Ester compound-containing composition and method for producing the same, polymerizable composition, and method for producing (meth)acrylic polymer

Abstract

The purpose of the present invention is to provide an ester-compound-containing composition that has excellent storage stability and a method for producing the same, and methods for producing a polymerizable composition and a (meth)acrylic polymer that use this ester-compound-containing composition. An ester-compound-containing composition containing an ester compound (1) represented by formula (1): CH2=CR1-C(=O)-O-R2 (where, R1 is a hydrogen atom or a methyl group, R2 is a C2-20 hydrocarbon group, a C2-8 linear or branched alkyl group in which at least one hydrogen atom has been substituted by a hydroxy group, a C2-8 linear or branched alkyl group in which one or two hydrogen atoms have been substituted by (meth)acryloyloxy groups, or a group having an etheric oxygen between the carbon atoms of a C2-8 hydrocarbon group.) and a component A: α-olefin, in which the content of the component A is 1-1500 mass ppm inclusive, and the moisture content is 5000 mass ppm or less.

Description

[Technical Field]

[0001] The present invention relates to an ester compound-containing composition and a method for producing the same, a polymerizable composition, and a method for producing a (meth)acrylic polymer. This application claims priority based on Japanese Patent Application Nos. 2022-149219, 2022-149220, and 2022-149221, filed on September 20, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] (Meth)acrylic polymers obtained using (meth)acrylic acid esters are used in a variety of fields, such as paints, adhesives, resin modifiers, artificial marble, and paper latex. Known methods for producing (meth)acrylic acid esters include, for example, a method in which a raw material alkyl (meth)acrylate is subjected to an ester exchange reaction with an alkyl alcohol in the presence of a catalyst, Ti(OR)4 (R is an alkyl group), to produce the target alkyl (meth)acrylate (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-274986 Summary of the Invention [Problem to be solved by the invention]

[0004] When an ester compound-containing composition containing a (meth)acrylic acid ester is stored for a certain period of time after production, the quality of the ester compound-containing composition may deteriorate.

[0005] An object of the present invention is to provide an ester compound-containing composition having excellent storage stability, a method for producing the same, a polymerizable composition using the ester compound-containing composition, and a method for producing a (meth)acrylic polymer. [Means for solving the problem]

[0006] As a result of intensive investigations, the present inventors have found that during storage of an ester compound-containing composition, the concentration of the pure component decreases due to the generation of impurities such as (meth)acrylic acid ester dimers. Impurities such as (meth)acrylic acid ester dimers can be a factor that leads to a decrease in the physical properties of the (meth)acrylic polymer. The present inventors have further conducted research and found that when an ester compound-containing composition contains a specific component, the production of impurities such as a dimer of a (meth)acrylic acid ester is suppressed and storage stability is improved, thereby completing the present invention.

[0007] That is, the present invention includes the following aspects. [1] An ester compound (1) represented by the following formula (1) and component A: an α-olefin, The content of the component A is 1 ppm by mass or more and 1500 ppm by mass or less, An ester compound-containing composition having a water content of 5000 ppm by mass or less. CH2=CR 1 -C(=O)-OR 2 ···(1) (However, in the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom or a functional group. [2] In the formula (1), R 2 is a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms in which one or two hydrogen atoms are substituted with a (meth)acryloyloxy group, or a group having an etheric oxygen atom between carbon atoms in a hydrocarbon group having 2 to 8 carbon atoms. [3] The ester compound-containing composition according to [1], wherein the ester compound (1) includes an ester compound (1-1) represented by the following formula (1-1): CH2=CR a1 -C(=O)-OR a2 (1-1) (However, in the formula (1-1), R a1 is a hydrogen atom or a methyl group, and R a2 is a hydrocarbon group having 2 to 20 carbon atoms. [4] R a2 The ester compound-containing composition according to [3], which contains the ester compound (1-1) in which is a linear or branched alkyl group having 2 to 20 carbon atoms. [5] The ester compound-containing composition according to [3] or [4], wherein the content of the ester compound (1-1) is 85.00% by mass or more and 99.99% by mass or less. [6] The ester compound-containing composition according to any one of [1] to [5], wherein the ester compound (1) comprises one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23): [ka] (However, in the formulas (1-21) to (1-23), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, and R b2 and R b4 are each independently a linear or branched alkylene group or a hydroxyalkylene group having 2 to 8 carbon atoms, and R b7 is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms. [7] The ester compound-containing composition according to [6], wherein the ester compound (1-2) comprises one or more selected from the group consisting of ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and trimethylolpropane tri(meth)acrylate. [8] The ester compound-containing composition according to [6] or [7], wherein the content of the ester compound (1-2) is 85.00% by mass or more and 99.99% by mass or less. [9] The ester compound-containing composition according to any one of [1] to [8], wherein the ester compound (1) includes an ester compound (1-3) represented by the following formula (1-3): CH2=CR c1 -C(=O)-OR c2 (1-3) (However, in the formula (1-3), R c1 is a hydrogen atom or a methyl group, and R c2 is a group having an etheric oxygen atom between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[10] R c2 The ester compound-containing composition according to [9], comprising an ester compound (1-3) in which is a 2-methoxyethyl group, a glycidyl group, or a tetrahydrofurfuryl group.

[11] The ester compound-containing composition according to [9] or

[10] , wherein the content of the ester compound (1-3) is 85.00% by mass or more and 99.99% by mass or less.

[12] The ester compound-containing composition according to any one of [1] to

[11] , wherein the component A contains an α-olefin having 6 to 12 carbon atoms.

[13] Component B: The ester compound-containing composition according to any one of [1] to

[12] , further comprising a polymerization inhibitor.

[14] The ester compound-containing composition according to any one of [1] to

[13] , which is an ester compound-containing composition that has been stored for one day or more.

[15] A method for producing an ester compound-containing composition containing an ester compound (1) represented by the following formula (1): Component A: A method for producing an ester compound-containing composition, comprising carrying out a transesterification reaction between methyl (meth)acrylate and an alcohol (a) having 2 to 20 carbon atoms in the presence of an α-olefin. CH2=CR 1 -C(=O)-OR 2 ···(1) (However, in the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom or a functional group.

[16] In the formula (1), R 2 is a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a group in which one or two hydrogen atoms of a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms are substituted with a (meth)acryloyloxy group, or a group having an etheric oxygen atom between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms, The method for producing an ester compound-containing composition according to

[15] , wherein the alcohol (a) is at least one selected from the following alcohols (a1) to (a3): (a1) Monoalcohols having 2 to 20 carbon atoms (a2) one or more alcohols selected from the group consisting of dialcohols having 2 to 8 carbon atoms and trialcohols having 2 to 8 carbon atoms (a3) Alcohols containing 2 to 8 carbon atoms and containing an ether bond

[17] The method for producing an ester compound-containing composition according to

[16] , comprising carrying out a transesterification reaction between methyl (meth)acrylate and the alcohol (a1) in the presence of the component A to obtain an ester compound (1-1) represented by the following formula (1-1): CH2=CR a1 -C(=O)-OR a2 (1-1) (However, in the formula (1-1), R a1 is a hydrogen atom or a methyl group, and R a2 is a hydrocarbon group having 2 to 20 carbon atoms.

[18] The method for producing an ester compound-containing composition according to

[17] , wherein the alcohol (a1) comprises a linear or branched monoalcohol having 2 to 20 carbon atoms.

[19] The method for producing an ester compound-containing composition according to any one of

[15] to

[18] , wherein a transesterification reaction is carried out between methyl (meth)acrylate and the alcohol (a2) in the presence of the component A to obtain an ester compound (1-2) containing one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23): [ka] (However, in the formulas (2-1) to (2-3), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, and R b2 and R b4 are each independently a linear or branched alkylene group or a hydroxyalkylene group having 2 to 8 carbon atoms, and R b7 is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

[20] The method for producing an ester compound-containing composition according to

[19] , wherein the alcohol (a2) comprises one or more selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, and trimethylolpropane.

[21] A method for producing an ester compound-containing composition according to any one of

[15] to

[20] , comprising carrying out a transesterification reaction between methyl (meth)acrylate and the alcohol (a3) ​​in the presence of the component A to obtain an ester compound (1-3) represented by the following formula (1-3): CH2=CR c1 -C(=O)-OR c2 (1-3) (However, in the formula (1-3), R c1is a hydrogen atom or a methyl group, and R c2 is a group having an etheric oxygen atom between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[22] The method for producing an ester compound-containing composition according to

[21] , wherein the alcohol (a3) ​​includes one selected from 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol.

[23] The method for producing an ester compound-containing composition according to any one of

[15] to

[22] , wherein the component A contains an α-olefin having 6 to 12 carbon atoms.

[24] A polymerizable composition for producing a (meth)acrylic polymer, comprising the ester compound-containing composition according to any one of [1] to

[14] .

[25] Component C: The content of at least one compound selected from the group consisting of compounds of transition metals and compounds of Group 13 elements is 7 × 10 relative to the total mass of component A in the ester compound-containing composition. 4 The polymerizable composition according to

[24] , wherein the total amount of the polymerizable compound is ppm by mass or less.

