Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/48—Separation; Purification; Stabilisation; Use of additives
  • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

• 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 short-term exposure to active energy rays such as ultraviolet rays, visible light, and electron beams, and are highly productive and are widely used in applications such as inks, coating agents, and resist materials.
• active energy rays such as ultraviolet rays, visible light, and electron beams
• the neutralization step is preferably carried out in order to prevent polymerization during removal of the solvent from the epoxy acrylate.
• it is generally considered desirable to neutralize polyfunctional (meth)acrylates, but not neutralizing them has the advantage of reducing wastewater. If the physical properties after curing are the same regardless of whether neutralization is performed or not, and if the final product (meth)acrylate can be produced without polymerization, then there are great benefits to not neutralizing the compound.
• Patent Document 3 discloses a polyester polyol produced from (a) recycled polyester, (b) glycol, and (c) lignin or tannin.
• the polyester polyol obtained above is converted into a urethane to be used as a raw material for paint.
• Patent Document 4 describes a radiation-curable coating agent for flooring materials that contains polyacrylate, which is a compound derived from renewable resources.
• Patent Document 4 does not describe a purification process for removing the catalyst from the product, and there are concerns about problems due to the catalyst remaining in the product.
• sebacic acid of vegetable oil which is a compound derived from renewable resources, is a raw material for soft resins used in applications such as adhesives, the hardness of the cured product is insufficient, and it is insufficient for use in applications such as coating agents.
• the inventors have conducted extensive research to find a manufacturing method that uses compounds derived from renewable resources as raw materials, can produce the desired (meth)acrylate mixture in high yield with less wastewater (waste) than conventional manufacturing methods, significantly reduces the environmental impact, and produces a (meth)acrylate mixture with excellent curing properties and hardness.
• a method for producing a (meth)acrylate mixture which comprises the steps of: subjecting (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups to a dehydration esterification reaction in an organic solvent containing an acid catalyst to produce an acrylate mixture having a specific hydroxyl value; adding a reaction liquid containing a hydroxyl-containing (meth)acrylate having a specific hydroxyl value obtained by a similar method to (B) a dicarboxylic acid, (C) a diol, (meth)acrylic acid, etc.
• a desired (meth)acrylate mixture can be obtained in high yield using a compound derived from a renewable resource as a raw material.
• the obtained (meth)acrylate mixture also corresponds to a compound derived from a renewable resource, and can greatly contribute to reducing the environmental load.
• Any (meth)acrylate mixture obtained by the production method of the present invention can be used as a raw material for a curable composition, has fast curing properties, and the cured product has high hardness and can be preferably used as an ink, a coating agent, a resist material, etc.
• the product can be obtained in high yield, and no alkaline aqueous solution (heavy liquid) is discharged after the neutralization process, making it possible to reduce the environmental load.
• the present invention relates to a method for producing a (meth)acrylate mixture by sequentially carrying out the following steps 1 and 2:
• Step 1 A step of carrying out the following step (1-1), step (1-2) or step (1-3).
• ⁇ Step (1-1) A step of carrying out a dehydration esterification reaction of (meth)acrylic acid and (A) an alcohol having 3 or more hydroxyl groups [hereinafter referred to as "compound (A)"] in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl-containing (meth)acrylate having a hydroxyl value (hereinafter simply referred to as "hydroxyl value”) calculated from the solid content excluding the organic solvent of 1 to 80 mgKOH/g.
• hydroxyl value a hydroxyl value
• ⁇ Step (1-2) A step of carrying out the following steps (1-2-1) and (1-2-2) in sequence.
• ⁇ Step (1-2-1) A step of carrying out a dehydration esterification reaction of (meth)acrylic acid and compound (A) in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl-containing (meth)acrylate having a hydroxyl value of 90 to 175 mgKOH/g.
• Step (1-3) A step of sequentially carrying out the following steps (1-3-1) and (1-3-2): A step of carrying out a dehydration esterification reaction between (meth)acrylic acid and compound (A) in the presence of an acid catalyst to obtain a reaction solution containing a hydroxyl group-containing (meth)acrylate having a hydroxyl group value of 90 to 175 mgKOH/g.
• Step (1-3-2) A step of adding (B) a dicarboxylic acid and (D) a hydroxyalkyl (meth)acrylate to the reaction solution containing the hydroxyl group-containing (meth)acrylate obtained in the step (1-3-1) to perform a dehydration esterification reaction to obtain a reaction solution having a hydroxyl group value of 70 mgKOH/g or less.
• Step 2 A step of washing the reaction solution obtained in the step 1 with only water.
• step (1-2-2) of the above-mentioned step (1-2) it is preferable to use 0.8 to 50 times the molar amount of the dicarboxylic acid (B) per mole of the total number of moles of hydroxyl groups in the reaction solution obtained in the step (1-2-1).
• step (1-2-2) of the step (1-2) it is preferable to use the diol (C) in a molar ratio of 1 to 50 times the total of 1 mole of the dicarboxylic acid (B).
• step (1-3-2) of the above process (1-3) it is preferable to use 0.8 to 50 times the molar amount of (B) dicarboxylic acid per mole of the total number of moles of hydroxyl groups in the reaction solution obtained in step (1-3-1).
• step (1-3-2) of the above process (1-3) it is preferable to use 1.0 to 2.0 times the molar ratio of (D) hydroxyalkyl (meth)acrylate to the total molar number of the residual (meth)acrylic acid and (B) dicarboxylic acid in the reaction solution obtained in step (1-3-1).
