Set including discharge container and discharge tool including discharge structure of viscous material and viscous material

Abstract

To provide a set including a discharge container or discharge tool and viscous material, the discharge container or discharge tool including a discharge structure that can discharge a viscous material in an intended shape by reducing deformation of the viscous material at the time of discharge, and can suppress adhesion of the viscous material to an unintended portion by reducing an amount of the viscous material adhering to a nozzle distal end, and make an anti-dripping property of the viscous material preferable by reducing dripping of the viscous material.SOLUTION: Provided is a discharge structure that discharges a viscous material from a discharge port 33b. The discharge structure includes: a flow path 33a formed around a virtual center line and through which the viscous material can move; and a taper flow path 33c formed in between the flow path and the discharge port and having a cross-sectional area gradually increasing toward the discharge port.SELECTED DRAWING: Figure 12

Description

[Technical field]

[0001] The present invention relates to a set including a dispensing container or a dispensing tool having a dispensing structure for dispensing a viscous material from a dispensing port, and a viscous material. [Background technology]

[0002] In the field of dentistry, pastes such as dental filling materials and materials for making dental crowns are sometimes filled into an injector such as a compule that contains the paste inside as described in Patent Document 1, or a syringe as described in Patent Document 2, in order to optimize the amount of paste dispensed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 4,391,590 [Patent Document 2] U.S. Patent No. 5,445,523 Summary of the Invention [Problem to be solved by the invention]

[0004] In the conventional syringe tip described in Patent Document 1, due to the characteristics of the paste (viscous material), a part of the paste discharged from the discharge port of the syringe tip may adhere to the outer wall of the tip of the syringe tip, such as the annular tip surface of the syringe tip surrounding the discharge port or the outer wall along the flow path of the syringe tip via this tip surface. When the amount of viscous material adhering to the outer wall of the tip of the syringe tip increases, the viscous material falls from the outer wall of the tip of the syringe tip, and the viscous material adheres to a portion where the viscous material is not intended to be applied. Therefore, with the conventional syringe tip, there is a problem that it is difficult to apply the viscous material to a desired position. In addition, when the viscous material adhering to the outer wall of the tip of the syringe tip falls to a desired position, more viscous material than the desired amount is applied, and there is a problem that it is difficult to apply the desired amount of viscous material. In addition, when the viscous material adhering to the outer wall of the tip of the syringe tip does not fall, the adhering viscous material is discarded, resulting in a problem of low efficiency in use of the viscous material.

[0005] The object of the present invention is to provide a set comprising a dispensing container or dispensing device and a viscous material, which has a dispensing structure that reduces deformation of the viscous material during dispensing, enabling the viscous material to be dispensed in the intended shape, reduces the amount of viscous material adhering to the nozzle tip, suppresses adhesion of the viscous material to unintended areas, and reduces dripping of the viscous material to ensure good cutting of the viscous material.

[0006] Another object of the present invention is to provide a set comprising a dispensing container or dispensing device and a viscous material, which can apply a desired amount of viscous material to a desired location by reducing the amount of viscous material adhering to the outer wall portion, and preferably preventing the viscous material from adhering to the outer wall portion, thereby increasing the efficiency of use of the viscous material. [Means for solving the problem]

[0007] In one embodiment, the present invention provides a set including a viscous material and a discharge container or a discharge tool having a discharge structure for discharging the viscous material from a discharge port, The viscous material comprises (a) a polymerizable monomer and (b) a polymerization initiator; The discharge structure is as follows: a flow path formed around a virtual center line and capable of moving a viscous material; a tapered flow path formed between the flow path and the discharge port, the cross-sectional area of ​​which gradually increases toward the discharge port; A viscous material and a set of dispensing containers or dispensing devices are provided. Effect of the Invention

[0008] According to the present invention, it is possible to provide a set comprising a viscous material and a dispensing container or dispensing device having a dispensing structure that can reduce deformation of the viscous material during dispensing, thereby dispensing the viscous material in the intended shape, reduce the amount of viscous material adhering to the nozzle tip, thereby preventing the viscous material from adhering to unintended areas, and reduce dripping of the viscous material to improve cutting of the viscous material. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram showing a configuration of a set according to an embodiment; [Diagram 2] FIG. 1 is a front view of a syringe according to an embodiment; [Diagram 3] FIG. 1 is a plan view of a syringe according to an embodiment; [Figure 4] Cross section of line II in Figure 2 [Diagram 5] FIG. 1 is a front view of a push bar according to an embodiment; [Figure 6] 1 is a plan view of a push rod according to an embodiment; [Figure 7] Cross-sectional view of line III-III in Figure 5 [Figure 8] FIG. 1 is a front view of a syringe tip according to an embodiment; [Figure 9] FIG. 1 is a plan view of a syringe tip according to an embodiment; [Figure 10] Cross-sectional view of line II-II in Figure 8 [Figure 11] FIG. 1 is an enlarged cross-sectional view of a discharge port of a syringe tip according to an embodiment of the present invention; [Figure 12] Schematic diagram of a discharge port portion of a syringe tip according to an embodiment. [Figure 13] FIG. 2 is a cross-sectional view of the syringe tip and the syringe with the syringe tip attached to the tip of the syringe. [Figure 14] Schematic diagram showing the measurement target in flow value measurement [Figure 15] Front view of a two-component mixing container according to one embodiment. [Figure 16] A bottom view of a two-component mixing vessel according to one embodiment. [Figure 17] Sectional view of line IIA-IIA in Figure 16 [Figure 18] Plan view of the piston member [Figure 19] Front view of piston member [Figure 20] FIG. 13 is a perspective view showing a combined state of the partition member and the second component housing member before the piston member is inserted. [Figure 21] Front view of two-component mixing vessel with nozzle displaced [Figure 22] Bottom view of a two-component mixing vessel with nozzle displacement [Diagram 23] Sectional view of line XVIC-XVIC in Figure 22 [Figure 24] FIG. 1 is a bottom view of a two-component mixing container when a piston member is pushed by a dedicated extruder to move a partition part of a partition member toward a first bottom wall part of a housing. [Diagram 25] Sectional view of line XVIIIB-XVIIIB in Figure 24 [Figure 26] FIG. 1 is a schematic diagram showing a state in which a compule having an ejection structure according to an embodiment is attached to an ejector holder; [Figure 27] FIG. 1 is a perspective view of a computer according to one embodiment; [Figure 28] FIG. 1 is a left side view of a computer according to an embodiment; [Figure 29] Cross section of plane AA in Figure 27 [Diagram 30] FIG. 1 is an enlarged cross-sectional view of a discharge port portion in one embodiment. [Diagram 31] FIG. 1 is a side view of a cap of a Compule according to one embodiment. [Diagram 32]FIG. 1 is a cross-sectional view of a Compule according to one embodiment with a cap attached. [Diagram 33] FIG. 1 is a perspective view of a computer according to another embodiment; [Diagram 34] 1 is a left side view of a computer according to another embodiment. [Diagram 35] Cross-sectional view of plane B in Figure 33 [Diagram 36] FIG. 13 is an enlarged cross-sectional view of a discharge port according to another embodiment. [Figure 37] A perspective view of the piston [Figure 38] FIG. 1 is a schematic diagram showing the configuration of a double-syringe type injector having a discharge structure according to one embodiment; [Figure 39] Schematic diagram showing the disassembled state of the injector [Diagram 40] Sectional view of line XXXIII-XXXIII in Figure 39 [Diagram 41] XXXIV-XXXIV line cross-sectional view of FIG. [Diagram 42] Schematic cross-sectional view of a mixing element DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] In one embodiment of the set of the present invention, in a cross section including the imaginary center line, the angle between the extension direction of the peripheral wall of the flow path at the end on the discharge port side and the extension direction of the peripheral wall of the tapered flow path can be 5° to 85°.

[0011] In one embodiment of the set of the present invention, the tapered flow passage may have a frusto-conical shape.

[0012] In one embodiment of the set of the present invention, the tapered flow passage may have a cylindrical shape.

[0013] In one embodiment of the set of the present invention, the tapered flow passage and the outer peripheral wall of the discharge container or the outer peripheral wall of the discharge implement can be connected by an annular tip surface.

[0014] In one embodiment of the set of the present invention, the annular tip surface may have a circular ring shape.

[0015] In one embodiment of the set of the present invention, the viscous material can contain 0.01 to 10 parts by mass of a polymerization initiator relative to 100 parts by weight of the (a) polymerizable monomer.

[0016] In one embodiment of the set of the present invention, the viscous material may further include (c) a filler.

[0017] In one embodiment of the set of the present invention, the viscous material contains (a) a polymerizable monomer and (c) a filler in a ratio of 10:90 to 99.9:0.1, and can contain 0.01 to 10 parts by mass of a polymerization initiator per 100 parts by weight in total of the (a) polymerizable monomer and (c) filler.

[0018] In one embodiment of the set of the present invention, the viscous material may not contain (c) a filler.

[0019] In one embodiment of the set of the present invention, the viscous material may be a dental material.

[0020] In one embodiment of the set of the present invention, when the flow value (mm) of the viscous material is D, D can satisfy the following relational expression (1). D ≧ 20 (1)

[0021] In one embodiment of the set of the present invention, the discharge container or the discharge device may be a compule.

[0022] In one embodiment of the set of the present invention, the discharge container or the discharge device may be a capsule.

[0023] In one embodiment of the set of the present invention, the discharge container or the discharge device can be a syringe.

[0024] In one embodiment of the set of the present invention, the discharge container or the discharge device is a syringe, The syringe may further include a syringe tip that is attached to the tip of the syringe and has a discharge structure.

[0025] In one embodiment of the set of the present invention, the discharge container or the discharge device is a syringe, The syringe further includes a syringe tip that is attached to the tip of the syringe and has a discharge structure; The syringe has a main body portion formed in a cylindrical shape and a tip portion provided at one end of the main body portion and to which a syringe tip is attached, The tip portion can have a shape that allows it to come into contact with the nozzle portion inside the syringe tip.

[0026] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic diagram showing the configuration of a nozzle-replaceable injector 1 having a discharge structure according to one embodiment of the present invention. In this embodiment, the injector 1 includes a syringe 2 and a syringe tip 3 that is detachably screwed to a tip 21 of the syringe 2. In this embodiment, a viscous material is stored inside the syringe 2. In this embodiment, the injector 1 constitutes a set of the present invention. The syringe tip 3 of this embodiment is attached and fixed to the tip of the syringe 2 by rotating it in a predetermined direction from the tip of the syringe 2.

