WO2023234232A1

WO2023234232A1 - Method for producing (meth)acrylate mixture and method for producing renewable resource-derived (meth)acrylate mixture

Info

Publication number: WO2023234232A1
Application number: PCT/JP2023/019834
Authority: WO
Inventors: 貴雅磯; 康之佐内; 忍鏡味; 桃子吉岡
Original assignee: 東亞合成株式会社
Priority date: 2022-05-30
Filing date: 2023-05-29
Publication date: 2023-12-07
Also published as: TW202346397A

Abstract

[Problem] To provide a production method by which a desired (meth)acrylate mixture can be obtained at extremely high yield by using a renewable resource-derived raw material, environmental load reduction is significant, the obtained mixture has excellent curability, and a cured product thereof has excellent various physical properties. [Solution] This method for producing a (meth)acrylate mixture sequentially carries out the following steps: step 1 which is a step for reacting (meth)acrylic acid with an alcohol having at least three hydroxyl groups in the presence of an acid catalyst to obtain a reaction solution having a specific hydroxyl value; step 2 which is a step for carrying out the following step 2-1 or step 2-2 to obtain a product having at most a specific hydroxyl value, where step 2-1 is a step for adding dicarboxylic acid, diol, and (meth)acrylic acid to the reaction solution of step 1 to obtain a product, and step 2-2 is a step for adding dicarboxylic acid and hydroxyalkyl (meth)acrylate to the reaction solution of step 1 to obtain a product; and step 3 which is a step for neutralizing the reaction solution of step 2 with an aqueous solution of ammonia or/and an amine compound.

Description

Method for producing (meth)acrylate mixture and method for producing (meth)acrylate mixture derived from renewable resources

The present invention relates to a method for producing a (meth)acrylate mixture, a method for producing a (meth)acrylate mixture derived from renewable resources, and a method for producing a composition containing the (meth)acrylate mixture obtained thereby.

Active energy ray-curable compositions can be cured by irradiation with active energy rays such as ultraviolet rays, visible light, and electron beams for a very short time, and are highly productive, making them suitable for applications such as inks, coating agents, and resist materials. Widely used.
As a component of the active energy ray curable composition, (meth)acrylate is used, and polyester (meth)acrylate is known as one of them.

However, many of the raw materials used to manufacture compounds such as (meth)acrylates are derived from fossil fuels such as petroleum and coal, which contributes to the environmental burden.
Furthermore, when producing (meth)acrylate, the final product is obtained through a neutralization and water washing process in the reactant purification process, but wastewater is generated during the neutralization and water washing process, and its treatment is difficult. Most of the methods involve combustion, which is also a cause of environmental impact.
For this reason, there is a need to find a production method that produces (meth)acrylate using raw materials of compounds derived from renewable resources that have less environmental impact, and that also suppresses the amount of waste water after the esterification reaction.

Against the background of the above, in recent years, the production of compounds using compounds derived from renewable resources has been studied, and polyesters and acrylates have also been studied.
For example, U.S. Pat. No. 5,001,302 discloses polyester polyols made from (a) recycled and digested polyester, (b) glycol, and (c) lignin or tannin. In Patent Document 1, the polyester polyol obtained above is converted into urethane and used as a raw material for a paint.
However, when producing (meth)acrylate using the polyester polyol obtained in this process, complicated steps are required to produce the polyester polyol, and there are concerns about high costs.
Patent Document 2 describes a radiation-curable coating agent for flooring materials containing polyacrylate, etc., which is a compound derived from renewable resources.
However, Patent Document 2 does not include any description regarding a purification process for removing the catalyst from the product, and there is concern about problems caused by the catalyst remaining in the product. In addition, because the main ingredient is sebacic acid, a vegetable oil derived from renewable resources, the hardness of the cured product is insufficient to be used as a coating agent, etc. there were.

Special table 2018-508611 publication Special Publication No. 2011-519396

The present inventors can obtain a desired (meth)acrylate mixture in high yield using a renewable resource-derived compound as a raw material, and the obtained (meth)acrylate mixture also corresponds to a renewable resource-derived compound, We conducted extensive research to find a manufacturing method that greatly reduces environmental impact, provides a (meth)acrylate mixture with excellent curability, and provides a cured product with excellent physical properties such as hardness, adhesion, and low curling properties. .

As a result of intensive studies to solve the above problems, the present inventors conducted a dehydration esterification reaction between (meth)acrylic acid and an alcohol having three or more hydroxyl groups in the presence of an acid catalyst, and achieved a specific hydroxyl value. A step of obtaining a reaction solution containing a hydroxyl group-containing (meth)acrylate, and a step of obtaining a (meth)acrylate mixture with a specific hydroxyl value by adding dicarboxylic acid, diol, (meth)acrylic acid, etc. to the obtained reaction solution. The method for producing (meth)acrylate mixtures, which includes the step of neutralizing this mixture using a specific method, allows the use of raw materials derived from renewable resources and disposes of (meth)acrylates etc. dissolved in the aqueous phase. The present invention was completed based on the discovery that all the reaction raw materials can be converted into products without any problems.
The present invention will be explained in detail below.

According to the production method of the present invention, a desired (meth)acrylate mixture can be obtained in high yield using a compound derived from renewable resources as a raw material, and can greatly contribute to reducing environmental load.
The (meth)acrylate mixture contained in the organic phase obtained by the production method of the present invention and the waste water after the neutralization and purification process serves as a raw material for a curable composition and has fast curing properties, and the cured product thereof is It has high hardness, excellent adhesion to plastic substrates, and low curling properties, so it can be preferably used as ink, coating agent, resist material, etc. In addition, since the wastewater after the neutralization and purification process, which is normally disposed of as wastewater, also serves as a raw material for the curable composition, there is no need to dispose of the wastewater, making it possible to reduce the environmental burden.

FIG. 1 refers to a ¹ H NMR chart of the organic phase acrylate obtained in Example 1-1. FIG. 2 refers to a ¹ H NMR chart of the aqueous phase acrylate obtained in Example 1-1.

The present invention relates to a method for producing a (meth)acrylate mixture in which the following steps 1 to 3 are performed sequentially.
・Step 1: (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups are subjected to a dehydration esterification reaction in the presence of an acid catalyst to produce a hydroxyl group-containing (meth) having a hydroxyl value of 55 to 175 mgKOH/g. Step 2 of obtaining a reaction solution containing acrylate: Step 2-1 or step 2-2 below to obtain a product with a hydroxyl value of 55 mgKOH/g or less Step 2-1; (B) dicarboxylic acid, (C) diol, and (meth)acrylic acid are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate to obtain a product.
Step 2-2: To the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in Step 1, (B) dicarboxylic acid and (D) hydroxyalkyl (meth)acrylate are added to obtain a product.
・Step 3: A step of neutralizing the reaction solution obtained in Step 2 with one or more neutralizing agents selected from an aqueous solution of ammonia and an aqueous solution of an amine compound.

In step 2-1, the diol (C) is preferably used in a molar ratio of 1 to 50 times the total mole of the dicarboxylic acid (B).
As the step 2, it is preferable to carry out the step 2-2.
In addition, at least one of the above-mentioned (A) alcohols having three or more hydroxyl groups, (B) dicarboxylic acids, (C) diols, and (D) hydroxyalkyl (meth)acrylates is a renewable resource-derived compound. It is preferable to include.