• At least one of the compounds (A), (B) dicarboxylic acid, (C) diol, and (D) hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource.
• the present invention also relates to a method for producing a curable composition, which comprises stirring and mixing the (meth)acrylate mixture obtained by sequentially carrying out steps 1 and 2 above with (E) an ethylenically unsaturated compound other than the (meth)acrylate mixture [hereinafter referred to as "component (E)"].
• At least one of the compounds (A), (B) dicarboxylic acid, (C) diol, and (D) hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource.
• a preferred production method involves stirring and mixing in a ratio containing 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of the (E-1) component, and 0 to 40 parts by weight of the (E-2) component. It is also preferred that after the step 1 is carried out, the organic layer containing the (meth)acrylate mixture obtained in the step
• the present invention also relates to a method for producing an active energy ray-curable composition, which comprises stirring and mixing the (meth)acrylate mixture obtained by sequentially carrying out steps 1 and 2, component (E), and photopolymerization initiator (F-1), and uses 0.01 to 20 parts by weight of photopolymerization initiator (F-1) per 100 parts by weight of the total of the (meth)acrylate mixture and component (E).
• At least one of the compounds (A), (B) dicarboxylic acid, (C) diol, and (D) hydroxyalkyl (meth)acrylate contains a compound derived from a renewable resource.
• a (meth)acrylate mixture obtained by sequentially carrying out steps 1 and 2 and a component containing components (E-1) and (E-2) as component (E) are mixed,
• a preferred production method involves stirring and mixing in a ratio containing 40 to 100 parts by weight of the (meth)acrylate mixture, 0 to 20 parts by weight of the (E-1) component, and 0 to 40 parts by weight of the (E-2) component.
• the organic layer containing the (meth)acrylate mixture obtained in the step 2 is used as a compounding component of the curable composition.
• the production method is preferably a method for producing an active energy ray-curable composition for ink or an active energy ray-curable composition for coating agent.
• the present invention will be described in detail below.
• Step 1 is a step of carrying out step (1-1), step (1-2) or step (1-3) described below.
• steps (1-1) to (1-3) will be described respectively.
• Step (1-1) is a step of subjecting (meth)acrylic acid and a compound (A) [an alcohol having three or more hydroxyl groups] to a dehydration esterification reaction in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl group-containing (meth)acrylate having a hydroxyl value of 1 to 80 mgKOH/g.
• the compound (A) is an alcohol having three or more hydroxyl groups, and various compounds can be used.
• Specific examples of the compound (A) include trivalent or higher polyols such as glycerin, diglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol, alkylene oxide adducts of these trivalent or higher polyols, and tris(2-hydroxyethyl)isocyanurate.
• the compound (A) is preferably a compound derived from a renewable resource.
• the renewable resource-derived compound is a compound having a renewable resource structure, and more specifically, means a biological material (biomass) and a compound produced from a biological material.
• a plant-derived material and a compound produced from a plant-derived material are preferable.
• Specific examples of such compounds include glycerin, diglycerin, alkylene oxide adducts of glycerin, and alkylene oxide adducts of diglycerin.
• the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.
• a method for subjecting (meth)acrylic acid and compound (A) to a dehydration esterification reaction in an organic solvent containing an acid catalyst may be performed according to a conventional method, and examples of the method include a method in which (meth)acrylic acid and compound (A) are heated and stirred in an organic solvent containing an acid catalyst.
• the proportion of (meth)acrylic acid used is preferably 0.05 to 20 moles, more preferably 1.0 to 1.4 moles, per mole of the total of all hydroxyl groups in compound (A) so as to obtain the desired (meth)acrylate.
• the proportion of (meth)acrylic acid used is preferably 0.05 to 20 moles, more preferably 1.0 to 1.4 moles, per mole of the total of all hydroxyl groups in compound (A) so as to obtain the desired (meth)acrylate.
• the acid catalyst examples 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 strongly acidic cationic ion exchange resins.
• the proportion of the acid catalyst used is preferably 0.05 mol % to 20 mol % per mole of the total of all hydroxyl groups in 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, it is preferably 65 to 140° C., more preferably 75 to 120° C.
• the reaction temperature is preferably 65 to 140° C., more preferably 75 to 120° C.
• organic solvent In the dehydration esterification reaction, an organic solvent is used, and the dehydration is promoted by azeotroping the water produced in the dehydration esterification reaction with the organic solvent, which has low solubility in water.
• Preferred organic solvents include, for example, aromatic hydrocarbon compounds such as toluene, benzene, and xylene, aliphatic hydrocarbon compounds such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, chlorine-based hydrocarbon compounds such as trichloroethylene and tetrachloroethylene, and ketones such as methyl ethyl ketone.
• the amount of the organic solvent used is preferably such that the concentration of the organic solvent in the reaction solution is 30 to 60% by weight, more preferably 40 to 50% by weight.
• 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 liquid.
• the polymerization inhibitor 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, phenothiazine, and N-oxyl compounds; inorganic polymerization inhibitors such as copper chloride and copper sulfate; and organic salt-based polymerization inhibitors such as copper dibutyldithiocarbamate.
• the polymerization inhibitor may be used alone or in any combination of two or more kinds.
• the proportion of the polymerization inhibitor in the reaction liquid is preferably 5 to 20,000 wtppm, and more preferably 25 to 3,000 wtppm.
• the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium.
