WO2016031831A1 - 重合性単量体、硬化性組成物および樹脂部材 - Google Patents
重合性単量体、硬化性組成物および樹脂部材 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a polymerizable monomer, a curable composition and a resin member.
- the (meth) acrylate-based polymerizable monomer can be used in a wide range of dental materials such as dental curable compositions or dental adhesives, optical materials, printing plate making, photoresist materials, paints, adhesives, inks, optical shaping resins, etc. It is available in the field (eg, Patent Documents 1 to 4).
- a (meth) acrylate-based polymerizable monomer capable of obtaining a cured product excellent in mechanical strength it is represented by bisphenol A diglycidyl di (meth) acrylate (Bis-GMA) exemplified in Patent Documents 2 and 3.
- Bismerizable monomers having a bisphenol A skeleton, and polymerizable monomers having a biphenyl skeleton exemplified in Patent Documents 4 and 5 are known.
- the polymerizable monomer is a liquid or liquid substance having a low viscosity in a room temperature environment.
- the polymerizable monomer is often used as a mixed composition mixed with other components according to various uses, rather than used alone. In such a case, if the polymerizable monomer is a low viscosity liquid or liquid substance, blending with other components is also extremely easy.
- the present invention has been made in view of the above circumstances, and is a polymerizable monomer excellent in mechanical strength of a cured product and excellent in handleability at low viscosity even in a room temperature environment, and curability using the same
- An object of the present invention is to provide a composition and a resin member.
- the above object is achieved by the present invention described below. That is, The polymerizable monomer of the present invention is characterized by being represented by the following general formula (1).
- X represents a divalent group
- Ar 1 and Ar 2 each represent an aromatic group having any valence selected from divalent to tetravalent
- L 1 and L 2 may be the same or different
- each of L 1 and L 2 has a main chain atom number in the range of 2 to 60, and any valence selected from divalent to tetravalent
- It represents a hydrocarbon group having a number, each of which may be the same or different
- R 1 and R 2 each represent a hydrogen or a methyl group.
- m1, m2, n1 and n2 are each an integer selected from the range of 1 to 3.
- the divalent group X is preferably -O-.
- Another embodiment of the polymerizable monomer of the present invention has a hydrocarbon whose main chain has an atomic number in the range of 2 to 60 and any valence selected from divalent to tetravalent It is preferable that at least one of the groups L 1 and L 2 contains a hydroxyl group.
- L 3 and L 4 each represent a divalent hydrocarbon group having a main chain atom number in the range of 1 to 8, and may be the same or different.
- R 3 and R 4 each represent hydrogen or a methyl group.
- j is 0, 1 or 2
- k is 0, 1 or 2
- j + k 2.
- Another embodiment of the polymerizable monomer of the present invention is characterized in that the combination (j, k) of values j and k shown in the general formula (3) is a group consisting of (1, 1) and (0, 2) It is preferable that it is any selected.
- Another embodiment of the polymerizable monomer of the present invention is characterized in that the combination (j, k) of the values j and k shown in the general formula (3) is (2, 0), (1, 1) and (0, It is preferable to include any two or more structural isomers selected from the group consisting of 2).
- the average value of value k in all the polymerizable monomer molecules is 0.05 or more and less than 2.0.
- the method for producing the polymerizable monomer of the present invention comprises at least a reaction step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5).
- a polymerizable monomer comprising two or more structural isomers selected from the group consisting of the compounds shown in (8) is produced.
- X represents a divalent group
- Ar 1 and Ar 2 each represent a divalent aromatic group, which may be the same or different
- L 5 represents a divalent hydrocarbon group having the number of atoms of main chain 1-7. Also, p is 0 or 1.
- the curable composition of the present invention is characterized by containing the polymerizable monomer of the present invention and a polymerization initiator.
- the resin member of the present invention is characterized by containing a cured product obtained using the composition containing the polymerizable monomer of the present invention.
- the polymerizable monomer of the present embodiment is characterized by being represented by the following general formula (1).
- X represents a divalent group
- Ar 1 and Ar 2 each represent an aromatic group having any valence selected from divalent to tetravalent
- Each of L 1 and L 2 may be the same or different, and each of L 1 and L 2 has a main chain atom number in the range of 60 and any valence number selected from divalent to tetravalent
- each may be the same or different
- R 1 and R 2 each represent hydrogen or a methyl group.
- m1, m2, n1 and n2 are each an integer selected from the range of 1 to 3.
- the polymerizable monomer represented by the general formula (1) may be an isomer mixture containing two or more kinds of isomers.
- the polymerizable monomer of the present embodiment is excellent in the mechanical strength of the cured product and has a low viscosity even in a room temperature environment, and therefore, the handleability is excellent. Although the reason why such an effect is obtained is not clear, the present inventors estimate as follows. First, the reason why the cured product is excellent in mechanical strength is considered to be that it has a structure (Ar 1 -X-Ar 2 ) containing an aromatic group with high rigidity in the central part of the molecule.
- the structure (Ar 1 -Ar 2 ) is easy to be crystallized because of the high symmetry of the molecular structure
- the structure (Ar 1 -X-Ar 2 ) in which a divalent group X is further introduced to such a structure has a molecular structure It is thought that as a result, the crystallinity is lowered and the viscosity is lowered because the flexibility of the is increased and the symmetry is lowered.
- the ester bond connected to the aromatic groups Ar 1 and Ar 2 significantly contributes to the decrease in viscosity.
- the flexibility of the molecular structure is larger in the structure (Ar 1 -X-Ar 2 ) than in the structure (Ar 1 -Ar 2 ). Therefore, in the polymerizable monomer of the present embodiment, the cured product is less likely to be brittle and the bending strength is excellent as compared with the polymerizable monomer in which the structure (Ar 1 -Ar 2 ) is introduced at the molecular center. .
- Ar 1 and Ar 2 each represent an aromatic group having any valence selected from divalent to tetravalent, and they may be the same or different. Good.
- aromatic groups Ar 1 and Ar 2 include divalent to tetravalent benzenes represented by the following structural formulas Ar-a 1 to Ar-a 3, and bivalents to 4 represented by the following structural formulas Ar-a 4 to Ar-a 6 And naphthalene or divalent to tetravalent anthoselans represented by the following structural formulas Ar-a7 to Ar-a9.
- the bond is to be provided on any carbon of the benzene ring constituting the aromatic groups Ar 1 and Ar 2 (except for the carbon which forms a condensed portion between the benzene ring and the benzene ring).
- Ar-a1 divalent benzene
- two bonds may be provided at any of the ortho position, the meta position, and the para position.
- the valence of the aromatic group Ar 1 is determined according to the number of m1, represented by m1 + 1.
- the valence of the aromatic group Ar 2 is determined according to the number of m 2 and is represented by m 2 +1.
- Each of the aromatic groups Ar 1 and Ar 2 may have a substituent, in which case the hydrogen of the benzene ring constituting the aromatic groups Ar 1 and Ar 2 is replaced with another substituent.
- the substituent of the aromatic group Ar 1 and Ar 2 is not particularly limited as long as it does not contain a reactive group (that is, an acryl group or a methacryl group) shown on the left side of the general formula (1) at its terminal.
- the total number of atoms constituting the substituent (the number of atoms) can be suitably selected within the range of 1 to 60.
- monovalent hydrocarbon groups having 1 to 20 carbon atoms, -COOR 3 , -OR 3 , halogen groups, amino groups, nitro groups, carboxyl groups and the like can be mentioned.
- R 3 is the same as the monovalent hydrocarbon group having 1 to 20 carbon atoms.
- a linear or branched hydrocarbon group such as a methyl group or an ethyl group, an alicyclic hydrocarbon group such as a cyclohexyl group, a phenyl group, a monovalent group And heterocyclic groups such as furan and the like.
- X represents a divalent group, and specifically, the number of atoms of the main chain bridging the aromatic group Ar 1 and the aromatic group Ar 2 as exemplified in the following structural formulas X-1 to X-13 Is a monovalent group of 1 to 3;
- the number of atoms in the main chain of the divalent group X is more preferably 1 or 2, and most preferably 1.
- the divalent group X is an electron donating group capable of donating an electron to a benzoate structure (electron withdrawing group) composed of an aromatic group Ar 1 (or Ar 2 ) and an ester bond connected thereto. Is preferred.
- an electron donating divalent group X -O-, -CH 2- , -CH (R 5 )-or -S- can be mentioned, and among these, -O- or -CH 2- Is more preferred, and -O- is particularly preferred.
- R 5 is an alkyl group having 1 to 6 carbon atoms.
- the polarity of the central part of the molecule becomes relatively high because it can have a resonance structure as exemplified in the following resonance structural formula. Therefore, the affinity with the highly polar hydrophilic material can be further improved, and as a result, the compatibility with the hydrophilic material is improved, or the affinity / adhesivity with respect to the hydrophilic surface is improved. It becomes easy.
