Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/61—Cationic, anionic or redox initiators
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/62—Three oxygen atoms, e.g. ascorbic acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1565—Five-membered rings

Definitions

• the present disclosure relates to ascorbic acid derivatives or salts thereof, additives for polymerization initiation, polymerization initiators, kits for preparing curable compositions, curable compositions, cured products, and dental materials.
• cement is used as a tooth substitute for repairing large tooth defects.
• the scope of use of cement has expanded.
• a photopolymerization initiator, a chemical polymerization initiator, and the like may be used for polymerization of a curable composition for dental materials such as cement.
• a chemical polymerization initiator system is a redox type polymerization initiator that combines an oxidizing agent and a reducing agent.
• a redox type polymerization initiator for example, a polymerization initiator system using an organic peroxide as an oxidizing agent and an aromatic amine compound as a reducing agent is known.
• Patent Document 1 discloses a redox initiator system containing ascorbic acid or ascorbic acid ester, a transition metal component, an organic peroxide, and the like. [Patent Document 1] International Publication No. 2016/007453
• the problem to be solved by an embodiment of the present disclosure is an ascorbic acid derivative or a salt thereof that can improve the adhesiveness of the obtained cured product, an additive for polymerization initiation obtained using the same, a polymerization initiator,
• the present invention provides a kit for preparing a curable composition, a curable composition, a cured product, and a dental material.
• R 1B and R 2B are each independently a hydrogen atom or a monovalent organic group.
• one of R 1B or R 2B is a hydrogen atom
• the other of R 1B or R 2B is a monovalent organic group having 1 to 15 carbon atoms
• a calcium salt The ascorbic acid derivative or salt thereof according to ⁇ 3>.
• An additive for polymerization initiation comprising the ascorbic acid derivative or its salt according to any one of ⁇ 1> to ⁇ 4>.
• a polymerization initiator comprising the ascorbic acid derivative or its salt according to any one of ⁇ 1> to ⁇ 4>, a transition metal compound, and an organic peroxide.
• the first agent includes the transition metal compound and the organic peroxide,
• the monomer (A) in the first agent includes the acidic group-containing monomer
• At least one of the first agent and the second agent contains at least one polymerization accelerator (1) selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds ⁇ 7>
• ⁇ 12> The kit for preparing a curable composition according to any one of ⁇ 7> to ⁇ 11>, wherein the second agent contains the ascorbic acid derivative or its salt and the polymerization accelerator (1).
• ⁇ 13> The kit for preparing a curable composition according to any one of ⁇ 7> to ⁇ 12>, wherein the first agent and the second agent contain a filler.
• the total content of the ascorbic acid derivative or its salt contained in the first agent and the second agent is 0.1% by mass to 5% by mass based on the total mass of the curable composition to be prepared. %.
• ⁇ 15> A curable composition comprising the ascorbic acid derivative or its salt according to any one of ⁇ 1> to ⁇ 4>, a transition metal compound, an organic peroxide, and a monomer.
• ⁇ 16> A cured product of the curable composition according to ⁇ 15>.
• ⁇ 17> A dental material comprising the cured product according to ⁇ 16>.
• an ascorbic acid derivative or a salt thereof capable of improving the adhesiveness of the obtained cured product, and a polymerization initiating additive, a polymerization initiator, and a curable composition obtained using the same.
• Preparation kits, curable compositions, cured products, and dental materials can be provided.
• a numerical range indicated using “ ⁇ ” means a range that includes the numerical values listed before and after " ⁇ " as the minimum and maximum values, respectively.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the amount of each component means the total amount of the multiple types of substances, unless otherwise specified.
• (meth)acrylic means acrylic and methacryl
• (meth)acryloyl means acryloyl and methacryloyl.
• a or B means at least one of A and B, and may include both A and B (for example, a mixture of A and B).
• the ascorbic acid derivative or its salt of the present disclosure includes a structure in which at least one of the hydroxyl groups contained in ascorbic acid is replaced with an ether bond bonded to a carbon atom.
• the ascorbic acid derivative or its salt of the present disclosure may be an additive used in a polymerization initiator (additive for a polymerization initiator), and may be combined with other components (for example, a transition metal compound, an organic peroxide, etc.). They may be used in combination as a polymerization initiator.
• Examples of the salts of the ascorbic acid derivatives of the present disclosure include alkali metal salts of ascorbic acid derivatives, alkaline earth metal salts of ascorbic acid derivatives, and more specifically, sodium salts, potassium salts, magnesium salts of ascorbic acid derivatives, etc.