[0027] FIG. 2 is a front view of the syringe 2, FIG. 3 is a plan view of the syringe 2, and FIG. 4 is a cross-sectional view of the syringe 2 taken along line II in FIG. 2. The syringe 2 is sometimes referred to as a barrel. The syringe 2 is a cylindrical member centered on a central axis C1, and is made of, for example, a resin material or a glass material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, and polycarbonate. In this embodiment, the syringe 2 is made of polypropylene.

[0028] The syringe 2 of this embodiment includes a push rod 4. The push rod 4 is sometimes called a plunger. The syringe 2 of this embodiment includes a tip portion 21 having a discharge port 21a at one end, a rear end portion 22 having an insertion port 22a at one end into which the push rod 4 described below is inserted, and a main body portion 23 located between the tip portion 21 and the rear end portion 22. The outer diameter of the syringe 2 can be, for example, 3 mm to 15 mm.

[0029] The tip portion 21 of this embodiment is formed in a tapered tubular shape with a cross-sectional size decreasing toward the discharge port 21a. The dimension of the tip portion 21 in the longitudinal direction of the syringe can be, for example, 1 mm to 20 mm. The main body portion 23 of this embodiment is formed in a cylindrical shape so that the cross-sectional size is constant. The dimension of the main body portion 23 in the longitudinal direction of the syringe can be, for example, 30 mm to 150 mm. The rear end portion 22 of this embodiment is formed with a finger grip attachment portion 22b for attaching the finger grip 5. The dimension of the rear end portion 22 in the longitudinal direction of the syringe can be, for example, 1 mm to 20 mm.

[0030] The finger grip attachment portion 22b of this embodiment is composed of a pair of flange portions 22c and 22d formed around the entire circumference of the circumferential surface of the syringe 2, and eight recesses 22e formed between the pair of flange portions 22c and 22d. The pair of flange portions 22c and 22d restrict the movement of the finger grip 5 along the longitudinal direction of the syringe 2. In this embodiment, the flange portion 22d is formed larger than the flange portion 22c. In this embodiment, the flange portion 22d is formed at the rear end of the rear end portion 22. Eight protrusions (not shown) provided in a hollow portion (not shown) of the finger grip 5 are fitted into the eight recesses 22e. This fitting restricts the finger grip 5 from rotating in the circumferential direction of the syringe 2.

[0031] Inside the syringe 2, a hollow portion 24 is formed around the central axis C1 over the entire longitudinal direction, for storing a viscous material therein. At the tip 21, the hollow portion 24 is formed in a tapered shape in which the size of the cross section decreases toward the discharge port 21a. Specifically, at the tip 21, the hollow portion 24 is composed of a first tapered portion 24a, a first cylindrical portion 24b, a second tapered portion 24c, and a second cylindrical portion 24d. One end of the first tapered portion 24a is continuous with the main body portion 23, and the size of the cross section is configured to be smaller than the size of the cross section at the main body portion 23 toward the discharge port 21a. One end of the first cylindrical portion 24b is continuous with the first tapered portion 24a, and the size of the cross section is configured to be constant, for example, to have an inner diameter of 0.1 mm to 13 mm. One end of the second tapered portion 24c is continuous with the cylindrical portion 24b, and the size of the cross section is configured to become smaller from the size of the cross section at the cylindrical portion 24b toward the discharge port 21a. One end of the second cylindrical portion 24d is continuous with the second tapered portion 24c, and the other end is in communication with the discharge port 21a, and the size of the cross section is constant, for example, with an inner diameter of 0.1 mm to 10 mm.

[0032] In the main body 23, the hollow section 24 is formed in a cylindrical shape with a constant cross-sectional size, for example, an inner diameter of 0.1 mm to 13 mm. In the rear end 22, the hollow section 21 is formed in a cylindrical shape with a constant cross-sectional size, for example, an inner diameter of 0.1 mm to 15 mm. Particularly in this embodiment, in the rear end 22, the hollow section 21 is formed in a portion continuous with the insertion opening 22a, in which the cross-sectional size slightly increases toward the insertion opening 22a, in order to facilitate the insertion of the push rod 4.

[0033] In the syringe 2 of this embodiment, a syringe tip mounting portion 25 is formed on the outer periphery of the tip portion 21. In this embodiment, the syringe tip mounting portion 25 is provided in an annular shape centered on the central axis C1. In this embodiment, the syringe tip mounting portion 25 is formed integrally with the syringe 2.

[0034] The syringe chip mounting part 25 of this embodiment has the same outer diameter as the main body part 23, and the outer peripheral surface 25a of the syringe chip mounting part 25 is configured to be substantially flush with the outer peripheral surface 23a of the main body part 23. The syringe chip mounting part 25 of this embodiment is provided so that a gap is formed between the inner peripheral surface 25b of the syringe chip mounting part 25 and the outer peripheral surface 21b of the tip part 21. The inner peripheral surface 25b of the syringe chip mounting part 25 of this embodiment is provided with a female thread. The syringe chip mounting part 25 of this embodiment is formed so that the inner peripheral surface 25b becomes slightly smaller in diameter as it reaches the tip side in the longitudinal direction. The tip part 21 is extended toward the tip side in the longitudinal direction from the syringe chip mounting part 25.

[0035] The tip portion 21 of the syringe 2 of this embodiment has a shape capable of abutting against a cylindrical portion of the syringe tip 3 in the syringe tip 3 described later. Specifically, an end face 21c on the longitudinal tip side of the tip portion 21 of the syringe 2 of this embodiment is formed to be capable of abutting against an end face on the longitudinal rear end side of the cylindrical portion of the syringe tip 3.

[0036] 5 is a front view of the push bar 4 of this embodiment, FIG. 6 is a plan view of the push bar 4 of this embodiment, and FIG. 7 is a cross-sectional view of the push bar 4 taken along line III-III in FIG.

[0037] The push rod 4 is a member for pushing the viscous material contained in the syringe 2 toward the tip 21 (i.e., the discharge port 21a) of the syringe 2, and is made of, for example, a resin material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the push rod 4 is made of low-density polyethylene.

[0038] The push rod 4 of this embodiment has a hollow cylindrical main body 41, a seal portion 42 formed at one end of the main body, and a finger hook portion 43 formed at the other end of the main body.

[0039] The main body 41 has an outer diameter smaller than the inner diameter of the syringe 2. Therefore, when the push rod 4 is housed in the syringe 2, a gap is generated between the main body 41 and the syringe 2.

[0040] The seal portion 42 is disk-shaped, and its outer peripheral end is in slidable and fluid-tight contact with the inner peripheral surface of the syringe 2. Although the seal portion 42 and the main body portion 41 are integrated as one component, the seal portion 42 and the main body portion 41 may be separate components.

[0041] In addition, since the outer peripheral end of the seal portion 42 is in fluid-tight contact with the inner peripheral surface of the syringe 2, the seal portion 42 has an outer diameter larger than the inner diameter of the syringe 2. The outer diameter of the seal portion 42 is larger than the outer diameter of the main body portion 41.

[0042] The viscous material contained in the syringe can be, for example, a dental material. A specific example of the viscous material is one that contains, for example, (a) a polymerizable monomer and (b) a polymerization initiator. In this case, the viscous material can contain, for example, 0.01 to 10 parts by mass of the polymerization initiator relative to 100 parts by weight of the (a) polymerizable monomer. In this case, the viscous material can contain (c) a filler. Also, the viscous material can not contain (c) a filler. When the viscous material contains (c) a filler, the viscous material can contain, for example, the (a) polymerizable monomer and the (c) filler in a ratio of 10:90 to 99.9:0.1, and can contain 0.01 to 10 parts by mass of the polymerization initiator relative to a total of 100 parts by weight of the (a) polymerizable monomer and the (c) filler.

[0043] The ratio of (a) the polymerizable monomer and (c) the filler can be from 10:90 to 60:40. By setting the ratio of the filler to (a) the polymerizable monomer and (c) the filler to 40 or more, it is possible to avoid the problem of the viscous material having a low viscosity and being unable to obtain sufficient shaping ability, which has the advantage of making it easier to use as a dental material. By setting the ratio of the filler to 90 or less in the ratio of (a) polymerizable monomer and (c) filler, it is possible to prevent the viscosity of the viscous material from becoming too high, which would result in low fluidity, and to avoid the viscous material becoming difficult to push out from the syringe tip. It is also possible to avoid the viscous material becoming difficult to cut off, which would result in the viscous material becoming easily stringy.

[0044] [(a) Polymerizable monomer] The polymerizable monomer (a) contained in the viscous material used in the present invention can be used without any restriction as long as it is a known one. In the polymerizable monomer or compound having a polymerizable group described in the present invention, the polymerizable group is preferably one that exhibits radical polymerizability, and specifically, from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic group and / or acrylamide group can also be preferably used. Examples of such polymerizable monomers include those having one radical polymerizable group, those having two radical polymerizable groups, those having three or more radical polymerizable groups, those having an acidic group, an alkoxysilyl group, and those having a sulfur atom.

[0045] Specific examples of polymerizable monomers having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N -hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl) (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, (meth)acrylamide, and the like.

[0046] Specific examples of polymerizable monomers having two radical polymerizable groups and no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxyphenyl)propane. 2-(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,Examples include 4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, etc.

[0047] Specific examples of polymerizable monomers having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0048] [(a1) Polymerizable monomer having an acidic group] The viscous material used in the present invention can contain (a1) a polymerizable monomer having an acidic group. (a1) The polymerizable monomer having an acidic group can be used without limitation as long as it has one or more polymerizable groups and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group. (a1) By containing a polymerizable monomer having an acidic group, when the viscous material is a dental material, it is possible to impart adhesion to tooth structure and prosthetic devices. Furthermore, when a basic filler is contained in the viscous material, it is expected that the stability of the hardened body of the viscous material is improved.

[0049] Specific examples of polymerizable monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyethyl dihydrogen phosphate, 9-(meth)acryloyloxypropyl dihydrogen phosphate, 10-(meth)acryloyloxybutyl dihydrogen phosphate, 11-(meth)acryloyloxybutyl dihydrogen phosphate, 12-(meth)acryloyloxybutyl dihydrogen phosphate, 13-(meth)acryloyloxypentyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth)acryloyloxyhexyl dihydrogen phosphate, 25-(meth)acryloyloxyhexyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27-(meth)acrylo Acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di( Examples of the acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0050] Specific examples of polymerizable monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl]pyrophosphate, bis[4-(meth)acryloyloxybutyl]pyrophosphate, bis[6-(meth)acryloyloxyhexyl]pyrophosphate, bis[8-(meth)acryloyloxyoctyl]pyrophosphate, bis[10-(meth)acryloyloxydecyl]pyrophosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0051] Specific examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, and 9-(meth)acryloyloxyhexyl dihydrogen thiophosphate. Examples of the acryloyloxynonyl dihydrogen thiophosphate include 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0052] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0053] Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl(meth)acrylate, and the like.