- the divalent group X is —O—
- the aromatic groups Ar 1 and Ar 2 are phenylene groups (provided that two bonds are provided at the para position). It shows about the molecular center part of the polymerizable monomer of this embodiment.
- L 1 and L 2 each represent a hydrocarbon group having any number of valences selected from divalent to tetravalent, in which the number of atoms in the main chain is in the range of 2 to 60, and each is identical Or may be different.
- the number of atoms in the main chain is preferably in the range of 2 to 12, more preferably in the range of 2 to 10, still more preferably in the range of 2 to 6, and particularly preferably in the range of 2 to 3.
- the number of atoms in the main chain is in the range of 2 to 3, it becomes easy to further increase the bending strength of the cured product.
- the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but part of carbon atoms constituting the main chain may be replaced by heteroatoms. it can.
- this hetero atom an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom can be mentioned.
- an ether bond or an ester bond can be introduced into the main chain.
- the number of heteroatoms that can be introduced into the main chain is preferably about half or less of the number of atoms in the main chain, and when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one. .
- a substituent may be bonded to at least one atom (usually a carbon atom).
- an alkyl group having 1 to 3 carbon atoms such as a methyl group, a hydroxyl group, a monovalent hydrocarbon group having a hydroxyl group, halogen, -COOR 4 , -OR 4 and the like can be mentioned.
- R 4 is the same as the alkyl group having 1 to 3 carbon atoms.
- the monovalent hydrocarbon group having a hydroxyl group preferably has a carbon number in the range of 1 to 3, and more preferably 1 to 2. Specific examples of the monovalent hydrocarbon group having a hydroxyl group include —CH 2 OH, —CH 2 CH 2 OH, and —CH (CH 3 ) OH.
- At least one of L 1 and L 2 contains a hydroxyl group, in other words, L 1 and L 2
- the substituent is preferably a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group.
- a compound having a plurality of hydroxyl groups in a molecule forms an intermolecular hydrogen bond, and as a result, the viscosity tends to increase. Therefore, even when the polymerizable monomer of the present embodiment has a hydroxyl group in the molecule, the viscosity tends to easily increase.
- a hydroxyl group is present in the vicinity of an ester bond directly bonded to the aromatic groups Ar 1 and Ar 2 , it is more preferable because a rise in viscosity is relatively suppressed.
- “when there is a hydroxyl group in the vicinity of the ester bond” specifically means that when either or both of L 1 and L 2 have a hydroxyl group, the main component of L 1 or L 2 having a hydroxyl group is The number of chain atoms means a range of 2 to 10, and the number of atoms of the main chain is particularly preferably in a range of 2 to 3.
- the viscosity is increased when the hydroxyl group is contained in the molecule, but the hydroxyl group in the conventional molecule is increased. It is possible to prevent the viscosity from being significantly increased to the same level of viscosity as a polymerizable monomer (such as Bis-GMA).
- the hydroxyl group is more precisely a molecule than an intermolecular hydrogen bond. It is thought that the degree of contribution to internal hydrogen bonding is relatively higher, and it is considered that it also contributes to the formation of a gradual hydrogen bond network between molecules. Furthermore, when a plurality of hydroxyl groups are contained in the molecule, as in the case where both L 1 and L 2 have a hydroxyl group, it becomes easy to form a high-density hydrogen bond network between molecules. In this case, it is considered that the mechanical strength of the cured product can be made higher than that of the polymerizable monomer of the present embodiment having no hydroxyl group in the molecule.
- the bond marked * means a bond bonded to the oxygen atom of the ester bond constituting the benzoate structure at the molecular center.
- a represents an integer selected from the range of 1 to 11
- b represents an integer selected from the range of 1 to 19
- c represents 0 to 11
- d represents an integer selected from the range of 0 to 5
- e represents an integer selected from the range of 2 to 5
- f is selected from the range of 1 to 6, Represents an integer.
- the values of a to f are preferably selected in the structural formulas L-b1 to L-b14 within a range in which the number of atoms in the main chain is 12 or less.
- the polymerizable monomer of this embodiment is a polymerizable monomer shown by following General formula (3).
- X is the same as that shown in the general formula (1)
- Ar 1 and Ar 2 have the general formula (1) except that the valence can be only divalent.
- L 3 and L 4 each represent a bivalent hydrocarbon group in which the number of atoms in the main chain is in the range of 1 to 8 and each may be the same or different; R 3 and R 4 each represent hydrogen or a methyl group.
- j is 0, 1 or 2
- k is 0, 1 or 2
- j + k 2.
- the group shown in the left parenthesis in General Formula (3) may be bonded to both sides of the group shown in the center, but the right side in General Formula (3) may
- the groups shown in parentheses may be bonded to both sides of the group shown in the middle.
- atoms constituting the main chain are basically composed of carbon atoms, and all atoms may be carbon atoms, but a part of carbon atoms constituting the main chain Can also be replaced by heteroatoms.
- this hetero atom an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom can be mentioned.
- the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain.
- the number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of hetero atoms that can be introduced into the main chain is one.
- the number of atoms of the main chain in L 3 and L 4 may be 1 to 8, preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
- L 3 and L 4 include an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, an n-propylene group and an n-butylene group, and a main chain of the alkylene group. And groups in which a part or the whole is substituted with an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more is limited).
- Examples of combinations (j, k) of the values j and k shown in the general formula (3) include (2, 0), (1, 1) and (0, 2). (1, 1) and (0, 2) are more preferable from the viewpoint that suppression of decomposition of body molecules can be expected. For this reason, the present inventors speculate as follows.
- a dental composition a dental filling restorative, a dental adhesive, etc.
- a polymerizable monomer even after long-term storage, the adhesive strength immediately after production and the mechanical strength of the cured product are maintained. It will be easier to do.
- the combination (j, k) of the values j and k shown in the general formula (3) is (2, 0), (1, 1) and (0, 2) It is preferable that it contains any two or more types of structural isomers selected from the group consisting of
- the polymerizable monomer contains two or more kinds of structural isomers for the combination (j, k) shown in the general formula (3), the mechanical strength of the cured product and the storage stability are well-balanced. It becomes easy to improve.
- the average value of value k in all polymerizable monomer molecules is in the range of 0.05 or more and less than 2.0 (in other words, the average value of value j is in the range of more than 0 and 1.95 or less) Is preferred.
- the lower limit of the average value of the value k is preferably 0.1 or more
- the upper limit of the average value of the value k is more preferably 1.7 or less, and still more preferably 1.5 or less
- 0.4 or less is particularly preferable.
- the polymerizable monomer of this embodiment can be synthesized by appropriately combining known starting materials and known synthesis reaction methods, and the production method thereof is not particularly limited.
- a production method including at least a reaction step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5)
- You may use In this case, a polymerizable monomer containing two or more structural isomers selected from the group consisting of compounds represented by the following general formulas (6) to (8) can be produced.
- X, Ar 1 and Ar 2 are the same as those shown in the general formula (3), and L 5 has 1 to 7 atoms in its main chain Represents a divalent hydrocarbon group.
- p is 0 or 1.
- the average value of the value k in other words, the abundance ratio of structural isomers represented by the general formulas (6) to (8) can be easily adjusted by appropriately selecting the synthesis conditions.
- the average value of the value k is adjusted to be closer to a desired value. May be
- atoms constituting the main chain are basically composed of carbon atoms, and all atoms may be carbon atoms, but the main chain is constituted Some of the carbon atoms may be replaced by heteroatoms.
- this hetero atom an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom can be mentioned.
- the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain.
- the number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of hetero atoms that can be introduced into the main chain is one.
- the number of atoms in the main chain of L 5 may be 1 to 7, preferably 1 to 4, and more preferably 1 to 2.
- L 3 and L 4 include an alkylene group having 1 to 7 carbon atoms, such as a methylene group, ethylene group, n-propylene group and n-butylene group, and a main chain of the alkylene group. And groups in which a part or the whole is substituted with an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more is limited).
- each L 5 may be the same or different. The same applies to general formulas (7) and (8).
- each L 5 mutually different as a compound shown to General formula (5) used for a synthesis
- polymerizable monomers substantially containing no structural isomers for example, a general formula Only the polymerizable monomer shown in (6) may be isolated and purified.
- the polymerizable monomer obtained by isolation and purification has mechanical strength and storage stability of the cured product, as compared with the polymerizable monomer containing two or more types of structural isomers before isolation and purification treatment. It tends to be inferior in the point of coexistence with sex.
- an isolation and purification treatment is further required, so that the cost tends to be disadvantageous. Therefore, from these viewpoints, it is preferable to omit the isolation and purification treatment.
- the polymerizable monomer of the present embodiment can be used as a composition containing this polymerizable monomer. However, from the viewpoint of use in various applications, it is also suitable to use as a composition containing the polymerizable monomer of the present embodiment and other materials.
- the curable composition may be prepared by further adding a polymerization initiator to the composition containing at least the polymerizable monomer of the present embodiment.
