JP6275518B2 - Polymerizable monomer, composition, curable composition, and resin member - Google Patents

Description

  The present invention relates to a polymerizable monomer, a composition, a curable composition, and a resin member.

  Examples of (meth) acrylate polymerizable monomers that are generally widely used as dental materials include Bis-GMA (2,2-bis (4- (2-hydroxy-) having a bisphenol A skeleton). 3-methacryloyloxypropoxy) phenyl) propane) and Bis-MPEPP (2,2-bis (4- (methacryloyloxypolyethoxy) phenyl) propane), a low molecular weight type polymerizable monomer D-2.6E It has been known. In addition, as the above-described (meth) acrylate polymerizable monomer having a bisphenol A skeleton, use of the polymerizable monomer shown in Patent Document 1 as a dental material has also been proposed. On the other hand, a (meth) acrylate polymerizable monomer having a biphenyl skeleton similar to the bisphenol A skeleton is used in various applications such as dental materials, optical parts, printing plate making, photoresist materials, paints, adhesives, and inks. Utilization has also been proposed (Patent Documents 2 to 4).

JP 2007-126417 A (Claim 1) International Publication No. WO2010 / 048067 (Claim 12) JP-A-6-134772 (Claims 2-3) Japanese Unexamined Patent Publication No. 2000-240669 (Abstract, Paragraph 0001)

  Since the above-described bisphenol A skeleton and the biphenyl skeleton similar thereto have high rigidity, these skeleton structures improve the hardness of a cured product obtained by curing the above-described (meth) acrylate polymerizable monomer. Contribute.

  On the other hand, regardless of whether it has a bisphenol A skeleton or a biphenyl skeleton, generally, when a cured product is obtained by polymerizing a (meth) acrylate polymerizable monomer, volume shrinkage (polymerization shrinkage) accompanying polymerization Will occur. For this reason, depending on the intended use of the (meth) acrylate polymerizable monomer, polymerization shrinkage may be a problem. For example, when a (meth) acrylate polymerizable monomer is used as a main component of a composite resin constituting a two-component dental adhesive, polymerization shrinkage often becomes a problem. This is because, when polymerization shrinkage occurs, peeling is likely to occur between the bonding material applied to the cavity wall of the tooth and the cured composite resin filled in the cavity.

  General methods for suppressing such polymerization shrinkage include a method of increasing the molecular weight of the polymerizable monomer and a method of improving the molecular structure of the polymerizable monomer so as to reduce the shrinkage stress generated during the polymerization. There is. However, in the method of increasing the molecular weight of the polymerizable monomer, polymerization shrinkage can be reduced as the molecular weight increases, but at the same time, the crosslinking density is also reduced. For this reason, as a result, the strength (hardness) of the cured product also decreases. Further, in the method of improving the molecular structure of the polymerizable monomer so as to reduce the shrinkage stress generated during the polymerization, the molecular structure is eventually improved in the direction of decreasing the crosslinking density. For this reason, the intensity | strength (hardness) of hardened | cured material falls also in this case. That is, in the conventional (meth) acrylate polymerizable monomer, there is a trade-off relationship between suppression of polymerization shrinkage and improvement in hardness of the cured product, and at the same time, the polymerization shrinkage is further suppressed and the hardness of the cured product is further increased. It is difficult to improve.

  On the other hand, when the (meth) acrylate-based polymerizable monomer is used in various applications, the functions and properties required for the cured product in each application are greatly different. For this reason, the (meth) acrylate polymerizable monomer is often used in a state of being mixed with other materials in order to easily ensure the function and characteristics of the cured product according to the application. For this reason, it is also important that the (meth) acrylate-based polymerizable monomer is easy to ensure compatibility with various other materials.

  The present invention has been made in view of the above circumstances, and it is easy to ensure compatibility with various materials, and the ratio of polymerization shrinkage to the hardness of the cured product (polymerization shrinkage / hardness of the cured product). It is an object of the present invention to provide a smaller (meth) acrylate polymerizable monomer and a composition, a curable composition, and a resin member using the same.

The above-mentioned subject is achieved by the following present invention. That is,
The polymerizable monomer of the first aspect of the present invention is represented by the following general formula (1) and the following general formula (2).

[In General Formula (1), m is 0, Y and Ar ² are directly bonded, Y and Z are monovalent groups represented by the following General Formula (2), and Ar ² is divalent Each of which is the same as or different from the divalent anthracene group. Also, o and p are 1 . ]

[In General Formula (2), R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² is hydrogen or a methyl group. L represents the number of carbon atoms in the main chain (provided that the carbon number refers to the number of carbon atoms constituting the main chain and carbon atoms when some or all of the carbon atoms constituting the main chain are substituted with hetero atoms. refers to the sum of the number of atoms) Ri hydrocarbon radical der of 2 to 50, wherein the main chain, hydroxyl alkylene chain, linear or branched alkylene glycol chain and substituent group having 2 to 5 carbon atoms It includes any selected from the group consisting of alkylene chains having groups containing groups . Further, R ¹ constituting Y shown in the general formula (1) and R ¹ constituting Z shown in the general formula (1), R ² constituting Y shown in the general formula (1), and the general formula (1) R ² constituting Z shown, L constituting Y shown in the general formula (1), and L constituting Z shown in the general formula (1) may be the same or different. ]

Polymerizable monomer of the second invention is characterized in that shown by a general formula (3).

[In the general formula (3), X ¹ is oxygen, sulfur, alkylene group having 1 to 20 carbon atoms, a sulfonic group, an ester group, an amide group or a carbonate group. Here, n is 0 or 1, and when n is 0, the two phenylene groups shown in the general formula (3) are directly bonded. R ²¹ and R ²² are hydrogen or a methyl group, and R ²¹ and R ²² may be the same or different, and L ¹ and L ² are the number of carbons in the main chain (however, the carbon The number means that when some or all of the carbon atoms constituting the main chain are substituted with heteroatoms, it means the total number of heteroatoms and carbon atoms constituting the main chain). Wherein the main chain is selected from the group consisting of an alkylene chain, a linear or branched alkylene glycol chain having 2 to 5 carbon atoms, and an alkylene chain having a hydroxyl group as a substituent. It comprises or Ruizure, may be the same or different and L ¹ and L ^2. ]

  The composition of the present invention includes the polymerizable monomer of the present invention and other polymerizable monomers.

  The curable composition of this invention is characterized by including the polymerizable monomer of this invention, another polymerizable monomer, and a polymerization initiator.

  The resin member of the present invention includes a cured product obtained using the polymerizable monomer of the present invention.

  According to the present invention, it is easy to ensure compatibility with various materials, and the (meth) acrylate polymerization is smaller than the ratio of the polymerization shrinkage to the hardness of the cured product (polymerization shrinkage / hardened product hardness). Monomer, a composition using the monomer, a curable composition, and a resin member can be provided.

-Polymerizable monomer-
The polymerizable monomer of this embodiment is represented by the following general formula (1) and the following general formula (2).

Here, in the general formula (1), X is a divalent group, Y and Z are monovalent groups represented by the following general formula (2), and Ar ¹ and Ar ² each represent an aromatic group. May be the same or different. O and p are integers selected from a range of 1 to 3. Further, m and n are each an integer selected from 0 or 1. Here, when m is 0, Y and Ar ² are directly bonded, and when n is 0, Ar ¹ and Ar ² are directly bonded.

Further, in the general formula (2), ^{R 1} is hydrogen or an alkyl group having 1 to 6 carbon atoms, ^{R 2} is hydrogen or a methyl group. L is a hydrocarbon group having 2 to 50 carbon atoms in the main chain.