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

In the method for producing the curable composition, in step 2-1, it is preferable to use the diol (C) in a molar ratio of 1 to 50 times the total mole of the dicarboxylic acid (B).
Further, as the step 2, it is preferable to carry out the step 2-2.
In addition, at least one of the above-mentioned (A) alcohols having three or more hydroxyl groups, (B) dicarboxylic acids, (C) diols, and (D) hydroxyalkyl (meth)acrylates is a renewable resource-derived compound. It is preferable to include.
Further, the (meth)acrylate mixture obtained by sequentially carrying out the above steps 1 to 3 and (E-1) a compound having one (meth)acryloyl group [hereinafter referred to as "(E-1)"] is used as the (E) component. 1) component"] and (E-2) a compound having two or more (meth)acryloyl groups [hereinafter referred to as "(E-2) component"],
A preferred production method involves stirring and mixing 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, after performing steps 1 to 3 in sequence, the (meth)acrylate mixture obtained in step 3 in the organic phase and/or in the aqueous phase after neutralization is used as a component of a curable composition. The method is preferred.

Further, the present invention provides a manufacturing method in which the (meth)acrylate mixture obtained by sequentially performing the steps 1 to 3, the component (E), and the photopolymerization initiator (F-1) are stirred and mixed. An active energy ray-curable composition using 0.01 to 20 parts by weight of (F-1) photoinitiator based on a total of 100 parts by weight of the (meth)acrylate mixture and component (E). It also relates to the manufacturing method.

In the method for producing the active energy ray-curable composition, in step 2-1, (C) diol may be used in a molar ratio of 1 to 50 times with respect to 1 mole of dicarboxylic acid (B) in total. preferable.
Further, as the step 2, it is preferable to carry out the step 2-2.
In addition, at least one of the above-mentioned (A) alcohols having three or more hydroxyl groups, (B) dicarboxylic acids, (C) diols, and (D) hydroxyalkyl (meth)acrylates is a renewable resource-derived compound. It is preferable to include.
In addition, the (meth)acrylate mixture obtained by sequentially carrying out the above steps 1 to 3, and a component containing the (E-1) component and (E-2) component as the (E) component,
A preferred production method involves stirring and mixing 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, after performing steps 1 to 3 in sequence, the (meth)acrylate mixture obtained in step 3 in the organic phase and/or in the aqueous phase after neutralization is used as a component of a curable composition. The method is preferred.
Moreover, as the manufacturing method, a method for manufacturing an active energy ray-curable composition for ink or an active energy ray-curable composition for coating agent is preferable.
The present invention will be explained in detail below.

1. Method for producing (meth)acrylate mixture In the present invention, the (meth)acrylate mixture obtained by sequentially performing the steps 1 to 3 below is also simply referred to as "(meth)acrylate mixture."

1-1. Process 1
In step 1, (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 hydroxyl value of 55. This is a step to obtain a reaction solution containing hydroxyl group-containing (meth)acrylate of ~175 mgKOH/g.

1-1-1. Compound (A)
Compound (A) is an alcohol having three or more hydroxyl groups, and various compounds can be used.
Specific examples of compound (A) include trivalent or higher polyols such as glycerin, diglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol, and alkylene oxides of these trivalent or higher polyols. Examples include adducts, tris(2-hydroxyethyl)isocyanurate, and the like.
The compound (A) is preferably a compound derived from renewable resources. Specific examples of the compound include glycerin, diglycerin, an alkylene oxide adduct of glycerin, and an alkylene oxide adduct of diglycerin, with the alkylene oxide adduct of diglycerin being more preferred.
In addition, examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.
In the present invention, a compound derived from a renewable resource is a compound having a renewable resource structure, and more specifically refers to a biological raw material (biomass) and a compound produced from a biological raw material. As the renewable resource-derived compound, plant-derived raw materials and compounds produced from plant-derived raw materials are preferred.

1-1-2. Dehydration esterification reaction The dehydration esterification reaction may be carried out in a conventional manner, including a method of heating and stirring (meth)acrylic acid and compound (A) in the presence of an acid catalyst.

The ratio of (meth)acrylic acid used is preferably 0.05 mol to 20 mol, and 0.05 mol based on the total 1 mol of all hydroxyl groups of compound (A) so as to obtain the desired (meth)acrylate. ~5 mol is more preferred.
The proportion of (meth)acrylic acid used is preferably 0.625 to 0.875 mol, more preferably 0.7 to 0.8 mol, per 1 mol of compound (A).

Examples of acid catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and fluoroboric acid, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and strong acidic cation type ion exchange resins. can be mentioned.
The proportion of the acid catalyst to be used is preferably 0.05 mol % to 20 mol % based on the total 1 mol of all hydroxyl groups of compound (A).

The dehydration esterification reaction may be carried out according to a conventional method.
The reaction temperature may be appropriately set depending on the raw materials used and the purpose, but from the viewpoint of shortening the reaction time and preventing polymerization, the reaction temperature is preferably 65 to 140°C, more preferably 75 to 120°C. By setting the reaction temperature to 65°C or higher, the esterification reaction can be carried out quickly and a decrease in yield can be suppressed. On the other hand, by setting the reaction temperature to 140°C or lower, (meth)acrylic acid or the produced Thermal polymerization of (meth)acrylate can be suppressed.

In the dehydration esterification reaction, it is preferable to promote dehydration while azeotropically distilling the water produced in the dehydration esterification reaction with an organic solvent having low solubility in water.
Preferred organic solvents include aromatic hydrocarbon compounds such as toluene, benzene, and xylene, aliphatic hydrocarbon compounds such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and chlorine-based solvents such as trichlorethylene and tetrachloroethylene. Examples include hydrocarbon compounds and ketones such as methyl ethyl ketone.
The amount of organic solvent used is preferably such that the organic solvent concentration in the reaction solution is 30 to 60% by weight, more preferably 40 to 50% by weight.

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

In step 1, a reaction solution with a hydroxyl value of 55 to 175 mgKOH/g is obtained, preferably a reaction solution with a hydroxyl value of 105 to 115 mgKOH/g is obtained, and the reaction is stopped to reach the hydroxyl value. .
If the hydroxyl value of the reaction solution exceeds 175 mgKOH/g, crosslinkable (meth)acrylate will be produced in Step 2, which may cause 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 decrease significantly.
In the present invention, the hydroxyl value means a value measured according to JIS K 0070.

1-2. Process 2
Step 2 is a step of performing Step 2-1 or Step 2-2 below to obtain a product having a hydroxyl value of 55 mgKOH/g or less.
Step 2-1; Add (B) dicarboxylic acid [hereinafter referred to as "compound (B)"], (C) diol [hereinafter referred to as "compound (B)"] to the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in step 1. C)] and (meth)acrylic acid to obtain the product.
Step 2-2; Compound (B) and (D) hydroxyalkyl (meth)acrylate [hereinafter referred to as "compound (D)"] are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in Step 1. Add to obtain the product.