• the reaction liquid obtained in step (1-1) according to the above method has a hydroxyl value calculated from the solid content excluding the solvent of 1 to 80 mgKOH/g, preferably 1 to 35 mgKOH/g or less, more preferably 1 to 5 mgKOH/g or less.
• the hydroxyl value is monitored during the reaction, and the esterification reaction is stopped when the hydroxyl value reaches the monitored value. If the hydroxyl value of the reaction solution exceeds 80 mgKOH/g, the content of mono(meth)acrylate in the mixture increases, which deteriorates the curability and hardness of the cured product.
• the hydroxyl value of the reaction solution falls below 1 mgKOH/g, the viscosity increases and dilution with a solvent is required, which may become a source of VOC emissions.
• the hydroxyl value means a value measured in accordance with JIS K0070.
• the compound (A) is a compound derived from a renewable resource
• the resulting (meth)acrylate mixture corresponds to a compound derived from a renewable resource.
• Step (1-2) is a step of sequentially carrying out the following steps (1-2-1) and (1-2-2).
• Step (1-2-1) A step of subjecting (meth)acrylic acid and compound (A) to a dehydration esterification reaction in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl group-containing (meth)acrylate having a hydroxyl value of 90 to 175 mgKOH/g.
• Step (1-2-2) A step of adding (B) a dicarboxylic acid, (C) a diol, and (meth)acrylic acid to the reaction liquid containing the hydroxyl group-containing (meth)acrylate obtained in the step (1-2-1) to perform a dehydration esterification reaction to obtain a reaction liquid having a hydroxyl value of 70 mgKOH/g or less.
• Step (1-2-1) is a step of subjecting (meth)acrylic acid and compound (A) to a dehydration esterification reaction in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl group-containing (meth)acrylate having a hydroxyl value of 90 to 175 mgKOH/g.
• the compound (A) in the step (1-2-1) may be the same as the compound in the step (1-1).
• the method of dehydration esterification may be the same as that in the above step (1-1) except for the proportion of (meth)acrylic acid used.
• the proportion of (meth)acrylic acid used is preferably 0.625 to 0.875 times by mole, and more preferably 0.70 to 0.80 times by mole, per mole of the total of all hydroxyl groups in compound (A).
• By using (meth)acrylic acid in an amount of 0.625 times by mole or more it is possible to prevent the proportion of diacrylate in the step (1-2-1) from becoming high and to prevent gelation due to unintended polymerization.
• By using (meth)acrylic acid in an amount of 0.875 times by mole or less it is possible to prevent a decrease in the proportion of the target (meth)acrylate in the final product.
• the reaction liquid containing a hydroxyl group-containing (meth)acrylate obtained in step (1-2-1) according to the above method has a hydroxyl value, calculated from the solid content excluding the solvent, of 90 to 175 mgKOH/g, preferably 95 to 105 mgKOH/g.
• the hydroxyl value is monitored during the reaction, and the esterification reaction is stopped when the hydroxyl value reaches the monitored value. If the hydroxyl value of the reaction solution exceeds 175 mgKOH/g, a crosslinkable (meth)acrylate may be generated in step (1-2-2), which may cause gelation or difficulty in stirring.
• the hydroxyl value of the reaction solution is less than 90 mgKOH/g, the proportion of the desired (meth)acrylate contained in the final product may be significantly reduced.
• Step (1-2-2) Step (1-2-2) is a step of 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 liquid containing the hydroxyl group-containing (meth)acrylate obtained in step (1-2-1) to carry out a dehydration esterification reaction to obtain a product having a hydroxyl value of 70 mgKOH/g or less.
• compound (B), compound (C), and the reaction method will be described below.
• Compound (B) is a dicarboxylic acid, and various compounds can be used.
• Specific examples of the compound (B) include aliphatic dicarboxylic acids such as itaconic acid and succinic acid, aromatic dicarboxylic acids such as terephthalic acid, and dicarboxylic acids having a heterocyclic skeleton such as 2,5-furandicarboxylic acid.
• Compound (B) is preferably a compound derived from a renewable resource.
• Compound (B) preferably has 2 to 12 carbon atoms, and when compound (B) has 9 or more carbon atoms, a cyclic structure is essential.
• Specific examples of the compound include itaconic acid, succinic acid, and 2,5-furandicarboxylic acid.
• the compound (C) is a diol, and various compounds can be used.
• Specific examples of the compound (C) include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol, cyclic ether diols such as 2,5-tetrahydrofuran dimethanol, and diols having a heterocyclic skeleton such as 2,5-furan dimethanol.
• Compound (C) is preferably a compound derived from a renewable resource.
• Compound (C) preferably has 1 to 10 carbon atoms, and when the carbon number is 7 or more, a cyclic structure is essential.
• Specific examples of the compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,5-tetrahydrofuran diethanol, and 2,5-furan diethanol.
• step (1-2-2) Reaction in step (1-2-2)
• step (1-2-2) compound (B), compound (C) and (meth)acrylic acid are added to the reaction liquid containing the hydroxyl group-containing (meth)acrylate obtained in step (1-2-1) to carry out a dehydration esterification reaction.
• the proportion of compound (B) used is preferably 0.8 to 50 moles, more preferably 0.9 to 1.1 moles, per mole of the total number of moles of hydroxyl groups in the reaction solution obtained in step (1-2-1).
• the compound (B) at a molar ratio of 0.8 or more, it is possible to prevent a decrease in the ratio of (meth)acrylate having a polyester unit in the (meth)acrylate mixture, and to prevent an increase in highly hydrophilic components, which dissolve in water during the process of washing the reaction liquid with water and cause a loss of raw materials.