Further, R ¹ constituting Y shown in the general formula (1) and R ¹ constituting Z shown in the general formula (1), R ² constituting Y shown in the general formula (1), and the general formula (1) R ² constituting Z shown, L constituting Y shown in the general formula (1), and L constituting Z shown in the general formula (1) may be the same or different. .

Specific examples of Ar ¹ and Ar ² include divalent to tetravalent aromatic groups having 1 to 3 benzene rings. For example, in the case of a divalent aromatic group, the following structural formula A1-A11 can be mentioned. These aromatic groups are monocyclic aromatic groups having 1 benzene ring as exemplified in the following structural formulas A1 to A3 and 2 or 2 benzene rings as exemplified in the following structural formulas A4 to A11. And a condensed polycyclic aromatic group in which all the benzene rings constituting the aromatic group are condensed.

Ar ¹ and Ar ² are divalent aromatic groups as exemplified in the following structural formulas A1 to A11 when the values of o and p are 1, and 3 when the values of o and p are 2. Is a tetravalent aromatic group, and when the values of o and p are 3, it is a tetravalent aromatic group. Therefore, when Ar ¹ and Ar ² are a trivalent aromatic group or a tetravalent aromatic group, the third or fourth bond in the structural formulas A1 to A11 forms a benzene ring. Any carbon atom bonded to a hydrogen atom among carbon atoms can be provided at any position.

  Specific examples of X include divalent groups exemplified by the following structural formulas B1 to B13. That is, oxygen (structural formula B1), sulfur (structural formula B2), an alkylene group having 1 to 20 carbon atoms exemplified by structural formulas B3 to B9, a sulfone group (structural formula B10), an ester group (structural formula B11) ), An amide group (structural formula B12), and a carbonate group (structural formula B13). The divalent group X may contain an amide group as exemplified in the structural formula B12, but the divalent group X may be selected from those not containing an amide group.

In addition, as an alkylene group having 1 to 20 carbon atoms, the carbon atom constituting the main chain as exemplified in structural formulas B3 to B9 has 1 carbon atom (that is, ¹ directly bonded to both Ar ¹ and Ar ² ). Particularly preferred are alkylene groups having 2 carbon atoms. In this case, one or two monovalent substituents are bonded to the carbon atoms constituting the main chain as exemplified in Structural Formulas B4 to B6, or exemplified in Structural Formulas B7 to B9. Thus, one divalent substituent is bonded.

  Here, examples of the monovalent substituent include a hydrogen atom or a hydrocarbon group having 1 to 19 carbon atoms. As this C1-C19 hydrocarbon group, alkyl groups, such as a methyl group and an ethyl group, are mentioned, for example.

  Moreover, as a bivalent substituent, the C1-C19 hydrocarbon group which comprises a ring with the carbon atom which comprises a principal chain is mentioned. Here, the ring is preferably a 5-membered ring or a 6-membered ring. In addition, as the divalent group X, for example, another polymerizable monomer compatible with the polymerizable monomer of the present embodiment is a polymerizable monomer containing an alkylene glycol chain (for example, triethylene glycol). In the case of polyalkylene glycol dimethacrylates such as dimethacrylate), oxygen (structural formula B1) is preferable.

o and p are integers selected from a range of 1 to 3, but 1 is usually preferable.

m and n are each an integer selected from 0 or 1, and a combination of m and n (m
, N) are (1, 1), (1, 0) and (0, 0).

  In addition, L shown in the general formula (2) is the number of carbon atoms in the main chain (provided that the carbon number is a main chain when a part or all of the carbon atoms constituting the main chain are substituted with hetero atoms. Is a hydrocarbon group having 2 to 50). Here, as the atoms constituting the main chain, in addition to the carbon atoms, hetero atoms such as oxygen atoms, nitrogen atoms, sulfur, silicon and the like are in the range of 1 to 20 in the form of replacing the carbon atoms constituting the main chain May be included. In addition, a substituent other than hydrogen may be bonded to the carbon atom and hetero atom constituting the main chain. Examples of the substituent include a hydrocarbon group containing a hydroxyl group such as a hydroxyl group or a hydroxymethyl group, and an alkyl group having 1 to 3 carbon atoms. Specific examples of the hydrocarbon group L include the following structural formulas C1 to C14. Here, in structural formulas C1 to C14, a represents an integer selected from 1 to 11, b represents an integer selected from 1 to 20, c represents an integer selected from 0 to 20, and d Represents an integer selected from 0 to 5, e represents an integer selected from 2 to 5, and f represents an integer selected from 1 to 10.

  The hydrocarbon group L may include an amide group as exemplified in structural formulas C13 and C14, but the hydrocarbon group L may be selected from those not including an amide group.

  Here, from the viewpoint of ensuring compatibility with other hydrophilic materials (especially hydrophilic polymerizable monomers), the hydrocarbon groups L are exemplified in structural formulas C2 to C7 and C13 to C14. It is preferable that a linear or branched alkylene glycol chain having 2 to 5 carbon atoms is included, and when a substituent is introduced into the hydrocarbon group L, the substituent is as exemplified in structural formulas C8 to C12. It is preferably a group containing a hydroxyl group.

In the polymerizable monomer of the present embodiment represented by the general formula (1) and the general formula (2) described above, the central part of the molecule in the general formula (1) (Y and Z located at both ends of the molecule are represented by The skeletal structure of (excluded part) includes an aromatic group Ar ¹ (provided only when m = 1) and Ar ₂ that contribute to improving the rigidity of the molecule. For this reason, the hardness of the hardened | cured material obtained by superposing | polymerizing and hardening using the composition containing the polymerizable monomer of this embodiment can be made higher.

  Further, in the polymerizable monomer of this embodiment, Y and Z located at both ends of the molecule are other than the reactive (meth) acrylate group portion, the skeleton structure at the center of the molecule, and two Includes a hydrocarbon group L linked via an ether bond and a carbon atom at the benzyl position. Therefore, by appropriately selecting the molecular structure of L, it is easy to ensure compatibility between the polymerizable monomer of this embodiment and other materials (particularly other polymerizable monomers).

  On the other hand, when L is not introduced into the molecule as in the conventional (meth) acrylate-based polymerizable monomer exemplified in Patent Document 4, the molecule substantially contributes to improvement of the molecular rigidity. It is comprised only from the frame structure of the central part and the reactive (meth) acrylate group part. Therefore, in such a molecular structure, only a molecule having a high affinity with the skeleton structure at the center of the molecule and the reactive (meth) acrylate group can be compatible, so it can be blended with various other materials. It becomes extremely difficult to use. Therefore, as a result, it is difficult to produce a cured product having various functions and characteristics for various uses.

  In addition to this, the main part of the molecule consists only of a skeleton structure at the center of the molecule that contributes to improving the rigidity of the molecule. For this reason, even if the hardness of the cured product can be improved, it is difficult to relax and absorb such stress by deformation of the skeleton structure when bending stress is applied to the cured product. Therefore, as a result, even if the hardness of the cured product is high, the bending strength is insufficient. However, in the polymerizable monomer of the present embodiment, there is a hydrocarbon group L that is relatively less rigid and easily deformable than the skeleton structure at the center of the molecule. For this reason, it is easy to ensure both the hardness and bending strength of the cured product.

  In addition to ensuring compatibility with other materials, the hydrocarbon group L has its molecular structure selected to acquire or control other properties and functions as needed. You can also

Furthermore, since the polymerizable monomer of this embodiment is a (meth) acrylate type, it is considered that the polymerization shrinkage is likely to occur essentially like the conventional (meth) acrylate type polymerizable monomer. However, in the polymerizable monomer of the present embodiment, compared to conventional (meth) acrylate polymerizable monomers as exemplified in Bis-GMA, D-2.6E, or Patent Documents 1 to 4, etc. In order to suppress polymerization shrinkage, the hardness of the cured product may not be significantly sacrificed by increasing the molecular weight. For this reason, it is possible to make the polymerization shrinkage ratio at the time of polymerization with respect to the hardness of the cured product smaller. The reason why such an effect is obtained is unclear, but from the comparison of the molecular structure of the conventional (meth) acrylate polymerizable monomer and the molecular structure of the polymerizable monomer of this embodiment, benzyl Of carbon atoms (in general formulas (1) and (2), R ¹ , oxygen atom, and Ar ¹ (provided that m = 1 only) or Ar ² bonded to Ar ² ) The present inventors presume that the presence or absence is involved.