1-2-1. Process 2-1
In step 2-1, compound (B), compound (C), and (meth)acrylic acid are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in step 1 to carry out a dehydration esterification reaction. .
Compound (B), compound (C), and reaction method will be explained below.

1-2-1-1. Compound (B)
Compound (B) is a dicarboxylic acid, and various compounds can 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 heterocyclic skeletons such as 2,5-furandicarboxylic acid. Examples include dicarboxylic acids having the following.
The compound (B) is preferably a compound derived from renewable resources. Specific examples of the compound include itaconic acid, succinic acid, fumaric acid, adipic acid, and 2,5-furandicarboxylic acid, with itaconic acid being more preferred.

The proportion of compound (B) to be used is preferably 0.8 to 50 times, more preferably 0.9 to 1.1 times, per mole of the total number of moles of hydroxyl groups in the reaction solution obtained in step 1. It is twice the mole. When the proportion of compound (B) used is less than 0.8 times the mole, the proportion of (meth)acrylate having polyester units in the (meth)acrylate mixture decreases, and the highly hydrophilic component The amount increases and dissolves in water during the process of washing the reaction solution with water, causing loss of raw materials. When the proportion of compound (B) used is more than 50 times the molar ratio, the acrylate equivalent in the (meth)acrylate mixture decreases, which may lead to a decrease in the hardness of the resulting cured composition.

1-2-1-2. Compound (C)
Compound (C) is a diol, and various compounds can be used.
Specific examples of compound (C) include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol, and cyclic ether diols such as 2,5-tetrahydrofurandimethanol. , and diols having a heterocyclic skeleton such as 2,5-furandimethanol.
The compound (C) is preferably a compound derived from renewable resources. Specific examples of such compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,5-tetrahydrofurandimethanol, and 2,5-furandimethanol.

The usage ratio of compound (C) is preferably 1 to 50 times, more preferably 1.3 to 1.5 times, per mole of compound (B). If the proportion of compound (C) used is less than 1 mole, the proportion of the target polyester diol will decrease, the proportion of dicarboxylic acid monoester as a by-product will increase, and furthermore, the proportion of dicarboxylic acid monoester produced as a by-product will increase. Since the ester dissolves in water during the process of washing the reaction solution with water, it may cause loss of raw materials. If the ratio of compound (C) used is more than 50 times the mole, the ratio of the target (meth)acrylate will decrease, resulting in a decrease in the acrylate equivalent of the reactant, resulting in a decrease in the hardness of the cured product of the composition. It may lead to

1-2-1-3． The ratio of (meth)acrylic acid added in reaction step 2-1 in step 2-1 is preferably 1.0 to 1.2 moles per mole of compound (C).

The hydroxyl value of the product at which step 2-1 is stopped is 55 mgKOH/g or less, preferably 35 mgKOH/g or less. When the hydroxyl value of the product exceeds 55 mgKOH/g, a large amount of hydrophilic components remain, resulting in a low yield of the desired (meth)acrylate.

In step 2-1, the acid catalyst contained in the reactant of step 1 causes a dehydration esterification reaction between an acid and an alcohol to proceed, and reactions with various compounds proceed.
The reaction temperature in step 2-1 is preferably 75 to 110°C, more preferably 85 to 100°C.

Specifically, the dehydration esterification reaction of acid and alcohol in step 2-1 includes dehydration esterification reaction of (meth)acrylic acid and alcohol, dehydration esterification reaction of compound (B) and compound (C), etc. progresses, and examples of the main reactions are listed below (2-1-1) to (2-1-6).
(2-1-1) The reaction between the hydroxyl group-containing (meth)acrylate obtained in Step 1 [hereinafter referred to as "hydroxyl group-containing (meth)acrylate (1)"] and (meth)acrylic acid ( Production of meth)acrylate and hydroxyl group-containing (meth)acrylate [hereinafter referred to as "hydroxyl group-containing (meth)acrylate (2)"]
(2-1-2) Polyester diol [hereinafter referred to as polyester diol (2)] is produced by the reaction between compound (B) and compound (C), and by the reaction between polyester diol (2) and (meth)acrylic acid. Production of polyester (meth)acrylate
(2-1-3) Production of (meth)acrylate by reaction of hydroxyl group-containing (meth)acrylate (1) or hydroxyl group-containing (meth)acrylate (2) and compound (B)
(2-1-4) Production of (meth)acrylate by reaction of polyester diol (2) and compound (B)
(2-1-5) Production of (meth)acrylate by reaction of hydroxyl group-containing (meth)acrylate (1), hydroxyl group-containing (meth)acrylate (2), and/or polyester diol (2) with compound (B) Generate
(2-1-6) Production of (meth)acrylate by reaction of compound (C) and (meth)acrylic acid

Furthermore, when at least one of compound (A), compound (B), and compound (C) is a renewable resource-derived compound, the obtained (meth)acrylate mixture corresponds to a renewable resource-derived compound.

1-2-2． Process 2-2
In step 2-2, compound (B) and compound (D) are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in step 1 to carry out a dehydration esterification reaction.
Compound (B), compound (D), and reaction method will be explained below.

1-2-2-1． Compound (B)
Compound (B) is a dicarboxylic acid, and various compounds can be used, specific examples of which include the same compounds as mentioned above.
The compound (B) is preferably a compound derived from renewable resources, and specific examples thereof include the same compounds as mentioned above.

1-2-2-2． Compound (D)
Compound (D) is a hydroxyalkyl (meth)acrylate, and various compounds can be used.
Specific examples of compound (D) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
The compound (D) is preferably a compound derived from renewable resources. Specific examples of the compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, with hydroxybutyl (meth)acrylate being more preferred.

The ratio of compound (D) to be used is preferably 1.0 to 2.0, more preferably 1.0 to 1.0, based on the total number of moles of the remaining (meth)acrylic acid from step 1 and compound (B). It is 5. If the ratio of compound (D) used is less than 1.0, a large amount of monoester of dicarboxylic acid will be produced, resulting in poor curability. If the ratio of compound (D) used is greater than 2.0, a large amount of di(meth)acrylate will be produced, resulting in poor curability.

1-2-2-3． The hydroxyl value of the product that terminates reaction step 2-2 in step 2-2 is 55 mgKOH/g or less, preferably 35 mgKOH/g or less. When the hydroxyl value of the product exceeds 55 mgKOH/g, a large amount of hydrophilic components remain, resulting in a low yield of the desired (meth)acrylate.

In Step 2-2, the acid catalyst contained in the reactant of Step 1 causes a dehydration esterification reaction between the acid and the alcohol, and reactions with various compounds proceed.
The reaction temperature in step 2-2 is preferably 75 to 110°C, more preferably 85 to 100°C.

In the dehydration esterification reaction of acid and alcohol in step 2-2, the following (2-2-1) proceeds, and the following (2-2-2) proceeds as a side reaction.
(2-2-1) Production of (meth)acrylate by reaction of hydroxyl group-containing (meth)acrylate (1), compound (B), and compound (D).
(2-2-2) Production of carboxy group-containing (meth)acrylate by reaction of hydroxyl group-containing (meth)acrylate (1) and compound (B).

Furthermore, when at least one of compound (A), compound (B), and compound (D) is a renewable resource-derived compound, the obtained (meth)acrylate mixture corresponds to a renewable resource-derived compound.