• Examples include salt, calcium salt, and the like. Among these, calcium salts are preferred from the viewpoint of balance between polymerizability and adhesiveness.
• the ascorbic acid derivative or salt thereof of the present disclosure may include a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is replaced with an ether bond bonded to a carbon atom. It is preferable that ascorbic acid contains a structure in which two of the four hydroxyl groups contained in the ascorbic acid are substituted with ether bonds bonded to carbon atoms.
• the ascorbic acid derivative of the present disclosure preferably includes a structure represented by the following general formula (A).
• * indicates the bonding position with the carbon atom.
• Two * in the general formula (A) may be bonded to the same carbon atom to form a 1,3-dioxolane skeleton.
• the ascorbic acid derivative of the present disclosure preferably contains a compound represented by the following general formula (B).
• R 1B and R 2B are each independently a hydrogen atom or a monovalent organic group. At least one of R 1B and R 2B is preferably a monovalent organic group.
• the monovalent organic group in R 1B and R 2B is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms, and an organic group having 3 to 10 carbon atoms. It is more preferable that On the other hand, in view of the balance between polymerizability and adhesiveness, the monovalent organic group in R 1B and R 2B is preferably an organic group having 1 to 15 carbon atoms, more preferably an organic group having 3 to 14 carbon atoms. More preferably, it is an organic group having 8 to 12 carbon atoms.
• one of R 1B or R 2B may be a hydrogen atom, and the other of R 1B or R 2B may be a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group in R 1B and R 2B may be an organic group containing an oxygen atom, a nitrogen atom, a sulfur atom, etc., or a hydrocarbon group to which an oxygen atom, a nitrogen atom, a sulfur atom, etc. are bonded. It may also be a hydrocarbon group.
• the salt of the ascorbic acid derivative of the present disclosure may be a salt of a compound represented by general formula (B), or an alkali metal salt or alkaline earth metal salt of a compound represented by general formula (B). From the viewpoint of balance between polymerizability and adhesive properties, a calcium salt of a compound represented by general formula (B) is preferred.
• R 1B and R 2B are preferably each independently a hydrogen atom or a monovalent organic group. Furthermore, one of R 1B or R 2B is a hydrogen atom, and the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms, or R 1B and R 2B are each independently It is preferably a monovalent organic group having 1 to 10 carbon atoms.
• R 1B or R 2B When one of R 1B or R 2B is a hydrogen atom, and the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms, the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms. It is preferably a monovalent organic group having 5 carbon atoms, more preferably a monovalent organic group having 1 to 3 carbon atoms, and even more preferably a methyl group, ethyl group, propyl group or isopropyl group, and isopropyl group. A group is particularly preferred.
• R 1B and R 2B are each independently a monovalent organic group having 1 to 10 carbon atoms
• R 1B and R 2B are each independently a monovalent organic group having 1 to 5 carbon atoms. It is preferably a monovalent organic group having 1 to 3 carbon atoms, more preferably a methyl group, ethyl group, propyl group or isopropyl group, and particularly preferably a methyl group.
• ascorbic acid represented by the following general formula (C) is acetalized with an aldehyde compound represented by the following general formula (D) or a ketone compound represented by the following general formula (E) (see broken line).
• R in the above general formula (D) is the same as R 1B or R 2B in the above general formula (B).
• the two R's in the above general formula (E) are the same as R 1B and R 2B in the above general formula (B).
• the two R's in the above general formula (E) may be the same or different.
• Examples of the aldehyde compound represented by the above general formula (D) include butanal, isobutanal, hexanal, octanal, dodecanal, and the like.
• Examples of the ketone compound represented by the above general formula (E) include acetone, methyl ethyl ketone, and methyl isobutyl ketone. These compounds may be used alone or in combination of two or more.
• the lower limit of the reaction temperature of the acetalization reaction is not particularly limited, and for example, it is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.
• the upper limit of the reaction temperature of the acetalization reaction is not particularly limited, and for example, it is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.
• the lower limit of the reaction time of the acetalization reaction is not particularly limited, and for example, it is preferably 5 hours or more, more preferably 10 hours or more, and even more preferably 20 hours or more.
• the upper limit of the reaction time of the acetalization reaction is not particularly limited, and for example, it is preferably 100 hours or less, more preferably 80 hours or less, and even more preferably 60 hours or less.
• a solvent, an acetalization catalyst, etc. may be added as necessary.
• the solvent examples include amides such as dimethylacetamide and dimethylformamide. These solvents may be used alone or in combination of two or more.
• the blending ratio of the solvent is not particularly limited, and is appropriately set depending on the purpose and use.