[26] A method for producing a (meth)acrylic polymer, comprising polymerizing the polymerizable composition according to

[24] .

[27] A method for producing a (meth)acrylic polymer, comprising polymerizing the polymerizable composition according to

[25] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an ester compound-containing composition having excellent storage stability, a method for producing the same, a polymerizable composition using the ester compound-containing composition, and a method for producing a (meth)acrylic polymer. DETAILED DESCRIPTION OF THE INVENTION

[0009] As used in the specification and claims, the following terms have the following definitions: "Monomer" means a compound having a polymerizable carbon-carbon double bond. The "(meth)acrylate" is selected from "acrylate" and "methacrylate". The "(meth)acrylic acid" is selected from "acrylic acid" and "methacrylic acid". An "α-olefin" is an olefinic hydrocarbon having a carbon-carbon double bond at the α-position. "Transition metal" refers to metallic elements located in groups 3 to 12 of the periodic table. Typically, these elements include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), lanthanum (La), cerium (Ce), and praseodymium (Pr). ), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and mercury (Hg). "Group 13 elements" means elements located in Group 13 of the periodic table, typically boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl). "Periodic Table" means the "Periodic Table of Elements" (URL https: / / pubchem.ncbi.nlm.nih.gov / periodic-table / ).

[0010] [Ester compound-containing composition] An ester compound-containing composition according to an embodiment of the present invention contains an ester compound (1) described below and component A: an α-olefin.

[0011] (Ester compound (1)) The ester compound (1) is a (meth)acrylic acid ester represented by the following formula (1). CH2=CR 1 -C(=O)-OR 2 ···(1) However, in the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom or a functional group. R 2 Examples of the heteroatom that may be contained include nitrogen, oxygen, phosphorus, sulfur, etc., with nitrogen and oxygen being preferred. R 2 Examples of the functional group that may be contained include a hydroxy group, an aldehyde group, a carbonyl group, a carboxy group, an amino group, a nitro group, a nitroso group, a thiol group, a sulfonic acid group, a fluoro group, a chloro group, a bromo group, and an iodo group, and a hydroxy group, a carbonyl group, a carboxy group, an amino group, a thiol group, a sulfonic acid group, a fluoro group, a chloro group, and a bromo group are preferred.

[0012] R 2 The alkyl group is preferably a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom has been substituted with a hydroxy group, a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms in which one or two hydrogen atoms have been substituted with a (meth)acryloyloxy group, or a hydrocarbon group having 2 to 8 carbon atoms in which an etheric oxygen atom is present between the carbon atoms. The linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom has been substituted with a hydroxy group is preferably a linear or branched alkyl group having 2 to 8 carbon atoms in which one or two hydrogen atoms have been substituted with a hydroxy group.

[0013] An ester compound-containing composition according to an embodiment can contain, as the ester compound (1), an ester compound (1-1) represented by the following formula (1-1): 2 is a (meth)acrylic acid ester in which the hydrocarbon group has 2 to 20 carbon atoms. CH2=CR a1-C(=O)-OR a2 (1-1) However, in the formula (1-1), R a1 is a hydrogen atom or a methyl group. a2 is a hydrocarbon group having 2 to 20 carbon atoms.

[0014] R a2 The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. R a2 The hydrocarbon group R may be linear, branched, or may have a ring. a2 When the hydrocarbon group has a ring, the ring may be an aliphatic ring or an aromatic ring. R a2 The hydrocarbon group has 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and more preferably 2 to 12 carbon atoms.

[0015] R a2 Examples of the hydrocarbon group include an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aromatic alkyl group having 7 to 20 carbon atoms. However, the term "aromatic alkyl group" refers to a group in which one or more hydrogen atoms of an alkyl group are substituted with an aryl group.

[0016] R a2 Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, a lauryl group, and a stearyl group. R a2 Examples of the cycloalkyl group include a cyclopropyl group, a cyclohexyl group, and an isobornyl group. R a2 Examples of the alkenyl group include a vinyl group and an allyl group. R a2 Examples of the cycloalkenyl group include a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexenyl group. R a2 An example of the alkynyl group is a propynyl group. R a2 Examples of the aryl group include a phenyl group and a naphthyl group. R a2 An example of the aromatic alkyl group is a benzyl group.

[0017] The ester compound (1-1) is relatively easy to obtain and relatively easy to handle in terms of physical properties. a2 As the alkyl group, an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aromatic alkyl group having 7 to 20 carbon atoms are preferred, and an ethyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, a lauryl group, a cyclohexyl group, an allyl group, a phenyl group, and a benzyl group are more preferred.

[0018] Examples of the ester compound (1-1) include ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0019] As the ester compound (1-1), R a2 is a linear or branched alkyl group having 2 to 20 carbon atoms; R is an alkyl (meth)acrylate; a2 cycloalkyl(meth)acrylate, R is a cycloalkyl group having 3 to 20 carbon atoms; a2 is an alkenyl group having 2 to 20 carbon atoms, R a2 is an aryl group having 6 to 20 carbon atoms, R a2is an aromatic alkyl group having 7 to 20 carbon atoms, and more preferred are ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. The ester compound (1-1) may be used alone or in combination of two or more kinds.

[0020] An ester compound-containing composition according to one embodiment can contain, as ester compound (1), one or more ester compounds (1-2) selected from the group consisting of ester compounds (1-21) represented by the following formula (1-21), ester compounds (1-22) represented by the following formula (1-22), and ester compounds (1-23) represented by the following formula (1-23). 2 is a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom has been substituted with a hydroxy group, or a (meth)acrylic acid ester in which one or two hydrogen atoms of a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms have been substituted with a (meth)acryloyloxy group.

[0021] [ka]

[0022] However, in the formulas (1-21) to (1-23), R b1 , R b3 , R b5 , R b6 , R b8 and R b9 are each independently a hydrogen atom or a methyl group, and R b2 and R b4 are each independently a linear or branched alkylene group or a hydroxyalkylene group having 2 to 8 carbon atoms, and Rb7 is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

[0023] R b2 and R b4 The alkylene group or hydroxyalkylene group has 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms. R b2 and R b4 Examples of the alkylene group include an ethylene group, a propylene group, an isopropylene group, and a butylene group. R b2 and R b4 Examples of the hydroxyalkylene group include a hydroxyethylene group, a hydroxypropylene group, and a hydroxybutylene group.

[0024] R b7 The trivalent hydrocarbon group has 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. R b7 An example of the trivalent hydrocarbon group is -CH2-C(-CH2-)(-CH3)-CH2-.

[0025] Examples of the ester compound (1-21) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Examples of the ester compound (1-22) include ethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. An example of the ester compound (1-23) is trimethylolpropane tri(meth)acrylate.

[0026] As the ester compound (1-2), it is preferable to include at least one selected from the group consisting of ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and trimethylolpropane tri(meth)acrylate, because they are relatively easy to obtain. The ester compound (1-2) may be used alone or in combination of two or more kinds.

[0027] The ester compound-containing composition of one embodiment can contain, as the ester compound (1), an ester compound (1-3) represented by the following formula (1-3): 2 is a (meth)acrylic acid ester, which is a group having an etheric oxygen between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms. CH2=CR c1 -C(=O)-OR c2 (1-3) However, in the formula (1-3), R c1 is a hydrogen atom or a methyl group, and R c2 is a group having an etheric oxygen atom between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

[0028] R c2 The number of etheric oxygen atoms in the hydrocarbon group is preferably one, but is not limited thereto, and may be two or more. R c2 The hydrocarbon group R may be linear, branched, or may have a ring. c2 When the ring has the formula: the ring may or may not contain an etheric oxygen atom. R c2 The hydrocarbon group has 2 to 8 carbon atoms, preferably 2 to 7 carbon atoms.

[0029] R c2 Examples of the hydrocarbon group include a 2-methoxyethyl group, a 2-(2-methoxyethoxy)ethyl group, a 2-[2-(2-methoxyethoxy)ethoxy]ethyl group, a glycidyl group, and a tetrahydrofurfuryl group. It is relatively easy to obtain and relatively easy to handle in terms of physical properties. c2 As the alkyl group, a 2-methoxyethyl group, a glycidyl group, or a tetrahydrofurfuryl group is preferred.

[0030] Examples of the ester compound (1-3) include 2-methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0031] As the ester compound (1-3), 2-methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate are preferred because they are relatively easy to handle in terms of physical properties. The ester compound (1-3) may be used alone or in combination of two or more kinds.

[0032] As the ester compound (1), only one selected from the ester compound (1-1), the ester compound (1-2) and the ester compound (1-3) may be used, or two or more selected therefrom may be used in combination.

[0033] (Component A) The inclusion of component A inhibits the dimerization reaction of ester compound (1) and the generation of oxidation products of ester compound (1) during storage, resulting in an ester compound-containing composition with excellent storage stability. The reason for this is unclear, but is presumed to be as follows. During storage of an ester compound-containing composition, ultraviolet-induced radicals, such as hydroxyl radicals, are generated when oxygen molecules absorb ultraviolet light from sunlight. Such radicals can cause the formation of dimers of ester compound (1) or oxidation products of ester compound (1). α-olefins are presumed to have excellent radical scavenging properties because the coupling products of olefins to which radicals generated by ultraviolet light are added are stable. Therefore, it is presumed that α-olefins trap radicals, thereby suppressing the dimerization of ester compound (1) through the radical polymerization mechanism and the formation of oxidation products.