In the present invention, by performing Step 2-2 as Step 2, the obtained (meth)acrylate mixture has excellent curability, and the obtained cured product has physical properties such as hardness, adhesion, and low curling property. It is preferable because it has excellent properties.

1-3. Process 3
Step 3 is a step in which acidic components in the reaction solution obtained in Step 2 are neutralized with one or more neutralizing agents selected from an aqueous solution of ammonia and an aqueous solution of an amine compound.

The reaction solution obtained in step 2 contains acidic components such as unreacted (meth)acrylic acid and an acid catalyst in addition to the (meth)acrylate mixture that is the product. The neutralization treatment in step 3 is performed for the purpose of removing acidic components such as unreacted (meth)acrylic acid and acid catalyst in the reaction solution.
The neutralization treatment is carried out by bringing the reaction solution into contact with a neutralizing agent, which is an alkaline aqueous solution. Specifically, it may be carried out according to a conventional method. For example, the neutralizing agent is added to the reaction solution, stirring and Examples include a method of mixing.
Examples of the amine compound in the neutralizing agent include ethylamine, ethylenediamine, diethylamine, pyrrolidine, piperidine, triethylamine, and pyridine.
In the present invention, an aqueous solution of ammonia and/or an aqueous solution of an amine compound is used as the neutralizing agent. In the present invention, since 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, Wastewater can be made so-called metal-free, meaning that it does not contain metal compounds.

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, examples of the ammonium salt include ammonium sulfate and the like.

The concentrations of the ammonia aqueous solution and the amine compound aqueous solution may be appropriately set depending on the purpose, and are preferably 1 to 50% by weight, more preferably 10 to 20% by weight.
The proportion of the neutralizing agent used is preferably adjusted so that the base value is 1 to 1.5 times the acid value of the organic phase, preferably 1 to 1.5 times the acid value of the organic phase after preliminary water washing.

When carrying out Step 3, which is a neutralization step, it is preferable to add an organic solvent to dilute the reaction solution obtained in Step 2 or to perform preliminary water washing before carrying out Step 3.

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 organic solvent and the organic solvent after dilution is 50 to 70% by weight.

As the water detergent used for preliminary washing, it is preferable to use distilled water, purified water, etc. The water washing treatment may be performed only once, or may be performed multiple times.

As an aqueous detergent, an aqueous solution of ammonium salt or sodium salt can be used in combination, if necessary, in order to create a difference in specific gravity. Specific examples include ammonium sulfate, sodium ammonium sulfate, and sodium chloride, with ammonium sulfate being more preferred for the purpose of being metal-free.
The water washing treatment may be performed only once or multiple times depending on the purpose.

The liquid after the neutralization treatment is separated into two layers, an organic phase and an aqueous phase, and since the organic phase has a lower specific gravity than the aqueous phase, the organic phase is separated into the upper layer and the lower aqueous phase.
The lower aqueous phase is drawn off and separated from the organic phase.
The method for using the separated organic phase may be appropriately selected depending on the contents of the organic phase. Examples of how to use the separated organic phase include using it as it is as a raw material for a curable composition, and using it as a raw material for a curable composition after distilling off the organic solvent.
The method for using the extracted aqueous phase may be appropriately selected depending on the contents of the aqueous phase. The extracted aqueous phase can be used as it is as a raw material for a curable composition, after water is removed by distillation etc., it can be used as a raw material for a curable composition, or it can be disposed of. Can be mentioned.

1-4. Method of using (meth)acrylate mixture The ( meth)acrylate mixture obtained by the production method of the present invention can be either the (meth)acrylate mixture in the organic phase obtained in the neutralization step of step 3 or the (meth)acrylate mixture in the aqueous phase. It is also possible to use meth)acrylate mixtures.

Examples of the (meth)acrylate mixture contained in the organic phase subjected to Step 2-1 and then Step 3 include the following (O-1-1) to (O-1-5).
(O-1-1) (Meth)acrylate without hydroxyl group obtained in Step 1, (meth)acrylate without hydroxyl group obtained in Step 2
(O-1-2) Polyester di(meth)acrylate without hydroxyl group produced by reaction of polyester diol (2) and (meth)acrylic acid
(O-1-3) (meth)acrylate without hydroxyl group resulting from reaction of hydroxyl group-containing (meth)acrylate (1) and/or hydroxyl group-containing (meth)acrylate (2) with compound (B)
(O-1-4) Hydroxyl group-containing (meth)acrylate (1), hydroxyl group-containing (meth)acrylate (2), and/or polyester diol (2) reacted with compound (B), which does not have a hydroxyl group ( Meta) acrylate
(O-1-5) Di(meth)acrylate without hydroxyl group produced by reaction of compound (C) and (meth)acrylic acid

The (meth)acrylate mixture contained in the aqueous phase after Step 2-1 and Step 3 is a compound having a hydroxyl group and a (meth)acryloyl group, a compound having a carboxy group and a (meth)acryloyl group, etc. Examples include (W-1-1) to (W-1-5) below. Note that the compound having a carboxyl group and a (meth)acryloyl group exists as an ammonium salt or a salt of an amine compound in the aqueous phase.
(W-1-1) Hydroxyl group-containing (meth)acrylate (1), hydroxyl group-containing (meth)acrylate (2)
(W-1-2) Hydroxyl group-containing polyester mono(meth)acrylate produced by reaction of polyester diol (2) and (meth)acrylic acid
(W-1-3) Hydroxyl group-containing mono(meth)acrylate produced by reaction of compound (B) and (meth)acrylic acid
(W-1-4) Carboxy group-containing mono(meth)acrylate obtained by reacting hydroxyl group-containing (meth)acrylate (1) or hydroxyl group-containing (meth)acrylate (2) with compound (B)
(W-1-5) Unreacted (meth)acrylic acid

Examples of the (meth)acrylate mixture contained in the organic phase subjected to Step 3 through Step 2-2 include the following (O-2-1) and (O-2-2).
(O-2-1) (Meth)acrylate without hydroxyl group obtained in step 1
(O-2-2) (Meth)acrylate obtained by reaction of hydroxyl group-containing (meth)acrylate (1), compound (B) and compound (D)

The (meth)acrylate mixture contained in the aqueous phase after Step 2-2 and Step 3 is a compound having a hydroxyl group and a (meth)acryloyl group, a compound having a carboxy group and a (meth)acryloyl group, etc. Examples include (W-2-1) to (W-2-4) below. Note that the compound having a carboxyl group and a (meth)acryloyl group exists as an ammonium salt or a salt of an amine compound in the aqueous phase.
(W-2-1) Hydroxyl group-containing (meth)acrylate (1)
(W-2-2) Carboxy group-containing (meth)acrylate obtained by reaction of hydroxyl group-containing (meth)acrylate (1) and compound (B)
(W-2-3) Carboxy group-containing mono(meth)acrylate obtained by reaction of compound (B) and compound (C)
(W-2-4) Unreacted (meth)acrylic acid

In this case, the organic phase or aqueous phase containing the (meth)acrylate mixture can be used as is, or the (meth)acrylate mixture after removing the organic solvent or water from the organic phase or aqueous phase can be used. You can also do it.

