Method for producing monomer composition and monomer composition

Abstract

A method for producing a monomer composition containing a polymerizable group-containing phosphate compound, the method comprising causing, in the presence of an urethane compound, a reaction between diphosphorus pentaoxide and a polymerizable group-containing alcohol compound which is a compound not including an urethane bond, to obtain a monomer composition containing a polymerizable group-containing phosphate compound.

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a monomer composition and to a monomer composition. [Background technology]

[0002] 2. Description of the Related Art Polymerizable monomers, such as allyl compounds, have been widely used in various fields, such as coating materials, printing plate making, optical materials, and dental materials, taking advantage of their properties, such as good curability and transparency.

[0003] In particular, in the field of dental materials, polymerizable monomers are widely used in dental restorative materials such as dental composite resins used to repair caries, fractures, etc. of natural teeth, various dental adhesives used to bond dental composite resins to teeth, and further in artificial teeth, denture base materials, etc.

[0004] For example, Patent Document 1 discloses a composition for crowns and bridges that contains a diallyl phthalate prepolymer, a diallyl phthalate monomer, and a polymerization initiator.

[0005] Patent document 1: Japanese Patent Application Laid-open No. 149608 / 1983 Summary of the Invention [Problem to be solved by the invention]

[0006] In the dental field, a monomer composition containing a polymerizable monomer may be required to have transparency. For example, in applications such as dental restorative materials, if the transparency of the monomer composition is low when hardening the polymerizable monomer contained in the monomer composition, it may be difficult to harden the polymerizable monomer by light. For example, when a polymerizable group-containing phosphoric acid compound obtained by reacting a polymerizable group-containing alcohol compound such as an allyl group-containing alcohol compound with diphosphorus pentoxide is used as a polymerizable monomer, the transparency of a composition containing the polymerizable group-containing phosphoric acid compound may decrease. The composition disclosed in Patent Document 1 leaves room for improvement in terms of transparency.

[0007] An object of the present disclosure is to provide a method for producing a monomer composition capable of producing a monomer composition capable of suppressing a decrease in transparency, and the monomer composition. [Means for solving the problem]

[0008] Means for solving the above problems include the following aspects. <1> A method for producing a monomer composition containing a polymerizable group-containing phosphoric acid compound, comprising the step of reacting a polymerizable group-containing alcohol compound, which is a compound not containing a urethane bond, with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound. <2> The urethane compound has a molecular weight of 700 or less per urethane bond. <1> A method for producing the monomer composition according to claim 1. <3> The polymerizable group-containing alcohol compound is at least one selected from the group consisting of an allyl group-containing alcohol compound and a (meth)acryloyl group-containing alcohol compound. <1> or <2> A method for producing the monomer composition according to claim 1. <4> The polymerizable group-containing alcohol compound includes at least one selected from the group consisting of compounds represented by the following formulas (B-1) to (B-7) and compounds represented by the following formula (Ba): <1> ~ <3> A method for producing the monomer composition according to claim 1.

[0009] [ka]

[0010] [ka]

[0011] In formula (Ba), R 1B-arepresents a hydrogen atom or a methyl group, X 1B-a is n with carbon number 2 to 20 B-a represents a +1-valent organic group, n B-a represents an integer of 1 or 2. <5> The amount of the urethane compound added is 20% by mass or more based on the total amount of the urethane compound and the polymerizable group-containing alcohol compound added. <1> ~ <4> 13. A method for producing the monomer composition according to claim 12. <6> A monomer composition comprising a polymerizable group-containing phosphoric acid compound and a urethane compound. <7> The spectral transmittance in the range of 400nm to 800nm ​​at 25℃ and an optical path length of 10mm is 40% or more. <6> The monomer composition according to claim 1. <8> Used for dental materials <6> or <7> The monomer composition according to claim 1. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a method for producing a monomer composition capable of producing a monomer composition capable of suppressing a decrease in transparency, and the monomer composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In this disclosure, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate. In this disclosure, "iso(thio)cyanate" means an isocyanate or an isothiocyanate. In the present disclosure, the term "urethane bond" encompasses, for example, a bond formed by a reaction between an isocyanate group and a hydroxyl group, and a bond formed by a reaction between an isocyanate group and a hydroxyl group. In this disclosure, when referring to the amount of each component in a composition, if multiple substances corresponding to each component are present in the composition, it means the total amount of multiple substances present in the composition, unless otherwise specified.