• the amount of compound (C) used is preferably 1 to 50 moles, more preferably 1.3 to 1.5 moles, per mole of compound (B).
• the compound (C) is preferably 1 to 50 moles, more preferably 1.3 to 1.5 moles, per mole of compound (B).
• the ratio of (meth)acrylic acid added in step (1-2-2) is preferably 1.0 to 1.2 moles per mole of compound (C).
• the hydroxyl value of the product at which the reaction in step (1-2-2) is terminated is 70 mgKOH/g or less, preferably 60 mgKOH/g or less, and more preferably 1 to 50 mgKOH/g. If the hydroxyl value of the product exceeds 70 mgKOH/g, a large amount of hydrophilic components will remain, resulting in a low yield of the desired (meth)acrylate.
• a dehydration esterification reaction of an acid and an alcohol proceeds due to the acid catalyst contained in the reaction product of step (1-2-1), and reactions with various compounds proceed.
• the reaction temperature in the reaction of step (1-2-2) is preferably 75 to 110° C., more preferably 85 to 100° C. If the reaction temperature is lower than 75° C., the desired esterification does not proceed easily, and if the reaction temperature is higher than 110° C., the Michael addition proceeds, consuming (meth)acryloyl groups and decreasing the proportion of the desired (meth)acrylate.
• step (1-2-2) the dehydration esterification reaction of an acid and an alcohol specifically proceeds as a dehydration esterification reaction of (meth)acrylic acid and an alcohol, a dehydration esterification reaction of compound (B) and compound (C), and the like.
• Examples of the main reactions are shown in the following reactions (1-2-1-1) to (1-2-1-6).
• Reaction (1-2-1-1) Production of a hydroxyl-free (meth)acrylate and a hydroxyl-containing (meth)acrylate (hereinafter referred to as "hydroxyl-containing (meth)acrylate (1-2-2)" by the reaction of the hydroxyl-containing (meth)acrylate obtained in step (1-2-1) [hereinafter referred to as "hydroxyl-containing (meth)acrylate (1-2-1)] with (meth)acrylic acid.
• Reaction (1-2-1-2) Production of a polyester diol [hereinafter referred to as “polyester diol (1-2)” by the reaction of compound (B) with compound (C).
• (1-2-1-3) is a reaction between polyester diol (1-2) and (meth)acrylic acid to produce a polyester (meth)acrylate.
• (1-2-1-4) is a reaction between hydroxyl group-containing (meth)acrylate (1-2-1) or hydroxyl group-containing (meth)acrylate (1-2-2) and compound (B) to produce a (meth)acrylate.
• (1-2-1-5) is a reaction between hydroxyl group-containing (meth)acrylate (1-2-1), hydroxyl group-containing (meth)acrylate (1-2-2), and/or polyester diol (1-2) and compound (B) to produce a (meth)acrylate.
• (1-2-1-6) is a reaction between compound (C) and (meth)acrylic acid to produce a (meth)acrylate.
• the resulting (meth)acrylate mixture corresponds to a compound derived from a renewable resource.
• Step (1-3) is a step of sequentially carrying out the following steps (1-3-1) and (1-3-2).
• Step (1-3-1) A step of subjecting (meth)acrylic acid and (A) an alcohol having three or more hydroxyl groups to a dehydration esterification reaction in the presence of an acid catalyst to obtain a reaction liquid containing a hydroxyl group-containing (meth)acrylate having a hydroxyl value of 90 to 175 mgKOH/g.
• Step (1-3-2) A step of adding (B) a dicarboxylic acid and (D) a hydroxyalkyl (meth)acrylate [hereinafter referred to as "compound (D)"] to the reaction liquid containing the hydroxyl group-containing (meth)acrylate obtained in the step (1-3-1) to perform a dehydration esterification reaction to obtain a reaction liquid having a hydroxyl value of 70 mgKOH/g or less.
• Step (1-3-1) is a step of subjecting (meth)acrylic acid and compound (A) to a dehydration esterification reaction in an organic solvent containing an acid catalyst to obtain a reaction liquid containing a hydroxyl group-containing (meth)acrylate having a hydroxyl value of 90 to 175 mgKOH/g.
• the step (1-3-1) may be carried out by using the raw material compounds in the above-mentioned step (1-2-1) and by the same reaction method as in the step (1-2-1).
• the proportion of (meth)acrylic acid used is preferably the same as that described above for the same reasons as in step (1-2-1).
• Step (1-3-2) Step (1-3-2) is a step of adding compound (B) and compound (D) to the reaction liquid containing the hydroxyl group-containing (meth)acrylate obtained in step (1-3-1) to carry out a dehydration esterification reaction, thereby obtaining a reaction liquid having a hydroxyl value of 70 mgKOH/g or less.
• Compound (B), compound (D) and the reaction method will be described below.
• Compound (B) is a dicarboxylic acid, and various compounds can be used, specific examples of which include the same compounds as those mentioned above.
• Compound (B) is preferably a compound derived from a renewable resource, and specific examples thereof include the same compounds as those mentioned above.
• the compound (D) is a hydroxyalkyl (meth)acrylate, and various compounds can be used. Specific examples of the compound (D) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. Compound (D) is preferably a compound derived from a renewable resource. Specific examples of the compound include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
• step (1-3-2) Reaction in step (1-3-2)
• step (1-3-2) compound (B) and compound (D) are added to the reaction liquid containing the hydroxyl group-containing (meth)acrylate obtained in step (1-3-1) to carry out a dehydration esterification reaction to obtain a product.