[0054] Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, and 4-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4 ...4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth) Examples of the acid anhydride and acid halide of these compounds include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0055] The amount of the (a1) polymerizable monomer having an acidic group in the viscous material used in the present invention is 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers contained in the viscous material, from the viewpoint of imparting adhesiveness when the viscous material is a dental material. If the amount is less than 1 part by mass, adhesiveness to teeth, metals, and metal oxides may not be fully exhibited, and if the amount is 30 parts by mass or more, storage stability may be reduced.

[0056] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyl trimethoxysilane, 3-(meth)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropyl methyl dimethoxysilane, 4-(meth)acryloxybutyl trimethoxysilane, 5-(meth)acryloxypentyl trimethoxysilane, 6-(meth)acryloxyhexyl trimethoxysilane, 7-(meth)acryloxyheptyl trimethoxysilane, 8-(meth)acryloxyoctyl trimethoxysilane, 9-(meth)acryloxynonyl trimethoxysilane, 10-(meth)acryloxydecyl trimethoxysilane, and 11-(meth)acryloxyundecyl trimethoxysilane.Furthermore, examples of compounds having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate. acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecane-19-yl)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecan-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, and 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0057] The viscous material used in the present invention may contain a polymerizable monomer having a sulfur atom as a polymerizable monomer (a) in order to impart adhesion to precious metals when the viscous material is a dental material. The polymerizable monomer having a sulfur atom may be any known compound without any restrictions, so long as it is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specifically, it refers to a compound having a partial structure such as -SH, -SS-, >C=S, >CSC<, >P=S, or a compound resulting from tautomerization. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0058] In addition to these polymerizable monomers, there is no limitation in using oligomers or prepolymers having at least one polymerizable group in the molecule. In addition, there is no problem in having a substituent such as a fluoro group in the same molecule. The above-mentioned polymerizable monomers can be used alone or in combination.

[0059] The viscous material used in the present invention may contain a silane coupling agent as a polymerizable monomer (a) in order to impart adhesion to glass ceramics when the viscous material is a dental material. Any known silane coupling agent may be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, etc. are preferred. From the viewpoint of imparting adhesion when the viscous material is a dental material, the blending amount is 1 part by mass or more, more preferably 5 parts by mass or more and less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the viscous material. The silane coupling agent as a polymerizable monomer is blended separately from the surface treatment agent for the filler, since the purpose of the silane coupling agent is to impart adhesion to glass ceramics or resin materials containing a filler made of glass ceramics.

[0060] The viscous material used in the present invention may contain a polymerizable monomer having a sulfur atom as a polymerizable monomer (a) in order to impart adhesiveness to precious metals when the viscous material is a dental material. The amount of the polymerizable monomer having a sulfur atom is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more and less than 10 parts by mass, based on the total amount of 100 parts by mass of the polymerizable monomers contained in the viscous material in terms of imparting adhesiveness.

[0061] The viscous material may be free of polymerizable monomers having an acidic group, and the viscous material may be free of polymerizable monomers not having an acidic group.

[0062] [(b) Polymerization initiator] The polymerization initiator is not particularly limited, and known polymerization initiators, such as radical generators, can be used without any restrictions. Polymerization initiators are roughly classified into those that start polymerization by mixing immediately before use (chemical polymerization initiators), those that start polymerization by heating or warming (thermal polymerization initiators), and those that start polymerization by light irradiation (photopolymerization initiators). Any of the polymerization initiators can be used without any restrictions in the viscous material used in the present invention. Moreover, these polymerization initiators can be used alone or in combination with a plurality of them, regardless of the polymerization mode or polymerization method. Furthermore, these polymerization initiators can be used without any problems even if they are subjected to secondary treatment such as encapsulation in microcapsules to realize polymerization stabilization or polymerization delay. Among these polymerization initiators, it is preferable to use a thermal polymerization initiator.

[0063] As the chemical polymerization initiator, a redox type polymerization initiator system consisting of organic peroxide / amine compound, organic peroxide / amine compound / sulfinate, organic peroxide / amine compound / barbituric acid or barbituric acid derivative, organic peroxide / amine compound / borate compound, or an organometallic type polymerization initiator system that reacts with oxygen or water to initiate polymerization, may be used. Sulfinate salts and borate compounds can also be used because they can initiate polymerization by reacting with a polymerizable monomer having an acidic group. Specific examples of chemical polymerization initiators are shown below, but are not limited to these.

[0064] Examples of organic peroxides include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, peroxy dicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of peroxy esters include α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxy pivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxy isophthalate, di-t-butyl peroxy hexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxy acetate, t-butyl peroxy benzoate, and t-butyl peroxy malelic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy)parate, and 1,1-di(t-amylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, and diallylperoxydicarbonate, etc. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, etc.

[0065] The viscous material used in the present invention may be one of the exemplified organic peroxides or a combination of two or more of them. Among these organic peroxides, diacyl peroxides, peroxy esters, and hydroperoxides are preferred from the viewpoint of curability, and for example, benzoyl peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and t-butylperoxy-3,3,5-trimethylhexanoate are preferred. From the viewpoint of improving curability, the organic peroxide as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer (a). In addition, if the amount of the organic peroxide is more than 5 parts by mass, it may be difficult to ensure sufficient operation time, while if the amount of the organic peroxide is less than 0.1 parts by mass, the mechanical strength may be insufficient.

[0066] Specific examples of the amine compound include secondary or tertiary amines in which an amine group is bonded to an aryl group, and specific examples include pN,N-dimethyl-toluidine, N,N-dimethylaniline, N-β-hydroxyethyl-aniline, N,N-di(β-hydroxyethyl)-aniline, pN,N-di(β-hydroxyethyl)-toluidine, N-methyl-aniline, and pN-methyl-toluidine.

[0067] Specific examples of sulfinic acid salts include sodium benzenesulfinate, lithium benzenesulfinate, and sodium p-toluenesulfinate.

[0068] Specific examples of barbituric acid and its derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-tert-butylbarbituric acid, 1,3-dimethyl- Examples of barbituric acids include 5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, as well as salts thereof (particularly preferred are salts of alkali metals or alkaline earth metals), such as sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, calcium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0069] Specific examples of borate compounds include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, and tetramethylammonium salts of trialkylphenylboron and trialkyl(p-chlorophenyl)boron (wherein the alkyl group is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like).

[0070] Further, specific examples of organometallic polymerization initiators include organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide.

[0071] Specific examples of perborates include sodium perborate, potassium perborate, ammonium perborate, etc., specific examples of permanganates include ammonium permanganate, potassium permanganate, sodium permanganate, etc., and specific examples of persulfates include ammonium persulfate, potassium persulfate, sodium persulfate, etc. As the thermal polymerization initiator by heating or warming, in addition to the above organic peroxides, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, azobiscyanovaleric acid, etc. are preferably used.

[0072] Specific examples of the thermal polymerization initiator that can be suitably used include organic peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate, and azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid. Among these, the use of organic peroxides is preferred, and benzoyl peroxide is more preferred.

[0073] These polymerization initiators do not require secondary processing to control the polymerization characteristics or ensure stability. There are no limitations on the type of coating that can be used.

[0074] The photopolymerization initiator includes a photosensitizer, a photoacid generator, a photopolymerization accelerator, and the like, which may be used alone or in combination of two or more.

[0075] Specific examples of photosensitizers include α-diketones such as benzil, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthone; 2-chlorophenyl ether; and the like. Thioxanthones such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, and other benzophenones; bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, ... bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, Bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide acylphosphine oxides such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium; acylgermanium compounds such as 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1; α-aminoacetophenones such as benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal), and other ketals; and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0076] The photosensitizer can be appropriately selected according to the wavelength, intensity, and light irradiation time of the light used for polymerization, and the type and amount of other components to be combined. The photosensitizer can be used alone or in combination of two or more kinds. Among them, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid are more preferably used, and camphorquinone is particularly preferred because it is easily available.

[0077] The amount of the photosensitizer is preferably 0.02 to 1.0 parts by mass, more preferably 0.05 to 0.5 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (a) contained in the viscous material. If the amount of the photosensitizer is less than 0.02 parts by mass, the polymerization activity to the irradiated light may be poor, resulting in insufficient curing. If the amount of the photosensitizer is more than 1.0 part by mass, sufficient curing properties are exhibited, but the environmental light stability is shortened and the yellowing increases. The viscous material used in the present invention may contain only an α-diketone compound as a photosensitizer.

[0078] The photoacid generator may be any known compound without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. More preferred are iodonium salt compounds. Iodonium salt compounds are easily sensitized by photosensitizers that have absorption in the visible light region.

[0079] Specific examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples of the 6-bis(trichloromethyl)-s-triazine include 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0080] Any known iodonium salt compound can be used. To give a specific example, the structural formula of an iodonium salt compound can be represented by the following formula (13). [Formula (13)] [(R1)2I] + [A] - (In the formula, [(R1)2I] + is the cationic portion, [A] - is an anion moiety, and R1 in formula (13) represents an organic group bonded to I, and R1 may be the same or different. R1 represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen.

[0081] In the above, examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as a phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0082] Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and condensed polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0083] Specific examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0084] Specific examples of alkenyl groups having 2 to 30 carbon atoms include straight-chain or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0085] Furthermore, specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0086] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one type of substituent, and specific examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, and octadecyl; branched alkyl groups having 1 to 18 carbon atoms, such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups having 3 to 18 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, aryl ... Linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; phenoxycarbonyl aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, 4-(ptert-butylbenzoyl)phenylthio, etc.; linear or branched alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; Examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0087] Among the iodonium salt compounds, aryl iodonium salts are preferred because they are highly stable. In addition, it is preferred that the aryl group has a substituent in order to improve fat solubility. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, or functional groups in which one or more H of these groups are replaced with F, perfluoroalkyl groups, and halogens are preferred as the substituent.