[0014] <Method for producing monomer composition> The method for producing a monomer composition according to the present disclosure is a method for producing a monomer composition containing a polymerizable group-containing phosphoric acid compound, and includes a step of reacting a polymerizable group-containing alcohol compound, which is a compound not containing a urethane bond (also referred to simply as a "polymerizable group-containing alcohol compound" in the present disclosure), with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound (also referred to as a monomer composition production step in the present disclosure).

[0015] The method for producing a monomer composition according to the present disclosure includes the above-described configuration, and therefore can suppress a decrease in the transparency of the resulting monomer composition.

[0016] As described above, when diphosphorus pentoxide is used to phosphorylate a polymerizable group-containing alcohol compound in producing a polymerizable group-containing phosphoric acid compound, which is a polymerizable monomer, the transparency of the resulting monomer composition containing the polymerizable group-containing phosphoric acid compound may be reduced. In contrast, in the method for producing a monomer composition of the present disclosure, a polymerizable group-containing alcohol compound is reacted with diphosphorus pentoxide in the presence of a urethane compound. That is, in the method for producing a monomer composition of the present disclosure, a urethane compound is present when the polymerizable group-containing alcohol compound is reacted with diphosphorus pentoxide, rather than simply reacting the polymerizable group-containing alcohol compound with diphosphorus pentoxide. This makes it possible to suppress a decrease in transparency of the resulting monomer composition containing the polymerizable group-containing phosphoric acid compound. The monomer composition containing a polymerizable group-containing phosphoric acid compound obtained by the method for producing a monomer composition of the present disclosure may further contain, in addition to the polymerizable group-containing phosphoric acid compound, the above-mentioned urethane compound, a phosphoric acid group-containing urethane compound that contains a urethane bond, etc.

[0017] <Monomer composition production process> The monomer composition production step is a step of reacting a polymerizable group-containing alcohol compound with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound. That is, the monomer composition production step is a step of phosphorylating a polymerizable group-containing alcohol compound with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound.

[0018] In the monomer composition production process, the reaction temperature is not particularly limited, but is preferably 10°C to 50°C, more preferably 20°C to 40°C, and even more preferably 20°C to 30°C.

[0019] From the viewpoint of suppressing a decrease in transparency, the amount of the urethane compound added is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, based on the total amount of the urethane compound and the polymerizable group-containing alcohol compound added. The amount of the urethane compound added may be 90% by mass or less, or may be 80% by mass or less, based on the total amount of the urethane compound and the polymerizable group-containing alcohol compound added.

[0020] (Urethane compounds) The urethane compound in the present disclosure can be any compound containing a urethane bond without any particular limitations. The urethane compound in the present disclosure preferably contains one urethane bond, and also preferably contains two or more urethane bonds.

[0021] The urethane compound in the present disclosure may contain one allyl group, or may contain two or more allyl groups. The urethane compound in the present disclosure may contain one or two or more (meth)acryloyloxy groups. The urethane compound in the present disclosure may contain one hydroxyl group, or may contain two or more hydroxyl groups. In the monomer composition production process, when the urethane compound of the present disclosure contains a hydroxyl group, the hydroxyl group in the urethane compound may be phosphorylated with diphosphorus pentoxide to obtain a phosphate group-containing urethane compound.

[0022] The urethane compound in the present disclosure includes, for example, a urethane compound that includes a polymerizable group. Examples of the urethane compound containing a polymerizable group include a urethane (meth)acrylate compound (A) containing a urethane bond and a (meth)acroyl group but not an allyl group (hereinafter, may be referred to as "urethane (meth)acrylate compound (A)"), and a urethane allyl compound (B) containing a urethane bond and an allyloxy group (hereinafter, may be referred to as "urethane allyl compound (B)").