  In addition, it is especially preferable that the polymerizable monomer of this embodiment shown by the general formula (1) and the general formula (2) described above is a polymerizable monomer shown by the following general formula (3).

Here, in the general formula (3), X ¹ is selected from the divalent group X in the general formula (1), specifically oxygen, sulfur, an alkylene group having 1 to 20 carbon atoms, a sulfone group, An ester group, an amide group or a carbonate group. Here, n is 0 or 1, and when n is 0, the two phenylene groups shown in the general formula (3) are directly bonded. R ²¹ and R ²² are the same as R ² shown in the general formula (2), and R ²¹ and R ²² may be the same or different. L ¹ and L ² are It is the same as L shown in Formula (2), and L ¹ and L ² may be the same or different. The general formula (3) has a molecular structure having two aromatic groups (specifically, phenylene groups) by setting m = 1 in the general formula (1). Thus, the molecular structure shown in the general formula (3) containing two aromatic groups is compared with the range excluding the molecular structure shown in the general formula (3) among the molecular structures shown in the general formula (1). Other materials, in particular, bifunctional (meth) acrylates (for example, triethylene glycol dimethacrylate (3G), tricyclodecane dimethanol dimethacrylate (TCD), which have a viscosity of 150 mPa · S or less at 25 ° C. described below, and 1. It becomes easy to improve the compatibility with other polymerizable monomers such as 9-nonanediol dimethacrylate (ND).

-Composition, curable composition and resin member-
The polymerizable monomer of the present embodiment can be used as a composition containing this polymerizable monomer as a main component. However, from the viewpoint of use in various applications, it is preferable to use it as a composition containing the polymerizable monomer of this embodiment and other materials as main components. In this case, the curable composition may be prepared by further adding a polymerization initiator to the composition. In addition, when the composition containing the polymerizable monomer of this embodiment is a composition not containing a polymerization initiator, when using this composition (agent A), other compositions containing a polymerization initiator ( B agent) can also be used in combination. In this case, a cured product can be obtained by mixing and polymerizing agent A and agent B (first cured form).

  Moreover, also about the curable composition (C agent) containing the polymerizable monomer and polymerization initiator of this embodiment, you may obtain hardened | cured material by hardening this C agent single-piece | unit (2nd hardening). Form). However, if necessary, it can be used in combination with the C agent and other compositions (D agent). In this case, a cured product can be obtained by curing a mixture obtained by mixing the C agent and the D agent (third cured form). Moreover, after apply | coating D agent to a solid surface, a hardened | cured material can also be obtained by arrange | positioning and hardening C agent further on it. In this case, when the agent D functions as a pretreatment material for improving the compatibility between the adhesive and / or agent C and the solid surface, a cured product bonded to the solid surface can be obtained (fourth curing). Form). Moreover, when D agent functions as a mold release agent, a hardened | cured material can be easily separated from a solid surface and collect | recovered, without damaging the surface of hardened | cured material after hardening (5th hardening form).

  Examples of materials that can be suitably used in the first and third cured forms include a two-component adhesive, and examples of materials that can be suitably used in the second cured form include, for example, a 3D printer using an additive manufacturing method. Resin raw materials used in the present invention, examples of materials that can be suitably used in the fourth cured form include, for example, dental materials (particularly composite resins used for filling in the cavity of a tooth), and materials that can be suitably used in the fifth cured form Examples thereof include resin raw materials used for the production of molded products using a mold.

  Further, other materials used together with the polymerizable monomer of the present embodiment are not particularly limited, and are appropriately selected depending on the use of the composition or the curable composition containing the polymerizable monomer of the present embodiment. can do. Specific examples of other materials include, for example, other polymerizable monomers other than the polymerizable monomer of the present embodiment, a low molecular organic compound having no reactivity, a resin, a filler, an organic-inorganic composite material, Various additives other than the polymerization initiator described above, solvents and the like can be mentioned, and two or more of these materials can be used in combination.

  However, as other materials used in combination with the polymerizable monomer of this embodiment, other polymerizable monomers are particularly preferable. Here, as the other polymerizable monomer, a known polymerizable monomer can be used without limitation, but from the viewpoint of ensuring compatibility, the molecular structure of the polymerizable monomer of the present embodiment. It is preferable to have a polymerizable monomer having a molecular structure identical to that of a part. For example, examples of such other polymerizable monomers include polymerizable monomers having the same or similar partial structure as L shown in the general formula (2), and also have the same polymerization mechanism. From the viewpoint that can be made, there can be mentioned a polymerizable monomer having at least one (meth) acrylate group, more preferably two. From the viewpoint of ensuring compatibility with the polymerizable monomer of the present embodiment, it is also preferable to use a polymerizable monomer having a viscosity of 150 mPa · S or less at 25 ° C. from the viewpoint of physical properties. In view of the above-described similarity in molecular structure and viscosity characteristics, the other polymerizable monomer is particularly preferably a bifunctional (meth) acrylate having a viscosity of 150 mPa · S or less at 25 ° C. Examples of the bifunctional (meth) acrylate having such viscosity characteristics include polyalkylene glycol dimethacrylate having a viscosity of 150 mPa · S or less at 25 ° C. (more specifically, the degree of polymerization of alkylene glycol units is 1 or more and 14 or less. Polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate having an alkylene glycol unit polymerization degree of 1 to 7 or less, polymethylene glycol dimethacrylate having 2 to 10 carbon atoms, etc.), neopentyl glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, etc. Can be mentioned.

  In the present specification, 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 select according to the use of the resin member containing. For example, when the composition using the polymerizable monomer of the present embodiment or the curable composition 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.

  As the polymerization initiator used in the curable composition using the polymerizable monomer of the present embodiment, a known polymerization initiator can be used, such as a radical type, cationic type or anionic type photopolymerization initiator, Various polymerization initiators such as thermal polymerization initiators or peroxide-based thermal polymerization initiators can be used as appropriate. For example, in the case of polymerization / curing by light irradiation, for example, a photopolymerization initiator such as camphorquinone or ethyl p-N, N-dimethylaminobenzoate can be used. These polymerization initiators can be used in combination of two or more. Furthermore, other additives such as a polymerization inhibitor and a sensitizer can be used in combination with the polymerization initiator.

  Moreover, it is also suitable to add a filler to the composition or curable composition using the polymerizable monomer of the present embodiment. By using a filler, the effect of suppressing polymerization shrinkage can be further increased. Moreover, by using a filler, the operability of the composition before curing or the curable composition can be improved, or the mechanical properties after curing can be improved. As the filler, for example, an inorganic filler made of inorganic oxide particles such as amorphous silica, silica-titania, silica-zirconia, silica-titania-barium oxide, quartz, alumina, etc. can be used. Or an organic inorganic composite filler can also be used. Further, the particle size and shape of the filler are not particularly limited. For example, particles having a spherical shape or an indefinite shape and an average particle size of about 0.01 μm to 100 μm can be appropriately used according to the purpose. In addition, these fillers improve the familiarity with other materials such as the polymerizable monomer of the present embodiment and other polymerizable monomers used together as necessary, and have improved mechanical strength and water resistance. From the viewpoint of improving, it may be treated with a surface treatment agent typified by a silane coupling agent.

