims 11 to 16.

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