- the composition containing the polymerizable monomer of this embodiment is a composition which does not contain a polymerization initiator
- agent A other compositions containing a polymerization initiator
- a cured product can be obtained by mixing and polymerizing agent A and agent B (first cured form).
- a cured product may be obtained by curing the agent C alone (second curing Form). However, if necessary, it can be used in combination with the agent C and the other composition (agent D). In this case, a cured product can be obtained by curing the mixture obtained by mixing the agent C and the agent D (third curing form). Moreover, after apply
- the agent D functions as a pretreatment for improving the compatibility between the adhesive and / or the agent C and the solid surface
- a cured product in a state of being bonded to the solid surface can be obtained (fourth curing Form).
- the agent D functions as a release agent, the cured product can be easily pulled away from the solid surface and recovered without damaging the surface of the cured product after curing (fifth curing form).
- a thing which can be suitably utilized by a 1st and 3rd hardening form for example, a two-component type
- group adhesive agent is mentioned
- a thing which can be suitably utilized by a 2nd hardening form it is a 3D printer using lamination modeling, for example
- dental materials in particular, composite resins used for filling in cavities of teeth
- resin materials used for the fourth curing form can be suitably used in the fifth curing form, for example
- the resin include resin raw materials used for producing molded products using a mold.
- other materials used together with the polymerizable monomer of the present embodiment are not particularly limited, and may be appropriately selected according to the application of the composition containing the polymerizable monomer of the present embodiment or the curable composition. can do.
- Specific examples of the other material include, for example, other polymerizable monomers other than the polymerizable monomer of the present embodiment, a low molecular weight organic compound having no reactivity, a resin, a filler, an organic-inorganic composite material, The various additives other than the polymerization initiator mentioned above, a solvent, etc. can be mentioned, It can also be used combining two or more types of these materials.
- the other polymerizable monomers are particularly preferable.
- known polymerizable monomers can be used without limitation.
- the viscosity of the other polymerizable monomer is preferably 150 mPa ⁇ S or less at room temperature (25 ° C.).
- bifunctional (meth) acrylate type polymerizability Monomers are preferred.
- polyalkylene glycol dimethacrylates such as triethylene glycol dimethacrylate (3G) (more specifically, the polymerization degree of the alkylene glycol unit is 1 or more and 14 or less polyethylene glycol dimethacrylates, polypropylene glycol dimethacrylates having a degree of polymerization of alkylene glycol units of 1 to 7 or less, 2 to 10 carbon atoms of polymethylene glycol dimethacrylate, etc.), neopentyl glycol dimethacrylate, tricyclodecane Methanol dimethacrylate (TCD), 1.9-nonanediol dimethacrylate (ND) etc.
- 3G triethylene glycol dimethacrylate
- TCD tricyclodecane Methanol dimethacrylate
- ND 1.9-nonanediol dimethacrylate
- the other polymerizable monomer is preferably one having a polyalkylene glycol chain, and more preferably one having a polyethylene glycol chain. This is because the polyalkylene glycol chain has high affinity to the benzoate structure (that is, a non-hydrogen bonding polar group) constituting the molecular center of the polymerizable monomer of the present embodiment.
- the other polymerizable monomer polyalkylene glycol dimethacrylate is preferable, and triethylene glycol dimethacrylate is particularly preferable.
- the viscosity of the polymerizable monomer means a value measured at 25 ° C. using an E-type viscometer.
- the other polymerizable monomer is a composition using the polymerizable monomer of the present embodiment, a curable composition, or a cured product obtained using the polymerizable monomer of the present embodiment. It can be selected according to the use of the resin member containing. For example, when a composition or a curable composition using the polymerizable monomer of this embodiment is used as a dental material, triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1.9-nonanediol It is preferable to use a polymerizable monomer such as dimethacrylate.
- the content of the polymerizable monomer of the present embodiment in the total polymerizable monomers is 20% by mass or more. Is preferably 30% by mass or more, more preferably 60% by mass or more.
- a well-known polymerization initiator can be used as a polymerization initiator used for the curable composition using the polymerizable monomer of this embodiment, and a radical type, cation type or anion type photopolymerization initiator, azo,
- Various polymerization initiators such as thermal polymerization initiators of a system or a peroxide system can be appropriately used.
- a photopolymerization initiator such as camphor quinone or ethyl pN, N-dimethylaminobenzoate can be used.
- these polymerization initiators can also be used in combination of 2 or more types.
- other additives such as a polymerization inhibitor and a sensitizer may be used in combination with the polymerization initiator.
- a filler to the composition or curable composition which used the polymerizable monomer of this embodiment.
- a filler By using a filler, the effect of suppressing polymerization shrinkage can be further increased.
- the operability of the composition before curing or the curable composition can be improved, or the mechanical physical properties after curing can be improved.
- the filler for example, inorganic fillers composed of particles of inorganic oxides such as amorphous silica, silica-titania, silica-zirconia, silica-titania-barium oxide, quartz, alumina and the like can be used, and organic fillers Or, organic-inorganic composite fillers can also be used.
- the particle diameter and shape of the filler are not particularly limited, but for example, particles having an average particle diameter of about 0.01 ⁇ m to 100 ⁇ m in a spherical shape or an irregular shape can be appropriately used according to the purpose.
- these fillers improve the compatibility with the polymerizable monomer of the present embodiment and other materials such as other polymerizable monomers which are optionally used in combination, and provide mechanical strength and water resistance. From the viewpoint of improvement, it may be treated with a surface treatment agent represented by a silane coupling agent.
- the polymerizable monomer of this embodiment is a dental material such as a dental curable composition or a dental adhesive, an optical material, a printing plate, a photoresist material, a paint, an adhesive, an ink, a light shaping resin, woodworking Coating, Hard Coating, Film Coating, Paper Coating, Optical Fiber Coating, PVC Floor Coating, Ceramic Wall Coating, Resin Hard Coat, Metallized Base Coat, Release Coating, Metal Coating, Glass Coating, Inorganic Coating, Elastic Coating, Flat Plate Ink, Metal Can Ink , Screen printing ink, gravure varnish, gloss processing, paint, sealant, adhesive for paper, adhesive for film, adhesive for woodworking, adhesive for inorganic material, adhesive for plastic, adhesive for plastic, solvent-based adhesive, water-based adhesive, Hot melt adhesive , Reactive adhesive, pressure sensitive adhesive, sealing agent, gloss coating agent, OP varnish, etching resist, solder resist, dry film, interlayer adhesion agent for buildup circuit board, photosensitive material,
- cured material obtained by using the composition containing the polymerizable monomer of this embodiment is excellent in mechanical strength. For this reason, it is preferable to use the resin member containing this hardened
- the polymerizable monomer of the present embodiment and the Bis-GMA in which each substituent of L 1 and L 2 is a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group, have a) a hydroxyl group B) the structure of the reactive group at the terminal of the molecule is identical (methacrylic group and methacrylic group) or substantially identical (acrylic group and methacrylic group), and c) the molecular central part is mainly composed of an aromatic group
- the structure is similar in the above three points.
- the polymerizable monomer of this embodiment has a benzoate structure having a polarity higher than that of the bisphenol A structure constituting the central skeleton of Bis-GMA. Therefore, the polymerizable monomer of the present embodiment in which each substituent of L 1 and L 2 is a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group (hereinafter referred to as “polymerization of this embodiment having a hydroxyl group (Sometimes referred to as “sex monomer”) is considered to be more hydrophilic than Bis-GMA. Moreover, the polymerizable monomer shown to patent document 4 does not have a hydroxyl group.
- the polymerizable monomer of this embodiment having a hydroxyl group is hydrophilic
- the polymerizable monomer shown in Patent Document 4 is hydrophobic.
- the polymerizable monomer shown in Patent Documents 4 and 5 has a biphenyl structure with high symmetry and low polarity in the central part of the molecule, but the polymerizable unit amount of this embodiment having a hydroxyl group In the body, the central part of the molecule has a structure in which a divalent group X is introduced between two aromatic groups Ar 1 and Ar 2 which tends to be more polar than the biphenyl structure.
- the polymerizable monomer of the present embodiment having a hydroxyl group is required to be more hydrophilic when compared to the polymerizable monomers shown in Bis-GMA, Patent Document 4 and Patent Document 5 It can be said that it is preferable and advantageous to use it in applications.
- the surface to which the adhesive is applied is preferably hydrophilic
- the polymerizable monomer of the present embodiment having a hydroxyl group When used in combination with other materials, it is preferable that the other material is a hydrophilic material.
- the adhesive containing the polymerizable monomer of the present embodiment When the adhesive containing the polymerizable monomer of the present embodiment is used on the hydrophilic surface, the adhesive containing the polymerizable monomer shown in Bis-GMA or Patent Document 4 or 5 is used. Better adhesive strength can be obtained as compared with.