• the proportion of compound (B) used is preferably 0.8 to 50 times, more preferably 0.9 to 1.1 times, the total number of moles of hydroxyl groups in the reaction solution obtained in step (1-3-1).
• the compound (B) at a molar ratio of 0.8 or more, it is possible to prevent a decrease in the ratio of (meth)acrylate having a polyester unit in the (meth)acrylate mixture, and to prevent an increase in highly hydrophilic components, which dissolve in water during the process of washing the reaction liquid with water and cause a loss of raw materials.
• the proportion of compound (D) used is preferably 1.0 to 2.0 times by mole, more preferably 1.0 to 1.5 times by mole, based on the total number of moles of unreacted (meth)acrylic acid and compound (B) after step (1-3-1).
• the proportion of compound (D) used is preferably 1.0 to 2.0 times by mole, more preferably 1.0 to 1.5 times by mole, based on the total number of moles of unreacted (meth)acrylic acid and compound (B) after step (1-3-1).
• the hydroxyl value of the product at which the reaction in step (1-3-2) is terminated is 70 mgKOH/g or less, preferably 60 mgKOH/g or less, and more preferably 1 to 50 mgKOH/g. If the hydroxyl value of the product exceeds 70 mgKOH/g, a large amount of hydrophilic components will remain, resulting in a low yield of the desired (meth)acrylate.
• step (1-3-2) a dehydration esterification reaction of an acid and an alcohol proceeds due to the acid catalyst contained in the reaction product of step (1-3-1), and reactions with various compounds proceed.
• the reaction temperature in the step (1-3-2) is preferably 75 to 110°C, more preferably 85 to 100°C.
• reaction (1-3-2-1) Production of a (meth)acrylate by reaction of the hydroxyl-containing (meth)acrylate obtained in step (1-3-1) [hereinafter referred to as "hydroxyl-containing (meth)acrylate (1-3-1)"], compound (B) and compound (D).
• reaction (1-3-2-2) Production of a carboxyl-containing (meth)acrylate by reaction of the hydroxyl-containing (meth)acrylate (1-3-1) and compound (B).
• the resulting (meth)acrylate mixture corresponds to a compound derived from a renewable resource.
• Step 2 is a step in which the reaction solution obtained in step 1 is washed only with water.
• the reaction liquid obtained in step 1 contains, in addition to the (meth)acrylate mixture that is the product, unreacted (meth)acrylic acid and acidic components such as an acid catalyst. This is done for the purpose of removing acidic components such as the acid catalyst.
• the washing treatment with water is carried out by contacting the reaction liquid with water, and specifically, may be carried out according to a conventional method, for example, a method in which water is added to the reaction liquid and stirred and mixed, etc. may be mentioned.
• the water detergent used for washing it is preferable to use distilled water, purified water, etc.
• the number of washing steps can be set appropriately depending on the purpose, but from the viewpoint of reducing wastewater, it is preferable to wash once.
• step 2 which is a water washing step
• step 2 it is preferable to dilute the reaction liquid obtained in step 1 by adding an organic solvent before carrying out step 2.
• the organic solvent used for dilution is preferably the same compound as the organic solvent used in step 1.
• 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.
• the liquid after the water washing treatment separates into two layers, an organic phase and an aqueous phase. Since the organic phase has a lower specific gravity than the aqueous phase, the organic phase is separated into an upper layer and the aqueous phase is separated into a lower layer. The lower aqueous phase is drained off and separated from the organic phase.
• the method of using the separated organic phase may be appropriately selected depending on the content of the organic phase. Examples of the method of using the extracted organic phase include a method of using it as it is as a raw material for a curable composition, a method of using it as a raw material for a curable composition after distilling off the organic solvent, and the like.
• the extracted aqueous phase is disposed of.
• Examples of the (meth)acrylate mixture contained in the organic layer after step (1-2) and step (2) include the following (O-2-1) to (O-2-10).
• (O-2-1) A (meth)acrylate having no hydroxyl groups obtained in step (1-2-1) and a (meth)acrylate having no hydroxyl groups obtained in step (1-2-2).
• (O-2-2) A polyester di(meth)acrylate having no hydroxyl groups obtained by the reaction of polyester diol (1-2) with (meth)acrylic acid.
• (O-2-3) A polyester di(meth)acrylate having no hydroxyl groups obtained by the reaction of hydroxyl-containing (meth)acrylate (1-2-1) and/or hydroxyl-containing (meth)acrylate (1-2-2) with compound (B).
• Examples of the (meth)acrylate mixture contained in the organic layer after step (1-3) and step (2) include the following (O-3-1) to (O-3-6).
• (O-3-1) (meth)acrylate not having a hydroxyl group obtained in step (1-3-1) (O-3-2) (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate (1-3-1), compound (B) and compound (D) (O-3-3) (meth)acrylate containing a hydroxyl group (1-3-1) (O-3-4)
• a carboxyl group-containing (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate (1-3-1) with compound (B) (O-3-5) A carboxyl group-containing mono(meth)acrylate obtained by reacting compound (B) with compound (C) (O-3-6) Unreacted (meth)acrylic acid
• the organic layer containing the (meth)acrylate mixture can be used as is, or the (meth)acrylate mixture after removing the organic solvent can be used as the organic layer.
• 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.