[0088] The structure of the anion portion of the iodonium salt compound is not particularly limited, but examples include those having atoms such as halogen, P, S, B, Al, and Ga. From the viewpoint of safety, anions having As or Sb can be used, but are not preferred for dental applications. In addition, the anion preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group, and more preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Since the iodonium salt compound having such an anion has high solubility in viscous materials, it is expected to prevent precipitation during low-temperature storage or long-term storage, and to shorten the manufacturing time because it dissolves in the composition in a short time. In addition, an iodonium salt compound consisting of an anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which one or more H is substituted with F can be expected to have even higher solubility. If the photoacid generator precipitates, it may cause a decrease in light color stability and a decrease in bending strength, which is not preferred. As the anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one or more H may be substituted with F, an anion having any atom can be used. From the viewpoints of versatility and safety, however, an anion having P, S, B, Al or Ga is preferable.

[0089] Examples of anions having no alkyl group and / or alkoxy group and / or aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenolate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, etc. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

[0090] [A] of the iodonium salt compound of formula (13) - In order to improve the solubility in viscous materials, the anion part of the iodonium salt compound of formula (13) is preferably an anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H is substituted with F. Specifically, [A] of the iodonium salt compound of formula (13) is - The alkyl group in the anion portion preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 4 or more, and preferably the ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 9 or more. More preferably, all hydrogen atoms in the hydrocarbon are substituted with fluorine. The viscous material may contain an iodonium salt consisting of an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0091] Further specific examples of the alkyl group include linear or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0092] [A] of the iodonium salt compound of formula (13) - The alkoxy group in the anion portion preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, and tert-butoxy. The ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 4 or more, and preferably the ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 9 or more. More preferably, all of the hydrogen atoms in the hydrocarbon are substituted with fluorine. The viscous material may contain an iodonium salt consisting of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0093] Further specific examples of alkoxy groups include linear or branched perfluoroalkoxy groups such as CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2CF2O.

[0094] [A] of the iodonium salt compound of formula (13) -The phenyl group in the anion moiety has at least one hydrogen atom substituted with a fluorine atom, and / or an alkyl group and / or an alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Particularly preferred specific examples of the phenyl group include perfluorophenyl groups such as pentafluorophenyl group (CF5), trifluorophenyl group (CHF3), tetrafluorophenyl group (CHHF4), trifluoromethylphenyl group (CF3C6H4), bis(trifluoromethyl)phenyl group ((CF3)2C6H3), pentafluoroethylphenyl group (CF3CF2C6H4), bis(pentafluoroethyl)phenyl group ((CF3CF2)2C6H3), trifluoromethylfluorophenyl group (CF3C6H3F), bistrifluoromethylfluorophenyl group ((CF3)2C6H2F), pentafluoroethylfluorophenyl group (CF3CF2C6H3F), and bispentafluoroethylfluorophenyl group ((CF3CF2)2C6H2F). An iodonium salt consisting of an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms may be blended in the viscous material.

[0095] [A] of the iodonium salt compound of formula (13) - A specific example of the anion portion of the anion having P is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - The anion containing S is [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [CF3CF2CF2CF2SO3] - , [CF3CF2CF2SO3] - , [(CF3CF2SO2)3C] - , [(SO2CF3)3N] - , [(SO2CF2CF3]2N] - , [((CF3)C6H4)SO3] - , [SO3((CF2CF2CF2CF2)SO3] 2- Examples of anions containing B include [B(C6F5)4] - , [(C6H5)B((CF3)2C6H3)3] - , [(C6H5)B(C6F5)3] - , etc. An anion containing Ga is [((CF3)4Ga)] - , [Ga(C6F5)4] - Examples of anions containing Al include [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - etc.

[0096] The viscous material used in the present invention preferably contains 0.1 to 10 parts by mass of a photoacid generator relative to 100 parts by mass of the total amount of the polymerizable monomer (a), more preferably 0.2 to 5 parts by mass. If the amount of the photoacid generator is less than 0.1 parts by mass, the expected polymerization promotion ability may not be exhibited, resulting in insufficient curing. If more than 10 parts by mass is incorporated, sufficient curing properties may be exhibited, but the environmental light stability may be reduced, shortening the operating time, or discoloration may increase, such as the cured product turning brown.

[0097] The photoacid generator that can be used in the viscous material used in the present invention is not limited to the photoacid generators shown in the specific examples, and two or more types can be used in combination.

[0098] The viscous material used in the present invention may contain only an aryliodonium salt, which is a salt of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga, and an aryliodonium cation, as a photoacid generator.The viscous material used in the present invention may contain only a salt of an anion having an organic group in which at least one H is substituted with F, and one or more atoms of P, B, Al, S, or Ga, and an aryliodonium cation, as a photoacid generator.

[0099] The polymerization accelerator used in the present invention is not particularly limited as long as it has a polymerization accelerator ability, and for example, known polymerization accelerators generally used in the dental field can be used without any restrictions. As the polymerization accelerator, aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, phosphine compounds, organometallic compounds, transition metal compounds of the fourth period, thiourea derivatives, sulfinic acid and its salts, borate compounds, sulfur-containing reductive inorganic compounds, nitrogen-containing reductive inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds, etc. can be used as photopolymerization accelerators and / or chemical polymerization accelerators. Each compound can be used as an accelerator for photopolymerization and chemical polymerization, but those that can be used as photopolymerization accelerators in particular are amine compounds, phosphine compounds, sulfinic acid and its salts, and organometallic compounds, and those that can be used as chemical polymerization accelerators in particular can be classified as aromatic amine compounds, phosphine compounds, organometallic compounds, transition metal compounds of the fourth period, thiourea derivatives, sulfinic acid and its salts, borate compounds, sulfur-containing reductive inorganic compounds, nitrogen-containing reductive inorganic compounds, barbituric acid derivatives, triazine compounds, and halogen compounds.

[0100] Aromatic amine compounds refer to compounds in which one or more H atoms of ammonia (NH3) are substituted with an aromatic ring. Compounds in which one H atom of NH3 is substituted with an aromatic ring are classified as aromatic primary amine compounds, compounds in which one H atom of NH3 is substituted with an aromatic ring and another H atom is substituted with an aromatic ring or an alkyl group are classified as aromatic secondary amine compounds, and compounds in which one H atom of NH3 is substituted with an aromatic ring and two other H atoms are substituted with aromatic rings or alkyl groups are classified as aromatic tertiary amine compounds.

[0101] Specific examples of aromatic primary amine compounds include aniline, etc., specific examples of aromatic secondary amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, N-phenylglycine and other N-protected amino acids (esters), etc., and specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid. , p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic acid methyl ester, N,N-dihydroxyethyl aniline, N,N-diisopropanol aniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, etc. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

[0102] The phosphine compound refers to a compound in which the P atom is substituted with three organic groups, and the aromatic phosphine compound refers to a compound in which the P atom is substituted with a phenyl group which may have one or more substituents. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenylphosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, and 2-(phenylphosphino)benzoic acid. Acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, bis[2-(diphenylphosphino)phenyl]ether, etc. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0103] Aliphatic amine compounds are compounds in which one or more H in ammonia (NH3) is replaced by an alkyl group. The alkyl group is classified as follows: CH3- or -CH2- is a primary alkyl group, -CH2- with one H substituted is a secondary alkyl group, -CH2- with two H substituted is a tertiary alkyl group. Aliphatic amines are classified as aliphatic primary amine compounds in which one H in NH3 is replaced by an alkyl group, aliphatic secondary amine compounds in which two H in NH3 are replaced by alkyl groups, and aliphatic tertiary amine compounds in which three H in NH3 are replaced by alkyl groups.

[0104] Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids such as glycine, or amino acid esters. Specific examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids, or N-benzyl-protected amino acid esters. Specific examples of aliphatic tertiary amine compounds include tributylamine, tripropylamine, triethylamine, N,N-Dimethylhexylamine, N,N-Dimethyldodecylamine, N,N-Dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-Dimethylformamide dimethyl acetal, N,N-Dimethylacetamide dimethyl acetal, N,N-Dimethylformamide diethyl acetal, N,N-Dimethylformamide dipropyl acetal, N,N-Dimethylformamide di-tert-butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-Dimethylethanolamine, N,N- Dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N ,N-Dimethyl-2,3-dihydroxypropylamine, N,N-Diethylethanolamine, 1-Methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidine, 1-Isopropyl-3-pyrrolidinol, 1-Piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-Dimethylglycine, N,N-Dimethylglycine methyl, N,N-Diethylglycine methyl, N,N-Dimethylglycine ethyl, N,N-Diethylglycine sodium, 2-(Dimethylamino)ethyl acetate, N-Methyliminodiacetic acid, N,Examples of the amines include N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, and triallylamine.

[0105] Specific examples of organometallic compounds include organometallic compounds containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably organometallic compounds containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimaleate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, dioctyl-tin-diversatate, dioctyl-tin-S,S'-bis-isooctylmercaptoacetate, and tetramethyl-1,3-diacetoxydistannoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetate. Examples of the organometallic compounds containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octylate, copper stearate, and copper acetate.

[0106] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, and trivalent or tetravalent vanadium compounds having higher polymerization promoting ability are more preferred, and tetravalent vanadium compounds are most preferred. These fourth period transition metal compounds may be used in combination of a plurality of types as necessary. The blending amount of the transition metal compound is preferably 0.0001 to 1 part by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A). If the blending amount is less than 0.0001 part by mass, the polymerization promoting effect may be insufficient, and if the blending amount exceeds 1 part by mass, discoloration or gelation of the viscous material may occur, resulting in reduced storage stability.

[0107] Specific examples of thiourea derivatives include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea, etc. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. These thiourea derivatives may be used in combination as necessary. The amount of the thiourea derivative to be blended is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). If the amount is less than 0.1 part by mass, the polymerization-promoting ability may be insufficient, and if the amount is more than 5 parts by mass, the storage stability may decrease.