2. Curable Composition The (meth)acrylate mixture obtained by the production method of the present invention can be used in various applications in which (meth)acrylates have conventionally been used.
For example, it is suitably used in various industrial applications as a main component of a composition, a crosslinking component, or a reactive diluent component in applications such as coating agents such as paints, inks, adhesives, resists, fillers, and molding materials. be able to. As a molding material, it can also be used by processing it into shapes such as films and sheets, and the films and sheets can be used for optical applications such as optical lenses.
The (meth)acrylate mixture obtained by the production method of the present invention is preferably used as a component of a curable composition, and more preferably used as a coating agent and ink.

For the (meth)acrylate mixture obtained by the production method of the present invention, the components of the organic phase obtained in the neutralization step of step 3 can be used, or the components of the aqueous phase can be used.
In this case, the organic phase or aqueous phase containing the (meth)acrylate mixture can be used as is, or the (meth)acrylate mixture after evaporating the organic solvent or water in the organic phase or aqueous phase can be used. You can also do it.

If the organic phase containing the (meth)acrylate mixture is used as is, the composition will be an organic solvent-based composition, and if the aqueous phase containing the (meth)acrylate mixture is used as it is, the composition will be an aqueous composition.

When the (meth)acrylate mixture obtained by the production method of the present invention is used as a component of a curable composition, various components used in the curable composition can be blended.
Specific examples include ethylenically unsaturated compounds other than the (meth)acrylate mixture obtained by the production method of the present invention [hereinafter referred to as "component (E)"], and polymerization initiators [hereinafter referred to as "component (F)"] ”] etc.

2-1. Component (E) Component (E) includes a compound having one (meth)acryloyl group [hereinafter referred to as "component (E-1)"], and a compound having two or more (meth)acryloyl groups [hereinafter referred to as "component (E-1)"]. "component (E-2)"], etc.

2-1-1. Component (E-1) Component (E-1) is a compound having one (meth)acryloyl group in one molecule.
Specific examples of component (E-1) include (meth)acrylate having one (meth)acryloyl group (hereinafter referred to as "monofunctional (meth)acrylate"); (meth)acrylamide compounds (hereinafter referred to as "monofunctional (meth)acrylamide"), etc.

Specific examples of monofunctional (meth)acrylates include:
Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl ( Alkyl (meth)acrylates such as meth)acrylate and stearyl (meth)acrylate;
Cyclohexyl (meth)acrylate, menthyl acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate ) Monofunctional (meth)acrylates having alicyclic groups such as acrylates;
Glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexane spiro-2-(1,3-dioxolane) Monofunctional (meth)acrylates having a cyclic ether group such as -4-yl)methyl (meth)acrylate and 3-ethyl-3-oxetanylmethyl (meth)acrylate;
Aromatic monofunctional (meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxy (meth)acrylate and p-cumylphenolethylene (meth)acrylate;
Monofunctional (meth)acrylates having a maleimide group such as (meth)acryloyloxyethylhexahydrophthalimide;
(meth)acryloylmorpholine;
Monofunctional (meth)acrylates having an alkoxyalkyl group such as alkyl carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate and 2-ethylhexyl carbitol (meth)acrylate; and 3-(meth)acryloxypropylmethyl Alkoxy group-containing monofunctional (meth)acrylates such as dimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane etc. can be mentioned.

Specific examples of monofunctional (meth)acrylamide compounds include N-methyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, N- N-alkyl (meth)acrylamide such as -sec-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-n-hexyl (meth)acrylamide; N- such as N-hydroxyethyl (meth)acrylamide Hydroxyalkyl (meth)acrylamide; and N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide Acrylamide, N,N-di-n-propyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di-n-butyl (meth)acrylamide, N,N-dihexyl (meth)acrylamide, etc. Examples include N,N-dialkyl (meth)acrylamide and the like.

Component (E-1) is preferably a renewable resource-derived compound produced from a renewable resource-derived raw material.
Specific examples of the compound include octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, menthyl acrylate, and isobornyl (meth)acrylate.
The content ratio of component (E-1) may be appropriately set depending on the purpose, and it is preferably contained in the total amount of curable components from 0 to 20 parts by weight.

2-1-2. (E-2) Component (E-2) Component is a compound having two or more (meth)acryloyl groups.
In component (E-2), examples of compounds having two (meth)acryloyl groups include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. meth)acrylates and di(meth)acrylates of aliphatic diols such as nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate;
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, polypropylene glycol di(meth)acrylate, etc. polyalkylene glycol di(meth)acrylate;
Polyol di(meth)acrylate such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate and dipentaerythritol di(meth)acrylate ) acrylate;
Di(meth)acrylate of glycerol alkylene oxide adduct, Di(meth)acrylate of pentaerythritol alkylene oxide adduct, Di(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, Di(meth)acrylate of dipentaerythritol alkylene oxide adduct. ) Di(meth)acrylates of polyol alkylene oxide adducts such as acrylates;
Di(meth)acrylate of isocyanuric acid alkylene oxide adduct;
Urethane (meth)acrylate of pentaerythritol di(meth)acrylate and organic polyisocyanate;
Di(meth)acrylate of alicyclic diol such as tricyclodecane dimethylol di(meth)acrylate;
Examples include di(meth)acrylates of alkylene oxide adducts of bisphenol compounds, such as di(meth)acrylates of alkylene oxide adducts of bisphenol A and di(meth)acrylates of alkylene oxide adducts of bisphenol F.
In addition, examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

Examples of compounds having three or more (meth)acryloyl groups include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, ditrimethylolpropane tri- or polyol poly(meth)acrylates such as tri-, tetra-, penta- or hexa(meth)acrylates of tetra(meth)acrylate and dipentaerythritol;
Tri(meth)acrylate of glycerol alkylene oxide adduct, tri- or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, tri- or tetra(meth)acrylate of ditrimethylolpropane alkylene oxide adduct, diglycerol alkylene oxide adduct Poly(meth)acrylates of polyol alkylene oxide adducts such as tetra(meth)acrylate, dipentaerythritol alkylene oxide adducts tri, tetra, penta or hexa(meth)acrylate;
Tri(meth)acrylate of isocyanuric acid alkylene oxide adduct; and
Examples include urethane (meth)acrylate, which is a reaction product of a compound having a hydroxyl group and three or more (meth)acryloyl groups, such as pentaerythritol tri(meth)acrylate, and an organic polyisocyanate.
Examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.
Further, as the organic polyisocyanate, tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, Hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4'- Examples include dicyclohexylmethane diisocyanate, trimethylolpropane tris(tolylene diisocyanate) adduct, and isophorone diisocyanate.

As the component (E-2), oligomers can also be used, and examples include urethane (meth)acrylate, which is a reaction product of diol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate, and epoxy (meth)acrylate. I can do it.

Component (E-2) is preferably a renewable resource-derived compound produced from a renewable resource-derived raw material.
Specific examples of such compounds include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, di(meth)acrylate of glycerol alkylene oxide adducts, and glycerol triacrylate. Examples include (meth)acrylate and tetra(meth)acrylate of diglycerin alkylene oxide adduct.
The content ratio of the (E-2) component may be set as appropriate depending on the purpose. It is preferably contained in the total amount of 0 to 40 parts by weight (referred to as "curable component").