• acetalization catalyst examples include known acetalization catalysts such as acids such as p-toluenesulfonic acid. These acetalization catalysts may be used alone or in combination of two or more. The addition ratio of the esterification catalyst is appropriately set depending on the purpose and use.
• an ascorbic acid derivative represented by the following general formula (B) and an alkali metal salt or alkaline earth metal salt represented by the following general formula (F) are reacted.
• X represents an alkali metal element or an alkaline earth metal element
• R represents, for example, a carbonate group or a hydroxyl group.
• alkali metal salt or alkaline earth metal salt represented by the above general formula (F) include sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, and calcium carbonate. These may be used alone or in combination of two or more.
• the lower limit of the reaction temperature for the reaction with an alkali metal salt or alkaline earth metal salt (hereinafter also referred to as "alkali metalation reaction") is not particularly limited, and is preferably 0°C or higher, for example, 10°C or higher.
• the temperature is more preferably 20° C. or higher, and even more preferably 20° C. or higher.
• the upper limit of the reaction temperature of the alkali metalation reaction is not particularly limited, and for example, it is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower.
• the lower limit of the reaction temperature of the alkali metalation reaction is not particularly limited, and for example, it is preferably 0.1 hour or more, more preferably 0.5 hour or more, and even more preferably 1 hour or more.
• the upper limit of the reaction temperature of the alkali metalation reaction is not particularly limited, and for example, it is preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less.
• a solvent or the like may be added if necessary.
• the solvent examples include alcohols such as methanol, ethanol, 2-propanol, butanol, and hexanol, furans such as tetrahydrofuran, and ketones such as acetone and methyl ethyl ketone. These solvents may be used alone or in combination of two or more.
• the blending ratio of the solvent is not particularly limited, and is appropriately set depending on the purpose and use.
• the polymerization initiation additive of the present disclosure includes the ascorbic acid derivative of the present disclosure or a salt thereof.
• a combination of the polymerization initiating additive of the present disclosure and other components eg, a transition metal compound, an organic peroxide, etc. can be used as a polymerization initiator.
• the polymerization initiation additive of the present disclosure may be an additive consisting only of the ascorbic acid derivative of the present disclosure or a salt thereof, or may be an additive consisting of the ascorbic acid derivative of the present disclosure or a salt thereof and other components. You can.
• the polymerization initiator of the present disclosure includes the ascorbic acid derivative of the present disclosure or a salt thereof, a transition metal compound, and an organic peroxide.
• the total content of the ascorbic acid derivative and its salt is preferably 10 parts by mass to 70 parts by mass, and 15 parts by mass to 65 parts by mass, based on 100 parts by mass of the polymerization initiator.
• the amount is more preferably 20 parts by mass to 60 parts by mass.
• the polymerization initiator of the present disclosure includes a transition metal compound.
• the transition metal compound is preferably a compound that is soluble in the monomer component in the curable composition preparation kit described below.
• transition metal compound examples include copper compounds, vanadium compounds, molybdenum compounds, scandium compounds, titanium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, and nickel compounds.
• the transition metal compound contains at least one of a copper compound and a vanadium compound, and more preferably a copper compound.
• Copper compounds include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, and methacrylic acid.
• Copper copper 4-cyclohexylbutyrate; ⁇ -diketone copper, copper acetylacetone, copper trifluoroacetylacetone, copper hexafluoroacetylacetone, copper 2,2,6,6-tetramethyl-3,5-heptanedionato, copper benzoylacetone; - As copper ketoester, copper ethyl acetoacetate; as copper alkoxide, copper methoxide, copper ethoxide, copper isopropoxide, copper 2-(2-butoxyethoxy) ethoxide, copper 2-(2-methoxyethoxy) ethoxide; copper dithiocarbamate
• the salt include copper dimethyldithiocarbamate; examples of the salt of copper and an inorganic acid include copper nitrate; and copper chloride.
• copper carboxylate, copper ⁇ -diketone, and copper ⁇ -ketoester are preferred, and copper acetate and copper acetylacetone are more preferred, from the viewpoint of solubility and reactivity with monomers.
• Vanadium compounds include vanadyl acetylacetonate, vanadium (III) naphthenate, vanadyl stearate, vanadium benzoylacetonate, bis(maltolate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedioate) Examples include vanadium (IV).
• the content of the transition metal compound is preferably 0.1 parts by mass to 1.5 parts by mass, and 0.2 parts by mass to 1 part by mass, based on 100 parts by mass of the polymerization initiator. It is more preferably 0.3 parts by mass to 1 part by mass.