[0108] Specific examples of sulfinic acid and its salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, Examples of the sulfinic acid salt include sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, and calcium 2,4,6-triisopropylbenzenesulfinate. Of these, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

[0109] Specific examples of borate compounds having one aryl group per molecule include trialkylphenyl boron, trialkyl(p-chlorophenyl) boron, trialkyl(p-fluorophenyl) boron, trialkyl(3,5-bistrifluoromethyl) phenyl boron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, trialkyl(p-nitrophenyl) boron, trialkyl(m-nitrophenyl) boron, trialkyl(p-butylphenyl) boron, trialkyl(m-butylphenyl) boron, trialkyl(p-butylphenyl) boron, Examples of the alkyl group include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like).Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl). )boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), as well as sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts.Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri( Examples of the alkyl group include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, and the like).Specific examples of borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis(p-chlorophenyl) boron, tetrakis(p-fluorophenyl) boron, tetrakis(3,5-bistrifluoromethyl)phenyl boron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl] boron, tetrakis(p-nitrophenyl) boron, tetrakis(m-nitrophenyl) boron, tetrakis(p-butylphenyl) boron, tetrakis(m-butylphenyl) boron, tetrakis(p-butyloxyphenyl) boron, tetrakis(m-butyloxyphenyl) boron, tetrakis(p-octyloxyphenyl) boron, and tetrakis(m Examples of the suitable aryloxyphenyl)boron include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron.

[0110] Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. In addition, these aryl borate compounds can be used alone or in combination of two or more kinds.

[0111] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0112] The nitrogen-containing reducing inorganic compound may be a nitrite, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0113] Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propyl ... Examples of the salts of barbituric acids include pyrubarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids (preferably salts of alkali metals or alkaline earth metals). Specific examples of the salts of barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0114] Specific examples of the halogen compound include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, and dilauryl dimethyl ammonium bromide.

[0115] The polymerization accelerator is preferably contained in an amount of 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (a) contained in the viscous material. If it is less than 0.2 parts by mass, the mechanical strength may be insufficient. If it is blended in an amount of more than 10 parts by mass, although sufficient curability is obtained, the ambient light stability may be shortened, and discoloration of the cured body, such as brownish or yellowish, may increase, which is not preferable.

[0116] These photosensitizers, photoacid generators, organic peroxides, and polymerization accelerators may be subjected to secondary treatments such as fine pulverization, carrier adsorption, and encapsulation in microcapsules, if necessary, without any problems. Furthermore, these various types of photopolymerization initiators may be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

[0117] [(c) Filler] The filler may be, for example, a known filler generally used in dental materials. Examples of the filler include inorganic fillers, organic fillers, and organic-inorganic composite fillers, and these may be used alone or in combination regardless of the type of filler.

[0118] Specific examples of inorganic fillers include silica, aluminum silicate, alumina, titania, zirconia, various glasses (including fluorine glass, borosilicate glass, soda glass, barium glass, barium aluminum silica glass, glass containing strontium or zirconium, glass ceramics, fluoroaluminosilicate glass, and synthetic glass by the sol-gel method), Aerosil (registered trademark), calcium fluoride, strontium fluoride, calcium carbonate, kaolin, clay, mica, aluminum sulfate, calcium sulfate, barium sulfate, titanium oxide, calcium phosphate, hydroxyapatite, calcium hydroxide, strontium hydroxide, zeolite, etc. These inorganic fillers may be used as aggregates, and examples thereof include silica-zirconia composite oxide aggregates obtained by mixing silica sol and zirconia sol, spray drying and heat treatment.

[0119] Examples of organic fillers include elastomers such as polyvinyl acetate, polyvinyl alcohol, and styrene-butadiene rubber; non-crosslinkable (meth)acrylate polymers which are homopolymers of monofunctional (meth)acrylate polymerizable monomers such as polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate; crosslinkable (meth)acrylate polymers obtained by copolymerizing a monofunctional (meth)acrylate polymerizable monomer with a polymerizable monomer having two or more functional groups; polyvinyl acetate, polyethylene glycol, polypropylene glycol, and polyvinyl alcohol, but are not limited to these.

[0120] Examples of organic / inorganic composite fillers include, but are not limited to, fillers whose surfaces are polymerized and coated with a polymerizable monomer, fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to a suitable particle size, and fillers obtained by dispersing a filler in a polymerizable monomer in advance and subjecting the resulting mixture to emulsion polymerization or suspension polymerization.

[0121] These fillers can be any shape, such as spherical, needle-like, plate-like, crushed, or scaly. The average particle size of the filler varies depending on the type of filler. In the case of inorganic fillers, fillers having a particle size in the range of 0.05 to 200 μm can be used, preferably in the range of 0.5 to 100 μm, and more preferably in the range of 1 to 20 μm. In the case of organic-inorganic composite fillers, fillers having a particle size in the range of 0.05 to 150 μm can be used, preferably in the range of 0.5 to 100 μm, and more preferably in the range of 1 to 20 μm. In the case of organic fillers, there is no particular restriction on the average particle size, and fillers having an average particle size in any range can be used. The information on the average particle size can be obtained by a laser diffraction particle size measuring device. When the filler is an aggregate, the average particle size is the average particle size of the aggregate. In addition, the average particle size of the filler is preferably 0.5 to 100 μm, and more preferably in the range of 1 to 20 μm. The average particle size, the coefficient of variation of the particle size, and other information can be obtained by a laser diffraction particle size analyzer. If the filler is an aggregate, the above average particle size is the average particle size of the aggregate. If the average particle size is less than 0.5 μm, the viscous material may become sticky and air bubbles may easily be mixed in. If it exceeds 100 μm, the filler may easily settle in the viscous material and may not be uniformly dispersed.

[0122] Furthermore, the surface of the filler may be multifunctionalized by a surface treatment method using a surface treatment agent, etc., and these surface-treated fillers can be used without any restrictions. Specific examples of surface treatment agents used to multifunctionalize the surface of the filler include surfactants, fatty acids, organic acids, inorganic acids, various coupling agents (titanate coupling agents, aluminate coupling agents, and silane coupling agents), metal alkoxide compounds, etc. Specific examples of surface treatment methods include a method of spraying a surface treatment agent from above while the filler is in a flowing state, a method of dispersing the filler in a solution containing a surface treatment agent, and a method of multi-layer treatment of the filler surface with several types of surface treatment agents. However, the surface treatment agents and surface treatment methods are not limited to these. In addition, these surface treatment agents and surface treatment methods can be used alone or in a complex combination.

[0123] These fillers may be surface-treated with a known titanate coupling agent, aluminate coupling agent, or silane coupling agent without any problem. Examples of silane coupling agents include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane. γ-methacryloxypropyltrimethoxysilane is preferably used. The surface treatment of the aggregates and fillers may be performed with the same type of coupling agent or with a different type of coupling agent.

[0124] When the flow value (mm) of the viscous material is D, D can be made to satisfy the following relational expression (1). Flow value D≧20 (1)

[0125] By satisfying this relationship, the force exerted when discharging the viscous material can be reduced, the viscous material can be easily released from the syringe tip, and voids caused by the viscous material flowing into the unevenness of the cavity can be prevented from being created. In addition, air bubbles are less likely to be mixed into the viscous material.

[0126] Furthermore, when the flow value (mm) of the viscous material is D, D can be made to satisfy the following relational expression (2). 70≧D (2)

[0127] By satisfying such a relational expression, it is possible to obtain the effect that dripping does not occur and the intended amount of ink can be ejected.

[0128] In this specification, the flow value is an index showing the degree of pressure flow, and can be measured by the following steps 1 to 4.

[0129] Step 1: A cellophane sheet (disc-shaped) is inserted into a cylindrical glass tube (inner diameter 7.5 mm).

[0130] Step 2: The sample-filled section (volume 309 mm) at the top of the cylindrical glass tube (inner diameter 7.5 mm) 3 ) is filled with the sample while being careful not to trap air bubbles, and the top surface of the filled sample is made flat using a plastic spatula so that it fits snugly against the cylindrical glass tube.

[0131] Step 3: After removing the cylindrical glass tube, insert a glass rod from the side opposite the filled section and gently push the sample onto a 50 x 50 x 1 mm glass plate.

[0132] Step 4: Transfer this glass plate to a loader, place a glass plate of the same size on the sample, and at the same time gently apply the weight (385 gf) of the loader and leave for 3 minutes. After 3 minutes, remove the weight and use graph paper to select any point on the sample spread between the glass plates and determine the tangent. Determine a tangent parallel to that tangent and measure the dimension between the parallel tangents (see Figure 14). Measure the dimension between parallel tangents perpendicular to that parallel tangent. These two points are designated as Amm and Bmm, and the pressure flow rate (flow value) is calculated using the following formula. Pressure flow rate (mm)=(A+B) / 2 Note that the value is valid only when |AB|≦1 mm, and if |AB|>1 mm, the measurement is to be repeated. This procedure was carried out twice for each sample, and the average value was taken as the flow value.

[0133] Figure 8 is a front view of a syringe chip of one embodiment, Figure 9 is a plan view of a syringe chip of one embodiment, Figure 10 is a cross-sectional view along line II-II of Figure 8, Figure 11 is an enlarged cross-sectional view of the outlet portion of a syringe chip of one embodiment, Figure 12 is a schematic diagram of the outlet portion of a syringe chip of one embodiment, and Figure 13 is a cross-sectional view of the syringe chip and syringe with the syringe chip attached to the tip of the syringe.

[0134] The syringe tip 3 of this embodiment is attached to the tip of the syringe 2 that contains a viscous material and discharges the viscous material. The syringe tip 3 has a syringe engaging portion 31 that engages with the syringe 2, a cylindrical portion 32 that has a hollow portion 32a centered on the imaginary center line IC and is held by the user when engaging the syringe tip 3 with the syringe 2, and a nozzle portion 33 that discharges the viscous material contained in the syringe 2.

[0135] In this specification, the virtual center line of the hollow portion means a line connecting the maximum Feret diameter in the cross section of the hollow portion perpendicular to the nozzle direction from the engagement portion, the maximum Feret diameter being taken as the diameter, the center of a virtual circle tangent to the contour of the cross section of the hollow portion being taken as the virtual center, and the virtual center being taken from the portion adjacent to the engagement portion to the portion adjacent to the nozzle.

[0136] The syringe engagement portion 31 of this embodiment is a cylindrical member centered on the central axis C2, and has a syringe insertion portion 31a into which the tip of the syringe 2 is inserted. The outer diameter of the syringe engagement portion 31 can be, for example, 0.1 mm to 13 mm, and the dimension in the longitudinal direction of the syringe tip 3 can be, for example, 7 mm to 50 mm. In this embodiment, the syringe insertion portion 31a is provided in an annular shape centered on the central axis C2, and can have an inner diameter of, for example, 0.1 mm to 12 mm. One end of the syringe insertion portion 31a constitutes an insertion port 31b into which the syringe 2 is inserted. The other end of the syringe insertion portion 31a is continuous with the hollow portion 32a of the cylindrical portion 32.