[0023] Examples of the urethane (meth)acrylate compound (A) include a reaction product (a-1) of an alcohol compound containing two or more hydroxyl groups and an isocyanate compound containing one or more isocyanate groups and (meth)acryloyloxy groups, and a reaction product (a-2) of an isocyanate compound containing two or more isocyanate groups and an alcohol compound containing one or more hydroxyl groups and (meth)acryloyloxy groups.

[0024] The urethane (meth)acrylate compound (A) may or may not contain a hydroxyl group. The urethane (meth)acrylate compound (A) containing a hydroxyl group may be a reaction product (a-3) of an isocyanate compound containing one isocyanate group and a (meth)acryloyloxy group, with an alcohol compound containing three or more hydroxyl groups, which contains a hydroxyl group (i.e., a reaction product in which unreacted hydroxyl groups remain among the hydroxyl groups contained in the alcohol compound), and preferably contains one hydroxyl group.

[0025] The isocyanate compound containing two or more isocyanate groups in the reaction product (a-2) is not particularly limited, but preferably contains at least one selected from the group consisting of m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, a mixture of 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, and isophorone diisocyanate.

[0026] The alcohol compound containing one or more hydroxyl groups and (meth)acryloyloxy groups in the reaction product (a-2) is not particularly limited, but preferably contains at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0027] An example of the isocyanate compound containing one or more isocyanate groups and a (meth)acryloyloxy group in the reaction product (a-1) is 2-methacryloyloxyethyl isocyanate (MOI).

[0028] Examples of the alcohol compound containing two or more hydroxyl groups in the reaction product (a-1) include a diol compound containing two hydroxyl groups, and an alcohol compound containing three or more hydroxyl groups (trimethylolpropane, glycerin, etc.).

[0029] An example of the isocyanate compound containing one isocyanate group and a (meth)acryloyloxy group in the reaction product (a-3) is 2-methacryloyloxyethyl isocyanate (MOI).

[0030] Examples of the alcohol compound containing three or more hydroxyl groups in the reaction product (a-3) include trimethylolpropane and glycerin.

[0031] More specific examples of urethane (meth)acrylate compounds include, for example, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (UDMA), a reaction product of 2-methacryloyloxyethyl isocyanate (MOI) and glycerin (GLY), and a reaction product of MOI and trimethylolpropane (TMP).

[0032] Examples of the urethane allyl compound (B) include a urethane allyl compound (X) that does not contain a (meth)acryloyloxy group, and a urethane allyl (meth)acrylate compound (Y) that contains a (meth)acryloyl group. The urethane allyl compound (X) may be a reaction product (X1) of an isocyanate compound containing two or more isocyanate groups and an alcohol compound containing an allyloxy group.

[0033] As the isocyanate compound containing two or more isocyanate groups in the reaction product (X1), the same isocyanate compound containing two or more isocyanate groups as used as a raw material for the urethane (meth)acrylate compound can be used.

[0034] As the alcohol compound containing an allyloxy group in the reaction product (X1), the same compounds in which the polymerizable group is an allyloxy group can be used among the compounds shown in the section on polymerizable group-containing alcohol compounds described later. Examples of the urethane allyl (meth)acrylate compound (Y) containing a (meth)acryloyl group include a reaction product (Y1) of an isocyanate compound containing two or more isocyanate groups, an alcohol compound containing an allyloxy group, and an alcohol compound containing one or more hydroxyl groups and a (meth)acryloyloxy group.

[0035] As the isocyanate compound containing two or more isocyanate groups in the reaction product (Y1), the same isocyanate compound containing two or more isocyanate groups as used as a raw material for the urethane (meth)acrylate compound can be used.

[0036] As the alcohol compound containing an allyloxy group in the reaction product (Y1), the same compounds in which the polymerizable group is an allyloxy group can be used among the compounds shown in the section on polymerizable group-containing alcohol compounds described later. As the alcohol compound containing one or more hydroxyl groups and (meth)acryloyloxy groups in the reaction product (Y1), the same alcohol compound containing one or more hydroxyl groups and (meth)acryloyloxy groups in the reaction product (a-2) can be used.