  The specific application of the polymerizable monomer of the present embodiment is not particularly limited. For example, various applications such as dental materials, optical components, printing plate making, photoresist materials, paints, adhesives, inks and the like. However, it is particularly preferred that the cured product is used for applications requiring mechanical strength of the cured product and low polymerization shrinkage during polymerization. Such applications include the dental materials described above (especially composite resins (dental filling and restorative materials) that require adhesion to the cavity wall of the tooth and mechanical strength), mechanical strength and high dimensions. Resin materials used in the manufacture of various resin parts or resin products such as resin products that require shape accuracy (for example, photosensitive resin materials used in stereolithography, ink for inkjet 3D printers), precision parts An adhesive (for example, a precision adhesive for optical members) that requires adhesion with high dimensional accuracy, such as an adhesive used for assembly.

  Here, when the polymerizable monomer of the present embodiment is used for a composite resin, the composite resin includes at least the polymerizable monomer of the present embodiment and a photopolymerization initiator, and further includes other polymerizable monomers. It is preferable to contain a monomer and / or a filler.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, the abbreviations and abbreviations of the substances used in the preparation of the samples of the examples and the comparative examples, their structural formulas or substance names, various sample preparation methods, and various evaluation methods will be described.

(1) Abbreviations / abbreviations and structural formulas or substance names thereof [polymerizable monomer represented by general formula (1) and general formula (2)]

  Here, the repeating numbers g and h of the unit structure mean an average value, and the values of g and h can take an integer value of 0 or more in each molecule. That is, the polymerizable monomers 4-DPEEM and 4-BPEM shown above are a mixture of two or more kinds of polymerizable monomer molecules having different combinations of integer values (g, h). The same applies to the case where the number of repeating unit structures or the sum thereof is shown as an average value in the following description.

[Other polymerizable monomers]

3G: Triethylene glycol dimethacrylate TCD: Tricyclodecane dimethanol dimethacrylate ND: 1.9-nonanediol dimethacrylate

[Photopolymerization initiator]
CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate

[Polymerization inhibitor]
BHT: 2,6-di-t-butyl-p-cresol

[Inorganic filler]
F1: Spherical silica-zirconia (average particle size 0.4 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane and spherical silica-zirconia (average particle size 0.07 μm) γ-methacryloyloxypropyltrimethoxy A mixture obtained by mixing the material hydrophobized with silane at a mass ratio of 70:30.

(2) Compatibilization treatment 1 of main monomer and dilution monomer and evaluation of monomer compatibility time 30 g (60 parts by weight) of main monomer and 20 g (40 parts by weight) of dilution monomer were weighed into a 100 ml screw tube bottle, The mixture was stirred with a magnetic stirrer to obtain a compatible product of the main monomer and the diluted monomer. At this time, the stirring time (monomer compatibility time) until both monomers were completely compatible was measured up to 24 hours.

(3) Compatibilizing treatment 2 when the compatibilizing treatment 1 is not compatible.
If the main monomer and the diluted monomer are not compatible in the compatibilization treatment 1 even if the stirring is continued for 24 hours, the compatibility of the main monomer and the dilution monomer is performed by performing the compatibilization treatment 2 described below. A solute was obtained. First, 30 g (60 parts by weight) of the main monomer and 30 g of dichloromethane were weighed into a 200 ml eggplant-shaped flask to obtain a solution A in which the main monomer was completely dissolved in dichloromethane. Next, 20 g (40 parts by weight) of a diluted monomer was further added to the solution A and stirred with a magnetic stirrer until a solution B was obtained. After stirring, dichloromethane was removed from solution B using a rotary evaporator and a vacuum pump to obtain a compatible product of the main monomer and the diluted monomer.

(4) Preparation of matrix monomer sample For 100 parts by weight of the compatible product of the main monomer and the diluted monomer obtained by the above-described miscible treatment 1 or miscible treatment 2, or 100 parts by mass of one kind of monomer, 0.5 parts by weight of CQ (camphor quinone), 0.8 parts by weight of DMBE (ethyl p-N, N-dimethylaminobenzoate) and BHT (2,6-di-t-butyl-p-cresol) 0.1 After adding a weight part, it stirred until it became uniform in the dark place. Thereby, a matrix monomer sample was obtained.

(5) Preparation of Paste Sample 3.3 g of the matrix monomer sample and 6.7 g of inorganic filler F1 were weighed out and mixed in an agate mortar to obtain a mixture. Subsequently, the mixture was defoamed under vacuum to remove bubbles and obtain a paste sample.

(6) Evaluation of polymerization shrinkage ratio The matrix monomer sample before curing was placed in a 10 ml specific gravity bottle with a known weight, the liquid level was adjusted to the marked line, and stored overnight in an incubator at 23 ° C. After storage, the liquid level was confirmed to match the marked line, and the weight was measured. From the measured weight, the density of the composition was calculated by subtracting the weight of the specific gravity bottle before putting the matrix monomer sample into the specific gravity bottle, and further dividing by the volume (internal volume at the marked line of the specific gravity bottle). The above operation was performed on three or more samples, and the average value was defined as the density d1 (g / cm ³ ) of the matrix monomer sample.

A matrix monomer sample having the same composition as that used for calculating the density d1 of the matrix monomer sample was filled in a polypropylene resin container having a diameter of 3 cm and a depth of 1 cm to a depth of 0.5 cm. Thereafter, the matrix monomer sample in the container was subjected to a curing treatment by irradiating light with a dental light irradiator α light (manufactured by Tokuyama Dental Co., Ltd.) for 10 minutes to obtain a cured product. Cured. After the curing treatment, the cured product is allowed to stand at room temperature for 30 minutes, and then the density of the cured product is measured using water (water temperature 23 to 24 ° C.) as a buoyancy generating liquid using a digital hydrometer (manufactured by Sartorius). It was measured. The same operation was performed on three or more samples, and the average value was defined as the density d2 (g / cm ³ ) of the cured product.

Next, the measured shrinkage percentage (%) of the matrix monomer sample was determined by substituting the measured values of density d1 and d2 into the following formula (1).
Formula (1) Polymerization shrinkage rate (%) = (d2-d1) / d2 × 100

(7) Measurement of hardness of cured product (Vickers hardness) The hardness of the cured product was measured by the following procedure. First, a matrix monomer sample or a paste sample was filled into a through hole of a 1.0 mm-thick polytetrafluoroethylene mold having a through hole having a diameter of 6 mm, and then the opening of the through hole was pressed with a polypropylene film. A cured product (test piece) was obtained by irradiating light for 20 seconds with the irradiation port of a dental light irradiator (Tokuyama Dental Co., Ltd., Tokso Power Light) in close contact with the polypropylene film. Subsequently, using a Vickers indenter with a microhardness meter (Matsuzawa Seiki Co., Ltd., MHT-1 type), Vickers hardness is determined from the diagonal length of the indentation formed on the test piece under the measurement conditions of a load of 100 gf and a load holding time of 30 seconds. Asked.

(8) Measurement of bending strength of paste cured product The bending strength of the cured product of the paste sample was measured according to the bending strength measurement method for a class 2 dental filling composite resin specified by JIS T 6514. A universal testing machine (Autograph, manufactured by Shimadzu Corporation) was used for the measurement.

(9) Calculation of polymerization shrinkage ratio / hardness of cured product The ratio of the polymerization shrinkage rate to the hardness of the cured product (polymerization shrinkage rate / hardness of the cured product) is the matrix shrinkage rate (%) of the matrix monomer sample. It was calculated by dividing by the Vickers hardness of the cured product.

(10) Synthesis of main monomer Among the main monomers used in preparing the matrix monomer sample, those corresponding to the polymerizable monomers represented by the general formula (1) and the general formula (2) are as follows. Synthesized.