[0137] In particular, syringe insertion portion 31a in this embodiment is formed in a tapered shape in which the size of the cross section decreases toward cylindrical portion 32. In syringe insertion portion 31a in this embodiment, in order to facilitate the insertion of syringe 2, a tapered portion 31c is formed in a portion continuous with insertion port 31b, in which the size of the cross section increases slightly toward insertion port 31b.

[0138] In this embodiment, an engagement piece 31d that screws into the female thread of the syringe tip mounting part 25 is provided at the end of the outer periphery of the syringe engagement part 31 on the side of the insertion port 31b and protrudes radially outward. In this embodiment, a pair (two) of engagement pieces 31d are provided facing each other in the diameter direction, and each engagement piece 31d is configured as a flat protruding piece in the circumferential direction. It is also possible to provide three or more engagement pieces 31d, and it is also possible to provide multiple engagement pieces 31d at different positions along the central axis C2. Each engagement piece 31d may be formed to be slightly inclined in a spiral shape.

[0139] The syringe engagement portion 31 can be formed of, for example, a resin material. Examples of the resin material that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenol resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, and polycarbonate. In this embodiment, the syringe engagement portion 31 is made of polypropylene. The material of the syringe engagement portion 31 may be the same as or different from the material of the syringe 2.

[0140] The tubular portion 32 of this embodiment is a cylindrical member centered on the imaginary center line IC, and has a hollow portion 32a centered on the imaginary center line IC. Specifically, the tubular portion 32 of this embodiment has a cylindrical main body portion 32b with the hollow portion 32a formed therein. The outer diameter of the tubular portion 32 can be, for example, 0.1 mm to 13 mm, and the dimension in the longitudinal direction of the syringe tip 3 can be, for example, 0.5 mm to 5 mm. One end of the hollow portion 32a of this embodiment is connected to the syringe insertion portion 31a of the syringe engagement portion 31, and can have an inner diameter of, for example, 0.1 mm to 12 mm. The other end of the hollow portion 32a of this embodiment is continuous with a flow path of the viscous material formed inside the nozzle portion 33. The main body portion 32b of this embodiment is formed so that the size of the cross section is constant. Moreover, the hollow portion 32a of this embodiment is formed so that the size of the cross section is constant.

[0141] The cylindrical portion 32 can be formed of, for example, a resin material. Examples of the resin material that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenol resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, and polycarbonate. In this embodiment, the syringe engagement portion 31 is made of polypropylene. The material of the cylindrical portion 32 may be the same as or different from the material of the syringe 2 and the syringe engagement portion 31.

[0142] In this embodiment, an imaginary center line IC located at the center of the hollow portion 32a is coaxial with the central axis C1 of the syringe 2 and the central axis C2 of the syringe insertion portion 31a.

[0143] The cylindrical portion 32 of this embodiment has a connection portion 32c that connects the main body portion 32b and the syringe engagement portion 31. The connection portion 32c of this embodiment is configured to have a truncated cone shape.

[0144] In the present embodiment, a connecting hollow portion 32d is formed inside the connecting portion 32c, which connects the hollow portion 32a and the syringe insertion portion 31a of the syringe engagement portion 31. The connecting hollow portion 32d in the present embodiment is configured such that the radial dimension (hereinafter also simply referred to as the radial dimension) centered on the imaginary center line IC is larger than the radial dimension of the hollow portion 32a and smaller than the radial dimension of the syringe insertion portion 31a. The connecting hollow portion 32d in the present embodiment has, at the end on the hollow portion 32a side, an annular abutment surface 32e against which the end surface 21c on the longitudinal tip side of the tip portion 21 of the syringe 2 abuts.

[0145] The cylindrical portion 32 of this embodiment is provided with a pair of wing portions 34 on the outer wall of the main body portion 32b. The radial dimension of the wing portions 34 can be, for example, 8 mm to 12 mm, and the dimension in the longitudinal direction of the syringe tip 3 can be, for example, 0.5 mm to 5 mm. The pair of wing portions 34 of this embodiment are provided facing each other in the radial direction centered on the imaginary center line IC. The pair of wing portions 34 of this embodiment are formed from the end on the syringe engaging portion 31 side. In other words, the pair of wing portions 34 of this embodiment are formed across the main body portion 32b and the connecting portion 32c. In particular, the pair of wing portions 34 of this embodiment are formed so that the radial outer ends of the pair of wing portions 34 and the radial outer end of the syringe engaging portion 31 are flush with each other. The pair of wing portions 34 of this embodiment are also configured to have a reduced diameter portion 34a on the nozzle portion 33 side, the radial dimension of which decreases toward the nozzle portion 33.

[0146] In the above embodiment, the cylindrical portion 32 has a main body portion 32b in which the hollow portion 32a is formed, and a pair of blade portions 34 provided on the outer wall portion of the main body portion 32b.

[0147] The nozzle portion 33 discharges the viscous material contained in the syringe 2. Specifically, the nozzle portion 33 of this embodiment has a flow path 33a for the viscous material formed therein, and one end of the flow path 33a is connected to the discharge port 33b. The dimension of the nozzle portion 33 in the longitudinal direction of the syringe tip 3 can be, for example, 1 mm to 40 mm. The dimension of the nozzle portion 33 in the direction in which the flow path 33a extends can be 5 mm or more, and can be 8 mm or more. By setting the dimension of the nozzle portion in the direction in which the flow path 33a extends to such a length, it is possible to easily fill the viscous material, for example, into the molar at the back of the oral cavity.

[0148] The nozzle portion 33 of this embodiment is formed so that the size of the cross section becomes smaller toward the discharge port 33b. The nozzle portion 33 may be formed so that the size of the cross section is constant toward the discharge port 33b, or may be formed so that the size of the cross section becomes larger toward the discharge port 33b. The flow path 33a of this embodiment is formed so that the size of the cross section becomes smaller toward the discharge port 33b. In particular, the flow path 33a of this embodiment has a truncated cone shape. The flow path 33a may be formed so that the size of the cross section is constant toward the discharge port 33b, or may be formed so that the size of the cross section becomes larger toward the discharge port 33b. The flow path 33a can be cylindrical.

[0149] The nozzle portion 33 is made of, for example, a resin material or a metal material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the nozzle portion 33 is made of polypropylene.

[0150] In the syringe tip of this embodiment, the nozzle portion, the cylindrical portion, and the syringe engaging portion are integrally formed.

[0151] The nozzle portion 33 in this embodiment extends in a direction inclined with respect to the imaginary center line IC of the hollow portion 32a of the cylindrical portion 32. Moreover, the nozzle portion 33 is provided so that the extension direction of the nozzle portion 33 is parallel to the pair of blade portions.

[0152] As clearly shown in FIG. 8, the flow path 33a of this embodiment is formed around the virtual center line ICL. In this specification, the virtual center line of the flow path can be defined as a line connecting the centers of gravity of the flow path in a cross section perpendicular to the moving direction of the viscous material. The nozzle portion 33 of this embodiment has a tapered flow path 33c formed between the flow path 33a and the discharge port 33b, and the cross-sectional area of ​​which gradually increases toward the discharge port 33b. In this embodiment, the flow path 33a and the tapered flow path 33c are formed in the nozzle portion 33, and therefore, in this embodiment, the discharge structure is configured in the nozzle portion 33.

[0153] In the discharge structure of the nozzle portion 33 of this embodiment, the cross-sectional area of ​​the tapered flow path continuing to the discharge port 33b gradually increases toward the discharge port 33b. Therefore, the internal pressure of the viscous material moving from the flow path 33a toward the discharge port 33b is reduced in the tapered portion 33c, and the inherent distortion can be reduced. If the viscous material is discharged while it is distorted, the internal pressure is released during discharging, causing deformation of the viscous material. By reducing the distortion, the deformation of the viscous material during discharging can be reduced, and the viscous material can be discharged in the intended shape.

[0154] In addition, the nozzle portion 33 of this embodiment has a tapered portion 33c that is continuous with the discharge port 33b. The presence of the tapered portion 33c reduces the area of ​​the annular tip surface 33h, which inevitably reduces the amount of viscous material that adheres to the annular tip surface 33h, and prevents the inner surface of the cap from becoming dirty when the cap is fitted. In addition, the adhesion of the viscous material to undesired areas due to the paste adhering to the annular tip surface 33h dripping is also suppressed. Furthermore, the presence of the tapered portion 33c allows the viscous material discharged through the peripheral wall 33e, the peripheral wall 33d, and the annular tip surface 33h to pass smoothly without getting caught by the edge of the discharge port. Therefore, when the discharge of the viscous material is stopped, when the deformed push rod recovers to its original shape and the paste is reversed, the viscous material is pulled back into the nozzle without remaining on the annular tip surface 33h, so that the dripping of the viscous material can be reduced. In addition, the viscous material is smoothly pulled back into the nozzle, which improves the cutting of the viscous material.

[0155] Furthermore, in the nozzle portion 33 of this embodiment, the cross-sectional area gradually increases toward the discharge outlet 33b at the tapered portion 33c continuing from the discharge outlet 33b, increasing the internal volume of the nozzle portion. Even if the push rod 4, which will be described later, is pulled back, the paste volume inside the nozzle increases, and the air sucked in from the tip portion remains at the nozzle tip, thereby reducing the inclusion of air bubbles.

[0156] The tapered flow passage 33c in this embodiment has a truncated cone shape. Therefore, in a cross section including the imaginary center line of the flow passage 33a, the peripheral wall 33d of the tapered flow passage 33c has a straight line shape. By making the peripheral wall 33d of the tapered flow passage 33c have a straight line shape in the cross section including the imaginary center line of the flow passage 33a, the cutting of the viscous material can be improved.

[0157] In the nozzle portion 33 of this embodiment, in a cross section of the flow path 33a including the imaginary center line ICL of the flow path 33a, the angle between the extending direction of the peripheral wall 33e of the flow path 33a at the end portion on the discharge port 33b side and the extending direction of the peripheral wall 33d of the tapered flow path 33c is preferably 5° to 85°, and more preferably 10° to 60°. By setting the angle to 5° to 85°, it is possible to prevent adhesion of the viscous material to the outer wall portion 33f of the nozzle portion 33. In this embodiment, the angle between the extending direction of the peripheral wall 33e of the flow path 33a at the end portion on the discharge port 33b side and the extending direction of the peripheral wall 33d of the tapered flow path 33c is 45°.

[0158] In the nozzle portion 33 of this embodiment, the tapered flow path 33c and the outer circumferential wall portion 33g of the nozzle portion 33 are connected by an annular tip surface 33h. In particular, in this embodiment, the annular tip surface 33h has a flat circular ring shape, which can improve the cutting of the viscous material.