- a hydrophilic solid material such as an inorganic filler exhibiting relatively hydrophilicity and a polymerizable monomer are mixed after surface treatment with a silane coupling agent or the like
- Bis-GMA Compared with the polymerizable monomer shown in Patent Document 4 and the polymerizable monomer of the present embodiment, mixing is easy and, in addition, more hydrophilic solid materials can be blended, and the blending amount It is also easy to suppress the increase in viscosity of the mixed composition with the increase in.
- Pentaerieri is superior in handleability to low viscosity and excellent in handleability as compared with the polymerizable monomers shown in Patent Document 4 and Patent Document 5 and excellent in adhesion to the surface of a hydrophilic member.
- Non-aromatic (meth) acrylate type polymerizable monomers having a hydroxyl group such as stolen dimethacrylate are also useful.
- non-aromatic (meth) acrylate-based polymerizable monomers having a hydroxyl group do not have an aromatic skeleton in the molecule, and thus the mechanical strength of the cured product is inferior.
- the polymerizable monomer of this embodiment can be widely used as one component of a dental curable composition.
- the polymerizable monomer of the present embodiment having a hydroxyl group is formulated with a dental material, in particular, a dental adhesive used for adhesion to a hydrophilic tooth surface, and an inorganic filler to further enhance mechanical strength.
- a dental material in particular, a dental adhesive used for adhesion to a hydrophilic tooth surface, and an inorganic filler to further enhance mechanical strength.
- a polymerizable monomer which constitutes a dental filling and repairing material (composite resin) which is also required to have a high affinity to the tooth surface which is a hydrophilic adhesion surface.
- it can also be used as a dental adhesive composite resin having the functions of both a dental adhesive and a composite resin.
- the repetition number r and s of the unit structure can take integer values of 0 or more in each molecule, and the above structural formulas have different combinations of integer values (r, s) 2 It is a mixture of more than one kind of polymerizable monomer molecule.
- 4-DPEGMA is obtained as a mixture of the following compounds (a), (b) and (c), and the ratio is 65: 30: 5 in molar ratio.
- values g and h shown together with the above structural formula are average values of a mixture of the compounds (a), (b) and (c).
- values g and h shown with the above-mentioned structural formula and the structural formula shown below mean an average value, the value of g and h can take an integer value of 0, 1 or 2 in each molecule. .
- the structural formula in which the average value of the values g, h is indicated is two or three different types of combinations of integer values (g, h) By a mixture of structural isomers is meant.
- the value g is a value corresponding to the value j shown in the general formula (3)
- the value h is a general formula (3) ) Is a value corresponding to the value k shown in FIG.
- [Inorganic filler] F1 spherical silica-zirconia (average particle diameter 0.4 ⁇ m) hydrophobized with ⁇ -methacryloyloxypropyltrimethoxysilane, spherical silica-zirconia (average particle diameter 0.07 ⁇ m) ⁇ -methacryloyloxypropyl tri The mixture which carried out the hydrophobization treatment by methoxysilane at mass ratio 70:30.
- Viscosity Measurement The viscosity of the polymerizable monomer was measured using a CS rheometer.
- a viscoelasticity measuring device CS rheometer "CVO 120 HR" manufactured by Bolin Co.
- CS rheometer "CVO 120 HR" (manufactured by Bolin Co.) equipped with a cone / plate geometry 4 cm / 2 ° and a temperature control system was used. Then, measurement was performed three times under the measurement conditions of a measurement temperature (plate temperature) of 25 ° C. and a shear rate of 1 rps, and the average value of the three measurement values was taken as the viscosity.
- the curable composition sample was weighed in a state in which Bis-GMA was heated to 60 ° C. in an incubator at the time of weighing. Moreover, when using 4-BPDM, 4-BPGD, 4-DPHU, 4-BPHE as a 1st polymerizable monomer, these 1st polymerizable monomers and 2nd polymerizable unit amount are used. When mixing with the body, mixing was performed while heating with a dryer. On the other hand, when a curable composition sample is prepared using the polymerizable monomer represented by the general formula (1) as the first polymerizable monomer, the entire process of the adjustment operation is performed at room temperature (25 ° C.) I went down below.
- the measurement of the bending strength is a cured product sample (initial) obtained by curing the curable composition sample immediately after preparation and the prepared curable composition sample in an incubator at a temperature of 60 ° C. for 5 months. After storage, it was carried out on a cured cured sample (after storage at 60 ° C.).
- the measurement of bending strength after storage at 60 ° C. was performed only for some types of cured product samples.
- Adhesive strength test method evaluated using the member in which the surface shows hydrophilicity as an adhesion
- a member in which the surface exhibits hydrophilicity a tooth with dentin exposed on the surface was selected. Dentin is a hydrophilic material containing hydroxyapatite, moisture and other organic substances. Below, the detail of the adhesive strength test method is demonstrated.
- the curable composition sample for adhesive strength test (curable composition sample immediately after preparation) was applied to this simulated cavity, and after standing for 20 seconds, compressed air was sprayed and dried for about 10 seconds.
- the curable composition sample was cured by applying visible light for 10 seconds with a visible light irradiator (Tokso Power Light, manufactured by Tokuyama Co., Ltd.).
- a composite resin (Esthelite Sigma made by Tokuyama Dental Co., Ltd.) was filled thereon, and pressed with a polyester sheet, and after filling, it was irradiated with visible light for 10 seconds to be cured to prepare an adhesion test piece.
- Resin cement (Bistite II manufactured by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the cured composite resin of the adhesion test piece, and a cylindrical SUS attachment 8 mm in diameter and 25 mm in length was further adhered.
- the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece I with attachment.
- the adhesion test piece I with attachment is pulled at a crosshead speed of 1 mm / min using a universal testing machine (Autograph, manufactured by Shimadzu Corporation) to measure the tensile bond strength between the tooth and the cured composite resin. did.
- the tensile adhesive strength was measured for each of the eight test pieces prepared for each example or each comparative example. And the average value of eight times of tensile adhesive strength was made into the initial stage adhesive strength of each Example or a comparative example.
- A 4,4′-diphenyletherdicarboxylic acid chloride having the molecular structure shown below.
- A 4,4′-diphenyletherdicarboxylic acid chloride
- toluene solution is subjected to rotary evaporation to remove toluene, thionyl chloride and hydrogen chloride at 40 ° C. to obtain 26.9 g (0.091 mol, 95% yield) of a solid of 4,4'-diphenyletherdicarboxylic acid chloride.
- the data of the 1 H NMR spectrum of the obtained 4-DPEPE were as follows. 1 H NMR ⁇ 1.93 (s, 6 H), 3.64-3.82 (m, 8 H), 4.36-4. 42 (m, 8 H), 5.58 (s, 2 H), 6.17 (S, 2 H), 7.0 4 (d, 4 H), 7.99 (d, 4 H)
- 4-DPEHE was synthesized in the same manner as 4-DPEHE except that 14.4 g (0.052 mol) of 4,4'-diphenylmethanedicarboxylic acid chloride was used instead of 15.3 g of acid chloride (A).
- DPFHE yield 18.7 g, 75% yield, HPLC purity 94%) was obtained.
- the data of 1 H NMR spectrum of 4-DPFHE obtained are as follows. 1 H NMR ⁇ 1.93 (s, 6 H), 3.85 (s, 2 H), 4.52 to 4.63 (m, 8 H), 5.58 (s, 2 H), 6.12 (s, 2 H) ), 7.15 (d, 4 H), 7. 86 (d, 4 H)
- this solution was transferred to a separatory funnel, washed three times with 40 ml of 10 wt% aqueous potassium carbonate solution, and further three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate. The concentrate was further dried in vacuo to give 4-DPEGMA (22.8 g yield, 84% yield, 95% HPLC purity).
- a solution was prepared by mixing 33.3 g (0.208 mol) of glycerol-1-yl monomethacrylate, 12.1 g (0.104 mol) of tetramethylethylenediamine, 0.002 g of BHT and 20 ml of methylene chloride. This solution was gradually added dropwise to the above-mentioned methylene chloride solution in which acid chloride A was dissolved at -78.degree. C., and stirred for further 5 hours.
- the liquid obtained after dropping and stirring is washed 3 times with 60 ml of 0.4 mol / L hydrochloric acid water, then 3 times with 60 ml of 10 wt% aqueous potassium carbonate solution, and further 3 times with distilled water, and then methylene chloride
- the layers were collected. Thereafter, magnesium sulfate was added to the collected methylene chloride layer to remove water contained in the methylene chloride layer. Next, magnesium sulfate was filtered off from the methylene chloride layer, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate.
- this solution was transferred to a separatory funnel, washed three times with 40 ml of 10 wt% aqueous potassium carbonate solution, and further three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate. The concentrate was further dried in vacuo to give 4-DPEGMAII (25.3 g, 90% yield, 95% HPLC purity).