[0034] A chain α-olefin is preferred as the α-olefin of Component A. Component A also preferably contains an α-olefin having 6 to 12 carbon atoms, and more preferably contains an α-olefin having 8 to 10 carbon atoms. Examples of the α-olefin include 2-ethyl-1-hexene, 2-methyl-1-heptene, 4-methyl-1-heptene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene.

[0035] As component A, at least one selected from the group consisting of 2-ethyl-1-hexene, 1-octene, and 1-dodecene is preferred because it is available at relatively low cost, 1-octene or 1-dodecene is more preferred, and 1-octene is even more preferred. The α-olefins may be used alone or in combination of two or more.

[0036] The proportion of the α-olefin having 6 to 12 carbon atoms relative to the total mass of component A is not particularly limited, but is preferably 80 mass% or more, more preferably 90 mass% or more, particularly preferably 99 mass% or more, and most preferably 100 mass%. The higher the proportion of the α-olefin having 6 to 12 carbon atoms, the more likely it is that the α-olefin will have the effect of improving the storage stability of the ester compound-containing composition.

[0037] (Component B) The ester compound-containing composition of the embodiment preferably further contains, in addition to the ester compound (1) and the α-olefin, Component B: a polymerization inhibitor. The inclusion of a polymerization inhibitor suppresses the progress of the polymerization reaction of ester compound (1) through a radical polymerization mechanism during storage. Furthermore, during storage, oxygen molecules in the ester compound-containing composition can absorb ultraviolet light from sunlight, generating hydroxyl radicals. However, the polymerization inhibitor can trap hydroxyl radicals, thereby suppressing the oxidation of ester compound (1) by hydroxyl radicals and further reducing the generation of oxidation products.

[0038] Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, nitrobenzene compounds, N-oxyl compounds, amine compounds, phosphorus-containing compounds, sulfur-containing compounds, iron-containing compounds, copper-containing compounds, and manganese-containing compounds. One or more types of polymerization inhibitors may be used.

[0039] Examples of the phenolic compound include alkylphenols, hydroxyphenols, aminophenols, nitrophenols, nitrosophenols, alkoxyphenols, and tocopherols.

[0040] Examples of alkylphenols include o-cresol, m-cresol, p-cresol, 2-t-butyl-4-methylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2-t-butylphenol, 4-t-butylphenol, 2,4-di-t-butylphenol, 2-methyl-4-t-butylphenol, 4-t-butyl-2,6-dimethylphenol, 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 3,5-di-t-butyl-4-hydroxytoluene.

[0041] Examples of hydroxyphenols include hydroquinone, 2-methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,6-di-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butylmethoxyhydroquinone, 2,3,5-trimethylhydroquinone, 2,5-dichlorohydroquinone, 1,2-dihydroxybenzene, 2-acetylhydroquinone, 4-methylcatechol, 4-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, and 2,3-dihydroxyacetophenone.

[0042] Examples of aminophenols include o-aminophenol, m-aminophenol, p-aminophenol, 2-(N,N-dimethylamino)phenol, and 4-(ethylamino)phenol.

[0043] Examples of nitrophenols include o-nitrophenol, m-nitrophenol, p-nitrophenol, and 2,4-dinitrophenol.

[0044] Examples of nitrosophenols include o-nitrosophenol, m-nitrosophenol, p-nitrosophenol, and α-nitroso-β-naphthol.

[0045] Examples of alkoxyphenols include 2-methoxyphenol, 2-ethoxyphenol, 2-isopropoxyphenol, 2-t-butoxyphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4-t-butoxyphenol, 4-heptoxyphenol, hydroquinone monobenzyl ether, t-butyl-4-methoxyphenol, di-t-butyl-4-methoxyphenol, pyrogallol-1,2-dimethyl ether, and hydroquinone monobenzoate.

[0046] Examples of tocopherols include α-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran.

[0047] Examples of quinone compounds include p-benzoquinone, chloro-p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone, 2,3-dimethyl-p-benzoquinone, 2,5-dimethyl-p-benzoquinone, methoxy-p-benzoquinone, and methyl-p-benzoquinone.

[0048] Examples of nitrobenzene compounds include nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrobenzene, dinitrodurene, and 2,2-diphenyl-1-picrylhydrazine.

[0049] Examples of the N-oxyl compounds include 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, piperidine-1-oxyl, 4-(dimethylamino)-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-amino-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-ethenoloxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethyl-piperidine-N-oxol. Examples include silyl, 2,2,5,5-tetramethyl-piperidine-N-oxyl, 3-amino-2,2,5,5-tetramethyl-piperidine-N-oxyl, 4,4',4"-tris(2,2,6,6-tetramethyl-piperidine-N-oxyl)phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, pyrrolidine-1-oxyl, 2,2,5,5-tetramethyl-1-oxa-3-azacyclopentyl-3-oxy, 2,2,5,5-tetramethyl-3-pyrrolinyl-1-oxy-3-carboxylic acid, 2,2,3,3,5,5,6,6-octamethyl-1,4-diazacyclohexyl-1,4-dioxy, di-t-butyl nitroxide, and di-t-amyl nitroxide.

[0050] Examples of the amine compounds include N,N-diphenylamine, alkylated diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyldiphenylamine, 4-aminodiphenylamine, p-nitrosodiphenylamine, N-nitrosodinaphthylamine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N'-dialkyl-p-phenylenediamine (the alkyl groups may be the same or different, each independently have 1 to 4 carbon atoms, and may be linear or branched), N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4 Examples of such amines include N,N'-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N-diethylhydroxylamine, 1,4-benzenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-benzenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, aldol-α-naphthylamine, N-phenyl-β-naphthylamine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, and 1-hydroxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

[0051] Examples of phosphorus-containing compounds include triphenylphosphine, triphenyl phosphite, triethyl phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [1,1-diphenyl-4,4'-diylbistetrakis-2,4-bis(1,1-dimethylethyl)phenyl] ester, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, and diphenyl phosphite. Examples include tearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphate diethyl ester, sodium bis(4-t-butylphenyl) phosphate, sodium 2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, and 1,3-bis(diphenoxyphosphonyloxy)benzene.

[0052] Examples of sulfur-containing compounds include diphenyl sulfide, phenothiazine, 3-oxophenothiazine, 5-oxophenothiazine, phenothiazine dimer, 1,4-dimercaptobenzene, 1,2-dimercaptobenzene, 2-mercaptophenol, 4-mercaptophenol, 2-(methylthio)phenol, 3,7-bis(dimethylamino)phenothiazinium chloride, and sulfur (element).

[0053] An example of the iron-containing compound is iron(III) chloride.

[0054] Examples of copper-containing compounds include copper dimethyldithiocarbamate, copper diethylthiocarbamate, copper dibutylthiocarbamate, copper salicylate, copper acetate, copper thiocyanate, copper nitrate, copper chloride, copper carbonate, copper hydroxide, copper acrylate, and copper methacrylate.

[0055] Examples of manganese-containing compounds include manganese dialkyldithiocarbamate (the alkyl groups are methyl, ethyl, propyl, or butyl groups, and may be the same or different), manganese diphenyldithiocarbamate, manganese formate, manganese acetate, manganese octanoate, manganese naphthenate, manganese permanganate, and manganese salts of ethylenediaminetetraacetic acid.

[0056] As the polymerization inhibitor, 4-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, N,N'-dialkyl-p-phenylenediamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl are preferred because they are more likely to exhibit the effect of improving storage stability.

[0057] The ester compound-containing composition of the embodiment may contain components other than the ester compound (1), component A, and component B. Examples of other components include additives such as a release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant assistant, a polymerization inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoaming agent, and a fluorescent agent. The ester compound-containing composition of the embodiment may contain unreacted raw materials, such as methyl (meth)acrylate, alcohol, and (meth)acrylic acid, that are present during the production of the ester compound-containing composition. The ester compound-containing composition according to an embodiment may contain a (meth)acrylic acid ester other than the ester compound (1).

[0058] (composition) The content of ester compound (1) in the ester compound-containing composition is preferably 85.00% by mass or more, more preferably 90.00% by mass or more, and even more preferably 95.00% by mass or more, based on the total mass of the ester compound-containing composition, and is preferably 99.99% by mass or less, more preferably 99.97% by mass or less, and even more preferably 99.95% by mass or less, based on the total mass of the ester compound-containing composition. The lower and upper limits of the content of the ester compound (1) can be arbitrarily combined, and are, for example, preferably 85.00% by mass or more and 99.99% by mass or less, more preferably 90.00% by mass or more and 99.97% by mass or less, and even more preferably 95.00% by mass or more and 99.95% by mass or less.