2-2. Component (F) Component (F) is a polymerization initiator.
When the curable composition is used as an active energy ray curable composition, particularly when it is used as a visible light or ultraviolet ray curable composition, a photopolymerization initiator [hereinafter referred to as "component (F-1)"] is added to the composition. ]. In addition, when preparing an electron beam curable composition, it is not necessarily necessary to add a photopolymerization initiator.
Component (F-1) is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group.

Specific examples of component (F-1) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo 2-hydroxy-2-methyl-1-[4- (1-methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-methyl- 1-[4-(Methylthio)]phenyl-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino- 2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n- Aromatic ketone compounds such as 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-Benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis Benzophenone compounds such as (diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2,6 acylphosphine oxide compounds such as -dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy]-2- Examples include thioxanthone compounds such as hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone.

When using the component in the organic phase obtained in the neutralization step of step 3 as the (meth)acrylate obtained by the production method of the present invention, the component (F-1) is α-hydroxyphenyl ketones, In the atmosphere, even a thin film coating has good surface hardening properties and is preferred. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one are preferred. More preferred.

When using the component in the aqueous phase obtained in the neutralization step of step 3 as the (meth)acrylate obtained by the production method of the present invention, the component (F-1) has excellent compatibility with water. and 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, phenyl Methyl glyoxylate is preferred.

When the curable composition is used as a thermosetting composition, a thermal polymerization initiator [hereinafter referred to as "component (F-2)"] is blended into the composition.
As component (F-2), various compounds can be used, including organic peroxides and azo compounds.

3. Method for producing a curable composition The present invention also relates to a method for producing a curable composition.
That is, the present invention relates to a method for producing a curable composition in which a (meth)acrylate mixture and component (E) are stirred and mixed.

The present invention also relates to a method for producing an active energy ray-curable composition.
That is, it is a manufacturing method in which a (meth)acrylate mixture, component (E), and component (F-1) are stirred and mixed, and 0.01 to 20 parts by weight of the curable components are mixed. The present invention relates to a method for producing an active energy ray-curable composition using parts by weight of component (F).

In the method for producing the composition, in step 2-1, compound (C) is preferably used in a molar ratio of 1 to 50 times per mole of compound (B) in total.
In addition, by performing Step 2-2 as Step 2, the obtained (meth)acrylate mixture has excellent curability, and the obtained cured product has excellent physical properties such as hardness, adhesion, and low curling properties. preferable.
Further, it is preferable that at least one of compound (A), compound (B), compound (C), and compound (D) contains a compound derived from a renewable resource.

Moreover, as a method for producing the composition, a method of stirring and mixing the (meth)acrylate mixture and component (E) at the ratio shown below is preferable.
Contains 40 to 100 parts by weight of a (meth)acrylate mixture, 0 to 20 parts by weight of component (E-1), and 0 to 40 parts by weight of component (E-2) as component (E).

In addition, as a method for producing the composition, after sequentially performing steps 1 to 3, the (meth)acrylate mixture in the organic phase obtained in step 3 and/or the neutralized aqueous phase is converted into a hardening type. Preferably, it is used as a component of a composition.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to these Examples.
Further, in the following, unless otherwise specified, "part" means part by weight, and "%" means weight %.

In this production example, ¹ H NMR was measured under the following conditions.

< ^1H NMR measurement conditions>
Equipment: AVANCE III (manufactured by Bruker)
Measurement mode: single mode Solvent: _CDCl3
Pulse angle: 45 degrees Sample concentration: 4 to 6% by weight Number of concentration accumulations: 16 times

1. Example [Method for producing acrylate mixture]
1-1. Example 1-1
1) Process 1
In a 1 L four-necked flask with a side tube equipped with a reflux tube, 196 g of an ethylene oxide adduct of diglycerin as compound (A) [manufactured by Kao Corporation, Emulgen G2E-4] was placed. Hereinafter, it will be referred to as "G2E4". ], 119 g of acrylic acid (ratio of 0.76 mol to 1 mol of total hydroxyl groups in alcohol), 8.3 g of 70% methanesulfonic acid (hereinafter referred to as "MSA"), 0.6 g of cupric chloride, and toluene. 240g was added.
While blowing oxygen-containing gas (5% by volume of oxygen, 95% by volume of nitrogen) into the flask, the reaction solution was heated and stirred at a temperature of 85 to 95°C. As the reaction progressed, the dehydration esterification reaction was carried out for 11 hours while the water produced was taken out of the system through a Dean-Stark tube.
The obtained reaction product had a hydroxyl value of 61 mgKOH/g.

2) Process 2
After completion of step 1, the pressure was returned to normal pressure, and 71 g of itaconic acid (hereinafter referred to as "ITA") was added as compound (B) and 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 were added, and while oxygen-containing gas was blown into the flask, the reaction solution was heated and stirred at a temperature of 85 to 95°C. As the reaction progressed, the dehydration esterification reaction was carried out for 13 hours while the water produced was taken out of the system through a Dean-Stark tube.

3) Process 3
After the reaction in step 2 was completed, 389 g of toluene was added to dilute the reaction mixture. Furthermore, 106 g of distilled water was added, stirred, and left to stand, and then the lower aqueous phase was removed.
Next, 53 g of 10% aqueous ammonia and 53 g of 4% aqueous ammonium sulfate were added with stirring, sufficiently stirred, and left to stand, after which 380 g of the lower phase was collected. Subsequently, 178 g of 4% ammonium sulfate water was added to the organic phase while stirring, and after the mixture was allowed to stand still, the lower aqueous phase was removed.
The upper organic phase was heated under reduced pressure to distill off toluene. The obtained acrylate mixture weighed 248 g (yield 60%), and the measurement results of APHA, hydroxyl value, acid value, and viscosity are shown in Table 2.
A ¹ H NMR chart of the obtained organic phase acrylate is shown in FIG. 1, and ^{a 1} H NMR chart of the obtained aqueous phase acrylate is shown in FIG.

1-2. Examples 1-2 to 1-7
In Example 1,

Steps

1 and 2 were carried out in the same manner as in Example 1, except that the raw materials and proportions shown in Tables 1 and 2 were used.
In the same manner as in Example 1, dilution with toluene, washing with distilled water, neutralization with 10% ammonia water and 4% ammonium sulfate water, recovery of the lower phase, washing with 4% ammonium sulfate water, and desolvation were performed. 3 was carried out.
The amount of aqueous phase shown in Table 2 was collected during neutralization. Table 2 shows the measurement results of the yield, APHA, acid value, and viscosity of the obtained acrylate mixture.

1-3. Comparative example 1-1
In Example 1,

Steps

1 and 2 were carried out in the same manner as in Example 1, except that the raw materials and proportions shown in Tables 1 and 2 were used.
After completing step 2, 389 g of toluene was added for dilution. Furthermore, 106 g of distilled water was added, stirred, and left to stand, and then the lower aqueous phase was removed. Next, 126 g of a 20% aqueous sodium hydroxide solution was added with stirring, sufficiently stirred, and left to stand, and then 243 g of the lower phase was collected. Subsequently, 207 g of 4% ammonium sulfate water was added to the organic phase while stirring, and after the mixture was allowed to stand still, the lower aqueous phase was removed.
The upper organic phase was heated under reduced pressure to distill off toluene. The amount of the acrylate mixture obtained was 340 g (yield: 82%).