- the solution obtained was stirred at room temperature for 3 hours, 100 ml of distilled water was added, and the mixture was extracted three times with methylene chloride. The solvent was removed from the methylene chloride layer obtained by extraction using a rotary evaporator to obtain a residue. Furthermore, the obtained residue was dissolved in 100 ml toluene. The obtained toluene solution was washed three times with 0.5 N hydrochloric acid solution, then three times with saturated brine solution, and dried over magnesium sulfate solution.
- the methylene chloride layer separated from the filtrate after reduction treatment was washed twice with a 5% by mass aqueous potassium carbonate solution, dried over magnesium sulfate, and concentrated by a rotary evaporator to obtain a concentrate.
- the concentrate was further dried under vacuum to obtain 44.8 g (yield 90%) of 5,6-epoxyhexan-1-yl methacrylate.
- the residue obtained by removing the solvent from the obtained methylene chloride layer using a rotary evaporator was dissolved in 100 ml of toluene to obtain a toluene solution.
- the toluene solution was washed three times with a 0.5 N hydrochloric acid solution, then three times with a saturated saline solution, and dried over a magnesium sulfate solution. After drying, the magnesium sulfate solution was filtered off, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate. Furthermore, this concentrate was dried under vacuum to obtain 46.0 g (yield 90%) of methacrylic acid-allyloxyethyl.
- a solution was prepared by dissolving 46.0 g (0.27 mol) of the obtained allyloxyethyl methacrylate in 100 ml of methylene chloride and further adding 196 g (equivalent to 0.675 mol) of a 60 mass% metachloroperbenzoic acid / water mixture. The mixture was stirred at room temperature for 10 hours. From the solution after stirring, by-product metachlorobenzoic acid was filtered off, and the filtrate was subjected to reduction treatment with 150 ml of a 15% by mass aqueous sodium sulfite solution.
- the method is the same as the synthesis method of 4-DPEGMA except that 13.7 g (0.05 mol) of the above-mentioned 4,4'-dicarboxydiphenyl sulfide is used instead of 12.9 g of 4,4'-diphenylether dicarboxylic acid.
- 4-DPSGMA yield 22.3 g, yield 80%, HPLC purity 95%) was obtained by the method of The data of the obtained 1 H NMR spectrum of 4-DPSGMA are as follows.
- Evaluation results The evaluation results of the composition of the curable composition sample produced using the first polymerizable monomer and the flexural strength of the cured product are shown in Tables 1 to 3, and the first polymerizable unit amount. Table 4 shows the evaluation results of the composition and adhesive strength of the curable composition sample prepared using the body.
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Abstract
Description
本発明の重合性単量体は、下記一般式(1)で示されることを特徴とする。
本実施形態の重合性単量体は、この重合性単量体を含む組成物として利用することができる。しかしながら、様々な用途において利用する観点からは、本実施形態の重合性単量体とその他の材料とを含む組成物として用いることも好適である。この場合、本実施形態の重合性単量体を少なくとも含む組成物に対してさらに重合開始剤を添加することで、硬化性組成物を調合してもよい。なお、本実施形態の重合性単量体を含む組成物が重合開始剤を含まない組成物である場合、この組成物(A剤)の使用に際しては、重合開始剤を含むその他の組成物(B剤)と組み合わせて使用することもできる。この場合は、A剤とB剤とを混合して重合させることにより硬化物を得ることができる(第一の硬化形態)。
[第一の重合性単量体(一般式(1)に示される重合性単量体)]
3G:トリエチレングリコールジメタクリレート
ND:1.9-ノナンジオールジメタクリレート
TCD:トリシクロデカンジメタノールジメタクリレート
PM:2-メタクリロイルオキシエチルジハイドロジェンフォスフェートおよびビス(2-メタクリロイルオキシエチル)ハイドロジェンフォスフェートをモル比1:1の割合で混合した混合物
HEMA:2-ヒドロキシエチルメタクリレート
CQ:カンファーキノン
DMBE:p-N,N-ジメチルアミノ安息香酸エチル
BHT:2,6-ジ-t-ブチル-p-クレゾール
F1:球状シリカージルコニア(平均粒径0.4μm)をγ―メタクリロイルオキシプロピルトリメトキシシランにより疎水化処理したものと、球状シリカージルコニア(平均粒径0.07μm)をγ ―メタクリロイルオキシプロピルトリメトキシシランにより疎水化処理したものとを質量比70:30にて混合した混合物。
重合性単量体の粘度は、CSレオメーターを用いて測定した。測定装置としてはコーン/プレートジオメトリ4cm/2°及び温度制御システムを具備した粘弾性測定装置CSレオメーター「CVO120HR」(ボーリン社製)を用いた。そして、測定温度(プレート温度)25℃、ずり速度1rpsの測定条件にて、3回の測定を行い、3回の測定値の平均値を粘度とした。
第一の重合性単量体と第二の重合性単量体とを表1~表3に示す所定の質量比で混合し、これら重合性単量体の混合物100質量部に対して、CQ0.5質量部、DMBE0.8質量部、およびBHT0.1質量部を添加した後、暗所にて均一になるまで攪拌した。これにより、マトリックスモノマーサンプルを得た。
表1~表3に示すように上述したマトリックスモノマーサンプルを101.4質量部、無機フィラーF1を205.9質量部を秤り取り、メノウ乳鉢で混合して混合物を得た。続いてこの混合物を真空下にて、脱泡して気泡を取り除きペースト状の曲げ強度評価用の硬化性組成物サンプルを得た。なお、この無機フィラー入りの硬化性組成物は、歯科用硬化性組成物、好ましくはコンポジットレジンとしても利用できるものである。なお、表1~表3に示すように、一部のマトリックスモノマーサンプルについては、無機フィラーと混合せずに真空下にて、脱泡して気泡を取り除くことで曲げ強度評価用の硬化性組成物サンプルも準備した。
JIS T6514:2013によって規定される、クラス2グループ1の歯科充填用コンポジットレジンに対する曲げ強さ測定法に従って、可視光線照射器(トクソーパワーライト、株式会社トクヤマ製)により可視光照射を各々20秒間行って硬化物サンプルを作製し、曲げ強度を測定した。尚、測定には万能試験機(オートグラフ、株式会社島津製作所製)を用いた。
第一の重合性単量体と第二の重合性単量体とを表4に示す所定の質量比で混合した。次に、これら重合性単量体の混合物100質量部に対して、CQ1.5質量部、DMBE1.5質量部、精製水10質量部、アセトン85質量部、およびBHT0.3質量部を添加した後、暗所にて均一になるまで攪拌した。これにより、接着強度試験用の硬化性組成物サンプルを得た。この硬化性組成物サンプルは、歯科用接着剤(いわゆるボンディング材)としても利用できるものである。
接着強度試験は、接着対象物として、表面が親水性を示す部材を用いて評価を行った。ここで、表面が親水性を示す部材としては、象牙質が表面に露出した歯牙を選択した。なお、象牙質は、ヒドロキシアパタイト、水分およびその他の有機物を含む親水性材料である。以下に、接着強度試験方法の詳細を説明する。