[0037] A more specific example of the urethane allyl compound (B) is a reaction product (UDAR) of a mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate (TMHDI) with ethylene glycol monoallyl ether (EGMA).

[0038] An example of the urethane compound in the present disclosure is a urethane compound (C) that does not contain a polymerizable group. Examples of the urethane compound (C) not containing a polymerizable group include ethyl carbamate.

[0039] As the urethane compound in the present disclosure, among the above, it is more preferable to include at least one selected from the group consisting of a urethane (meth)acrylate compound (A) containing a urethane bond and a (meth)acroyl group but not containing an allyl group, a urethane allyl compound (B) containing a urethane bond and an allyloxy group, and a urethane compound (C) containing no polymerizable group.

[0040] In order to suppress a decrease in transparency, the urethane compound in the present disclosure preferably has a molecular weight per urethane bond (hereinafter also referred to as a "urethane bond equivalent") of 700 or less, more preferably 500 or less, even more preferably 400 or less, and particularly preferably 300 or less. The urethane compound in the present disclosure may have a urethane bond equivalent of 50 or more, 60 or more, or 70 or more.

[0041] The urethane compound in the present disclosure preferably has a molecular weight of 2000 or less, more preferably 1000 or less, and even more preferably 800 or less. The urethane compound in the present disclosure preferably has a molecular weight of 70 or more, more preferably 100 or more, and even more preferably 150 or more.

[0042] (Polymerizable group-containing alcohol compound) The polymerizable group-containing alcohol compound is an alcohol compound that contains a polymerizable group. The polymerizable group-containing alcohol compound in the present disclosure is a compound that does not contain a urethane bond. The polymerizable group in the polymerizable group-containing alcohol compound is preferably a group containing an ethylenically unsaturated bond, and more preferably contains at least one group selected from the group consisting of an allyl group, an allyloxy group, a (meth)acryloyl group, and a (meth)acryloyloxy group. The polymerizable group-containing alcohol compound preferably contains an allyl group or a (meth)acryloyl group, and more preferably contains an allyloxy group or a (meth)acryloyloxy group, as the polymerizable group.

[0043] The polymerizable group-containing alcohol compound is preferably a compound containing one hydroxyl group and B-1 allyloxy groups in a linking group having a valence of B. Here, B is an integer of 2 or more, and more preferably 2 to 4, from the viewpoints of superior breaking energy of the obtained cured product and smaller polymerization shrinkage rate.

[0044] The B-valent linking group is not particularly limited, and examples thereof include a group obtained by removing B hydrogen atoms from an alkane, a group obtained by removing B hydrogen atoms from an arene, and a group obtained by removing B hydrogen atoms from these groups, such as -C(=O)-, -SO 2 Examples of the group include a group having one or more -, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom) bonded thereto, and a group consisting of a combination of the above groups. A group obtained by removing B hydrogen atoms from an alkane has a hydrocarbon group in which part of the hydrocarbon group is -C(=O)-, -SO 2 It may be substituted with -, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom), etc. As the B-valent linking group, a group in which B hydrogen atoms have been removed from an alkane is particularly preferable.

[0045] The number of carbon atoms in the alkane is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6. The alkane may have a substituent or may be unsubstituted. The alkane may be linear, branched, or cyclic. The cyclic alkane may be monocyclic or polycyclic. Specific examples of the alkane include methane, ethane, propane, butane, 2-methylpropane, heptane, 2-methylbutane, and 2,2-dimethylpropane.

[0046] The number of carbon atoms in the arene is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10. Specific examples of the arene include benzene and condensed polycyclic aromatic compounds in which two or more aromatic rings are condensed.

[0047] The polymerizable group-containing alcohol compound is not particularly limited, and examples thereof include ethylene glycol monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and glycerin monoallyl ether. The polymerizable group-containing alcohol compound may be used alone or in combination of two kinds.

[0048] The polymerizable group-containing alcohol compound is preferably at least one selected from the group consisting of an allyl group-containing alcohol compound and a (meth)acryloyl group-containing alcohol compound.