[0159] In this embodiment, when viewed in the longitudinal direction of the syringe tip, the angle formed between the plane along which the pair of wing portions extend and the plane along which the nozzle portion extends can be 45° or less.

[0160] In the above embodiment, the tip of the syringe is configured to be able to abut against the syringe tip inside the syringe tip, which makes it possible to prevent air bubbles from being mixed in when the viscous material moves from the syringe to the syringe tip, and also makes it possible to reduce the amount of viscous material remaining in the syringe tip, thereby making it possible to prevent the viscous material from dripping from the syringe when replacing the syringe tip.

[0161] In the syringe tip of the above embodiment, the nozzle portion, the cylindrical portion, and the syringe engagement portion are integrally molded from a resin material. Therefore, the nozzle press-fitting operation is not required during manufacturing, making manufacturing easier. In addition, since the nozzle portion, the cylindrical portion, and the syringe engagement portion are made of only a resin material, separation of metals is not required when disposing of the syringe tip, making disposal easier.

[0162] In the above embodiment, a dental material is used as the viscous material, but the viscous material may be a medicine, a medical material, a cosmetic, a food, or the like.

[0163] In the above embodiment, the cylindrical portion has a main body portion having a hollow portion and a pair of wing portions provided on the outer wall portion of the main body portion, but the syringe tip does not have to have wing portions. Also, in the above embodiment, the syringe tip has two wing portions, but the number of wing portions is not limited to two, and may be one, or three or more.

[0164] Although in the above embodiment the syringe tip has a symmetrical shape, the syringe tip may have an asymmetrical shape.

[0165] Although the syringe tip of the above embodiment is configured such that the extension direction of the nozzle portion is bent from the extension direction of the cylindrical portion, the nozzle portion and the cylindrical portion can be configured to be linear.

[0166] In the syringe tip of the above embodiment, the flow channel of the nozzle portion is formed linearly, but the flow channel of the nozzle portion can be formed in a curved shape.

[0167] In the syringe tip of the above embodiment, the nozzle portion, the cylindrical portion, and the syringe engaging portion are integrally molded, but the nozzle portion, the cylindrical portion, and the syringe engaging portion can be molded individually as separate members.

[0168] In the syringe tip of the above embodiment, nozzle portion 33 is formed so that the size of the cross section decreases toward discharge port 33b, but the size of the cross section of nozzle portion 33 can be constant.

[0169] In the syringe tip of the above embodiment, flow channel 33a is formed so that the size of the cross section decreases toward discharge port 33b, but the size of the cross section of flow channel 33a can be constant.

[0170] In the above embodiment, the syringe tip and the syringe are screwed together using an internal thread. However, the syringe tip and the syringe can also be screwed together using a so-called external thread.

[0171] FIG. 15 is a front view of a two-component mixing container 101 such as a cement capsule having a discharge structure according to one embodiment of the present invention, FIG. 16 is a bottom view of the two-component mixing container 101, and FIG. 17 is a cross-sectional view taken along line IIA-IIA in FIG. 16. The two-component mixing container 101 in this embodiment stores two types of drugs (components), particularly a powder material and a liquid material, for producing dental materials such as amalgam and medical materials such as bone cement, in isolation, and when used, mixes the two types of drugs and discharges (pushes out) the desired viscous material as needed. The viscous material can have the same composition as that of the syringe tip. The two-component mixing container 101 includes a housing 103, a nozzle 105, a nozzle holding structure 106, a partition member 107, a second component storage member 109, and a piston member 111. The two-component mixing container 101 shown in Figures 15 to 17 shows an unused state in which the two-component mixing container 101 is filled with two components (powder and liquid) not shown, and the piston member 111 is not operated.

[0172] The two-component mixing container 101 can be made of a resin material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylstyrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the two-component mixing container 101 is made of polypropylene.

[0173] The housing 103 has a first cylindrical portion 133 having a first opening 131 at one end and a first bottom wall portion 135 closing the other end of the first cylindrical portion 133. The housing 103 has two recesses 137 spaced 180 degrees apart around the first opening 131. The housing 103 also has a mixing chamber 139 therein in which a first component (powder) is accommodated and in which the first component and the second component are mixed when a second component (liquid) is injected from one end side, and the first bottom wall portion 135 has an outlet 141 for discharging the mixture from the mixing chamber 139. The nozzle 105 has a flow path 151 formed therein, and one end of the flow path 151 is connected to an outlet 152. The nozzle 105 is provided relative to the housing 103, and when the mixture is discharged from the outlet 141, the mixture discharged from the outlet 141 is discharged from the outlet 152. The nozzle mounting structure 106 is configured to position the nozzle 105 in a first position that blocks the outlet 141 before the mixture is discharged from the outlet 141, and to position the nozzle 105 in a second position that connects the outlet 141 with the flow path 151 of the nozzle 105 when the mixture is discharged from the outlet 141.

[0174] The partition member 107 is accommodated in the first cylindrical portion 133 of the housing 103, and integrally includes a second cylindrical portion 173 having a second opening 171 at one end, a second bottom wall portion 175 closing the other end of the second cylindrical portion 173, and a partition portion 177 provided on the second bottom wall portion 175 and sliding liquid-tightly inside the mixing chamber 139. A columnar portion 179 extending along the second cylindrical portion 173 is integrally formed at the center of the second bottom wall portion 175 of the partition member 107. In addition, a pair of radially extending protruding pieces 181 are integrally provided at the end of the second opening 171 side of the second cylindrical portion 173 of the partition member 107. The pair of protruding pieces 181 are spaced 180 degrees apart in the circumferential direction. When the partition member 107 is fitted to the housing 103, the pair of protruding pieces 181 are fitted to a pair of recesses 137 provided in the first cylindrical portion 133. In this embodiment, the pair of protruding pieces 181 and the pair of recesses 137 constitute a holding structure. The holding structure is configured to hold the partition member 107 in a fixed state relative to the housing 103 until the second component is injected into the mixing chamber 139, and to release the fixed state when the mixture is discharged from the nozzle 105. The pair of protruding pieces 181 are provided so as to bend or break when pressed toward the third bottom wall portion 195 of the second component containing member 109 with a force of a predetermined value or more by the piston member 111 described later. In this way, the fixed state can be realized with a simple structure, and the fixed state is released by bending or breaking the pair of protruding pieces 181, so that the structure for release is simplified. Note that three or more protruding pieces 181 and recesses 137 may be provided.

[0175] Second component accommodating member 109 is fitted into second cylindrical portion 173 of partition member 107. Second component accommodating member 109 is fitted into second cylindrical portion 173 and has third cylindrical portion 193 with third opening 191 at one end and third bottom wall portion 195 closing the other end of third cylindrical portion 193. Second component accommodating member 109 has second component accommodating chamber 201 therein for accommodating the second component (liquid). A circular through hole (not shown) into which columnar portion 179 is fitted is formed in the center of third bottom wall portion 195 of second component accommodating member 109.

[0176] A first communication passage is formed in second bottom wall portion 175 and cylindrical portion 179 of partition member 107, one end of which opens to the outer surface of cylindrical portion 179 and the other end of which opens to the outer wall surface of second bottom wall portion 175. A second communication passage is formed in the inner wall of third bottom wall portion 195 of second component accommodating member 109, one end of which communicates with a circular through-hole (not shown) and the other end of which opens toward second component accommodating chamber 201. That is, second bottom wall portion 175 of partition member 107 and third bottom wall portion 195 of second component accommodating member 109 are respectively formed with a first communication passage and a second communication passage that are in a communicating state when second component accommodating member 109 and partition member 107 are in a predetermined positional relationship, thereby enabling the second component to flow into mixing chamber 139. The piston member 111 has a piston portion 113 at one end which is inserted into the third cylindrical portion 193 from the third opening 191 of the second component storage member 109 and slides liquid-tightly within the third cylindrical portion 193, and has an operating rod portion 115 at the other end which protrudes to the outside from the third opening 191.

[0177] Fig. 18 is a plan view of piston member 111, Fig. 19 is a front view of piston member 111, and Fig. 20 is a perspective view showing the combined state of the partition member and the second component accommodating member before the piston member is inserted. A pair of spring structures 119 having contact portions 117 and deforming when contact portion 117 comes into contact with inner wall portion 194 of third cylindrical portion 193 when piston member 111 is inserted from third opening 191 of second component accommodating member 109 to apply a pressing force to the inner wall surface of third cylindrical portion 193 are provided at equal intervals in the circumferential direction of piston portion 113. In addition, a pair of fitting grooves 196 into which contact portions 117 are inserted and fitted are formed at equal intervals in the circumferential direction of third cylindrical portion 193 in third cylindrical portion 193 of second component accommodating member 109.

[0178] The piston member 111 used in this embodiment is integrally molded from a synthetic resin material such as polypropylene. The spring structure 119 has a pair of arm portions 121 integrally provided on both sides of the contact portion 117. A space 123 that allows deformation of the arm portion 121 is formed between the arm portion 121 and the operating rod portion 115. Therefore, the contact portion 117 can be given spring properties with a simple structure. In particular, since the contact portion 117 is supported by the pair of arm portions 121, a decrease in the mechanical strength of the spring structure 119 can be prevented. Furthermore, a mold required for manufacturing the piston member 111 is also simple. In this embodiment, two spring structure portions 119 are provided, but it is of course possible to provide three or more spring structure portions 119. In that case, it is sufficient to provide three or more fitting grooves 196 in the third cylindrical portion 193 of the second component storage member 109.

[0179] As a result of deformation of a pair of spring structures 119 provided on piston member 111, contact portions 117 provided on spring structures 119 and fitting grooves 196 provided on third cylindrical portion 193 of second component accommodating member 109 come into a fitting state. Even if the operating rod portion of the piston member is rotated in this state, contact portions 117 will not come out of fitting grooves 196.

[0180] When the first communication passage and the second communication passage are in a communication state, the spring structure portion 119 and the mating groove 196 are formed so that when a force greater than a predetermined value is applied to the operating rod portion 115 in a direction toward the third bottom wall portion 195, the contact portion 117 of the spring structure portion 119 comes out of the mating groove 196.

[0181] When the second component containing chamber 201 and the mixing chamber 139 are in a connected state, if a force greater than a predetermined value is applied to the operating rod portion 115 in a direction toward the third bottom wall portion 195, the contact portion 117 comes out of the fitting groove 196, and the piston member 111 moves toward the third bottom wall portion 195 of the second component containing member 109, making it possible to inject the second component into the mixing chamber 139.