屠殺後24時間以内に抜去した牛前歯を、注水下、耐水研磨紙P600で研磨し、唇面に平行かつ平坦になるように、象牙質平面を削り出した。次に、削り出した平面に圧縮空気を約10秒間吹き付けて乾燥させた。次に、この平面に直径3mmの穴を有する両面テープを貼り付け、さらに、厚さ0.5mmおよび直径8mmの穴を有するパラフィンワックスを、先に貼り付けられた両面テープの穴の中心に、パラフィンワックスの穴の中心をあわせて固定することで、模擬窩洞を形成した。この模擬窩洞に、接着強度試験用の硬化性組成物サンプル(調整直後の硬化性組成物サンプル)を塗布し、20秒間放置後、圧縮空気を約10秒間吹き付けて乾燥した。可視光線照射器(トクソーパワーライト、株式会社トクヤマ製)により可視光照射を10秒間行い硬化性組成物サンプルを硬化させた。更にその上にコンポジットレジン(トクヤマデンタル製エステライトシグマクイック)を充填し、ポリエステルシートで圧接し、充填後同じく可視光を10秒間照射して硬化させて、接着試験片を作製した。
アタッチメント付き接着試験片Iを熱衝撃試験器に入れ、4℃の水槽に1分間浸漬後、60℃の水槽に移し1分間浸漬し、再び4℃の水槽に戻す操作を、3000回繰り返す耐久試験を実施した。その後、この耐久試験を実施した接着試験片Iについて、初期接着強度を求める場合と同様に引張り接着強度を測定し、耐久試験後の接着強度とした。
初期接着強度の測定に際して用いた調整直後の硬化性組成物サンプルの代わりに、調整した硬化性組成物サンプルを、インキュベーター中にて60℃の環境下で20日間保存したものを用いた以外は、(5B-1)に示す手順にて接着強度を測定した。
マトリックスモノマーサンプルの調整に際して用いた第一の重合性単量体のうち、一般式(1)に示される重合性単量体に該当するものについては、以下の手順で合成した。
4,4’-ジフェニルエーテルジカルボン酸25.3g(0.096mol)、ジメチルホルムアミド0.85g(0.012mol)およびトルエン80mlの第一の混合液を作製した。攪拌状態の第一の混合液に対して、塩化チオニル58.4g(0.46mol)およびトルエン20mlからなる第二の混合液を室温下で徐々に滴下した。滴下終了後に得られた液体を95℃に昇温し、3h還流した。そして加温・還流後に得られた黄色透明液体を放冷することで、下記に示す分子構造を有する4,4’-ジフェニルエーテルジカルボン酸クロライド(以下、「酸クロライド物(A)」と称す場合がある)のトルエン溶液を得た。さらに、このトルエン溶液をロータリーエバポレーターにかけ、40℃でトルエン、塩化チオニルおよび塩化水素を除去し、4,4’-ジフェニルエーテルジカルボン酸クロライドの固体26.9g(0.091mol、収率95%)を得た。
酸クロライド物(A)15.3g(0.052mol)に塩化メチレン120mlを加えることで、酸クロライド物(A)を含む分散液を得た。2-ヒドロキシエチルメタクリレート16.9g(0.13mol)、トリエチルアミン7.7g(0.13mol)、4-ジメチルアミノピリジン0.16g(0.0013mol)、BHT0.002gおよび塩化メチレン10mlを混合した混合液を滴下ロートを利用して上記の酸クロライド物(A)の分散液に-78℃で徐々に滴下し、さらに5時間攪拌した。滴下・撹拌後に得られた液体に水を加え、ロータリーエバポレーターを用いて、溶媒を除去した。溶媒除去後に得られた残さを100mlのトルエンに溶解し、0.5規定塩酸溶液で洗浄、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、ろ別した。得られたろ液をロータリーエバポレーターで濃縮後、濃縮液をさらに真空乾燥して、4-DPEHE(収量19.0g、収率76%、HPLC純度97%)を得た。なお、得られた4-DPEHEの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),4.58(t,4H),4.63(t,4H),5.59(s,2H),6.14(s,2H),7.06(d,4H),7.96(d,4H)
4,4’-ジフェニルエーテルジカルボン酸25.3gの代わりに2,2’-ジフェニルエーテルジカルボン酸25.3g(0.096mol)を用いた以外は酸クロライド物(A)を合成する場合と同様の方法で、2,2’-ジフェニルエーテルジカルボン酸クロライド27.8g(0.094mol、収率98%)を得た。
1H NMR δ1.93(s,6H),4.54(t,4H),4.62(t,4H),5.58(s,2H),6.16(s,2H),7.06(d,4H),7.45(d,2H),7.96(d,2H)
メタクリル酸8.6g(0.1mol)、1,3-プロパンジオール15.2g(0.2mol)、p-トルエンスルホン酸0.86g(0.005mol)、および、重合禁止剤としてBHT0.1gをガラス容器に入れ、85℃に加熱、攪拌する。この加熱撹拌状態の反応系中を減圧状態にし、反応系中から水分を除去しながら5時間攪拌を続けた。その後、得られた液体を冷却し、シリカゲルカラムクロマトグラフィーを用いて精製、濃縮後、3-ヒドロキシプロピルメタクリレート6.3g(収率44%)を得た。
1H NMR δ1.93(s,6H),2.10(m,4H),4.18(t,4H),4.27(t,4H),5.59(s,2H),6.13(s,2H),7.05(d,4H),7.93(d,4H)
-プロセス1-
メタクリル酸8.6g(0.1mol)、1,4-ブタンジオール18.0g(0.2mol)、p-トルエンスルホン酸0.86g(0.005mol)、および、重合禁止剤としてBHT0.1gをガラス容器に入れ、85℃に加熱、攪拌した。次に、この加熱撹拌状態の反応系中を減圧状態にし、反応系中から水分を除去しながら5時間攪拌を続けた。その後、得られた液体を冷却し、シリカゲルカラムクロマトグラフィーを用いて精製、濃縮後、4-ヒドロキシブチルメタクリレート6.7g(収率42%)を得た。
次に、別のガラス容器に酸クロライド物(A)3.0g(0.01mol)、塩化メチレン70ml、ジ-tertブチルメチルフェノール0.001gを入れた溶液を攪拌しながら、この溶液に対して、上記の4-ヒドロキシブチルメタクリレート3.5g(0.022mol)、トリエチルアミン2.0g(0.02mol)、4-ジメチルアミノピリジン0.025g(0.0002mol)を10ml塩化メチレンに溶解させた溶液を1時間かけて、ゆっくり滴下した。滴下終了後に得られた溶液を、室温で1時間撹拌した後に、水を加え、ロータリーエバポレーターを用いて、溶媒を除去した。溶媒除去後に得られた残さを100mlのトルエンに溶解し、0.5規定塩酸溶液で洗浄、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、ろ別した。得られたろ液を再びロータリーエバポレーターで濃縮後、濃縮液をさらに真空乾燥して、4-DPEHBを得た(収量4.1g、収率76%、HPLC純度97%)を得た。なお、得られた4-DPEHBの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.52-1.63(m,8H),1.93(s,6H),4.14(t,4H),4.27(t,4H),5.59(s,2H),6.13(s,2H),7.05(d,4H),7.93(d,4H)
1,4-ブタンジオール18.0gの代わりに1,6-ヘキサンジオール23.6gを用いた以外は<4-DPEHBの合成>のプロセス1に示す合成方法に従って、6-ヒドロキシヘキシルメタクリレート19.7g(収率53%)16.0g(収率43%)を得た。
1H NMR δ1.29(m,8H),1.57(t,4H),1.77(t,4H),1.93(s,6H),4.16(t,4H),4.22(t,4H),5.58(s,2H),6.14(s,2H),7.04(d,4H),7.96(d,4H)
2-ヒドロキシエチルメタクリレート16.9gの代わりに2-ヒドロキシプロピルメタクリレートを18.7g(0.13mol)を用いた以外は、4-DPEHEの合成方法と同様の方法で、4-DPEHP(収量19.9g、収率75%、HPLC純度97%)を合成した。なお、得られた4-DPEHPの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.40(d,6H),1.93(s,6H),4.61(d,4H),4.74(t,2H),5.56(s,2H),6.13(s,2H),7.01(d,4H),7.92(d,4H)
2-ヒドロキシエチルメタクリレート16.9gの代わりにポリエチレングリコールモノメタクリレート(エチレングリコール鎖(-CH2CH2O-)nの繰り返し数nの平均≒2)を22.6g(0.13mol)を用いた以外は、4-DPEHEの合成方法と同様の方法で、4-DPEPE(収量22.5g、収率78%、HPLC純度97%)を合成した。なお、得られた4-DPEPEの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.64-3.82(m,8H),4.36-4.42(m,8H),5.58(s,2H),6.17(s,2H),7.04(d,4H),7.99(d,4H)
2-ヒドロキシエチルメタクリレート16.9gの代わりにグリセロールジメタクリレート29.6g(0.13mol)を用いた以外は、4-DPEHEの合成方法と同様の方法で、4-DPEGAM(収量25.7g、収率73%,HPLC純度92%)を合成した。なお、得られた4-DPEGAMの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,12H),4.58(d,8H),5.20(m,2H),5.52(s,4H),6.10(s,4H),7.01(d,4H),7.92(d,4H)
エチレングリコール50.0g(0.8mol)、トリエチルアミン40.5g(0.4mol)、N,N-ジメチルアミノピリジン0.49g(4mol)を100ml塩化メチレンに溶解して得られた溶液を撹拌しながら、0℃に冷却した。次に、この溶液に対して、酸クロライド物(A)44.8g(0.2mol)を塩化メチレン(200ml)に溶解した溶液を2時間かけてゆっくり滴下した。滴下後に得られた溶液をさらに1時間撹拌した後に、水を加え、ロータリーエバポレーターを用いて、溶媒を除去した。溶媒除去後に得られた残さを100mlのトルエンに溶解し、0.5規定塩酸溶液で洗浄、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、ろ別した。得られたろ液を再びロータリーエバポレーターで濃縮後、濃縮液をシリカゲルカラムクロマトグラフィーで精製することで4,4’-ビス(2-ヒドロキシエトキシカルボニル)ジフェニルエーテル41.6g(収率60%)を得た。
1H NMR δ1.93(s,6H),3.30(t,4H),4.40-4.56(m,12H),5.60(s,2H),6.17(s,2H),7.06(d,4H),7.98(d,4H),8.03(s,2H)