[0059] The content of component A in the ester compound-containing composition is 1 ppm by mass or more and 1500 ppm by mass or less, based on the total mass of the ester compound-containing composition. When the content of component A is within this range, the effect of suppressing dimerization of ester compound (1) and a decrease in the purity of ester compound (1) due to the generation of oxidation products can be obtained. The content of Component A is preferably 1 ppm by mass or more, more preferably 3 ppm by mass or more, since the effect of suppressing dimerization of ester compound (1) and generation of oxidation products is easily obtained. The content of Component A is preferably 1500 ppm by mass or less, more preferably 1200 ppm by mass or less, since the amount of impurities during production of the (meth)acrylic polymer is reduced and deterioration of the physical properties of the (meth)acrylic polymer is easily suppressed. The lower and upper limits of the content of Component A can be arbitrarily combined, and are preferably, for example, from 1 ppm by mass to 1500 ppm by mass, and more preferably from 3 ppm by mass to 1200 ppm by mass.

[0060] The content of component B in the ester compound-containing composition is preferably 1 ppm by mass or more, more preferably 3 ppm by mass or more, and even more preferably 5 ppm by mass or more, relative to the total mass of the ester compound-containing composition. When the content of component B is equal to or greater than the above-mentioned lower limit, the effect of suppressing dimerization of ester compound (1) and the generation of oxidation products is likely to be obtained. The content of component B is preferably 1500 ppm by mass or less, more preferably 1200 ppm by mass or less, and even more preferably 1000 ppm by mass or less, relative to the total mass of the ester compound-containing composition. When the content of component B is equal to or less than the above-mentioned upper limit, the amount of impurities during production of the (meth)acrylic polymer is reduced, and deterioration of the physical properties of the (meth)acrylic polymer is likely to be suppressed. The lower and upper limits of the preferred content of Component B can be arbitrarily combined, and are, for example, preferably 1 mass ppm or more and 1500 mass ppm or less, more preferably 3 mass ppm or more and 1200 mass ppm or less, and even more preferably 5 mass ppm or more and 1000 mass ppm or less.

[0061] The water content of the ester compound-containing composition must be 5000 ppm by mass or less, because it adversely affects the physical properties of the (meth)acrylic polymer. The water content of the ester compound-containing composition is preferably 5000 ppm by mass or less, more preferably 4000 ppm by mass or less, and even more preferably 3000 ppm by mass or less.

[0062] (Analysis of Ester Compound-Containing Composition) The components A and B contained in the ester compound-containing composition can be measured by, for example, GC-MS measurement. If the GC-MS chart of an ester compound-containing composition shows a peak at the same retention time as a standard sample of component A, and the m / z value detected in the mass spectrum of that peak matches the exact mass of component A, then the ester compound-containing composition can be determined to contain component A. If a standard sample of component A is not available, then if the mass spectrum pattern of a peak appearing in the GC-MS chart of the ester compound-containing composition matches the mass spectrum pattern of component A recorded in a mass spectrum database, then the peak is determined to be a peak of component A, and the ester compound-containing composition can be determined to contain component A. Examples of mass spectrum databases include NIST20, NIST17, NIST14, and NIST14s. Furthermore, if a component is too volatile to be detected by GC-MS measurement, it can be detected using LC-MS. Component B can also be confirmed in the same manner as component A.

[0063] The content of the ester compound (1) can be calculated by subjecting the ester compound-containing composition to GC-FID measurement, quantifying the content using an area percentage method, and correcting the content using the amount of water quantified using a Karl Fischer moisture meter.

[0064] The content of component A can be determined, for example, by subjecting the ester compound-containing composition to GC measurement and quantifying it using the internal standard method. If a standard sample of component A cannot be obtained and quantification by the internal standard method cannot be performed, GC-FID measurement can be performed on any organic compound whose content is known, and the content of component A can be calculated using the following formula.

[0065]

number

[0066] In the formula, N is the number of carbon atoms contained in one molecule of any organic compound, and N A is the number of carbon atoms contained in one molecule of component A, and S Ais the peak area of ​​component A, S is the peak area of ​​an arbitrary organic compound, and M is the content (ppm by mass) of the arbitrary organic component. If the volatility is low and quantification by GC area is not possible, chromatographic methods such as LC can be used for quantification. The content of component B can be calculated in the same manner as component A.

[0067] The water content of the ester compound-containing composition can be confirmed by the Karl Fischer method.

[0068] [Method of producing an ester compound-containing composition] The ester compound-containing composition of the present invention can be produced, for example, by carrying out a transesterification reaction between methyl (meth)acrylate and an alcohol (a) having 2 to 20 carbon atoms in the presence of component A. As the alcohol (a), it is preferable to use at least one selected from the following alcohols (a1) to (a3). (a1) Monoalcohols having 2 to 20 carbon atoms (a2) one or more alcohols selected from the group consisting of dialcohols having 2 to 8 carbon atoms and trialcohols having 2 to 8 carbon atoms (a3) Alcohols containing 2 to 8 carbon atoms and containing an ether bond

[0069] Among (meth)acrylic acid esters, methyl (meth)acrylate is particularly prone to dimerization and oxidation to produce methyl pyruvate. However, by carrying out the transesterification reaction in the presence of component A, the dimerization of methyl (meth)acrylate and the production of methyl pyruvate are suppressed, thereby improving the yield of ester compound (1).

[0070] By carrying out a transesterification reaction between methyl (meth)acrylate and an alcohol (a1) in the presence of the component A, an ester compound-containing composition containing the ester compound (1-1) can be produced. More specifically, for example, in a reactor, methyl (meth)acrylate and alcohol (a1) are transesterified in the presence of a catalyst and component A, as shown in the following formula (2): a1 and R a2 is R in formula (1-1) a1 and R a2 is the same as

[0071] [ka]

[0072] Examples of the alcohol (a1) include ethanol, n-butanol, isobutanol, t-butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, allyl alcohol, phenol, and benzyl alcohol. As the alcohol (a1), one type may be used alone, or two or more types may be used in combination. The alcohol (a1) preferably contains a linear or branched monoalcohol having 2 to 20 carbon atoms.

[0073] The ratio of the amounts of methyl (meth)acrylate and alcohol (a1) charged can be appropriately determined. From the viewpoint of increasing productivity, the ratio of methyl (meth)acrylate to 1 mol of alcohol (a1) is preferably 0.1 mol or more and 10 mol or less, more preferably 0.3 mol or more and 4 mol or less.

[0074] By carrying out a transesterification reaction between methyl (meth)acrylate and an alcohol (a2) in the presence of the component A, an ester compound-containing composition containing the ester compound (1-2) can be produced.

[0075] More specifically, for example, in a reactor, in the presence of a catalyst and component A, methyl (meth)acrylate and alcohol (a2) are transesterified as shown in the following formulas (3) and (4). However, R in formula (3) and formula (4) b1 ~R b3, R b5 ~R b7 is R in formulas (1-21) to (1-23). b1 ~R b3 , R b5 ~R b7 Also, R b41 is a linear or branched alkylene group having 2 to 8 carbon atoms, and R b42 is a linear or branched hydroxyalkylene group having 2 to 8 carbon atoms.

[0076] [ka]

[0077] Examples of the alcohol (a2) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,6-hexanediol, and trimethylolpropane. Among these, the alcohol (a2) preferably includes at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, and trimethylolpropane. As the alcohol (a2), one type may be used alone, or two or more types may be used in combination.

[0078] The ratio of the amounts of methyl (meth)acrylate and alcohol (a2) charged can be appropriately determined. From the viewpoint of increasing productivity, the ratio of methyl (meth)acrylate to 1 mol of alcohol (a2) is preferably 0.1 mol or more and 10 mol or less, more preferably 0.3 mol or more and 4 mol or less.

[0079] By carrying out a transesterification reaction between methyl (meth)acrylate and an alcohol (a3) ​​in the presence of the component A, an ester compound-containing composition containing the ester compound (1-3) can be produced.

[0080] More specifically, for example, in a reactor, methyl (meth)acrylate and alcohol (a3) ​​are transesterified in the presence of a catalyst, Ti(OR)4 (where R is an alkyl group), and component A, as shown in the following formula (5): c1 and R c2 is R in formula (1-3) c1 and R c2 is the same as

[0081] [ka]

[0082] The number of ether bonds contained in the alcohol (a3) ​​is preferably one, but is not limited thereto. Examples of the alcohol (a3) ​​include 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol. As the alcohol (a3), one type may be used alone, or two or more types may be used in combination. The alcohol (a3) ​​preferably includes one selected from 2-methoxyethanol, glycidyl alcohol, and tetrahydrofurfuryl alcohol.

[0083] The ratio of the amounts of methyl (meth)acrylate and alcohol (a3) ​​charged can be determined appropriately. From the viewpoint of increasing productivity, the ratio of methyl (meth)acrylate to 1 mol of alcohol (a3) ​​is preferably 0.1 mol or more and 10 mol or less, more preferably 0.3 mol or more and 4 mol or less.

[0084] An ester compound-containing composition containing two or more of the ester compounds (1-1) to (1-3) may be produced by carrying out a transesterification reaction between methyl (meth)acrylate and two or more selected from the alcohols (a1) to (a3) ​​in the presence of component A. In this case, the ratio of the amounts of methyl (meth)acrylate and alcohol (a) charged can be appropriately determined. From the viewpoint of increasing productivity, the ratio of methyl (meth)acrylate to 1 mol of alcohol (a) is preferably 0.1 mol or more and 10 mol or less, more preferably 0.3 mol or more and 4 mol or less.