[0049] The polymerizable group-containing alcohol compound preferably includes at least one selected from the group consisting of compounds represented by the following formulas (B-1) to (B-7) and compounds represented by the following formula (Ba).

[0050] [ka]

[0051] [ka]

[0052] In formula (Ba), R 1B-a represents a hydrogen atom or a methyl group, X 1B-a is n with carbon number 2 to 20 B-a represents a +1-valent organic group, n B-a represents an integer of 1 or 2.

[0053] In formula (Ba), X 1B-a is n with carbon number 2 to 20 B-a There are no particular limitations on the organic group as long as it is a +1-valent group, and n is a group having 2 to 20 carbon atoms and containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. B-a It may be a +1-valent organic group or the like. X 1B-a is n with carbon number 2 to 20B-a A +1 valent hydrocarbon group is preferred. n with carbon number 2 to 20 B-a Examples of the +1-valent hydrocarbon group include a linear or branched divalent or trivalent acyclic hydrocarbon group having 2 to 20 carbon atoms, and a divalent or trivalent cyclic hydrocarbon group having 3 to 20 carbon atoms. X 1B-a The number of carbon atoms is preferably 2 to 16, and more preferably 2 to 14.

[0054] <Monomer composition> The monomer composition of the present disclosure includes a polymerizable group-containing phosphoric acid compound and a urethane compound. The monomer composition of the present disclosure includes the above-described components, and thus can suppress a decrease in transparency. The monomer composition of the present disclosure may be produced by the method for producing a monomer composition of the present disclosure. The polymerizable group-containing phosphoric acid compound is obtained by reacting the above-mentioned polymerizable group-containing alcohol compound with the above-mentioned diphosphorus pentoxide.

[0055] From the viewpoint of suppressing a decrease in transparency, the monomer composition of the present disclosure preferably has a spectral transmittance in the range of 400 nm to 800 nm at 25° C. and an optical path length of 10 mm of 40% or more, more preferably 65% ​​or more, and even more preferably 75% or more. The monomer composition of the present disclosure may have a spectral transmittance in the range of 400 nm to 800 nm at 25° C. and an optical path length of 10 mm of less than 100%, or may be 95% or less.

[0056] In the monomer composition of the present disclosure, the content of the urethane compound is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, based on the total content of the polymerizable group-containing phosphoric acid compound and the urethane compound. In the monomer composition of the present disclosure, the content of the urethane compound may be 90% by mass or less, or 80% by mass or less, based on the total content of the polymerizable group-containing phosphoric acid compound and the urethane compound.

[0057] In the monomer composition of the present disclosure, the total content of the polymerizable group-containing phosphoric acid compound and the urethane compound is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more, based on the total amount of the monomer composition.

[0058] The monomer composition of the present disclosure can be preferably used for dental materials. For example, when using a composite resin for filling caries cavities, the objective can be achieved by filling a cavity in the oral cavity with the composite resin for filling caries cavities and then photocuring the resin using a known light irradiation device. When used as a composite resin for dental crowns, the dental material composition can be processed into an appropriate shape, photocured using a known light irradiation device, and then heat-treated under specified conditions to obtain the desired dental crown material. In the above cases, the monomer composition of the present disclosure can be suitably used as a composite resin for filling dental cavities, a composite resin for dental crowns, and the like. The monomer composition of the present disclosure can suppress a decrease in transparency, and therefore allows easy transmission of light and can be satisfactorily photocured. The monomer composition of the present disclosure can more preferably be used for dental restorative materials such as composite resins. EXAMPLES

[0059] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples. The abbreviations of the compounds used in the examples of the present disclosure are shown below.