2-メタクリロイルオキシエチルイソシアネート31.0gの代わりに2-(2-メタクリロイルオキシエチルオキシ)エチルイソシアネート39.8g(0.2mol)を用いた以外は、4-DPEUの合成方法と同様の方法で、4-DPEUE(収量70.3g、収率95%、HPLC純度96%)を得た。なお、得られた4-DPEUEの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.10(m,4H),3.66(m,8H),4.33(t,4H),4.54(m,8H),5.58(s,2H),6.14(s,2H),7.06(d,4H),7.96(d,4H),8.02(s,2H)
t-ブタノール200mlおよび水50mlに対して、特開2005-154379号公報に記載の合成方法により合成した4,4-ジホルミルジフェニルスルフィド48.4g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50mlおよび2-メチル-2-ブテン140g(2mol)加え、さらに亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を準備した。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。洗浄後に得られた固体(化合物)を真空乾燥することにより、4,4’-ジカルボキシジフェニルスルフィド(収量45.5g,収率83%)を得た。
1H NMR δ1.93(s,6H),4.52(t,4H),4.63(t,4H),5.58(s,2H),6.11(s,2H),7.30(d,4H),7.81(d,4H)
4,4’-ジフェニルエーテルジカルボン酸25.3g(0.096mol)の代わりに4,4’-ジカルボキシジフェニルスルホン29.4g(0.096mol)を用いた以外は、酸クロライド物(A)の合成方法と同様の方法で、4,4’-ジフェニルスルホンジカルボン酸クロライド31.6g(0.092mol)を合成した。
1H NMR δ1.93(s,6H),4.58(t,4H),4.63(t,4H),5.59(s,2H),6.14(s,2H),8.06(d,4H),8.20(d,4H)
t-ブタノール200mlおよび水50mlに対して、特開2005-154379号公報に記載の合成方法により合成された4,4’-ジホルミルジフェニルメタン44.8g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50mlおよび2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を得た。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。得られた固体(化合物)を真空乾燥することにより、4,4’-ジカルボキシジフェニルメタン39.8g(収率83%)を得た。
1H NMR δ1.93(s,6H),3.85(s,2H),4.52-4.63(m,8H),5.58(s,2H),6.12(s,2H),7.15(d,4H),7.86(d,4H)
4,4’-ジフェニルエーテルジカルボン酸25.3gの代わりに英国特許GB753384に記載の合成方法により合成された2,2-ビス(4-カルボキシフェニル)プロパン27.2g(0.096mol)を用いた以外は、酸クロライド(A)の合成方法と同様の方法で2,2-ビス(4-クロロカルボニルフェニル)プロパン29.6g(収率96%)を得た。
1H NMR δ1.64(s,6H),1.93(s,6H),4.53-4.64(m,8H),5.59(s,2H),6.12(s,2H),7.22(d,4H),7.90(d,4H)
t-ブタノール200mlおよび水50mlに対して、特開2007-106779号公報に記載の合成方法により合成された4-ホルミルフェニル-4’-ホルミルベンゾエート50.8g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50mlおよび2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を得た。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。得られた固体(化合物)を真空乾燥することにより、4-カルボキシフェニル-4’-カルボキシベンゾエート45.4g(収率84%)を得た。
1H NMR δ1.93(d,6H),4.51(m,4H),4.61(t,4H),5.58(d,2H),6.13(d,2H),7.25(d,2H),8.02(d,2H),8.12(d,2H),8.272(d,2H)
t-ブタノール200mlおよび水50mlに対して、特許第3076603号に記載の合成方法により合成された1,1-ビス(4-ホルミルフェニル)シクロヘキサン58.4g(0.2mol)を溶解させた後に、リン酸水素ナトリウム水溶液50mlおよび2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を得た。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。得られた固体(化合物)を真空乾燥することにより、1,1-ビス(4-カルボキシルフェニル)シクロヘキサン54.4g(収率84%)を得た。
1H NMR δ1.45(m,6H),1.93(s,6H),2.01(m,4H),4.53-4.64(m,4H),5.58(s,2H),6.13(s,2H),7.23(d,4H),7.90(d,4H)
12.8gのメタクリル酸グリシジル(0.09モル)に4,4’-ジフェニルエーテルジカルボン酸12.9g(0.05モル)、ベンジルトリエチルアンモニウムクロリド0.02g(0.00009モル)、BHT0.02g(0.00009モル)、ジメチルホルムアミド20gを加えた混合液を、100℃で4時間反応させた。反応により得られた液体に酢酸エチル40mlを加えて、均一な溶液にした。次に、この溶液を分液ロートに移し、10wt%炭酸カリウム水溶液40mlで3回洗浄し、さらに蒸留水で3回洗浄した後、酢酸エチル層を回収した。その後、回収した酢酸エチル層に硫酸マグネシウムを加えて、酢酸エチル層中に含まれる水分を除去した。続いて、酢酸エチル層から硫酸マグネシウムをろ別し、ろ液をロータリーエバポレーターで濃縮して濃縮物を得た。この濃縮物を更に真空乾燥して、4-DPEGMA(収量22.8g、収率84%、HPLC純度95%)を得た。なお、得られた4-DPEGMAの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.90(d,0.8H),4.30~4.70(m,9.2H),5.59(s,2H),6.16(s,2H),7.07(d,4H),8.07(d,4H)
固体状の酸クロライド物(A)15.3g(0.052モル)を塩化メチレン30mlに溶解させた塩化メチレン溶液を作製した。
1H NMR δ1.93(s,6H),3.90(d,0.2H),4.30~4.70(m,9.8H),5.59(s,2H),6.16(s,2H),7.07(d,4H),8.07(d,4H)
12.8gのメタクリル酸グリシジル(0.09モル)に4,4’-ジフェニルエーテルジカルボン酸12.9g(0.05モル)、テトラブチルアンモニウムブロミド0.02g(0.00009モル)、BHT0.02g(0.00009モル)、ジメチルアセトアミド20gを加えた混合液を、100℃で4時間反応させた。反応により得られた液体に酢酸エチル40mlを加えて、均一な溶液にした。次に、この溶液を分液ロートに移し、10wt%炭酸カリウム水溶液40mlで3回洗浄し、さらに蒸留水で3回洗浄した後、酢酸エチル層を回収した。その後、回収した酢酸エチル層に硫酸マグネシウムを加えて、酢酸エチル層中に含まれる水分を除去した。続いて、酢酸エチル層から硫酸マグネシウムをろ別し、ろ液をロータリーエバポレーターで濃縮して濃縮物を得た。この濃縮物を更に真空乾燥して、4-DPEGMAII(収量25.3g、収率90%、HPLC純度95%)を得た。なお、得られた4-DPEGMAIIの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.90(d,0.4H),4.30~4.70(m,9.6H),5.62(s,2H),6.16(s,2H),7.07(d,4H),8.07(d,4H)
上記の方法で4-DPEGMAIIを合成後、シリカゲルカラムクロマトグラフィー(充填剤:SiO2、展開溶媒:酢酸エチル/ヘキサン=3/1~2/1)によって、精製することで、4-DPEGMAIII(収量18.7g、収率69%、HPLC純度99%)を得た。なお、得られた4-DPEGMAIIIの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),4.30~4.41(m,10H),5.62(s,2H),6.16(s,2H),7.07(d,4H),8.07(d,4H)
上記の方法で4-DPEGMAを合成後、シリカゲルカラムクロマトグラフィー(充填剤:SiO2、展開溶媒:酢酸エチル/ヘキサン=3/1~2/1)によって、精製することで、4-DPEGMAIV(収量2.2g、収率8%、HPLC純度99%)を得た。なお、得られた4-DPEGMAIVの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.90(d,3.2H),4.30~4.70(m,7.8H),5.62(s,2H),6.16(s,2H),7.07(d,4H),8.07(d,4H)
メタクリル酸グリシジル12.8g(0.09mol)の代わりにアクリル酸グリシジル11.5g(0.09mol)を用いた以外は、4-DPEGMAの合成方法と同様の方法で、4-DPEGA(収量21.8g、収率85%、HPLC純度96%)を得た。なお、得られた4-DPEGAの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.84(d,2H),4.00~4.65(m,8H),5.83(t,2H),6.12(d,2H),6.43(d,2H),7.09(d,4H),7.99(d,4H)
4,4’-ジフェニルエーテルジカルボン酸12.9g(0.05mol)の代わりに2,2’-ジフェニルエーテルジカルボン酸12.9g(0.05mol)を用いた以外は、4-DPEGMAの合成方法と同様の方法で、2-DPEGMA(収量23.0g、収率85%、HPLC純度95%)を得た。なお、得られた2-DPEGMAの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.80(d,1.8H),4.00~4.65(m,8.2H),5.59(s,2H),6.16(s,2H),7.07(d,2H),7.42(d,4H),8.17(d,2H)