• Organic peroxides include organic peroxides.
• Known organic peroxides can be used without particular limitations.
• Typical organic peroxides include hydroperoxide, peroxyester, ketone peroxide, peroxyketal, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and the like.
• hydroperoxide is preferable because even if the curable composition is provided in a packaged form and stored for a long period of time, there is little variation in the operable time.
• One type of organic peroxide may be used alone, or a plurality of types may be used in combination.
• the hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3, Examples include 3-tetramethylbutyl hydroperoxide and t-amyl hydroperoxide.
• any one containing an acyl group on one side of the peroxy group (-OO- group) and a hydrocarbon group (or a group similar thereto) on the other side can be used without any restrictions.
• Specific examples include ⁇ , ⁇ -bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-Methyl ethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1 , 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-eth)
• ketone peroxide examples include methyl ethyl ketone peroxide, cyclohexanoperoxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
• Peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butyl peroxy) 3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)cyclohexane, oxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, and the like.
• dialkyl peroxides examples include ⁇ , ⁇ -bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumylbenzene.
• dialkyl peroxides examples include luperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3, and the like.
• diacyl peroxide examples include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and succinic acid peroxide. , m-toluoylbenzoyl peroxide, and benzoyl peroxides.
• peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutyl)peroxydicarbonate.
• the content of the organic peroxide is preferably 20 parts by mass to 90 parts by mass, and preferably 30 parts by mass to 85 parts by mass, based on 100 parts by mass of the polymerization initiator. is more preferable, and even more preferably 40 parts by weight to 80 parts by weight.
• the kit for preparing a curable composition of the present disclosure includes a first agent containing a monomer (A) and a second agent containing a monomer (B), and at least one of the first agent and the second agent comprises the present invention.
• the first part contains a transition metal compound and an organic peroxide
• the second part contains the ascorbic acid derivative or its salt. It is preferable to include.
• the first agent contains the monomer (A), and the second agent contains the monomer (B).
• Monomer (A) and monomer (B) may be the same monomer or different monomers.
• known monomers can be used as the monomer (A) and the monomer (B).
• Monomer (A) and monomer (B) may be monomers that do not contain acidic groups or may be monomers that contain acidic groups (hereinafter also referred to as "acidic group-containing monomers").
• Monomer (A) and monomer (B) preferably include monomers that do not contain acidic groups.
• the monomer is a monomer that undergoes a radical polymerization reaction and becomes a polymer under the action of the ascorbic acid derivative or its salt of the present disclosure, a transition metal compound, and an organic peroxide.
• the number of monomers constituting the monomers in the present disclosure is not limited to one type, and two or more types may be used.
• Examples of monomers that do not contain acidic groups include (meth)acrylate monomers that do not contain acidic groups.
• Examples of (meth)acrylate monomers that do not contain acidic groups include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.
• the monomer content i.e., the total amount of monomer (A) and monomer (B) in the curable composition to be prepared
• the monomer content is 10 It is preferably from 20% to 75% by weight, even more preferably from 30% to 60% by weight.
• Monomer monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxy
• An example is propyl (meth)acrylate.
• 2-hydroxyethyl methacrylate (HEMA) is preferred.
• aromatic compound-based difunctional monomers examples include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxy] phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-( meth)acryloyloxypolypropoxyphenyl)propane, and the like.
• Bis-GMA 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl)propane
• Bis-GMA 2,2-bis(4-methacryloyloxypolyethoxyphenyl) Propane
• aliphatic compound-based difunctional monomers examples include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate.
• glycerol di(meth)acrylate ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), 1,2-bis(3-methacryloyloxy-2-hydroxy) Examples include propyloxy)ethane.
• UDMA 2,2,4-trimethylhexam
• glycerol dimethacrylate triethylene glycol dimethacrylate (TEGDMA), 1,6-hexanediol dimethacrylate (HexDMA), neopentyl glycol dimethacrylate (NPG), 2,2,4-trimethylhexamethylene bis( 2-Carbamoyloxyethyl) dimethacrylate (UDMA) and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.
• TEGDMA triethylene glycol dimethacrylate
• HexDMA 1,6-hexanediol dimethacrylate
• NPG neopentyl glycol dimethacrylate
• UDMA 2,2,4-trimethylhexamethylene bis( 2-Carbamoyloxyethyl) dimethacrylate
• 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.
• trifunctional or higher functional monomers examples include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
• acrylate dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-( Examples include aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.
• the above monomers may be blended singly or in combination of multiple types.