[0060] MOI: 2-Methacryloyloxyethyl isocyanate GLY: Glycerin TMP: Trimethylolpropane TMHDI: A mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate EGMA: Ethylene glycol monoallyl ether TMPDA: Trimethylolpropane diallyl ether PETA: Pentaerythritol triallyl ether HEMA: 2-hydroxyethyl methacrylate HPMA: Hydroxypropyl methacrylate 4HBA: 4-Hydroxybutyl acrylate GDMA: glycerol dimethacrylate DBTDL: Dibutyltin dilaurate BHT: Dibutyl hydroxytoluene DPPO: Diphosphorus pentoxide UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (urethane bond equivalent: 235) CAE: Ethyl carbamate (urethane bond equivalent: 89) M-GLY: Reaction product of MOI and GLY (urethane bond equivalent: 201) M-TMP: Reaction product of MOI and TMP (urethane bond equivalent: 222) UDAR: Reaction product of TMHDI and EGMA (urethane bond equivalent: 207)

[0061] [HPLC measurement method] The HPLC chart spectrum of the (meth)acrylate obtained in each Example was measured using an HPLC apparatus (LC-20AT) manufactured by Shimadzu Corporation. The (meth)acrylate obtained in each Example was dissolved in CH3CN, and then the (meth)acrylate was 3 CN / H 2 The measurements were carried out using an eluent of O=90 / 10.

[0062] [Measurement of transmittance L] In the examples and comparative examples of the present disclosure, L was measured in the visible region of 400-800 nm using a spectrophotometer (SD-3000 manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement temperature was controlled at 25° C., and the optical path length was set to 10 mm.

[0063] [Transmittance determination] The transmittance L in the examples and comparative examples of the present disclosure was judged according to the following criteria. A: The transmittance was 60% or more. B: The transmittance was 30% or more and less than 60%. C: The transmittance was less than 30%.

[0064] [Production example: hydroxyl group-containing urethane methacrylate M-GLY] In a 100 mL 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 0.05 parts by mass of DBTDL, 0.025 parts by mass of BHT, and 11.44 parts by mass of GLY were charged and dissolved to form a homogeneous solution, and the solution was heated to 80°C, and 38.56 parts by mass of MOI were added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the heat of reaction, so the amount of dropwise addition was controlled so that the temperature was 90°C or less. After the entire amount of MOI was added dropwise, the reaction temperature was kept at 90°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. 50 g of M-GLY was obtained by discharging the product from the reactor.

[0065] [Production example: hydroxyl group-containing urethane methacrylate M-TMP] In a 100 mL 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 0.05 parts by mass of DBTDL, 0.025 parts by mass of BHT, and 15.09 parts by mass of TMP were charged and dissolved to form a homogeneous solution, and then the solution was heated to 80°C, and 34.91 parts by mass of MOI were added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the reaction heat, so the amount of dropwise addition was controlled so that it was 90°C or less. After the entire amount of MOI was added dropwise, the reaction temperature was kept at 90°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. 50 g of M-TMP was obtained by discharging the product from the reactor.

[0066] [Manufacturing example: UDAR] In a 100 mL 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 0.05 parts by mass of DBTDL, 0.025 parts by mass of BHT, and 25.36 parts by mass of TMHDI were charged and dissolved to form a homogeneous solution, and then the solution was heated to 80°C, and 24.64 parts by mass of EGMA were added dropwise over 1 hour. During the dropwise addition, the internal temperature rose due to the reaction heat, so the amount of dropwise addition was controlled so that it was 90°C or less. After the entire amount of EGMA was added dropwise, the reaction temperature was kept at 90°C and the reaction was carried out for 5 hours. At this time, the progress of the reaction was tracked by HPLC analysis to confirm the end point of the reaction. 50g of UDAR was obtained by discharging the product from the reactor.

[0067] [Example 1] 20 parts by mass of PETA, 20 parts by mass of UDMA, and 80 mL of dehydrated methylene chloride were charged into a 100 mL four-neck flask equipped with a thoroughly dried stirring blade and a thermometer, and after dissolving them to form a homogeneous solution, the temperature of this solution was adjusted to 20°C. Next, 6.65 g of DPPO (1.2 times the theoretically required amount) was charged in three separate portions. The reaction temperature was kept at 20 to 30°C, and the reaction was carried out for 6 hours. After that, 150 mL of water was slowly added to the apparatus, and unreacted diphosphorus pentoxide was completely deactivated while maintaining the temperature at room temperature. The organic layer was extracted, and the volatile components were distilled off. The product was discharged from the reactor to obtain 35 g of composition (1) containing a polymerizable group-containing phosphoric acid compound. The transmittance at 25° C. was 82%.