• it is suitable for use in various industrial applications as a main component, crosslinking component, or reactive diluent component of a composition in applications such as coating agents such as paints, inks, adhesives, resists, fillers, and molding materials.
• the molding material can be used after being processed into the shape of a film, sheet, etc., and the film or sheet can be used for optical purposes such as an optical lens.
• the (meth)acrylate mixture obtained by the production method of the present invention is preferably used as a component of a curable composition, and its application can be more preferably used as a coating agent or ink.
• the components of the organic layer obtained in the water washing step of step 2 can be used.
• the organic layer containing the (meth)acrylate mixture can be used as it is, or the (meth)acrylates can be used after evaporating the organic solvent from the organic layer.
• organic layer containing the (meth)acrylate mixture is used as is, it becomes an organic solvent-based composition.
• component (E) an ethylenically unsaturated compound other than the (meth)acrylate mixture obtained by the production method of the present invention
• component (F) a polymerization initiator
• component (E) examples include 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-2)").
• component (E-1) a compound having one (meth)acryloyl group
• component (E-2) a compound having two or more (meth)acryloyl groups
• the component (E-1) is a compound having one (meth)acryloyl group in each molecule.
• Specific examples of the component (E-1) include (meth)acrylates having one (meth)acryloyl group (hereinafter referred to as “monofunctional (meth)acrylates”) and (meth)acrylamide compounds having one (meth)acryloyl group (hereinafter referred to as “monofunctional (meth)acrylamides").
• the monofunctional (meth)acrylate include alkyl (meth)acrylates such as 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 (meth)acrylate, and stearyl (meth)acrylate; monofunctional (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate, menthyl acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.
• Acrylates monofunctional (meth)acrylates having a cyclic ether group, such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-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)acrylolyloxyethylhexahydrophthalimide; Examples of the monofunctional
• monofunctional (meth)acrylamide compounds include N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-n-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-sec-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, and N-n-hexyl (meth)acrylamide; N-hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide; and N,N-dialkyl (meth)acrylamides such as 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)
• the component (E-1) is preferably a compound derived from renewable resources produced 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 of the component (E-1) may be appropriately set depending on the purpose, and it is preferable that the component (E-1) is contained in an amount of 0 to 20 parts by weight based on the total amount of the curable components.
• the component (E-2) is a compound having two or more (meth)acryloyl groups.
• examples of the compound having two (meth)acryloyl 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; polyalkylene glycol di(meth)acrylates 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; glycerin
• di(meth)acrylates of polyol alkylene oxide adducts such as 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)acrylate of isocyanuric acid alkylene oxide adduct; urethane (meth)acrylate of pentaerythritol di(meth)acrylate and organic polyisocyanate; di(meth)acrylates of alicyclic diols such as tricyclodecane dimethylol di(meth)acrylate; di(meth)acrylates of alkylene oxide adducts of bisphenol-based compounds such as di(meth)acrylate of alkylene oxide a
• Examples of compounds having three or more (meth)acryloyl groups include polyol poly(meth)acrylates such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri- or tetra(meth)acrylate of pentaerythritol, tri- or tetra(meth)acrylate of ditrimethylolpropane, and tri-, tetra-, penta-, or hexa(meth)acrylate of dipentaerythritol; tri(meth)acrylate of glycerol alkylene oxide adduct, tri- or tetra(meth)acrylate of pentaerythritol alkylene oxide adduct, ditrimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of dipentaerythritol, and dipentaerythritol alkylene oxide adduct
• poly(meth)acrylates examples include polyol alkylene oxide adducts such as tri- or tetra(meth)acrylates of polyol alkylene oxide adducts, tetra(meth)acrylates of diglycerol alkylene oxide adducts, and tri-, tetra-, penta-, or hexa(meth)acrylates of dipentaerythritol alkylene oxide adducts; tri(meth)acrylates of isocyanuric acid alkylene oxide adducts; and urethane (meth)acrylates which are reaction products of compounds having a hydroxyl group and three or more (meth)acryloyl groups with organic polyisocyanates, such as pentaerythritol tri(meth)acrylate.
• polyol alkylene oxide adducts such as tri- or tetra(meth)acrylates of polyol alkylene oxide adducts, t
• alkylene oxide adduct examples include an ethylene oxide adduct, a propylene oxide adduct, and an ethylene oxide and propylene oxide adduct.
• organic polyisocyanate examples include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 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 mutual adduct, 4,4'-dicyclohexylmethane diisocyanate, trimethylolpropane tri
• Oligomers can also be used as component (E-2), and examples of such materials include urethane (meth)acrylate, which is a reaction product of a diol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate, and epoxy (meth)acrylate.
• urethane (meth)acrylate which is a reaction product of a diol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate, and epoxy (meth)acrylate.
• a compound derived from a renewable resource produced from a raw material derived from a renewable resource is preferable.
• the compound include ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, di(meth)acrylate of a glycerol alkylene oxide adduct, glycerin tri(meth)acrylate, and tetra(meth)acrylate of a diglycerin alkylene oxide adduct.
• the content ratio of the (E-2) component may be appropriately set depending on the purpose, and it is preferably contained in an amount of 0 to 40 parts by weight in the total amount of the (meth)acrylate mixture and the (E) component (hereinafter, the (meth)acrylate mixture and the (E) component are collectively referred to as the "curable components").
• the component (F) is a polymerization initiator.
• a photopolymerization initiator hereinafter referred to as "component (F-1)
• the component (F-1) is a compound that generates radicals when irradiated with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group.