• the amount of the above-mentioned monomer not containing an acidic group is preferably in the range of 10 parts by mass to 100 parts by mass, and 20 parts by mass, based on 100 parts by mass of the total amount of monomer components in the curable composition preparation kit of the present disclosure.
• the range is more preferably 1 part to 100 parts by weight, and even more preferably 50 parts to 100 parts by weight.
• the monomer component in the kit for preparing a curable composition of the present disclosure includes an acidic group-containing monomer described below
• the amount of the monomer not containing an acidic group is the amount of the monomer component in the kit for preparing a curable composition of the present disclosure. It is preferably 10 parts by mass to 99 parts by mass, more preferably 30 parts by mass to 97 parts by mass, and even more preferably 50 parts by mass to 95 parts by mass, based on the total amount of 100 parts by mass.
• Monomer (A) and monomer (B) preferably contain a (meth)acrylic monomer (C) having a molecular weight of 100 to 5,000.
• the molecular weight of the (meth)acrylic monomer (C) is preferably from 120 to 3,000, even more preferably from 150 to 2,000, particularly preferably from 200 to 1,000.
• the content of the (meth)acrylic monomer (C) relative to the total content of the monomer (A) and the monomer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. % or more is more preferable.
• either the monomer (A) in the first agent or the monomer (B) in the second agent preferably contains an acidic group-containing monomer. Since at least one of the first agent and the second agent contains an acidic group-containing monomer, for example, when the curable composition preparation kit of the present disclosure is used for dental purposes, good tooth quality and dental prosthetic material can be obtained. It can provide high adhesion to.
• the monomer (A) in the first part may contain an acidic group-containing monomer, and the second part may contain the ascorbic acid derivative or its salt.
• the monomer (A) in the first agent contains an acidic group-containing monomer, and the second agent does not contain an acidic group-containing monomer and contains an ascorbic acid derivative or a salt thereof.
• the acidic group-containing monomer has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group, and an acryloyl group, a methacryloyl group, a vinyl group. , a monomer containing at least one polymerizable group such as a styrene group.
• the acidic group-containing monomer has an affinity with the adherend and has a demineralizing effect on the tooth substance.
• (meth)acryloyloxyalkyl dihydrogen phosphate such as 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), bis[2-(meth)acryloyloxyethyl]hydrogen phosphate , bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9- (meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl Phenyl hydrogen phosphate, 2-(meth)acryloyloxyalkyl dihydrogen phosphate
• pyrophosphate group-containing monomers include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, and their acid chlorides, alkali metal salts, and ammonium salts. be done.
• thiophosphoric acid group-containing monomers examples include 2-(meth)acryloyloxyethyldihydrogenthiophosphate, 3-(meth)acryloyloxypropyldihydrogenthiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. be done.
• Examples of phosphonic acid group-containing monomers include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, and acid chlorides, alkali metal salts, and ammonium salts thereof. be done.
• sulfonic acid group-containing monomer examples include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.
• carboxylic acid group-containing monomers examples include monomers containing one carboxy group in the molecule and monomers containing multiple carboxy groups in the molecule.
• Monomers containing one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyl Tyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxybenzoic acid, ) acryloy
• Examples of monomers containing multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, and 10-(meth)acryloyloxyhexane-1,1-dicarboxylic acid.
• 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP) and 1,3-di(meth)acryloyloxypropyl dihydrogen have high adhesive strength to adherends.
• the blending amount of the acidic group-containing monomer is preferably 1 part by mass to 50 parts by mass, and 3 parts by mass to 40 parts by mass, based on 100 parts by mass of the total amount of monomer components in the curable composition preparation kit of the present disclosure.
• the amount is more preferably 1 part by weight, and even more preferably 5 parts by weight to 30 parts by weight.
• the amount of the acidic group-containing monomer is 1 part by mass or more, it is easy to obtain high adhesiveness to various adherends. Further, when the amount of the acidic group-containing monomer is 50 parts by mass or less, it is easy to maintain a balance between polymerizability and adhesiveness.
• the total amount of monomer components means the total amount of the acidic group-containing monomer and the above-mentioned monomer not containing the acidic group.
• monomers in the present disclosure for example, monomers described in known documents such as WO 2012/157566, WO 2015/015220, WO 2015/015221, and JP 2016-094482 are used. be able to.
• the total content of the ascorbic acid derivative or its salt contained in the first part and the second part is 0.1% by mass to 5% by mass based on the total mass of the curable composition to be prepared. %, more preferably 0.3% by mass to 3% by mass, even more preferably 0.5% by mass to 2% by mass.