<Synthesis of BUEM>
In a solution of 13.8 g (0.1 mol) of p-xylylenediethanol and 0.32 g (0.5 mmol) of dibutyltin dilaurate in 20 ml of dimethylformamide, 41.0 g (0.21 mol) of 2- (2-Methacryloyloxyethyloxy) ethyl isocyanate was added and stirred at room temperature for 3 hours. After stirring, 50 ml of methylene chloride was added, washed 3 times with distilled water using a separatory funnel, and the recovered methylene chloride layer was dried over magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated with a rotary evaporator, and the concentrate was further dried under vacuum to obtain BUEM (53.0 g, yield 99%). In addition, the data of ¹ H NMR spectrum of the obtained BUEM were as follows.
¹ H NMR δ 1.93 (s, 6H), 3.38 (m, 4H), 3.57 (t, 4H), 3.69 (t, 4H), 4.29 (t, 4H), 5 .14 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.12 (d, 4H), 8.00 (s, 2H)

<Synthesis of NUEM>
As raw materials other than 20 ml of dimethylformamide, 18.8 g (0.1 mol) of 2,5-hydroxymethylnaphthalene, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) of 2 NUEM (58.0 g, yield 99%) was obtained by performing the synthesis in the same manner as in the BUEM synthesis procedure except that-(2-methacryloyloxyethyloxy) ethyl isocyanate was used. In addition, the data of ¹ H NMR spectrum of the obtained NUEM were as follows.
¹ H NMR δ 1.93 (s, 6H), 3.38 (m, 4H), 3.57 (t, 4H), 3.69 (t, 4H), 4.29 (t, 4H), 5 .25 (s, 2H), 5.38 (d, 2H), 5.55 (m, 2H), 6.11 (s, 2H), 7.17 (d, 1H), 7.18 (t, 1H), 7.43 (s, 1H), 7.48 (d, 1H), 7.71 (d, 1H), 8.01 (s, 2H)

<Synthesis of AUEM>
As raw materials other than 20 ml of dimethylformamide, 23.8 g (0.1 mol) of 9,10-hydroxymethylanthracene, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) of 2 AUEM (63.0 g, 100% yield) was obtained by carrying out the synthesis in the same manner as in the BUEM synthesis procedure except that-(2-methacryloyloxyethyloxy) ethyl isocyanate was used. The data of ¹ H NMR spectrum of the obtained AUEM was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.38 (m, 4H), 3.57 (t, 4H), 3.69 (t, 4H), 4.29 (t, 4H), 5 .32 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.37 (t, 4H), 7.94 (d, 4H), 8.00 (s, 2H)

<Synthesis of 4-BPUEM>
As raw materials other than 20 ml of dimethylformamide, 21.4 g (0.1 mol) of 4,4′-biphenyldimethanol, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) of 4-BPUEM (60.3 g, yield 98%) was obtained by performing synthesis in the same manner as the synthesis procedure of BUEM except that 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used. The data of ¹ H NMR spectrum of the obtained 4-BPUEM was as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .14 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.43 (d, 4H), 7.57 (d, 4H), 8.01 (s, 2H)

<Synthesis of DPMUEM>
4,4′-diformyldiphenylmethane (44.8 g, 0.2 mol) obtained by the method described in JP-A-2005-154379 is dissolved in 100 g of ethanol, and sodium borohydride (11.3 g, 0 .3 mol) was added slowly. After completion of the addition, the mixture was stirred for 2 hours, 30 ml of water was added, and ethanol was distilled off under reduced pressure. The residue was extracted 3 times with 30 ml of toluene, and the resulting toluene layer was dried over magnesium sulfate. After drying, magnesium sulfate is filtered off, the filtrate is concentrated on a rotary evaporator, and the concentrate is further dried in vacuo to give 4,4′-bis (hydroxymethyl) diphenylmethane (43.3 g, yield 95%). Obtained.

Next, as a raw material other than 20 ml of dimethylformamide, 22.8 g (0.1 mol) of 4,4′-bishydroxymethyldiphenylmethane, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0 .21 mol) except that 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used, and DPMUEM (62.1 g, 99% yield) was obtained by synthesizing in the same manner as the BUEM synthesis procedure. It was. The data of ¹ H NMR spectrum of the obtained DPMUEM was as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.82 (s, 2H), 3.58 (t, 4H), 3.70 (t, 4H), 4 .29 (t, 4H), 5.14 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.00 (d, 4H), 7.17 (d, 4H), 8.01 (s, 2H)

<Synthesis of DPPUEM>
As raw materials other than 20 ml of dimethylformamide, 2,2-bis (4-hydroxymethylphenyl) propane (25.6 g, 0.1 mol), 0.32 g (0.5 mmol) obtained by the method described in British Patent GB753384 The synthesis was carried out in the same manner as the synthesis procedure of BUUM except that 41.0 g (0.21 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used, and DPPUEM ( 65.3 g, 100% yield). The data of ¹ H NMR spectrum of the obtained DPPUEM was as follows.
¹ H NMR δ 1.67 (s, 6H), 1.94 (s, 6H), 3.39 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4 .29 (t, 4H), 5.14 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.01 (d, 4H), 7.16 (d, 4H), 8.00 (s, 2H)

<Synthesis of DPCUEM>
As raw materials other than 20 ml of dimethylformamide, 1,1-bis (4-hydroxymethylphenyl) cyclohexane (29.6 g, 0.1 mol) obtained by the method described in Japanese Patent No. 3076603, 0.32 g (0 .5 mmol) dibutyltin dilaurate and 41.0 g (0.21 mol) 2- (2-methacryloyloxyethyloxy) ethyl isocyanate were used in the same synthesis procedure as BUEM. , DPCUEM (68.2 g, yield 98%) was obtained. The data of ¹ H NMR spectrum of DPCUEM obtained was as follows.
¹ H NMR δ 1.40-2.03 (m, 10H), 1.95 (s, 6H), 3.39 (m, 4H), 3.57 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5.14 (s, 4H), 5.56 (m, 2H), 6.11 (s, 2H), 7.03 (d, 4H), 7. 13 (d, 4H), 8.00 (s, 2H)

<Synthesis of 4-DPPEEM>
As raw materials other than 20 ml of dimethylformamide, 23.0 g (0.1 mol) of bis (4-hydroxymethylphenyl) ether, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) 4-DPEUEM (61.0 g, 97% yield) was obtained by performing synthesis in the same manner as the synthesis procedure of BUEM except that 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used. . In addition, the data of ¹ H NMR spectrum of the obtained 4-DPPEEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.38 (m, 4H), 3.56 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .07 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H), 8.01 (s, 2H)

<Synthesis of DPSUEM>
4,4′-diformyldiphenyl sulfide (48.4 g, 0.2 mol) obtained by the method described in JP-A-2005-154379 is dissolved in 100 g of ethanol, and sodium borohydride (11.3 g, 0.3 mol) was gradually added. After completion of the addition, the mixture was stirred for 2 hours, 30 ml of water was added, and ethanol was distilled off under reduced pressure. The residue was extracted 3 times with 30 ml of toluene, and the resulting toluene layer was dried over magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further dried in vacuo to give 4,4′-bis (hydroxymethyl) diphenyl sulfide (48.1 g, yield 98%). Got.