[0085] The reactor is preferably a reactor equipped with a distillation column. Since this transesterification reaction is an equilibrium reaction, productivity can be improved by separating the by-product methanol using a distillation column. For example, it is preferable to carry out the transesterification reaction while separating methanol from the system as an azeotropic mixture with methyl (meth)acrylate. Examples of such a reactor include a reactor vessel called a reactor equipped with a distillation column on top, and a distillation column in which a still can be used as a reaction vessel. Examples of the distillation column include a packed column type and a tray type distillation column. The number of theoretical plates of the distillation column is preferably 5 or more, more preferably 7 or more, from the viewpoints of high separation capacity and stable operation.

[0086] The catalyst used is not particularly limited, but examples include hydroxides, carbonates, and bicarbonates of alkali metals such as lithium, sodium, and potassium; oxides, hydroxides, and carbonates of alkaline earth metals such as magnesium and calcium; alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, and potassium t-butoxide; alkali metal amides such as lithium amide, sodium amide, and potassium amide; titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetra(2-ethylhexyl) titanate; and tin compounds such as dibutyltin oxide and dioctyltin oxide. Among these, titanium alkoxides, dibutyltin oxide, and dioctyltin oxide are preferred due to their low Michael addition reaction by-product generation during the transesterification reaction and their high catalytic activity. The catalysts may be used alone or in combination.

[0087] The catalyst can be supplied to the reactor alone, or can be supplied to the reactor in a state of being dissolved in the same alcohol as the raw material alcohol (a) or in a state of being dissolved in the raw material (meth)acrylic acid ester. For example, there can be mentioned a method in which the catalyst is directly dissolved in the entire amount of the alcohol (a) used in the reaction and then supplied to the reactor, and a method in which the catalyst is dissolved in a part of the alcohol (a) used in the reaction and then supplied to the reactor. The amount of the catalyst used is preferably 0.001 mol % or more and 1 mol % or less, more preferably 0.01 mol % or more and 0.1 mol % or less, relative to 1 mol of the alcohol (a).

[0088] A solvent may be used in the transesterification reaction. When a solvent is used, it is preferable to use a solvent that forms an azeotropic composition with the by-produced methanol. Examples of solvents include n-pentane, n-hexane, n-heptane, n-octane, 2,3-dimethylbutane, 2,5-dimethylhexane, 2,2,4-trimethylpentane, cyclohexane, benzene, and toluene. Among these, n-hexane, n-heptane, and cyclohexane are preferred. One solvent may be used alone, or two or more solvents may be used in combination.

[0089] The reaction temperature for the transesterification reaction varies depending on the type of alcohol (a) and solvent, but is preferably 60°C or higher and 150°C or lower. The reaction pressure for the transesterification reaction is not particularly limited, and the reaction may be carried out under any of reduced pressure, normal pressure, and increased pressure. The type of transesterification reaction is not particularly limited, and can be carried out by a commonly used method such as a batch reaction or a continuous reaction. After the transesterification reaction, the reaction mixture may be purified to separate unreacted raw materials and by-products. Purification can be performed by known methods such as distillation, crystallization, extraction, and column chromatography.

[0090] The transesterification reaction may be carried out by adding component B to the reaction solution. The presence of component B in addition to component A further suppresses the dimerization of methyl (meth)acrylate and the production of methyl pyruvate, thereby making it easier to obtain the effect of improving the yield of ester compound (1).

[0091] Component B may be blended with a liquid containing ester compound (1) and component A after the transesterification reaction. In this case, a liquid containing ester compound (1) and component B (liquid B) may be prepared separately from a liquid containing ester compound (1) and component A (liquid A), and the liquids A and B may be mixed to prepare an ester compound-containing composition. Alternatively, the ester compound (1), liquid A, and liquid B may be mixed to prepare an ester compound-containing composition.

[0092] The method for producing the ester compound-containing composition of the present invention is not limited to the above-described method. For example, instead of methyl (meth)acrylate as a raw material, a (meth)acrylic acid ester other than methyl (meth)acrylate may be used. The ester compound (1) may be produced by carrying out an esterification reaction between the alcohol (a) and (meth)acrylic acid.

[0093] (Polymerizable composition) The polymerizable composition of the present invention is a polymerizable composition for producing a (meth)acrylic polymer, and includes the ester compound-containing composition of the present invention. In one embodiment, an ester compound-containing composition that has been stored for one day or more after production can be used in the polymerizable composition. The storage time of the ester compound-containing composition can be 1 day or more, 3 days or more, 7 days or more, or 14 days or more. The storage time of the ester compound-containing composition may be 180 days or less, 150 days or less, 120 days or less, or 90 days or less. Note that the "storage time" is not limited to the time during which the composition is left standing in a specific environment, but refers to the time elapsed from immediately after production, including the time for transportation, etc.

[0094] The material of the container for storing the ester compound-containing composition is not particularly limited, and for example, a metal container such as stainless steel, a resin container, or a glass container can be used. Either a transparent or opaque container can be used.

[0095] The temperature at which the ester compound-containing composition is stored is preferably −10° C. or higher, more preferably 0° C. or higher, and is preferably 60° C. or lower, more preferably 50° C. or lower. Setting the temperature at −10° C. or higher can reduce the load on the cooling device, while setting the temperature at 60° C. or lower makes it easier to suppress the generation of dimers and oxidation products of the (meth)acrylic acid ester.

[0096] The oxygen concentration in the gas phase during storage of the ester compound-containing composition is preferably 5% by volume or more, more preferably 7% by volume or more, and preferably 30% by volume or less, more preferably 22% by volume or less. By setting the oxygen concentration in the gas phase to 5% by volume or more, the polymerization-inhibiting effect of oxygen makes it easier to prevent unintended polymerization of the ester compound, and by setting it to 30% by volume or less, it becomes easier to suppress the oxidation of the (meth)acrylic acid ester by oxygen and the generation of various impurities.

[0097] In an embodiment, the ester compound-containing composition after storage may be used in a polymerizable composition without further blending any monomer therein, or the ester compound-containing composition after storage may be further blended with another monomer copolymerizable with ester compound (1) to form a polymerizable composition. In one embodiment, the produced ester compound-containing composition may be stored in a state where it is blended with another monomer copolymerizable with ester compound (1), and then used as a polymerizable composition. In this case, it is preferable not to blend a polymerization initiator during storage.

[0098] The proportion of the ester compound (1) relative to the total mass of the monomers in the polymerizable composition is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less.

[0099] Examples of other monomers copolymerizable with ester compound (1) include methyl(meth)acrylate, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, maleimide, hydroxy group-containing vinyl monomer, vinyl ester, nitrogen-containing vinyl monomer, epoxy group-containing monomer, aromatic vinyl monomer, alkanediol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, and vinyl monomer having two or more ethylenically unsaturated bonds in the molecule.

[0100] Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Examples of unsaturated carboxylic acid anhydrides include maleic anhydride and itaconic anhydride. Examples of maleimides include N-phenylmaleimide and N-cyclohexylmaleimide.

[0101] Examples of the hydroxy group-containing vinyl monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. Examples of vinyl esters include vinyl acetate and vinyl benzoate. Examples of the nitrogen-containing vinyl monomer include methacrylamide and acrylonitrile. Examples of epoxy group-containing monomers include glycidyl acrylate and glycidyl methacrylate.

[0102] Examples of aromatic vinyl monomers include styrene and α-methylstyrene. Examples of alkanediol di(meth)acrylates include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

[0103] Examples of polyoxyalkylene glycol di(meth)acrylates include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. An example of a vinyl monomer having two or more ethylenically unsaturated bonds in the molecule is divinylbenzene.

[0104] Other monomers that may be used include vinyl chloride, vinylidene chloride and derivatives thereof, unsaturated polyester prepolymers obtained from at least one polycarboxylic acid including an ethylenically unsaturated polycarboxylic acid and at least one diol, and vinyl ester prepolymers obtained by acrylic-modifying the terminals of epoxy groups. The other monomers may be used alone or in combination of two or more.

[0105] The polymerizable composition of the embodiment preferably contains a polymerization initiator. Examples of the polymerization initiator include an azo compound, an organic peroxide, a persulfate compound, and a redox-based polymerization initiator. One type of polymerization initiator may be used alone, or two or more types may be used in combination.

[0106] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(2-methylpropane), 1,1-azobis(cyclohexanecarbonitrile), and dimethyl-2,2'-azobisisobutyrate.

[0107] Examples of organic peroxides include benzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyacetate, and t-hexylperoxyisopropyl monocarbonate. Examples of peroxycarbonyl compounds include t-hexylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyethylhexanoate, 1,1,2-trimethylpropylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyisopropyl monocarbonate, 1,1,2-trimethylpropylperoxyisopropyl monocarbonate, 1,1,3,3-tetramethylbutylperoxyisonononaate, 1,1,2-trimethylpropylperoxyisonononaate, di-t-butyl peroxide, di-t-hexyl peroxide, lauroyl peroxide, and dilauroyl peroxide.