• the total content of the transition metal compound contained in the first agent and the second agent is 0.00005 parts by mass based on 100 parts by mass of the total amount of monomer components in the curable composition preparation kit of the present disclosure. It is preferably from 0.1 part by weight to 0.1 part by weight, more preferably from 0.0001 part to 0.05 part by weight, even more preferably from 0.001 part by weight to 0.03 part by weight.
• the total content of the organic peroxides contained in the first agent and the second agent is 0.00 parts by mass based on 100 parts by mass of the total amount of monomer components in the curable composition preparation kit of the present disclosure. It is preferably from 0.01 parts by weight to 6 parts by weight, more preferably from 0.01 parts by weight to 4 parts by weight, even more preferably from 0.05 parts by weight to 3 parts by weight.
• At least one of the first agent and the second agent contains at least one polymerization accelerator selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds. ) may be included.
• the second agent preferably contains the ascorbic acid derivative or its salt and the polymerization accelerator (1).
• the phosphonite compound may be any trivalent organic phosphorus compound in which a carbon atom is bonded to a phosphorus atom.
• the phosphonite compound contained in the polymerization accelerator (1) of the present disclosure preferably includes a structure represented by the following general formula (I).
• * indicates the bonding position to the carbon atom.
• the three * marks are preferably bonding positions to a carbon atom contained in a hydrocarbon group, and more preferably bonding positions to a carbon atom contained in a benzene ring.
• the phosphonite compound may contain one structure represented by general formula (I), or may contain two or more structures.
• the phosphonite compound preferably contains two structures represented by the general formula (I), and the two structures represented by the general formula (I) are bonded via a divalent linking group (preferably a biphenyl structure). It is more preferable to include a structure that
• the phosphonite compound contained in the polymerization accelerator (1) of the present disclosure preferably contains a compound represented by the following general formula (II).
• R B1 is an n-valent hydrocarbon group
• R B2 and R B3 are each independently a monovalent hydrocarbon group
• n is an integer of 1 or 2.
• n-valent hydrocarbon group in R B1 examples include an n-valent aliphatic hydrocarbon group, an n-valent alicyclic hydrocarbon group, an n-valent aromatic hydrocarbon group, a combination of two or more of these, etc. It will be done.
• the monovalent hydrocarbon group in R B1 is preferably an alkyl group, a phenyl group, a biphenyl group, or the like.
• the hydrogen atom of the phenyl group or biphenyl group in R B1 may be substituted with a substituent such as an alkyl group.
• the divalent hydrocarbon group in R B1 is preferably an alkylene group, a phenylene group, a 4,4'-biphenylene group, a 4,3'-biphenylene group, a biphenylene group such as a 3,3'-biphenylene group, or the like.
• the hydrogen atom contained in the phenylene group or biphenylene group in R B1 may be substituted with a substituent such as an alkyl group.
• R B2 and R B3 each independently represent a monovalent hydrocarbon group, preferably an alkyl group, a phenyl group, or the like.
• the hydrogen atom contained in the phenyl group in R B2 and R B3 may be substituted with an alkyl group such as a tert-butyl group or n-butyl group.
• n is an integer of 1 or 2, preferably 2.
• phosphonite compound contained in the polymerization accelerator (1) of the present disclosure include, for example, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-di-phosphonite, tetrakis(2, 4-di-tert-butyl-5-methylphenyl)4,4'-biphenylene-di-phosphonite, tetrakis(2,4-di-tert-butylphenyl)4,3'-biphenylene-di-phosphonite, tetrakis( 2,4-di-tert-butylphenyl)3,3'-biphenylene-di-phosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite, tetrakis(2 ,6-di-tert-butylphenyl)-4,3'-biphenylene
• phosphite compounds include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, tris Examples include (2,4-di-tert-butylphenyl) phosphite.
• sulfite compounds include ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethyl methyl sulfite, methyl-n-propyl sulfite, ethyl-n-propyl sulfite, and di-n-propyl sulfite.
• examples include sulfite, diphenyl sulfite, methylphenyl sulfite, ethyl sulfite, dibenzyl sulfite, benzyl methyl sulfite, benzylethyl sulfite, and the like.
• the total content of the polymerization accelerator (1) contained in the first part and the second part is 0.1 parts by mass to 100 parts by mass of the total amount of the first part and the second part.
• the amount is preferably 5 parts by weight, and more preferably 0.2 parts to 2 parts by weight.
• At least one of the first agent and the second agent may contain a polymerization accelerator (2) other than the polymerization accelerator (1).