• the (F-1) component examples include benzyl dimethyl ketal, benzil, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-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-methylpropanone, Aromatic ketone compounds such as propan-1-one, 2-methyl-1-[4-(methylthio)]phenyl-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan
• ⁇ -hydroxyphenyl ketones are preferred as the component (F-1) because they have good surface curing properties even in the form of a thin coating under atmospheric conditions.
• 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-phenyl ketone are preferred.
• -Methyl-1-phenyl-propan-1-one is more preferred.
• a thermal polymerization initiator (hereinafter referred to as “component (F-2)) is added when the curable composition is used as a thermosetting composition or when it is desired to promote polymerization during curing with active energy rays.
• component (F-2) various compounds can be used, including organic peroxides and azo compounds.
• the present invention also relates to a method for making the curable composition. That is, the present invention relates to a method for producing a curable composition, which comprises stirring and mixing a (meth)acrylate mixture and a component (E).
• the present invention also relates to a method for producing an active energy ray-curable composition. That is, the present invention relates to a method for producing an active energy ray-curable composition, which comprises stirring and mixing a (meth)acrylate mixture, a component (E), and a component (F-1), and uses 0.01 to 20 parts by weight of the component (F) per 100 parts by weight of the total of the curable components.
• step (1-2-2) of the step (1-2) it is preferable to use 0.8 to 50 times the molar amount of the dicarboxylic acid (B) per mole of the total number of moles of hydroxyl groups in the reaction solution obtained in step (1-2-1).
• step (1-2-2) of the step (1-2) it is preferable to use 1 to 50 times the molar amount of the compound (C) per 1 mole of the compound (B).
• step (1-3-2) of the step (1-3) it is preferable to use the dicarboxylic acid (B) in a molar ratio of 0.8 to 50 times the total number of moles of hydroxyl groups in the reaction solution obtained in the step (1-3-1).
• step (1-3-2) of the step (1-3) it is preferable to use the compound (D) in a molar ratio of 1.0 to 2.0 times the total molar amount of the residual (meth)acrylic acid and the compound (B) in the reaction solution obtained in the step (1-3-1).
• At least one of the compounds (A), (B), (C) and (D) contains a compound derived from a renewable resource. This will reduce dependency on petrochemical products, which are finite resources, and enable the use of renewable resources that have not been utilized much until now.
• the method for producing the composition is preferably a method of stirring and mixing the (meth)acrylate mixture obtained by sequentially carrying out steps 1 and 2 above with a component (E) that contains components (E-1) and (E-2) 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) in the total amount of the curable components.
• a method for producing the composition a method in which after carrying out step 1, the (meth)acrylate mixture of the organic layer obtained in step 2 is used as a compounding component of a curable composition is preferable.
• hydroxyl value means the hydroxyl value of the solid content excluding the solvent.
• Example 1-1 1) Step 1 [Step (1-1)] Into a 1 L four-neck flask equipped with a reflux condenser and equipped with a side tube, 220 g of an ethylene oxide adduct of diglycerin as compound (A) [manufactured by Kao Corporation, Emulgen G2E-4, hereinafter referred to as "G2E4"], 227 g of acrylic acid (a ratio of 1.29 moles per mole of the total hydroxyl groups in the alcohol), 8.3 g of 78% sulfuric acid, 0.7 g of methoxyphenol (hereinafter referred to as "MQ”), and 243 g of toluene were placed.
• A ethylene oxide adduct of diglycerin as compound (A) [manufactured by Kao Corporation, Emulgen G2E-4, hereinafter referred to as "G2E4"]
• 227 g of acrylic acid (a ratio
• Step 2 After the reaction in step 1 was completed, 231 g of toluene was added to dilute the mixture, and 168 g of distilled water was further added and stirred. After standing, 170 g of the lower aqueous layer was removed. The upper organic layer was heated under reduced pressure to distill off the toluene, and the resulting acrylate mixture weighed 351 g (yield 100%). The APHA, hydroxyl value, acid value, and viscosity of the resulting acrylate mixture were measured according to the following methods. The results are shown in Table 1.
• Evaluation method APHA Measured in accordance with JIS K 0071-1:2017. Hydroxyl value: Measured in accordance with JIS K 0070. Acid value: Measured in accordance with JIS K 0070. Viscosity: Measured at 25° C. using an E-type viscometer (Toki Sangyo Co., Ltd., "TV-22 viscometer," cone-plate type).
• Comparative Example 1-1 In Comparative Production Example 1, step 1 was carried out in the same manner as in Production Example 1, except that the raw materials and proportions shown in Table 1 were used. The mixture was diluted with 231 g of toluene in the same manner as in Production Example 1. Further, 168 g of distilled water was added, stirred, and allowed to stand, after which 170 g of the lower aqueous layer was removed. Next, 248 g of 20% NaOH water was added and stirred, and after standing, 292 g of the lower aqueous layer was removed. The upper organic layer was heated under reduced pressure to distill off toluene. The resulting acrylate mixture weighed 309 g (yield 88%), and its APHA, hydroxyl value, acid value, and viscosity were measured according to the methods described above. The results are shown in Table 1.
• Step 1 [Step (1-2)] (1) Process (1-2-1) Into a 1 L four-neck flask equipped with a reflux condenser and equipped with a side tube, 196 g of G2E-4, 119 g of acrylic acid (a ratio of 0.76 mol per mol of all hydroxyl groups in the alcohol), 8.3 g of 70% MSA, 0.6 g of cupric chloride, and 240 g of toluene were placed. While blowing oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) into the flask, the reaction solution was heated and stirred at a temperature of 85 to 95° C.