[0108] An example of the persulfate compound is potassium persulfate. The amount of the polymerization initiator to be added is not particularly limited, and can be, for example, 0.005 to 5 parts by mass relative to 100 parts by mass of the total mass of the monomers in the polymerizable composition.

[0109] In the polymerizable composition of the embodiment, the content of component C: at least one compound selected from the group consisting of compounds of transition metals and compounds of Group 13 elements is 7 × 10 relative to the total mass of component A. 4 The content is preferably ppm by mass or less, which improves the weather resistance of the (meth)acrylic polymer obtained and suppresses yellowing. The reason for this is thought to be as follows. The α-olefin, which is component A, does not provide a resonance stabilization effect and has significantly lower reactivity than the ester compound (1), which is a conjugated monomer. Therefore, unless a specific polymerization catalyst such as component C is used and special conditions are used to demonstrate its catalytic effect, unreacted α-olefin remains in the resulting (meth)acrylic polymer. It is thought that (meth)acrylic polymers containing unreacted α-olefin have good weather resistance and are less prone to yellowing.

[0110] The content of component C is 7 x 10 4 Preferably, it is less than ppm by mass, and 1×10 4 It is more preferably 1 ppm by mass or less, even more preferably 1000 ppm by mass or less, and particularly preferably does not contain component C. However, "does not contain component C" means that it is below the detection limit in GC-MS measurement.

[0111] Examples of component C include compounds of transition metals of Groups 5 to 12 having a chelating ligand, and Lewis acid catalysts. Specific examples of transition metals include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, platinum, ruthenium, cobalt, rhodium, nickel, palladium, and copper. Among these, transition metals of Groups 8 to 11 are preferred, transition metals of Group 10 are more preferred, and nickel or palladium is even more preferred. These transition metals may be used alone or in combination of two or more.

[0112] Chelating ligands have at least two atoms selected from the group consisting of P, N, O, and S, and include bidentate or multidentate ligands, and are electronically neutral or anionic. Exemplary chelating ligand structures are provided in a review by Ittel et al. (Ittel et al., "Late-Metal Catalysts for Ethylene Homo- and Copolymerization," Chemical Reviews, March 25, 2000, Vol. 100, No. 4, pp. 1169-1204).

[0113] An example of the chelating ligand is a bidentate anionic P,O ligand. Examples of the bidentate anionic P,O ligand include phosphorus sulfonic acid, phosphorus carboxylic acid, phosphorus phenol, and phosphorus enolate. Examples of chelating ligands other than the bidentate anionic P,O ligand include bidentate anionic N,O ligands. Examples of the bidentate anionic N,O ligand include salicylaldiminate and pyridinecarboxylic acid. Examples of chelating ligands other than the bidentate anionic P,O ligand and the bidentate anionic N,O ligand include diimine ligands, diphenoxide ligands, and diamide ligands.

[0114] Known catalysts that are compounds of transition metals of Groups 5 to 11 having a chelating ligand include SHOP catalysts and Drent catalysts. SHOP catalysts are catalysts in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to nickel metal. Drent catalysts are catalysts in which a phosphorus-based ligand having an aryl group, which may have a substituent, is coordinated to palladium metal.

[0115] Representative Lewis acid catalysts include cationic complexes of divalent palladium or platinum. The cationic complexes of divalent palladium or platinum exhibit Lewis acidity and are useful as Lewis acid catalysts for Diels-Alder reactions, etc. Compounds of boron and aluminum, which are Group 13 elements, titanium, which is a fourth-period transition metal, and zirconium, which is a fifth-period transition metal, are also preferred because they exhibit Lewis acidity.

[0116] In one example of an embodiment, various additives such as a mold release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, a polymerization inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, an antifoaming agent, a fluorescent agent, and a chain transfer agent may be blended into the ester compound-containing composition after storage, as needed.

[0117] [Method of producing (meth)acrylic polymer] A (meth)acrylic polymer can be produced by polymerizing the polymerizable composition of the present invention. The polymerization method is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. From the viewpoints of the environmental load caused by the use of solvents and the transparency of the resulting (meth)acrylic polymer, bulk polymerization is preferred. The specific means for the bulk polymerization method is not particularly limited, and examples thereof include known casting polymerization methods such as cell casting and continuous casting.

[0118] The polymerization temperature is preferably 125°C or higher and 210°C or lower, and more preferably 130°C or higher and 180°C or lower. The polymerization time is preferably 0.5 hours or more and 24 hours or less.

[0119] The weight average molecular weight (Mw) of the (meth)acrylic polymer is not particularly limited and can be, for example, from 100,000 to 1,000,000. The larger the Mw of the (meth)acrylic polymer, the higher the solvent resistance and chemical resistance can be. The Mw of the (meth)acrylic polymer can be controlled by adjusting the polymerization temperature, polymerization time, amount of polymerization initiator added, and the like.

[0120] (composition) The content of the ester compound (I) in the ester compound-containing composition is preferably 85.00% by mass or more, more preferably 90.00% by mass or more, and even more preferably 95.00% by mass or more, based on the total mass of the ester compound-containing composition, and is preferably 99.99% by mass or less, more preferably 99.97% by mass or less, and even more preferably 99.95% by mass or less, based on the total mass of the ester compound-containing composition. The lower and upper limits of the preferred content of the ester compound (I) can be arbitrarily combined, and are, for example, preferably 85.00% by mass or more and 99.99% by mass or less, more preferably 90.00% by mass or more and 97.97% by mass or less, and even more preferably 95.00% by mass or more and 99.95% by mass or less.

[0121] The proportion of the ester compound (I) relative to the total mass of the monomers in the polymerizable composition is preferably 10% by mass or more, more preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less.

[0122] Examples of other monomers copolymerizable with the ester compound (I) include methyl(meth)acrylate, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, maleimides, vinyl esters, nitrogen-containing vinyl monomers, epoxy group-containing monomers, aromatic vinyl monomers, polyoxyalkylene glycol di(meth)acrylates, and vinyl monomers having two or more ethylenically unsaturated bonds in the molecule.

[0123] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following descriptions.

[0124] <Ester compound-containing composition containing ester compound (1-1)> [GC-MS measurement] The ester compound-containing composition after storage was analyzed using GC-MS, and the composition was determined by the method described above in the section "Analysis of Ester Compound-Containing Composition." A QP-2010Ultra manufactured by Shimadzu Corporation was used for the GC-MS measurement. (GC conditions) Column (product name: InertCap1, manufactured by GL Sciences) Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm Injection volume: 1.0μL Vaporization chamber temperature: 280℃ Column oven temperature: held at 150°C for 1 minute, heated from 150°C to 260°C at 2.5°C / min, and held at 260°C for 15 minutes. Carrier gas: Helium Injection mode: Split (split ratio 25) Control mode: Constant linear velocity (35.0 cm / sec) Pressure: 262.8kPa Total flow: 47.2mL / min Purge flow rate: 3.0 mL / min Column flow rate: 1.70 mL / min

[0125] (MS conditions) Ionization method: EI (Electron Ionization) Ion source temperature: 200℃ Interface temperature: 300℃ m / z detection range: 30 to 600 Detection time: 60 minutes

[0126] [Moisture content] The moisture content was determined by the Karl Fischer method using a trace moisture analyzer (product name: CA-200, manufactured by Nitto Seiko Analytic Co., Ltd.).

[0127] [Example A1] Liquid A was prepared by adding 0.0208 g of 1-octane as component A to 10.0014 g of butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content 164 ppm by mass). Furthermore, 0.0200 g of 2,4-dimethyl-6-t-butylphenol as component B was added to 10.0089 g of BMA (water content: 164 ppm by mass) to prepare liquid B. Next, 0.0276 g of solution A and 0.0297 g of solution B were added to 4.9998 g of BMA (water content: 164 ppm by mass) to prepare an ester compound-containing composition. The resulting ester compound-containing composition was stored at 25°C for 21 days, and the amount of BMA dimer produced (ppm by mass) was determined from the ratio (area %) of the area value of the BMA dimer to the total area value of all components detected by GC-MS measurement. The BMA purity (%) was calculated from the ratio (area %) of the area value of BMA to the total area value of all components detected. The BMA dimer and BMA purity were calculated by subtracting the water content (mass %) from 100% and multiplying this value by the area % of each component.

[0128] [Examples A2 to A10, Comparative Example A1] An ester compound-containing composition was prepared in the same manner as in Example A1, except that the compositions of Solution A, Solution B, and the ester compound-containing composition were changed as shown in Table 1, and the amount of BMA dimer produced and the BMA purity were determined.

[0129] [Table 1]

[0130] The abbreviations in Table 1 have the following meanings. BMA: butyl methacrylate Oct: 1-octene 2EH: 2-ethyl-1-hexene Ddc: 1-dodecene DMTBP: 2,4-dimethyl-6-t-butylphenol 4MP: 4-methoxyphenol IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine PHT: Phenothiazine HO-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl

[0131] Table 2 shows the measurement results of the amount of BMA dimer produced and the purity of BMA in each example.