1-4. Comparative example 1-2
In a 1 L four-necked flask with a side tube equipped with a reflux tube, 117 g of G2E4, 42 g of itaconic acid (0.5 mole per mole of total hydroxyl groups in the alcohol), 13.5 g of 70% MSA, and sulfuric chloride. 0.6 g of copper and 381 g of toluene were charged.
While blowing oxygen-containing gas into the flask, the reaction solution was heated and stirred at a temperature of 85 to 95°C. As the reaction progressed, the dehydration esterification reaction was carried out for 6 hours while the water produced was taken out of the system through a Dean-Stark tube. However, a gel insoluble in toluene was formed and the gel entangled with the stirring blades, making stirring difficult, so the synthesis was stopped. The reaction rate calculated from the amount of distilled water was 30%.

In Table 1 above, the numbers mean the parts by weight of the ingredients, and the abbreviations mean the following.
・AA: Acrylic acid
◆Compound (A)
・G2E4: Diglycerin ethylene oxide denatured alcohol, Emulgen G2E-4 manufactured by Kao Corporation (contains diglycerin skeleton as a raw material derived from renewable resources)
・DGLY: Diglycerin ・PER: Pentaerythritol
◆Compound (B)
・ITA: Itaconic acid (manufactured by Itaconix, raw material derived from renewable resources)
◆Acid catalyst /MSA: 70% methanesulfonic acid aqueous solution
◆Polymerization inhibitor /CuCl ₂ : Cupric chloride
◆Organic solvent /TOL: Toluene

In Table 2 above, the numbers mean parts by weight of the ingredients, and the abbreviations mean the following. The number in parentheses in the yield row means the yield (%).
◆Compound (B)
・SUC: Succinic acid (manufactured by Roquette, raw material derived from renewable resources)
・FDC: 2,5-furandicarboxylic acid (manufactured by Avantium, raw material derived from renewable resources)
・ADI: Adipic acid (raw material derived from renewable resources)
◆Compound (C)
・BDOH: 1,4-butanediol (manufactured by BASF, raw material derived from renewable resources)
・PDOH: 1,3-propanediol (manufactured by Dupont Tate & Lyle, raw material derived from renewable resources)
・FDM: 2,5-furandimethanol (manufactured by OG Co., Ltd., raw material derived from renewable resources)
・EG: Ethylene glycol (manufactured by Grenncol Taiwan, raw material derived from renewable resources)
・TFM: 2,5-tetrahydrofurandimethanol (manufactured by OG Co., Ltd., raw material derived from renewable resources)
◆Compound (D)
・HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

Liquid property evaluation /APHA: Measured according to JIS K 0071-1:2017.
- Hydroxyl value: Measured according to JIS K 0070.
- Acid value: Measured according to JIS K 0070.
- Viscosity: Measured at 25°C using an E-type viscometer (“TV-22 type viscometer” manufactured by Toki Sangyo Co., Ltd., cone plate type).

1-5. Evaluation Results Compared to Examples 1-1 to 1-7, the reaction product produced in Comparative Example 1-1 contained a certain proportion of crosslinked products, and the product had high hydrophilicity. As a result, a toluene-insoluble gel was formed in the reaction solution, making further reaction difficult.

2. Example [Production of active energy ray-curable composition]
2-1. Example 2-1
1-Hydroxy-cyclohexyl-phenyl ketone (manufactured by IGM Resins, Omnirad 184, hereinafter) was added as component (E-1) to 100 parts by weight of the acrylate mixture produced in Example 1-1 and obtained after desolvation of the organic phase. , referred to as "Omn184") was added thereto, and the mixture was stirred and mixed at 60° C. for 3 hours to obtain a composition.

2-2. Examples 2-2 to 2-7 [Production of active energy ray-curable solvent-free composition]
Compositions were produced in the same manner as in Example 2-1, except that the acrylate mixtures produced in Examples 1-2 to 1-7 and obtained after desolvation of the organic phase were used.

2-3. Comparative Example 2-1 [Production of active energy ray-curable solvent-free composition]
A composition was produced in the same manner as in Example 2-1, except that the acrylate mixture produced in Comparative Example 1-1 and obtained after solvent removal was used.

2-4. Example 3-1 [Production of active energy ray-curable water dispersion composition]
Methyl benzoyl formate [Omnirad MBF manufactured by IGM Resins] was added as component (E-1) to 100 parts of the solid content in the aqueous phase separated in Example 1-1. Hereinafter referred to as "MBF". ] was added and stirred and mixed at 60° C. for 3 hours to obtain an aqueous dispersion composition.

2-5. Examples 3-2 to 3-7 [Production of active energy ray-curable water dispersion composition]
Compositions were produced in the same manner as in Example 3-1, except that the aqueous phase separated in Examples 1-2 to 1-7 was used.

2-6. Comparative Example 3-1 [Production of active energy ray-curable water dispersion composition]
5 parts of MBF as component (E-1) was added to 100 parts of the solid content in the water separated in Comparative Example 1-1, and the mixture was stirred and mixed at 60° C. for 3 hours to obtain a water-dispersed composition.

3. Cured product evaluation method
(1) Production of test specimen Using the obtained composition, an easily adhesive PET film manufactured by Toyobo Co., Ltd. [Cosmoshine (registered trademark) A4360, film thickness: 100 μm] was cut into 10 cm square pieces using a bar coater. Hereinafter referred to as "A4360"], the coating was applied to a film thickness of 10 μm.
Using this, irradiate with a UV-A lamp output illuminance of 80 W/cm and irradiation intensity of 290 mW/cm ² per pass using a high-pressure mercury lamp equipped with a conveyor [H06-L41 manufactured by Eye Graphics Co., Ltd.] Ultraviolet rays were irradiated at an energy of 400 mJ/cm ² .

(2) Curing property The cured product of the test specimen obtained after one pass was evaluated by touch using the following evaluation criteria.
○: No tack on the surface.
Δ: Slight tackiness on the surface.
×: There is tack on the surface.

(3) Appearance of cured product The cured product of the obtained test specimen was visually observed and evaluated according to the following evaluation criteria.
○: Colorless and transparent.
Δ: Slight cloudiness is observed.
×: Cloudiness is observed.

(4) Pencil hardness Evaluation was performed under a load of 750 g according to JIS K 5600-5-4.

(5) On the adhesion test specimen, use a cutter knife to make incisions at 1 mm intervals vertically and horizontally to form 25 squares of 1 mm x 1 mm in size, and place #405 cellophane tape manufactured by Nichiban Co., Ltd. on the grid. After pasting it on, I peeled it off strongly. The number of remaining films after peeling was evaluated. The larger the number of remaining films, the better the adhesion.

(6) Curl The average height of the four vertices of the cured product of the obtained test specimen was measured. It is preferably 1.0 mm or less.