• the polymerization accelerator (2) of the present disclosure is not particularly limited, and examples thereof include inorganic salts, thiourea, and the like.
• inorganic salts include sodium sulfite, calcium sulfite, potassium sulfite, potassium nitrate, potassium chloride, potassium sulfate, and sodium chloride.
• thiourea examples include acetylthiourea, phenylthiourea, triethylthiourea, tetramethylthiourea, dimethylthiourea, diphenylthiourea, and the like.
• the total content of the polymerization accelerator (2) contained in the first part and the second part is 0.0001 parts by mass to 100 parts by mass of the total amount of the first part and the second part.
• the amount is preferably 1 part by weight, and more preferably 0.001 part to 0.1 part by weight.
• the total content of inorganic salts contained in the first part and the second part is 0.0001 part by mass to 0.1 part by mass with respect to the total amount of 100 parts by mass of the first part and the second part.
• the amount is preferably 0.001 parts by mass to 0.01 parts by mass.
• the total content of thiourea contained in the first agent and the second agent is 0.001 parts by mass to 1.0 parts by mass based on 100 parts by mass of the total amount of the first agent and the second agent.
• the amount is preferably 0.01 parts by mass to 0.1 parts by mass.
• At least one of the first agent and the second agent may contain a filler, and it is preferable that the first agent and the second agent contain a filler.
• a filler may be used alone, or a combination of multiple types may be used.
• the filler include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.
• inorganic fillers include silica; silica-based minerals such as kaolin, clay, mica, and mica; silica-based minerals such as Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , BaO, and La; Examples include ceramics and glasses containing 2 O 3 , SrO, ZnO, CaO, P 2 O 5 , Li 2 O, Na 2 O, and the like.
• glasses lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used.
• Crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferably used. It will be done.
• fine particle silica having a primary particle diameter of 0.001 ⁇ m to 0.1 ⁇ m is preferably used in terms of adhesive strength and ease of handling.
• organic fillers examples include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.
• composite fillers of inorganic fillers and organic fillers include those in which inorganic fillers are dispersed in organic fillers, and inorganic/organic composite fillers in which inorganic fillers are coated with various polymers.
• the filler may be used after being previously surface-treated with a known surface treatment agent such as a silane coupling agent.
• Surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri( ⁇ -methoxyethoxy)silane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Examples include mercaptopropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane.
• the total content of the filler contained in the first part and the second part is preferably in the range of 10% by mass to 80% by mass, and 30% by mass to 80% by mass, based on the total mass of the curable composition to be prepared. More preferably, the range is from 50% by mass to 75% by mass.
• Non-conductive filler In the curable composition preparation kit of the present disclosure, at least one of the first agent and the second agent preferably contains a non-conductive filler.
• a non-conductive filler means a filler having a resistance value of 1.00 ⁇ 10 ⁇ 4 ⁇ m or more.
• the upper limit of the resistance value of the non-conductive filler is not particularly limited, and may be, for example, 1.00 ⁇ 10 20 ⁇ m.
• Non-conductive filler examples include, for example, organic materials such as polyethylene, polystyrene, phenol resin, epoxy resin, acrylic resin, and benzoguanamine resin; silica (dimethylsilylated silica, etc.); silicates (borosilicate glass (barium borosilicate glass, etc.)); ), aluminosilicate glasses (boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, barium aluminosilicate glass, etc.)), ceramics, and inorganic materials such as boron nitride and barium nitride.
• organic materials such as polyethylene, polystyrene, phenol resin, epoxy resin, acrylic resin, and benzoguanamine resin
• silica dimethylsilylated silica, etc.
• silicates borosilicate glass (barium borosilicate glass, etc.)
• aluminosilicate glasses
• silica and silicates are preferable, and dimethylsilylated silica and barium aluminosilicate are more preferable as materials for the non-conductive filler.
• the first part contains a non-conductive filler, and the content of the non-conductive filler relative to the total mass of the first part is preferably 10% by mass or more, more preferably 20% by mass or more, More preferably, it is 30% by mass or more.
• the second part contains a non-conductive filler
• the second part contains the non-conductive filler
• the content of the non-conductive filler with respect to the total mass of the second part is 10% by mass or more.
• the content is preferably 20% by mass or more, more preferably 30% by mass or more.
• the content of the non-conductive filler is 10% by mass or more based on the total mass of the first component, and the non-conductive filler is When a conductive filler is included in the second part, it is preferable that the content of the non-conductive filler is 10% by mass or more based on the total mass of the second part.
• At least one of the first agent and the second agent includes additives such as a photopolymerization initiator, a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber.