• oxygen-containing gas oxygen 5% by volume, nitrogen 95% by volume
• Step 2 After the reaction in step 1 was completed, 389 g of toluene was added for dilution, and 115 g of distilled water was further added and stirred. After standing, 113 g of the lower aqueous layer was removed. The upper organic layer was heated under reduced pressure to distill off the toluene. The resulting acrylate mixture weighed 417 g (yield 100%), and the APHA, hydroxyl value, acid value, and viscosity were measured according to the methods described above. The results are shown in Table 2.
• Example 1-3 A dehydration esterification reaction was carried out in the same manner as in step (1-2-1) in Example 1-2 to obtain a reaction liquid.
• Step 1 A dehydration esterification reaction was carried out in the same manner as in step (1-2-1) in Example 1-2 to obtain a reaction liquid. The reaction was carried out in the same manner as in the step (1-2-2) of Example 1-2, except that 119 g of acrylic acid was not used. The resulting reaction product had a hydroxyl value of 49 mgKOH/g. 2) Step 2 Following the same method as in step 2 of Example 1-2, after the reaction in step 1 was completed, 389 g of toluene was added for dilution. Further, 115 g of distilled water was added, stirred, and allowed to stand, after which 114 g of the lower aqueous layer was removed.
• Example 1-1 Evaluation results Comparing Example 1-1 and Comparative Example 1-1, the yield was 100% in Example 1-1, whereas the yield was reduced to 88% in Comparative Example 1-1, since a neutralization treatment was performed and acidic acrylates and the like were removed during neutralization.
• the total amount of wastewater was 170 g in Example 1-1, whereas the total amount of wastewater was 462 g in Comparative Example 1-1, due to an increase in the amount of the water layer during the neutralization treatment.
• the yields were all 100% in Examples 1-2 and 1-3, whereas in Comparative Example 1-3, a neutralization treatment was performed and acidic acrylates and the like were removed during neutralization, resulting in a reduced yield of 59%.
• Example [Production of active energy ray-curable composition] 2-1 Five parts of 1-hydroxycyclohexylphenylketone (Omnirad 184, manufactured by IGM Resins, hereinafter referred to as "Omn184") as component (E-1) was added to 100 parts by weight of the acrylate mixture produced in Example 1-1 and obtained after removing the solvent from the organic layer, and the mixture was stirred and mixed at 60°C for 3 hours to obtain a composition.
• component (E-1) 1-hydroxycyclohexylphenylketone (Omnirad 184, manufactured by IGM Resins, hereinafter referred to as "Omn184") as component (E-1) was added to 100 parts by weight of the acrylate mixture produced in Example 1-1 and obtained after removing the solvent from the organic layer, and the mixture was stirred and mixed at 60°C for 3 hours to obtain a composition.
• Examples 2-2 and 2-3 [Production of active energy ray-curable solventless composition] A composition was prepared in the same manner as in Example 2-1, except that the acrylate mixture prepared in Examples 1-2 and 1-3 and obtained after removing the solvent from the organic layer was used.
• Comparative Example 2-1 Production of active energy ray-curable solventless 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 removing the solvent was used.
• Comparative Example 2-2 Preparation of active energy ray-curable water-dispersed composition
• a composition was produced in the same manner as in Example 2-1, except that the acrylate mixture produced in Comparative Example 1-2 and obtained after removing the solvent was used.
• Evaluation method for cured product (1) Manufacturing of test specimens The obtained composition was used and applied to an easily adhesive PET film (Cosmoshine (registered trademark) A4360, film thickness: 100 ⁇ m) manufactured by Toyobo Co., Ltd., which was cut into a 10 cm square using a bar coater. Hereinafter referred to as "A4360”) was applied to a film thickness of 10 ⁇ m.
• A4360 Cosmoshine (registered trademark) A4360, film thickness: 100 ⁇ m
• ultraviolet rays were irradiated using a high-pressure mercury lamp equipped with a conveyor (H06-L41 manufactured by Eye Graphics Co., Ltd.) under the conditions of a UV-A lamp output illuminance of 80 W/cm, an irradiation intensity per pass of 290 mW/ cm2 , and an irradiation energy of 250 mJ/ cm2 .
• Pencil hardness The evaluation was carried out according to JIS K 5600-5-4 under a load of 750 g.
• compositions of Examples 2-1 to 2-3 and Comparative Examples 2-1 and 2-2 all had excellent curability, and the cured products thereof had excellent pencil hardness. That is, regardless of whether or not neutralization treatment is performed, the composition containing the acrylate obtained according to the present invention does not suffer from deterioration in curability and physical properties of the cured product. From the above results, it is apparent that the present invention can provide an industrially effective production method that prevents the generation of neutralization wastewater, which places a heavy burden on the environment.
• the production method of the present invention can obtain a desired (meth)acrylate mixture in high yield using a compound derived from a renewable resource as a raw material.
• the obtained (meth)acrylate mixture corresponds to a compound derived from a renewable resource, and can greatly contribute to reducing the environmental load.
• Any (meth)acrylate mixture obtained by the production method of the present invention can be used as a raw material for a curable composition, etc., and the curable composition can be preferably used as an ink, a coating agent, a resist agent, a filler, a molding material, etc., and can be more preferably used as a coating agent and an ink.

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