4. Evaluation Results The evaluation results are shown in Tables 3 and 4.

The compositions of Examples 2-1 to 2-7 had excellent curability, and the cured products thereof had excellent appearance and pencil hardness.
Furthermore, the water-dispersed compositions of Examples 3-1 to 3-7 had excellent curability, and the cured products had good appearance, pencil hardness, adhesion, and curl.
On the other hand, the aqueous dispersion composition of Comparative Example 3-1 had poor curability due to the presence of the sodium salt, and the appearance of the cured product also deteriorated, making it impossible to evaluate pencil hardness, adhesion, and curl.
From the above results, it is clear that in Examples 1-1 to 1-7, all of the charged reaction raw materials can be converted into raw materials for the curable composition. According to the invention, it is possible to prevent the generation of neutralized wastewater that has a large environmental load, and to provide an industrially effective manufacturing method.

The production method of the present invention can obtain a desired (meth)acrylate mixture in high yield using a renewable resource-derived compound as a raw material, and the obtained (meth)acrylate mixture corresponds to a renewable resource-derived compound, It can greatly contribute to reducing environmental impact.
The (meth)acrylate mixture contained in the organic phase obtained by the production method of the present invention and the wastewater after the neutralization purification step can both be used as a raw material for a curable composition, etc., and the curable composition can be It can be preferably used as ink, coating agent, resist agent, filler, molding material, etc., and more preferably used as coating agent and ink.

Claims

A method for producing a (meth)acrylate mixture by sequentially carrying out the following steps 1 to 3.
・Step 1: (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups are subjected to a dehydration esterification reaction in the presence of an acid catalyst to produce a hydroxyl group-containing (meth) having a hydroxyl value of 55 to 175 mgKOH/g. Step 2 of obtaining a reaction solution containing acrylate: Step 2-1 or step 2-2 below to obtain a product with a hydroxyl value of 55 mgKOH/g or less Step 2-1; (B) dicarboxylic acid, (C) diol, and (meth)acrylic acid are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate to obtain a product.
Step 2-2: To the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in Step 1, (B) dicarboxylic acid and (D) hydroxyalkyl (meth)acrylate are added to obtain a product.
・Step 3: A step of neutralizing the reaction solution obtained in Step 2 with one or more neutralizing agents selected from an aqueous solution of ammonia and an aqueous solution of an amine compound.
The method for producing a (meth)acrylate mixture according to claim 1, wherein in the step 2-1, the (C) diol is used in a ratio of 1 to 50 times the mole of the dicarboxylic acid (B).
The method for producing a (meth)acrylate mixture according to claim 1, wherein the step 2-2 is performed as the step 2.
A claim in which at least one compound of (A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource. A method for producing a (meth)acrylate mixture according to any one of claims 1 to 3.
Stirring the (meth)acrylate mixture obtained by sequentially performing the following steps 1 to 3 and (E) an ethylenically unsaturated compound other than the (meth)acrylate mixture [hereinafter referred to as "component (E)"]. - A method for producing a curable composition to be mixed.
・Step 1: (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups are subjected to a dehydration esterification reaction in the presence of an acid catalyst to produce a hydroxyl group-containing (meth) having a hydroxyl value of 55 to 175 mgKOH/g. Step 2 of obtaining a reaction solution containing acrylate: Step 2-1 or step 2-2 below to obtain a product with a hydroxyl value of 55 mgKOH/g or less Step 2-1; (B) dicarboxylic acid, (C) diol, and (meth)acrylic acid are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate to obtain a product.
Step 2-2: To the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in Step 1, (B) dicarboxylic acid and (D) hydroxyalkyl (meth)acrylate are added to obtain a product.
・Step 3: A step of neutralizing the reaction solution obtained in Step 2 with one or more neutralizing agents selected from an aqueous solution of ammonia and an aqueous solution of an amine compound.
The method for producing a curable composition according to claim 5, wherein in the step 2-1, the diol (C) is used in a ratio of 1 to 50 times the mole of the dicarboxylic acid (B).
The method for producing a curable composition according to claim 5, wherein the step 2-2 is performed as the step 2.
A claim in which at least one compound of (A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource. A method for producing a curable composition according to any one of claims 5 to 7.
The (meth)acrylate mixture obtained by sequentially carrying out the above steps 1 to 3, and (E-1) a compound having one (meth)acryloyl group as the component (E) [hereinafter referred to as "(E-1)"] (hereinafter referred to as "component (E-2)")] and (E-2) a compound having two or more (meth)acryloyl groups [hereinafter referred to as "component (E-2)"],
Claims 5 to 8 are stirred and mixed in a ratio containing 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). A method for producing a curable composition according to any one of the above.
5. After sequentially performing steps 1 to 3, the (meth)acrylate mixture obtained in step 3 in the organic phase and/or in the neutralized aqueous phase is used as a component of the curable composition. - A method for producing a curable composition according to any one of claims 9 to 9.
A production method comprising stirring and mixing a (meth)acrylate mixture obtained by sequentially carrying out the following steps 1 to 3, component (E), and (F-1) a photopolymerization initiator, the method comprising: ) A method for producing an active energy ray-curable composition using 0.01 to 20 parts by weight of the photopolymerization initiator (F-1) based on a total of 100 parts by weight of the acrylate mixture and component (E).
・Step 1: (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups are subjected to a dehydration esterification reaction in the presence of an acid catalyst to produce a hydroxyl group-containing (meth) having a hydroxyl value of 55 to 175 mgKOH/g. Step 2 of obtaining a reaction solution containing acrylate: Step 2-1 or step 2-2 below to obtain a product with a hydroxyl value of 55 mgKOH/g or less Step 2-1; (B) dicarboxylic acid, (C) diol, and (meth)acrylic acid are added to the reaction solution containing the hydroxyl group-containing (meth)acrylate to obtain a product.
Step 2-2: To the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in Step 1, (B) dicarboxylic acid and (D) hydroxyalkyl (meth)acrylate are added to obtain a product.
・Step 3: A step of neutralizing the reaction solution obtained in Step 2 with one or more neutralizing agents selected from an aqueous solution of ammonia and an aqueous solution of an amine compound.
Production of the active energy ray-curable composition according to claim 11, wherein in the step 2-1, the diol (C) is used in a ratio of 1 to 50 times in mole to a total of 1 mole of the dicarboxylic acid (B). Method.
The method for producing an active energy ray-curable composition according to claim 11, wherein the step 2-2 is performed as the step 2.
A claim in which at least one compound of (A) an alcohol having three or more hydroxyl groups, (B) a dicarboxylic acid, (C) a diol, and (D) a hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource. A method for producing an active energy ray-curable composition according to any one of claims 11 to 13.
A (meth)acrylate mixture obtained by sequentially carrying out steps 1 to 3, and a component containing components (E-1) and (E-2) as component (E),
Claims 11 to 14 are stirred and mixed in a ratio containing 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). A method for producing an active energy ray-curable composition according to any one of the above.
11. After sequentially carrying out steps 1 to 3, the (meth)acrylate mixture in the organic phase obtained in step 3 and/or in the aqueous phase after neutralization is used as a component of the curable composition. - A method for producing an active energy ray-curable composition according to any one of claims 15 to 16.
A method for producing an active energy ray-curable composition for ink according to any one of claims 11 to 16.
A method for producing an active energy ray-curable composition for a coating agent according to any one of claims 11 to 16.