[0068] [Examples 2 to 19] Compositions (2) to (19) containing a polymerizable group-containing phosphoric acid compound were obtained in the same manner as in Example 1, except that the reaction raw materials were changed to the combinations of compounds shown in Table 1. The transmittance at 25°C is as shown in Table 1. The compositions of Examples 3 to 6, 12 and 13 also contained a phosphoric acid group-containing urethane compound.

[0069] [Comparative Example 1] In a 100 mL 4-neck flask equipped with a thoroughly dried stirring blade and a thermometer, 40 parts by mass of PETA and 80 mL of dehydrated methylene chloride were charged and dissolved to form a homogeneous solution, and the temperature of this solution was adjusted to 20°C. Next, 13.29 g of DPPO (1.2 times the theoretically required amount) was charged in three separate portions. The reaction temperature was kept at 20 to 30°C, and the reaction was carried out for 6 hours. Then, 150 mL of water was slowly added to the apparatus, and unreacted diphosphorus pentoxide was completely deactivated while maintaining the temperature at room temperature. The organic layer was extracted, and the volatile components were distilled off. The product was discharged from the reactor to obtain 38 g of a composition (20) containing a polymerizable group-containing phosphoric acid compound. The transmittance at 25°C was 5%.

[0070] [Comparative Examples 2 to 6] Compositions (21) to (25) containing a polymerizable group-containing phosphoric acid compound were obtained in the same manner as in Example 1, except that the reaction raw materials were changed to the combinations of compounds shown in Table 1. The transmittance at 25°C is as shown in Table 1.

[0071] [Table 1]

[0072] As shown in Table 1, in the examples using the method for producing a monomer composition including a step of reacting a polymerizable group-containing alcohol compound with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound, the resulting monomer composition had excellent spectral transmittance L and its evaluation. Therefore, the monomer compositions according to the examples were able to suppress a decrease in transparency. On the other hand, in a comparative example in which a monomer composition containing a polymerizable group-containing phosphoric acid compound was obtained by reacting a polymerizable group-containing alcohol compound with diphosphorus pentoxide in the absence of a urethane compound, the resulting monomer composition had poor spectral transmittance L and was poor in its evaluation. Therefore, the monomer composition according to the comparative example could not suppress the decrease in transparency.

[0073] The disclosure of Japanese Patent Application No. 2021-023669, filed on February 17, 2021, is incorporated by reference in its entirety into this specification. All publications, patent applications, and standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a monomer composition containing a polymerizable group-containing phosphoric acid compound, comprising the steps of: A method for producing a monomer composition, comprising a step of reacting a polymerizable group-containing alcohol compound, which is a compound not containing a urethane bond, with diphosphorus pentoxide in the presence of a urethane compound to obtain a monomer composition containing a polymerizable group-containing phosphoric acid compound.

2. The method for producing a monomer composition according to claim 1, wherein the urethane compound has a molecular weight per urethane bond of 700 or less.

3. 3. The method for producing a monomer composition according to claim 1, wherein the polymerizable group-containing alcohol compound is at least one selected from the group consisting of an allyl group-containing alcohol compound and a (meth)acryloyl group-containing alcohol compound.

4. The method for producing a monomer composition according to any one of claims 1 to 3, wherein the polymerizable group-containing alcohol compound includes at least one selected from the group consisting of compounds represented by the following formulas (B-1) to (B-7), and compounds represented by the following formula (Ba): 【Chemistry 1】 【Chemistry 2】 In formula (B-a), R １Ｂ－ａ represents a hydrogen atom or a methyl group; X １Ｂ－ａ is n having 2 to 20 carbon atoms Ｂ－ａ represents a +1-valent organic group, n Ｂ－ａ represents an integer of 1 or 2.

5. The method for producing a monomer composition according to any one of claims 1 to 4, wherein the amount of the urethane compound added is 20 mass% or more based on the total amount of the urethane compound and the polymerizable group-containing alcohol compound added.

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