• a photopolymerization initiator a known photopolymerization initiator can be used, and examples thereof include camphorquinone (CQ), ethyl dimethylaminobenzoate (EDB), and the like.
• antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecyl ammonium chloride, and triclosan may be added. good.
• Known dyes and pigments may be added to the curable composition preparation kit of the present disclosure.
• the curable composition preparation kit of the present disclosure is preferably used for dental materials.
• dental materials include, but are not limited to, dental adhesives, dental filling materials, dental sealants (tooth fissure sealants), abutment building materials, denture base resins, and denture base lining materials. , dental crown prosthesis resins (hard resins for dental crowns), dental room temperature polymerization resins, and the like.
• the curable composition preparation kit of the present disclosure is particularly preferably used as a dental adhesive.
• dental adhesives include dental adhesive resin cement, orthodontic adhesives, adhesives for fixing loose teeth, cavity coating adhesives, and dental bonding materials. Cement is preferred.
• dental filling materials include dental composite resins (including dental self-adhesive composite resins), root canal filling materials, temporary sealants, backing materials, and the like.
• the curable composition of the present disclosure includes the ascorbic acid derivative of the present disclosure or a salt thereof, a transition metal compound, an organic peroxide, and a monomer.
• the curable composition of the present disclosure includes the above configuration, polymerizability can be favorably improved.
• Specific examples, preferred embodiments, etc. of the monomer in the curable composition are the same as those of the above-mentioned monomer.
• the curable composition of the present disclosure preferably further includes a non-conductive filler. Specific examples, preferred embodiments, etc. of the non-conductive filler in the curable composition are the same as those for the above-mentioned non-conductive filler.
• the curable composition of the present disclosure may include the aforementioned additives.
• the cured product of the present disclosure is a cured product of the curable composition of the present disclosure, or a cured product obtained using the curable composition preparation kit of the present disclosure.
• the cured product of the present disclosure can be suitably used as a dental material. That is, the dental material of the present disclosure preferably includes the cured product of the present disclosure.
• the obtained reaction product was extracted. Specifically, an equal amount of distilled water was added to the reaction solution, then an equal amount of diethyl ether was added, and the mixture was extracted and washed using a separating funnel. After repeating the above extraction three times, an equal amount of distilled water was added to the obtained organic layer and washed with a separatory funnel. After repeating the above washing three times, the resulting organic layer was dried by adding sodium sulfate, and then concentrated under reduced pressure. The obtained crude product was washed with a hexane/ethyl acetate solvent, and separated and purified by filtration.
• IPDAANa 2-(2,2-dimethyl-1,3-dioxolan-4-yl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-oleate
• IPDAACa 2-(2,2-dimethyl-1,3-dioxolan-4-yl)-4-hydroxy-5-oxo-2,5-dihydrofuran-3-oleate calcium (IPDAACa, 2.35 g, 10 mmol) , yield 99%, white solid) was obtained.
• the assignment of IPDAACa by 1 H-NMR (D 2 O) is shown below.
• Examples 1 to 14 and Comparative Examples 1 to 3 As shown in Tables 1 to 4, the first and second parts of Examples 1 to 14 and Comparative Examples 1 to 3 were prepared using each component.
• the numbers in each composition or component column shown in Tables 1 to 4 mean the amount (parts by mass) of each composition or component in the first agent or second agent.
• Adhesion strength was determined by applying a shear load parallel to the bovine tooth adherend and in contact with the surface at a crosshead speed of 1.0 mm/min, and the cylindrical cured material adhered to the bovine tooth adherend peeling off from the surface.
• Criterion 1 is an evaluation criterion for Examples and Comparative Examples in which the content of ascorbic acids is kept under the same conditions.
• Criterion 2 is an evaluation criterion for Examples in which the number of moles of ascorbic acids was adjusted to the same conditions.
• A Adhesive strength is 15 MPa or more and less than 23 MPa.
• B Adhesive strength is 13 MPa or more and less than 15 MPa.
• Adhesive strength is 10 MPa or more and less than 13 MPa.
• D Adhesive strength is less than 10 MPa.
• E All adherends were detached before the test, making it impossible to evaluate adhesiveness.
• A1 Adhesive strength is 17 MPa or more and less than 23 MPa.
• A2 Adhesive strength is 15 MPa or more and less than 17 MPa.
• B2 Adhesive strength is 13 MPa or more and less than 14 MPa.
• Example 13 C6AAACa was used as the calcium salt of the ascorbic acid derivative
• Example 14 using C12AAACa as the calcium salt of an ascorbic acid derivative

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