[0132] [Table 2]

[0133] As shown in Table 2, the ester compound-containing compositions of Examples A1 to A10, which contained component A, produced less BMA dimer and had higher BMA purity even after storage compared to the ester compound-containing composition of Comparative Example A1, which did not contain component A.

[0134] [Examples A11 to A13, Comparative Examples A2 and A3] An ester compound-containing composition was prepared in the same manner as in Example A1, except that ethyl methacrylate (EMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 245 ppm by mass) was used instead of BMA, and the compositions of Solution A, Solution B, and the ester compound-containing composition were changed as shown in Table 3. The results are shown in Table 4.

[0135] [Table 3]

[0136] [Table 4]

[0137] As shown in Table 4, the ester compound-containing compositions of Examples A11 to A13, which contained component A, had higher EMA purity even after storage compared to the ester compound-containing compositions of Comparative Examples A2 and A3, which did not contain component A.

[0138] <Ester compound-containing composition containing ester compound (1-2)> [GC-MS measurement] The ester compound-containing composition after storage was analyzed using GC-MS, and the composition was determined by the method described above in the section "Analysis of Ester Compound-Containing Composition." A QP-2010Ultra manufactured by Shimadzu Corporation was used for the GC-MS measurement. (GC conditions) Column (product name: InertCap1, manufactured by GL Sciences) Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm Injection volume: 1.0μL Vaporization chamber temperature: 280℃ Column oven temperature: When analyzing a composition containing 2-hydroxymethacrylate, hold at 150°C for 1 minute, increase the temperature from 150°C to 260°C at 2.5°C / min, and hold at 260°C for 15 minutes. When analyzing a composition containing ethylene glycol dimethacrylate, hold at 200°C for 1 minute, increase the temperature from 200°C to 260°C at 2.0°C / min, and hold at 260°C for 29 minutes. Carrier gas: Helium Injection mode: Split (split ratio 25) Control mode: Constant linear velocity (35.0 cm / sec) Pressure: 262.8kPa Total flow: 47.2mL / min Purge flow rate: 3.0 mL / min Column flow rate: 1.70 mL / min

[0139] (MS conditions) Ionization method: EI (Electron Ionization) Ion source temperature: 200℃ Interface temperature: 300℃ m / z detection range: 30 to 600 Detection time: 60 minutes

[0140] [Moisture content] The moisture content was determined by the Karl Fischer method using a trace moisture analyzer (product name: CA-200, manufactured by Nitto Seiko Analytic Co., Ltd.).

[0141] [Example B1] Liquid A was prepared by adding 0.0224 g of 2-ethyl-1-hexene as component A to 10.0028 g of 2-hydroxyethyl methacrylate (HEMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content 247 ppm by mass). Furthermore, 0.0218 g of 2,4-dimethyl-6-t-butylphenol as component B was added to 10.0158 g of HEMA (water content: 247 ppm by mass) to prepare liquid B. Next, 0.0304 g of solution A and 0.0334 g of solution B were added to 5.0098 g of HEMA (water content: 247 ppm by mass) to prepare an ester compound-containing composition. The obtained ester compound-containing composition was stored at 25°C for 21 days, and then the HEMA purity (%) was calculated from the ratio (area %) of the area value of HEMA to the total area value of all components detected by GC-MS measurement, by multiplying the value obtained by subtracting the water content (mass %) from 100% by the area % of HEMA.

[0142] [Examples B2 to B5, Comparative Examples B1 to B3] An ester compound-containing composition was prepared in the same manner as in Example B1, except that the compositions of Solution A, Solution B, and the ester compound-containing composition were changed as shown in Table 5, and the HEMA purity was determined.

[0143] [Table 5]

[0144] The abbreviations in Table 5 have the following meanings. HEMA: 2-hydroxyethyl methacrylate Oct: 1-octene 2EH: 2-ethyl-1-hexene DMTBP: 2,4-dimethyl-6-t-butylphenol 4MP: 4-methoxyphenol IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine HO-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl

[0145] The results of HEMA purity measurements for each example are shown in Table 6.

[0146] [Table 6]

[0147] As shown in Table 6, the ester compound-containing compositions of Examples B1 to B5, which contained component A, had higher HEMA purity even after storage compared to the ester compound-containing compositions of Comparative Examples B1 to B3, which did not contain component A.

[0148] [Examples B6 to B7, Comparative Examples B4 to B6] An ester compound-containing composition was prepared in the same manner as in Example B1, except that ethylene glycol dimethacrylate (EDMA, water content: 91 ppm by mass) was used instead of HEMA, and the compositions of Solution A, Solution B, and the ester compound-containing composition were changed as shown in Table 7. The results are shown in Table 8.

[0149] [Table 7]

[0150] [Table 8]

[0151] As shown in Table 8, the ester compound-containing compositions of Examples B3 and B4, which contained component A, had higher EDMA purity even after storage than the ester compound-containing compositions of Comparative Examples B4 and B5, which did not contain component A, and Comparative Example B6, which contained a very large amount of component A.

[0152] <Ester compound-containing composition containing ester compound (1-3)> [GC-MS measurement] The ester compound-containing composition after storage was analyzed using GC-MS, and the composition was determined by the method described above in the section "Analysis of Ester Compound-Containing Composition." A QP-2010Ultra manufactured by Shimadzu Corporation was used for the GC-MS measurement. (GC conditions) Column (product name: InertCap1, manufactured by GL Sciences) Length: 60m, inner diameter: 0.25mm, film thickness: 1.50μm Injection volume: 1.0μL Vaporization chamber temperature: 280℃ Column oven temperature: When analyzing compositions containing glycidyl methacrylate, hold at 150°C for 1 minute, increase the temperature from 1500°C to 260°C at 2.5°C / min, and hold at 260°C for 15 minutes. When analyzing compositions containing methoxyethyl methacrylate, hold at 60°C for 1 minute, increase the temperature from 60°C to 260°C at 5°C / min, and hold at 260°C for 9 minutes. Carrier gas: Helium Injection mode: Split (split ratio 25) Control mode: Constant linear velocity (35.0 cm / sec) Pressure: 262.8kPa Total flow: 47.2mL / min Purge flow rate: 3.0 mL / min Column flow rate: 1.70 mL / min

[0153] (MS conditions) Ionization method: EI (Electron Ionization) Ion source temperature: 200℃ Interface temperature: 300℃ m / z detection range: 30 to 600 Detection time: 50 minutes for the analysis of glycidyl methacrylate-containing compositions, 60 minutes for the analysis of methoxyethyl methacrylate-containing compositions.

[0154] [Moisture content] The moisture content was determined by the Karl Fischer method using a trace moisture analyzer (product name: CA-200, manufactured by Nitto Seiko Analytic Co., Ltd.).

[0155] [Example C1] Solution A was prepared by adding 0.0222 g of 1-octane as component A to 10.0085 g of glycidyl methacrylate (GMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content 174 ppm by mass). Furthermore, 0.0214 g of 2,4-dimethyl-6-t-butylphenol as component B was added to 10.0147 g of GMA (water content: 174 ppm by mass) to prepare liquid B. Next, 0.0337 g of solution A and 0.0309 g of solution B were added to 5.0003 g of GMA (water content: 174 ppm by mass) to prepare an ester compound-containing composition. The resulting ester compound-containing composition was stored at 25°C for 21 days, and then the GMA purity (%) was calculated from the ratio (area %) of the area value of GMA to the total area value of all components detected by GC-MS measurement by subtracting the water content (mass %) from 100% and multiplying the result by the area % of each component.

[0156] [Examples C2 to C9, Comparative Examples C1 to C3] An ester compound-containing composition was prepared in the same manner as in Example C1, except that the compositions of the solutions A, B, and ester compound-containing composition were changed as shown in Table 9, and the GMA purity was determined.

[0157] [Table 9]

[0158] The abbreviations in Table 9 have the following meanings. GMA: Glycidyl methacrylate Oct: 1-octene 2EH: 2-ethyl-1-hexene Ddc: 1-dodecene DMTBP: 2,4-dimethyl-6-t-butylphenol 4MP: 4-methoxyphenol IPPPD: N-isopropyl-N'-phenyl-p-phenylenediamine PHT: Phenothiazine HO-TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl

[0159] The results of measuring the GMA purity in each example are shown in Table 10.

[0160] [Table 10]

[0161] As shown in Table 10, the ester compound-containing compositions of Examples C1 to C9, which contained component A, produced less GMA dimer and glycidyl pyruvate even after storage and had higher GMA purity than the ester compound-containing compositions of Comparative Examples C1 and C2, which did not contain component A.

[0162] [Examples C10-C12, Comparative Examples C4-C6] An ester compound-containing composition was prepared in the same manner as in Example C1, except that 2-methoxyethyl methacrylate (MTMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 575 ppm by mass) was used instead of GMA, and the compositions of Solution A, Solution B, and the ester compound-containing composition were changed as shown in Table 11. The amount of MTMA dimer produced and the MTMA purity were determined. The amount of MTMA dimer produced (mass%) was calculated as the ratio (area%) of the area value of the MTMA dimer to the total area value of all detected components. The results are shown in Table 12.