As raw materials other than 20 ml of dimethylformamide, 24.6 g (0.1 mol) of 4,4′-bis (hydroxymethyl) diphenyl sulfide, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0 .21 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used in the same manner as the BUEM synthesis procedure to obtain DPSUEM (62.5 g, yield 97%). It was. In addition, the data of ¹ H NMR spectrum of the obtained DPSUEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .14 (s, 4H), 5.56 (m, 2H), 6.11 (s, 2H), 6.99 (d, 4H), 7.13 (d, 4H), 8.00 (s, 2H)

<Synthesis of PSUUEM>
4,4′-Diformyldiphenylsulfone (54.8 g, 0.2 mol) obtained by the method described in German Patent DE 939325 was dissolved in 100 g of ethanol, and sodium borohydride (11.3 g, 0.3 mol) was dissolved. Was gradually added. After completion of the addition, the mixture was stirred for 2 hours, 30 ml of water was added, and ethanol was distilled off under reduced pressure. The residue was extracted 3 times with 30 ml of toluene, and the resulting toluene layer was dried over magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further vacuum dried to give 4,4′-bis (hydroxymethyl) diphenylsulfone (52.1 g, yield 94%). Got.

Next, as raw materials other than 20 ml of dimethylformamide, 27.8 g (0.1 mol) of 4,4′-bis (hydroxymethyl) diphenylsulfone, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41. PSUUEM (65.3 g, 97% yield) was obtained by synthesizing in the same manner as the synthesis procedure for BUEM, except that 0 g (0.21 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used. ) In addition, the data of ¹ H NMR spectrum of the obtained PSUUEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .28 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.38 (d, 4H), 7.86 (d, 4H), 8.02 (s, 2H)

<Synthesis of PBUEM>
4-Formylphenyl-4′-formylbenzoate (50.8 g, 0.2 mol) obtained by the method described in JP-A-2007-106779 is dissolved in 100 g of ethanol, and sodium borohydride is ice-cooled. (11.3 g, 0.3 mol) was added slowly. After completion of the addition, the mixture was stirred for 2 hours, 30 ml of water was added, and ethanol was distilled off under reduced pressure. The residue was extracted 3 times with 30 ml of toluene, and the resulting toluene layer was dried over magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further vacuum dried to give 4-hydroxymethylphenyl-4′-hydroxymethylbenzoate (47.3 g, yield 92%). Got.

Next, as raw materials other than 20 ml of dimethylformamide, 25.8 g (0.1 mol) of 4-hydroxymethylphenyl-4′-hydroxymethylbenzoate, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41. PBUEM (61.2 g, 93% yield) was obtained by synthesizing in the same manner as BUEM synthesis procedure except that 0 g (0.21 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used. ) In addition, the data of ¹ H NMR spectrum of the obtained PBUEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .11 (s, 2H), 5.24 (s, 2H), 5.55 (m, 2H), 6.11 (s, 2H), 7.08 (d, 2H), 7.26 (d, 2H), 7.33 (d, 2H), 8.01 (s, 2H), 8.08 (d, 2H),

<Synthesis of 2-BPUEM>
As raw materials other than 20 ml of dimethylformamide, 21.4 g (0.1 mol) of 2,2′-biphenyldimethanol, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) of 2-BPUEM (60.3 g, 98% yield) was obtained by carrying out the synthesis in the same manner as the BUEM synthesis procedure except that 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used. The data of ¹ H NMR spectrum of the obtained 2-BPUEM was as follows.
¹ H NMR δ 1.94 (s, 6H), 3.40 (m, 4H), 3.58 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .12 (s, 4H), 5.55 (m, 2H), 6.11 (s, 2H), 7.15 (t, 2H), 7.21 (d, 2H), 7.26 (t, 2H), 7.43 (d, 2H), 8.01 (s, 2H)

<2-DPEUEM>
As raw materials other than 20 ml of dimethylformamide, 23.0 g (0.1 mol) of bis (2-hydroxymethylphenyl) ether, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 41.0 g (0.21 mol) Except for using 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2-DPEUEM (61.0 g, 97% yield) was obtained by synthesis in the same manner as the synthesis procedure of BUEM. . In addition, the data of ¹ H NMR spectrum of the obtained 2-DPEUEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.38 (m, 4H), 3.56 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5 .09 (s, 4H), 5.55 (s, 2H), 6.11 (s, 2H), 6.84 (d, 2H), 7.12 (d, 2H), 7.14 (t, 2H), 6.98 (t, 2H), 8.00 (s, 2H)

<Synthesis of 4-DPEEM>
Sodium hydride (16.7 g, 0.7 mol) washed with hexane was dispersed in 20 ml of dehydrated dimethylformamide, and dehydrated dimethylformamide of bis (4-hydroxymethylphenyl) ether (69 g, 0.3 mol) was dispersed in this dispersion. (50 ml) of solution was added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, and allyl bromide (36.3 g, 0.6 mol) was added dropwise. After completion of the dropwise addition, the mixture was heated to 40 ° C. in an oil bath, stirred for 2 hours, and after completion of heating and stirring, the mixture was allowed to cool to room temperature, 100 ml of water was added, and extracted with toluene three times. The obtained toluene layer was washed with 0.5N hydrochloric acid and dried over magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further dried in vacuo to obtain bis (4-allyloxymethylphenyl) ether (92.1 g, yield 99%). It was.

  The resulting bis (4-allyloxymethylphenyl) ether (62.1 g, 0.2 mol) was dissolved in dichloromethane (100 ml), and this solution was dissolved in a 60% metachloroperbenzoic acid / water mixture (144 g, 0.5 mol). And the mixture was stirred at room temperature for 10 hours. After stirring, by-product metachlorobenzoic acid was filtered off, and the filtrate was reduced with 150 ml of 15% aqueous sodium sulfite solution. The dichloromethane layer was then separated, washed twice with 1N aqueous sodium hydroxide solution, dried over magnesium sulfate, concentrated on a rotary evaporator, and the concentrate was further dried in vacuo to give bis (4-glycidyloxymethylphenyl). Ether (62.2 g, 91% yield) was obtained.

The resulting bis (4-glycidyloxymethylphenyl) ether (34.2 g, 0.1 mol), methacrylic acid (34.4 g, 0.4 mol), benzyltriethylammonium chloride (90 mg, 0.4 mmol), and p- Methoxyphenol (34 mg) was stirred with heating at 90 ° C. for 4 hours. After heating and stirring, the mixture was allowed to cool to room temperature, 50 ml of water was added, and the mixture was extracted with dichloromethane. The obtained dichloromethane layer was dried with magnesium sulfate and then concentrated with a rotary evaporator. The concentrate was further dried under vacuum to obtain 4-DPEEM (48.2 g, yield 94%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEEM were as follows.
¹ H NMR δ 1.94 (s, 4.8H), 1.97 (s, 1.2H), 2.51 (br, 2H), 3.58 (m, 3.2H), 3.75 ( m, 0.8H), 3.89 (m, 0.4H), 4.11 (m, 0.4H), 4.27 (m, 4H), 4.61 (s, 4H), 5.58 (M, 1.6H), 5.61 (m, 0.4H), 6.11 (s, 1.6H), 5.16 (s, 0.4H), 7.39 (d, 4H), 7.57 (d, 4H)

<4-BPEM>
Similar to the synthesis of bis (4-glycidyloxymethylphenyl) ether, 4,4′-bisglycidyloxymethylbiphenyl obtained from 4,4′-biphenyldimethanol (32.6 g, 0.1 mol), methacrylic acid (34.4 g, 0.4 mol), benzyltriethylammonium chloride (90 mg, 0.4 mmol), and p-methoxyphenol (34 mg) were used in the same manner as in the 4-DPEEM synthesis example, except that they were used in combination. Thus, 4-BPEM (48.2 g, yield 94%) was obtained. In addition, the data of ¹ H NMR spectrum of the obtained 4-BPEM were as follows.
¹ H NMR δ 1.93 (s, 4.8H), 1.96 (s, 1.2H), 2.51 (br, 2H), 3.58 (m, 3.2H), 3.75 ( m, 0.8H), 3.89 (m, 0.4H), 4.11 (m, 0.4H), 4.27 (m, 4H), 4.61 (s, 4H), 5.58 (M, 1.6H), 5.61 (m, 0.4H), 6.11 (s, 1.6H), 5.16 (s, 0.4H), 6.98 (d, 4H), 7.33 (d, 4H)