5-ヘキセン-1-オール(30.1g,0.3mol)を塩化メチレン100mlに溶解後、トリエチルアミン33.4g(0.33mol)、N,N-ジメチルアミノピリジン1.8g(0.015mol)を加えた溶液を調整し、さらにこの溶液を氷冷した。次に、氷冷した溶液に対して、メタクリル酸クロライド31.4g(0.3mol)を塩化メチレン(50ml)に溶解させた塩化メチレン溶液を滴下した。滴下終了後に得られた溶液を、室温で3時間撹拌した後に、蒸留水100mlを加え、さらに塩化メチレンで3回抽出した。抽出により得られた塩化メチレン層をロータリーエバポレーターを用いて溶媒を除去することで残さを得た。さらに、得られた残さを100mlトルエンで溶解した。得られたトルエン溶液を0.5規定塩酸溶液で3回洗浄後、飽和食塩水溶液で3回洗浄し、硫酸マグネシウム溶液で乾燥した。乾燥後、硫酸マグネシウム溶液をろ別し、ろ液をロータリーエバポレーターで濃縮、濃縮物をさらに真空乾燥して、メタクリル酸5-ヘキセン-1-イル46.4g(収率92%)を得た。
1H NMR δ1.29(t,4H),1.44(m,4H),1.57(t,4H),1.93(s,6H),3.85(d,1.9H),4.15~4.70(m,8.1H),5.59(s,2H),6.16(s,2H),7.05(d,4H),7.95(d,4H)
塩化メチレン100mlに、アリルオキシエタノール30.6g(0.3mol)を溶解した後、さらにトリエチルアミン33.4g(0.33mol)およびN,N-ジメチルアミノピリジン1.8g(0.015mol)を加えた溶液を準備した。次に、得られた溶液を氷冷し、この溶液に、メタクリル酸クロライド31.4g(0.3mol)を塩化メチレン50mlに溶解させた溶液を滴下した。滴下終了後に得られた溶液を、室温で3時間撹拌した後に、蒸留水100mlを加え、塩化メチレンで3回抽出した。次に、得られた塩化メチレン層をロータリーエバポレーターを用いて溶媒を除去することにより得られた残渣を100mlのトルエンに溶解することでトルエン溶液を得た。そして、このトルエン溶液を0.5規定塩酸溶液で3回洗浄後、飽和食塩水溶液で3回洗浄し、硫酸マグネシウム溶液で乾燥した。乾燥後硫酸マグネシウム溶液をろ別し、ろ液をロータリーエバポレーターで濃縮することで濃縮物を得た。さらに、この濃縮物を真空乾燥して、メタクリル酸-アリルオキシエチル46.0g(収率90%)で得た。
1H NMR δ1.93(s,6H),3.50~4.50(m,18H),4.15~4.70(m,8.1H),5.59(s,2H),6.16(s,2H),7.02(d,4H),8.02(d,4H)
t-ブタノール200mlおよび水50mlに対して、特開2005-154379号公報に記載の合成方法により合成された4,4-ジホルミルジフェニルスルフィド48.4g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50ml、2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を準備した。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。洗浄後に得られた固体(化合物)を真空乾燥することにより、4,4’-ジカルボキシジフェニルスルフィド45.5g(収率83%)を得た。
1H NMR δ1.93(s,6H),3.62(d,2H),3.90~4.70(m,8H),5.58(s,2H),6.14(s,2H),7.33(d,4H),7.78(d,4H)
4,4’-ジフェニルエーテルジカルボン酸12.9gの代わりに4,4’-ジカルボキシジフェニルスルホン15.3g(0.05mol)を用いた以外は、4-DPEGMAの合成方法と同様の方法で、4-DPSOGMA(収量24.5g、収率83%、HPLC純度97%)を得た。なお、得られた4-DPSOGMAの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.93(s,6H),3.70(d,2H),3.90~4.70(m,8H),5.58(s,2H),6.14(s,2H),8.04(d,4H),8.20(d,4H)
t-ブタノール200mlと水50mlに対して、特開2005-154379号公報に記載の合成方法により合成された4,4’-ジホルミルジフェニルメタン44.8g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50ml、2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を準備した。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。洗浄後に得られた固体(化合物)を真空乾燥することにより、4,4’-ジカルボキシジフェニルメタン39.8g(収率78%)を得た。
1H NMR δ1.93(s,6H),3.78(s,2H),3.90(d,2H),4.00~4.70(m,8H),5.58(s,2H),6.14(s,2H),7.20(d,4H),7.87(d,4H)
4,4’-ジフェニルエーテルジカルボン酸12.9gの代わりに英国特許GB753384に記載の合成方法により合成された2,2-ビス(4-カルボキシフェニル)プロパン14.2(0.05mol)を用いた以外は、4-DPEGMAの合成方法と同様の方法で、4-DPAGMA(収量22.7g、収率80%、HPLC純度93%)を得た。なお、得られた4-DPAGMAの1H NMRスペクトルのデータは、次の通りであった。
1H NMR δ1.65(s,6H),1.93(s,6H),3.85(d,2H),3.90~4.65(m,8H),5.57(s,2H),6.12(s,2H),7.23(d,4H),7.90(d,4H)
t-ブタノール200mlおよび水50mlに対して、特開2007-106779号公報に記載の合成方法により合成された4-ホルミルフェニル-4’-ホルミルベンゾエート50.8g(0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50ml、2-メチル-2-ブテン140g(2mol)加え、さらに、亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を準備した。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。洗浄後に得られた固体(化合物)を真空乾燥することにより、4-カルボキシフェニル-4’-カルボキシベンゾエート45.4g(収率79%)を得た。
1H NMR δ1.93(s,6H),3.87(d,2H),3.90~4.65(m,8H),5.60(s,2H),6.14(s,2H),7.25(d,2H),8.10(d,2H),8.15(d,2H),8.27(d,2H)
t-ブタノール200mlおよび水50mlに対して、特許第3076603号に記載の合成方法により合成された1,1-ビス(4-ホルミルフェニル)シクロヘキサン(58.4g,0.2mol)を溶解させた後、リン酸水素ナトリウム水溶液50ml、2-メチル-2-ブテン140g(2mol)加え、さらに亜塩素酸ナトリウム36g(0.4mol)を加えることで反応溶液を準備した。次に、この反応溶液を5時間撹拌後、1規定塩酸溶液を用いて、反応溶液を酸性にすることで、固体を析出させた。続いて固体が析出した反応溶液を、吸引ろ過後、水を用いて、析出した固体を洗浄した。洗浄後に得られた固体(化合物)を真空乾燥することにより、1,1-ビス(4-カルボキシルフェニル)シクロヘキサン54.4g(収率84%)を得た。
1H NMR δ1.42(t,6H),1.93(s,6H),2.10(t,4H),3.77(d,2H),3.85~4.60(m,8H),5.61(s,2H),6.15(s,2H),7.24(d,4H),7.90(d,4H)
第一の重合性単量体を用いて作製した硬化性組成物サンプルの組成および硬化物の曲げ強度の評価結果を表1~3に、また、第一の重合性単量体を用いて作製した硬化性組成物サンプルの組成および接着強度の評価結果を表4に示す。
Claims (11)
- 請求項1に記載の重合性単量体において、
2価の基Xが、-O-であることを特徴とする重合性単量体。 - 請求項1または2に記載の重合性単量体において、
主鎖の原子数が2~60の範囲内であり、かつ、2価~4価から選択されるいずれかの価数を持つ炭化水素基L1およびL2の少なくともいずれかが水酸基を含むことを特徴とする重合性単量体。 - 請求項5に記載の重合性単量体において、
前記一般式(3)に示す値j、kの組み合わせ(j、k)が、(1、1)および(0、2)からなる群より選択されるいずれかであることを特徴とする重合性単量体。 - 請求項5に記載の重合性単量体において、
前記一般式(3)に示す値j、kの組み合わせ(j、k)が、(2、0)、(1、1)および(0、2)からなる群より選択されるいずれか2種類以上の構造異性体を含むことを特徴とする重合性単量体。 - 請求項7に記載の重合性単量体おいて、
全ての重合性単量体分子における値kの平均値が0.05以上2.0未満であることを特徴とする重合性単量体。 - 請求項1~8のいずれか1つに記載の重合性単量体と、重合開始剤と、を含むことを特徴とする硬化性組成物。
- 請求項1~8のいずれか1つに記載の重合性単量体を含む組成物を用いて得られた硬化物を含むことを特徴とする樹脂部材。
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JP2017141213A (ja) * | 2016-02-12 | 2017-08-17 | 株式会社トクヤマデンタル | 粉液型歯科用硬化性材料 |
JP2017141212A (ja) * | 2016-02-12 | 2017-08-17 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
KR101833446B1 (ko) | 2016-11-30 | 2018-02-28 | 한국생산기술연구원 | 비스퓨란 유도체 화합물, 그를 포함하는 조성물 및 그의 제조방법 |
JP2018145097A (ja) * | 2017-03-01 | 2018-09-20 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
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US11214635B2 (en) * | 2017-02-08 | 2022-01-04 | Sumitomo Chemical Company, Limited | Compound, resin, resist composition and method for producing resist pattern |
CN111534032B (zh) * | 2020-06-24 | 2022-03-25 | 深圳永昌和科技有限公司 | 一种生物相容性好的3d打印材料 |
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