[0163] [Table 11]

[0164] [Table 12]

[0165] As shown in Table 12, the ester compound-containing compositions of Examples C10 to C12, which contained Component A, produced less MTMA dimer and had higher MTMA purity even after storage compared to the ester compound-containing compositions of Comparative Examples C4 to C6, which did not contain Component A.

[0166] [Example D1] A mixture of butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 164 ppm by mass) and ethyl methacrylate (EMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 245 ppm by mass) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-t-butylphenol was used as component B. An ester compound-containing composition was prepared in the same manner as in Example A1, except that the composition of the ester compound-containing composition was changed as shown in Table 13, and the amount of BMA dimer produced, as well as the BMA purity and EMA purity, were determined. The results are shown in Table 13. BMA purity (%) was calculated from the ratio of the area value of BMA to the total area value of all detected components (area %), and EMA purity (%) was calculated from the ratio of the area value of EMA to the total area value of all detected components (area %). BMA dimer, BMA purity, and EMA purity were calculated by subtracting the water content (mass %) from 100% and multiplying the result by the area % of each component.

[0167] [Comparative examples D1~D2] An ester compound-containing composition was prepared in the same manner as in Example D1, except that the formulation of the ester compound-containing composition was changed as shown in Table 13, and the amount of BMA dimer produced, as well as the BMA purity and EMA purity were determined. The results are shown in Table 13.

[0168] [Table 13]

[0169] As shown in Table 13, the ester compound-containing composition of Example D1, which contained component A, produced less BMA dimer and had higher BMA purity even after storage compared to the ester compound-containing compositions of Comparative Examples D1 and D2, which did not contain component A.

[0170] [Example D2] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 164 ppm by mass) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-t-butylphenol was used as component B. An ester compound-containing composition was prepared in the same manner as in Example A1, except that the composition of the ester compound-containing composition was changed as shown in Table 14, and the amount of BMA dimer produced and the BMA purity were determined. The results are shown in Table 14.

[0171] [Examples D3 to D4] An ester compound-containing composition was prepared in the same manner as in Example D2, except that the composition of the ester compound-containing composition was changed as shown in Table 14 by adding methanol (manufactured by Nacalai Tesque, for high performance liquid chromatography), and the amount of BMA dimer produced and the purity of BMA were determined. The results are shown in Table 14.

[0172] [Table 14]

[0173] As shown in Table 14, when the ester compound-containing compositions of Examples D3 and D4, which contained component A and had similar BMA concentrations, were compared, the amounts of BMA dimer produced were similar in Example D3, which used both component A and component B, and Example D4, which used only component A. On the other hand, the ester compound-containing composition of Example D2, which contained component A and had a high BMA concentration, produced a smaller amount of BMA than the ester compound-containing composition of Example D3, which contained component A and had a low BMA concentration.

[0174] [Example D5] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content: 164 ppm by mass) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-t-butylphenol was used as component B. An ester compound-containing composition was prepared in the same manner as in Example A1, except that the composition of the ester compound-containing composition was changed as shown in Table 15, and the amount of BMA dimer produced and the BMA purity were determined. The results are shown in Table 15.

[0175] [Example D6, Comparative Example D3] An ester compound-containing composition was prepared in the same manner as in Example D2, except that the formulation of the ester compound-containing composition was changed as shown in Table 15, and the amount of BMA dimer produced and the purity of BMA were determined. The results are shown in Table 15.

[0176] [Table 15]

[0177] As shown in Table 15, the ester compound-containing compositions of Examples D5 and D6, which contained an appropriate amount of Component A, produced less BMA dimer and had higher BMA purity even after storage compared to the ester compound-containing composition of Comparative Example D3, which contained too much Component A.

[0178] [Example D7] Butyl methacrylate (BMA, manufactured by Tokyo Chemical Industry Co., Ltd., water content 164 ppm by mass) was used as the ester compound, 1-octene was used as component A, and 2,4-dimethyl-6-t-butylphenol was used as component B. An ester compound-containing composition was prepared in the same manner as in Example A1, except that the composition of the ester compound-containing composition was changed as shown in Table 16, and the amount of BMA dimer produced was determined. The results are shown in Table 16.

[0179] [Example D8, Comparative Example D4] An ester compound-containing composition was prepared in the same manner as in Example D2, except that the formulation of the ester compound-containing composition was changed as shown in Table 16, and the amount of BMA dimer produced was determined. The results are shown in Table 16.

[0180] [Table 16]

[0181] As shown in Table 16, the ester compound-containing compositions of Examples D7 and D8, which contained component A and had a water content below the specified amount, produced less BMA dimer even after storage than the ester compound-containing composition of Comparative Example D4, which had an excessively high water content. [Industrial Applicability]

[0182] According to the present invention, an ester compound-containing composition that can be used as a raw material for (meth)acrylic polymers, etc., can be stably stored for a long period of time, which is industrially useful.

Claims

1. The composition contains an ester compound (1) represented by the following formula (1) and a component A: an α-olefin, the content of the ester compound (1-1) is 85.00% by mass or more and 99.99% by mass or less, The content of the component A is 1 ppm by mass or more and 1500 ppm by mass or less, An ester compound-containing composition having a water content of 5000 ppm by mass or less. CH ２ =CR １ -C(=O)-O-R ２ ・・・(1) (However, in the formula (1), R １ is a hydrogen atom or a methyl group, and R ２ is a hydrocarbon group having 2 to 20 carbon atoms which may have a heteroatom or a functional group.

2. In the formula (1), R ２ is a hydrocarbon group having 2 to 20 carbon atoms, a linear or branched alkyl group having 2 to 8 carbon atoms in which at least one hydrogen atom is substituted with a hydroxy group, a linear or branched alkyl group or hydroxyalkyl group having 2 to 8 carbon atoms in which one or two hydrogen atoms are substituted with a (meth)acryloyloxy group, or a hydrocarbon group having 2 to 8 carbon atoms in which an etheric oxygen atom is contained between carbon atoms.

3. The ester compound-containing composition according to claim 1, wherein the ester compound (1) includes an ester compound (1-1) represented by the following formula (1-1): CH ２ =CR ａ１ -C(=O)-O-R ａ２ ・・・(1-1) (However, in the formula (1-1), R ａ１ is a hydrogen atom or a methyl group, and R ａ２ is a hydrocarbon group having 2 to 20 carbon atoms.

4. The R ａ２ The ester compound-containing composition according to claim 3, comprising the ester compound (1-1), wherein is a linear or branched alkyl group having 2 to 20 carbon atoms.

5. The ester compound-containing composition according to claim 1, wherein the ester compound (1) comprises one or more ester compounds (1-2) selected from the group consisting of an ester compound (1-21) represented by the following formula (1-21), an ester compound (1-22) represented by the following formula (1-22), and an ester compound (1-23) represented by the following formula (1-23): 【Chemistry 1】 (However, in the formulas (1-21) to (1-23), R ｂ１ , R ｂ３ , R ｂ５ , R ｂ６ , R ｂ８ and R ｂ９ are each independently a hydrogen atom or a methyl group, and R ｂ２ and R ｂ４ are each independently a linear or branched alkylene group or a hydroxyalkylene group having 2 to 8 carbon atoms, and R ｂ７ is a linear or branched trivalent hydrocarbon group having 2 to 8 carbon atoms.

6. 6. The ester compound-containing composition according to claim 5, wherein the ester compound (1-2) comprises one or more compounds selected from the group consisting of ethylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and trimethylolpropane tri(meth)acrylate.

7. The ester compound-containing composition according to claim 5, wherein the content of the ester compound (1-2) is 85.00% by mass or more and 99.99% by mass or less.

8. The ester compound-containing composition according to claim 1, wherein the ester compound (1) includes an ester compound (1-3) represented by the following formula (1-3): CH ２ =CR ｃ１ -C(=O)-O-R ｃ２ ・・・(1-3) (However, in the formula (1-3), R ｃ１ is a hydrogen atom or a methyl group, and R ｃ２ is a group having an etheric oxygen atom between carbon atoms of a hydrocarbon group having 2 to 8 carbon atoms.

9. The R ｃ２ The ester compound-containing composition according to claim 8, comprising an ester compound (1-3) in which is a 2-methoxyethyl group, a glycidyl group, or a tetrahydrofurfuryl group.

10. The ester compound-containing composition according to claim 8, wherein the content of the ester compound (1-3) is 85.00% by mass or more and 99.99% by mass or less.

11. 2. The ester compound-containing composition according to claim 1, wherein the component A comprises an α-olefin having 6 to 12 carbon atoms.

12. Component B: The ester compound-containing composition according to claim 1, further comprising a polymerization inhibitor.

13. A polymerizable composition for producing a (meth)acrylic polymer, comprising the ester compound-containing composition according to claim 1.

14. Component C: The content of at least one compound selected from the group consisting of compounds of transition metals and compounds of Group 13 elements is 7 × 10 relative to the total mass of component A in the ester compound-containing composition. ４ The polymerizable composition of claim 13 , wherein the content is ppm by weight or less.

15. A method for producing a (meth)acrylic polymer, comprising polymerizing the polymerizable composition according to claim 13.

16. A method for producing a (meth)acrylic polymer, comprising polymerizing the polymerizable composition according to claim 14.

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