<4-DPEUEA>
As raw materials other than 20 ml of dimethylformamide, 23.0 g (0.1 mol) of bis (4-hydroxymethylphenyl) ether, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 38.9 g (0.21 mol) 4-DPEUEA (59.0 g, yield 98%) was obtained by performing synthesis in the same manner as the synthesis procedure of BUEM except that 2- (2-acryloyloxyethyloxy) ethyl isocyanate was used. . In addition, the data of ¹ H NMR spectrum of the obtained 4-DPPEUA were as follows.
¹ H NMR δ 3.39 (m, 4H), 3.57 (t, 4H), 3.70 (t, 4H), 4.29 (t, 4H), 5.07 (s, 4H), 5 .81 (d, 2H), 6.13 (d, 2H), 6.37 (m, 2H) 6.98 (d, 4H), 7.33 (d, 4H), 8.00 (s, 2H) )

<4-DPUM>
As raw materials other than 20 ml of dimethylformamide, 23.0 g (0.1 mol) of bis (4-hydroxymethylphenyl) ether, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 32.6 g (0.21 mol) 4-DPUM (56.0 g, yield 96%) was obtained by performing synthesis in the same manner as in the BUEM synthesis procedure, except that 2-methacryloyloxyethyl isocyanate was used. In addition, the data of ¹ H NMR spectrum of the obtained 4-DPUM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.51 (m, 4H), 4.23 (t, 4H), 5.08 (s, 4H), 5.58 (m, 2H), 6 .10 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H), 8.01 (s, 2H)

<4-DPEM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in 60 ml of dehydrated tetrahydrofuran, and ethylene glycol (55.8 g, 0.9 mol) was added dropwise to the dispersion. Thereafter, the mixture was refluxed with heating for 2 hours, and then allowed to cool to room temperature. Then, a dimethylformamide (100 ml) solution of bis (4-chloromethylphenyl) ether (80.1 g, 0.3 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Reacted. After completion of the reaction, 100 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed once with saturated brine. Then, after drying an organic layer with magnesium sulfate, it concentrated with a rotary evaporator, the concentrate was further vacuum-dried, and bis (4- (2-hydroxyethoxymethyl) phenyl) ether (78.2 g, yield 79%). )

The obtained bis (4- (2-hydroxyethoxymethyl) phenyl) ether (31.8 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p-toluenesulfonic acid (0.86 g, 0 0.5 mmol) and dibutylhydroxytoluene (0.05 g) were heated and stirred at 80 ° C. for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 50 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEM (44.1 g, yield 97%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPUM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.61 (t, 4H), 4.32 (t, 4H), 4.63 (s, 4H) 5.58 (m, 2H), 6. 10 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H)

<4-DPEEUM>
As raw materials other than 20 ml of dimethylformamide, 31.8 g (0.1 mol) of bis (4- (2-hydroxyethoxymethyl) phenyl) ether, 0.32 g (0.5 mmol) of dibutyltin dilaurate, and 32 4-DPEEUM (62.0 g, 99% yield) was obtained by carrying out the synthesis in the same manner as the BUEM synthesis procedure except that .6 g (0.21 mol) of 2-methacryloyloxyethyl isocyanate was used. It was. In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEEUM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.51 (m, 4H), 3.65 (t, 4H) 4.23 (t, 4H), 4.17 (t, 4H) 5.08 (S, 4H), 5.58 (m, 2H), 6.10 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H), 8.01 (s, 2H)

<Synthesis of 4-DPEHM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in 60 ml of dehydrated tetrahydrofuran, and a solution of 1,6-hexanediol (106.3 g, 0.9 mol) in tetrahydrofuran (150 ml) was dispersed in this dispersion. Was dripped. Thereafter, the mixture was refluxed with heating for 2 hours, and then allowed to cool to room temperature. Then, a dimethylformamide (100 ml) solution of bis (4-chloromethylphenyl) ether (80.1 g, 0.3 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Reacted. After completion of the reaction, 200 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed three times with saturated brine. Thereafter, the organic layer was dried with magnesium sulfate and then concentrated with a rotary evaporator. The concentrate was further dried under vacuum to obtain bis (4- (6-hydroxyhexyloxymethyl) phenyl) ether (120.2 g, yield 93). %).

The obtained bis (4- (6-hydroxyhexyloxymethyl) phenyl) ether (43.1 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p-toluenesulfonic acid (0.86 g, 0.5 mmol) and dibutylhydroxytoluene (0.05 g) were heated and stirred at 80 ° C. for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 50 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEHM (55.0 g, yield 97%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEHM were as follows.
¹ H NMR δ 1.28-1.60 (m, 16H), 1.94 (s, 6H), 3.37 (t, 4H), 4.28 (t, 4H), 4.63 (s, 4H) 5.58 (m, 2H), 6.10 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H)

<Synthesis of 4-DPEPEM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in 60 ml of dehydrated tetrahydrofuran, and triethylene glycol (135.1 g, 0.9 mol) was added dropwise to the dispersion. Thereafter, the mixture was refluxed with heating for 2 hours, and then allowed to cool to room temperature. Then, a dimethylformamide (100 ml) solution of bis (4-chloromethylphenyl) ether (80.1 g, 0.3 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Reacted. After completion of the reaction, 200 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed once with saturated brine. Then, after drying an organic layer with magnesium sulfate, it concentrates with a rotary evaporator, The concentrate is further vacuum-dried, bis (4- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxymethyl) phenyl) Ether (53.1 g, 59% yield) was obtained.

The obtained bisbis (4- (2- (2- (2-hydroxyethoxy) ethoxy) ethoxymethyl) phenyl) ether (49.5 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p -Toluenesulfonic acid (0.86 g, 0.5 mmol) and dibutylhydroxytoluene (0.05 g) were heated and stirred at 80 ° C for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 50 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEPEM (60.2 g, yield 95%). The data of ¹ H NMR spectrum of the obtained 4-DPEPEM were as follows.
¹ H NMR δ 1.94 (s, 6H), 3.52-3.68 (m, 10H), 4.30 (t, 4H), 4.63 (s, 4H) 5.58 (m, 2H) ), 6.11 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H)

<4-DPETFM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in 200 ml of dehydrated tetrahydrofuran, and polytetrahydrofuran (degree of polymerization about 3) (211.0 g, 0.9 mol) was added dropwise to the dispersion. Thereafter, the mixture was refluxed with heating for 2 hours, and then allowed to cool to room temperature. Then, a dimethylformamide (100 ml) solution of bis (4-chloromethylphenyl) ether (80.1 g, 0.3 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Reacted. After completion of the reaction, 200 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed once with saturated brine. Then, after drying an organic layer with magnesium sulfate, it concentrates with a rotary evaporator and refine | purifies a concentrate with a silica gel column chromatography, By bis (4- (4- (4- (4-hydroxybutoxy) butoxy) butoxy. Methyl) phenyl) ether (59.0 g, 87% yield) was obtained.

The obtained bisbisbis (4- (4- (4- (4-hydroxybutoxy) butoxy) butoxymethyl) phenyl) ether (67.9 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p -Toluenesulfonic acid (0.86 g, 0.5 mmol) and dibutylhydroxytoluene (0.05 g) were heated and stirred at 80 ° C for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 80 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPETFM (60.2 g, yield 95%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPETFM were as follows.
¹ H NMR δ 1.45-1.58 (m, 24H), 1.94 (s, 6H), 3.36-3.68 (m, 20H), 4.25 (t, 4H), 4. 63 (s, 4H) 5.58 (m, 2H), 6.11 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H)

<4-DPEPPM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in propylene oxide (232 g, 5.0 mol), and bis (4-hydroxymethylphenyl) ether (69.1 g, 0 mol) was dispersed in this dispersion. .3 mol) was added and allowed to react for 15 hours at room temperature. After completion of the reaction, 200 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed once with saturated brine. Then, after drying an organic layer with magnesium sulfate, it concentrated with the rotary evaporator and obtained the compound A shown below (96.8 g, yield 83%).

Next, Compound A (38.7 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p-toluenesulfonic acid (0.86 g, 0.5 mmol), and dibutylhydroxytoluene (0.05 g) ) Was stirred with heating at 80 ° C. for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 80 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEPPM (50.3 g, yield 96%). The data of ¹ H NMR spectrum of the obtained 4-DPEPPM was as follows.
¹ H NMR δ 1.21 (d, 2.1H), 1.40 (d, 6H), 1.94 (s, 6H), 3.34 (m, 1.4H) 3.60-3.62 (M, 5.4H), 4.27 (m, 2H), 4.63 (s, 4H) 5.58 (m, 2H), 6.11 (s, 2H), 6.98 (d, 4H) ), 7.33 (d, 4H)

<4-DPEPBM>
Sodium hydride (19.2 g, 0.8 mol) washed with hexane was dispersed in 1,2-butylene oxide (360 g, 5.0 mol), and bis (4-hydroxymethylphenyl) ether (69 0.1 g, 0.3 mol) was added and allowed to react at room temperature for 15 hours. After completion of the reaction, 200 ml of water was added and extracted three times with diethyl ether, and the resulting diethyl ether layer was washed once with saturated brine. Then, after drying an organic layer with magnesium sulfate, it concentrated with the rotary evaporator and obtained the compound B shown below (127 g, yield 98%).

Next, compound B (43.2 g, 0.1 mol), methacrylic acid (18.1 g, 0.21 mol), p-toluenesulfonic acid (0.86 g, 0.5 mmol), and dibutylhydroxytoluene (0.05 g) ) Was stirred with heating at 80 ° C. for 2 hours. Then, heating and stirring were continued for 1 hour while distilling off water produced as a by-product under reduced pressure conditions (40 mmHg). After releasing the reduced pressure, the mixture was allowed to cool to room temperature, 80 ml of heptane and 50 ml of water were added and stirred, and the organic layer was recovered using a separatory funnel. Further, the obtained organic layer was washed twice with water and dried over magnesium sulfate. After drying, the mixture was concentrated on a rotary evaporator, and the concentrate was further vacuum-dried to obtain 4-DPEBPM (54.2 g, yield 95%). In addition, the data of ¹ H NMR spectrum of the obtained 4-DPEBPM were as follows.
¹ H NMR δ 0.97 (m, 8.4), 1.46 (m, 1.6), 1.57 (m, 5.6H), 1.94 (s, 6H), 3.16 ( m, 0.8H), 3.50-3.62 (m, 4.8H), 4.28 (m, 2H), 4.63 (s, 4H) 5.58 (m, 2H), 6. 11 (s, 2H), 6.98 (d, 4H), 7.33 (d, 4H)

(11) Evaluation of sample ( Comparative Example 17 and Examples 2 to 26)
As the main monomer, the monomer of the present embodiment represented by the general formula (1) and the general formula (2) was used, and a matrix monomer sample having a composition described in Tables 1 to 3 and a paste sample using the same were prepared. Along with the composition of the matrix monomer of the samples of Examples 1 to 26, the monomer compatibility time measured when preparing the matrix monomer sample, the polymerization shrinkage S of the matrix monomer, the Vickers hardness H1 of the cured matrix monomer, the Vickers of the cured paste monomer Tables 1 to 3 show the hardness H2, the bending strength of the paste cured product, and the polymerization shrinkage ratio S / the hardness H1 of the cured product.

(Comparative Examples 1 to 13)
A matrix having the composition described in Table 1 by using a monomer different from the monomer of the present embodiment as the main monomer, measuring the solubility, polymerization shrinkage, and Vickers hardness with the compositions described in Tables 4-5. A monomer sample and a paste sample using the monomer sample were prepared. Along with the composition of the matrix monomer of the samples of Comparative Examples 1 to 13, the monomer compatibility time measured when preparing the matrix monomer sample, the polymerization shrinkage ratio S of the matrix monomer, the Vickers hardness H1 of the cured matrix monomer, the Vickers of the cured paste monomer Tables 4 to 5 show the hardness H2, the bending strength of the paste cured product, and the polymerization shrinkage S / the hardness H1 of the cured product.

Claims (9)

A polymerizable monomer represented by the following general formula (3).

[In the general formula (3), X ¹ represents oxygen, sulfur, an alkylene group having 1 to 20 carbon atoms in the main chain, a sulfone group, an ester group, an amide group, or a carbonate group. It is. Here, n is 0 or 1, and when n is 0, the two phenylene groups shown in the general formula (3) are directly bonded.
R ²¹ and R ²² are hydrogen or a methyl group, and R ²¹ and R ²² may be the same or different, and L ¹ and L ² are the number of carbons in the main chain (however, the carbon The number means the sum of the number of heteroatoms and carbon atoms constituting the main chain when part or all of the carbon atoms constituting the main chain are substituted with heteroatoms. The main chain is an alkylene chain, a linear or branched alkylene glycol chain having 2 to 5 carbon atoms, and an alkylene chain having a hydroxyl group as a substituent. Including any one selected, L ¹ and L ² may be the same or different. ] The polymerizable monomer according to claim 1, wherein the alkylene group selected as X ¹ has 1 to 6 carbon atoms. A polymerizable monomer represented by the following general formula (1) and the following general formula (2).

[In the general formula (1), m is 0, Y and Ar ² are directly bonded, Y and Z are monovalent groups represented by the following general formula (2), and Ar ² is 2 Represents a divalent naphthalene group or a divalent anthracene group, which may be the same or different.
Also, o and p are 1 . ]

[In the general formula (2), R ¹ is hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ² is hydrogen or a methyl group. L is the number of carbon atoms in the main chain (provided that the carbon number is the number of heteroatoms constituting the main chain when part or all of the carbon atoms constituting the main chain are substituted with heteroatoms). Is a hydrocarbon group having 2 to 50 carbon atoms, and the main chain is an alkylene chain, a linear or branched alkylene glycol chain having 2 to 5 carbon atoms and a substituent. It includes any selected from the group consisting of alkylene chains having groups containing hydroxyl groups.
Further, R ¹ constituting Y shown in the general formula (1) and R ¹ constituting Z shown in the general formula (1), R ² constituting Y shown in the general formula (1), and the general formula R ² constituting Z shown in (1), L constituting Y shown in the general formula (1), and L constituting Z shown in the general formula (1) may be the same. May be different. ] The number of carbon atoms of the main chain in L (wherein the carbon number is the number of carbon atoms constituting the main chain and the carbon atoms when some or all of the carbon atoms constituting the main chain are substituted with hetero atoms) The polymerizable monomer according to any one of claims 1 to 3, wherein a sum of the numbers of 2 to 14 is 2 to 14.   A composition comprising the polymerizable monomer according to any one of claims 1 to 4 and other polymerizable monomers.   A curable composition comprising the polymerizable monomer according to claim 1, another polymerizable monomer, and a polymerization initiator.   The resin member characterized by including the hardened | cured material obtained using the polymerizable monomer as described in any one of Claims 1-4.   The other polymerizable monomer includes at least one selected from the group consisting of triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, and 1,9-nonanediol dimethacrylate. The composition as described.   The other polymerizable monomer includes at least one selected from the group consisting of triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, and 1,9-nonanediol dimethacrylate. The curable composition as described.