[0182] After the second component (liquid material) is injected into the mixing chamber 139, the two-component mixing container 101 is shaken well to mix the liquid material and the powder material to form a mixture (or reactant). Figures 21 and 22 are front and bottom views of the two-component mixing container with the nozzle displaced to the second position, and Figure 23 is a cross-sectional view taken along line XVIC-XVIC in Figure 21. After the liquid material and the powder material are sufficiently mixed, as shown in Figures 21 to 23, the nozzle 105 is displaced to align the inlet of the nozzle 105 with the outlet 141 to form an outlet path.

[0183] The two-component mixing container 101 in the state shown in Figs. 22 to 24 is attached to a dedicated extruder (not shown). The dedicated extruder is equipped with a piston for pushing the piston member 111. Figs. 25 to 26 are diagrams used to explain the state in which the piston member 111 is pushed to move the partition wall portion 177 of the partition wall member 107 toward the first bottom wall portion 135 of the housing 103. In this embodiment, the partition wall portion 177 of the partition wall member 107 is shaped so as to deform along the shape of the inner wall surface of the first bottom wall portion 135 of the housing 103 when the piston member 111 is moved toward the first bottom wall portion 135 to discharge the mixture from the mixing chamber to the outside through the nozzle 105. Therefore, the mixture can be discharged from the mixing chamber to the maximum extent.

[0184] In this embodiment as well, the dimension of nozzle 105 in the longitudinal direction of housing 103 when outlet 141 and flow path 151 of nozzle 105 are in communication can be, for example, 1 mm to 40 mm. Moreover, the dimension of nozzle 105 in the direction in which flow path 151 extends can be 5 mm or more, and can be 8 mm or more. By setting the dimension of the nozzle portion in the direction in which flow path 151 extends to such a length, it is possible to easily fill the viscous material, for example, into the molar at the back of the oral cavity.

[0185] The nozzle 105 of this embodiment is formed so that the size of the cross section becomes smaller toward the discharge port 152. Note that the nozzle 105 may be formed so that the size of the cross section is constant toward the discharge port 152, or may be formed so that the size of the cross section becomes larger toward the discharge port 152.

[0186] The nozzle 105 of this embodiment has a curved shape that curves toward the discharge port 152. The nozzle 105 may also be configured to have a linear shape.

[0187] The flow path 151 of this embodiment is formed so that the size of the cross section decreases toward the discharge port 152. In particular, the flow path 151 of this embodiment has a curved shape that curves toward the discharge port 152. Note that the size of the cross section of the flow path 151 may be constant toward the discharge port 152, or may be increased toward the discharge port 152. Furthermore, the flow path 151 may be cylindrical.

[0188] In this embodiment, the flow path 151 is formed around the imaginary center line ICL. The nozzle 105 in this embodiment has a tapered flow path 153 that is formed between the flow path 151 and the discharge port 152 and has a cross-sectional area that gradually increases toward the discharge port 152. In this embodiment, the flow path 151 and the tapered flow path 153 are formed in the nozzle 105, and therefore, in this embodiment, the discharge structure is configured in the nozzle 105.

[0189] In the tapered flow passage 153 of this embodiment, in a cross section including the imaginary center line of the flow passage 151, the peripheral wall 153 of the tapered flow passage 153 has a curved shape.

[0190] In the nozzle 105 of this embodiment, in a cross section of the flow path 151 including the virtual center line of the flow path 151, the angle between the extending direction of the peripheral wall of the flow path 151 at the end on the discharge port 152 side and the extending direction of the peripheral wall of the tapered flow path 153 is preferably 5° to 85°, and more preferably 10° to 60°. In the case where the flow path is curved as in this embodiment, the extending direction of the peripheral wall of the flow path at the end on the discharge port side means the tangential direction of the peripheral wall of the flow path at the end on the discharge port side. Moreover, in a cross section of the flow path including the virtual center line of the flow path, in the case where the peripheral wall of the tapered flow path is not straight, the extending direction of the peripheral wall of the tapered flow path means the tangential direction of the peripheral wall of the tapered flow path at the end on the flow path side.

[0191] In the nozzle 105 of this embodiment, the tapered flow path 153 and the outer circumferential wall of the nozzle 105 are connected by an annular tip surface. In particular, in this embodiment, the annular tip surface has a flat circular ring shape, which can improve the cutting of the viscous material.

[0192] Figure 26 is a schematic diagram showing a compule 301 having an ejection structure in one embodiment of the present invention attached to an ejector holder 310, Figure 27 is an oblique view of the compule 301, Figure 28 is a left side view, Figure 29 is a cross-sectional view taken along line AA in Figure 27, and Figure 30 is an enlarged cross-sectional view of the ejection port portion.

[0193] The ejector holder 310 has a barrel, and an inner hole extends from the rear end to the front end of the barrel. A plunger 318 having approximately the same diameter as the inner hole 312 is inserted into the inner hole, and a small-diameter extension is provided at the front end of the plunger 318. A first handle member 324 extending at an angle to the longitudinal direction of the barrel is fixed to the rear end of the barrel. A second handle member is provided to the first handle member 324 via a connecting member. A button 330 is provided at the rear end of the plunger 318, and by pressing this button 330, the plunger 318 is displaced toward the compule 301.

[0194] The Compule 301 is made of a resin material. Examples of the resin material that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenol resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, etc. In this embodiment, the Compule 301 is made of polypropylene.

[0195] The compule 301 of this embodiment has an engagement portion 331 that engages with the ejector holder 310, a cylindrical portion 332 having a hollow portion 332a centered on an imaginary center line IC, and a nozzle portion 333. The hollow portion 332a of the cylindrical portion 332 is filled with a viscous material, and the nozzle portion 333 ejects the viscous material. The viscous material can have the same composition as that of the syringe tip.

[0196] The engagement part 331 of this embodiment has a hollow part 331a centered on the central axis. Therefore, the engagement part 331 of this embodiment has a cylindrical shape. A piston 334 is provided inside the engagement part 331. The outer diameter of the engagement part 331 can be, for example, 2.5 mm to 15 mm, and the dimension in the longitudinal direction of the compule 301 can be, for example, 10 mm to 50 mm. The inner diameter of the engagement part 331 of this embodiment can be, for example, 1 mm to 13 mm. One end of the hollow part 331a forms an insertion port 331b into which the plunger 318 is inserted. The other end of the hollow part 331a is continuous with the hollow part 332a of the tubular part 332. An annular flange 335 is formed on the outer periphery of the engagement part 331.

[0197] The tubular portion 332 of this embodiment is a cylindrical member centered on the imaginary center line IC, and has a hollow portion 332a centered on the imaginary center line IC. Specifically, the tubular portion 332 of this embodiment has a cylindrical main body portion 332b with a hollow portion 332a formed therein. The outer diameter of the tubular portion 332 can be, for example, 2.5 mm to 15 mm, and the dimension in the longitudinal direction of the compule 301 can be, for example, 9 mm to 48 mm. One end of the hollow portion 332a of this embodiment is connected to the hollow portion 331a of the engagement portion 331, and can have an inner diameter of, for example, 1 mm to 13 mm. The main body portion 332b of this embodiment is formed so that the size of the cross section is constant. Moreover, the hollow portion 332a of this embodiment is formed so that the size of the cross section is constant. The other end of the hollow portion 332a of this embodiment is continuous with a flow path of the viscous material formed inside the nozzle portion 333.

[0198] In this embodiment, an imaginary center line IC located at the center of the hollow portion 332a is coaxial with the central axis of the hollow portion 331a.

[0199] The nozzle portion 333 discharges the viscous material contained in the hollow portion 332a. Specifically, the nozzle portion 333 of this embodiment has a flow path 333a for the viscous material formed therein, and one end of the flow path 333a is connected to the discharge port 333b. The nozzle portion 333 may have a dimension in the longitudinal direction of the cylindrical portion 332 of, for example, 1 mm to 40 mm. The nozzle portion 333 may have a dimension in the direction in which the flow path 333a extends of, for example, 5 mm or more, and may have a dimension in the direction in which the flow path 333a extends of, for example, 8 mm or more. By setting the dimension of the nozzle portion in the direction in which the flow path 333a extends to such a length, it is possible to easily fill the viscous material into, for example, the molar tooth located at the back of the oral cavity.

[0200] The nozzle portion 333 of this embodiment is formed so that the size of the cross section becomes smaller toward the discharge port 333b. The nozzle portion 333 may be formed so that the size of the cross section is constant toward the discharge port 333b, or may be formed so that the size of the cross section becomes larger toward the discharge port 333b. The flow path 333a of this embodiment is formed in a cylindrical shape so that the size of the cross section is constant toward the discharge port 333b. The flow path 333a may be formed so that the size of the cross section becomes smaller toward the discharge port 333b, or may have a truncated cone shape. Furthermore, the flow path 333a may be formed so that the size of the cross section becomes larger toward the discharge port 333b.

[0201] The nozzle portion 333 of the present embodiment extends in a direction inclined with respect to the imaginary center line IC of the hollow portion 332 a of the cylindrical portion 332 .

[0202] The flow path 333a of this embodiment is formed around a virtual center line ICL. In this specification, the virtual center line of the flow path can be defined as a line connecting the centers of gravity of the flow path in a cross section perpendicular to the moving direction of the viscous material. The nozzle portion 333 of this embodiment has a tapered flow path 333c formed between the flow path 333a and the discharge port 333b, and the cross-sectional area of ​​which gradually increases toward the discharge port 333b.

[0203] In the nozzle portion 333 of this embodiment, the cross-sectional area gradually increases toward the outlet 333b in the portion of the tapered flow path continuing to the outlet 333b. Therefore, the internal pressure of the viscous material moving from the flow path 333a toward the outlet 333b can be reduced in the tapered portion 333c, reducing the inherent distortion. If the viscous material is discharged while still having distortion, the internal pressure is released during discharge, causing deformation of the viscous material. By reducing the distortion, the deformation of the viscous material during discharge can be reduced, making it possible to discharge the viscous material in the intended shape.

[0204] In addition, the nozzle portion 333 of this embodiment has a tapered portion 333c that is continuous with the discharge port 333b. The presence of the tapered portion 333c reduces the area of ​​the annular tip surface 333h, which inevitably reduces the amount of viscous material that adheres to the annular tip surface 333h, and prevents the inner surface of the cap from becoming dirty when the cap is fitted. In addition, the adhesion of the viscous material to undesired areas due to the paste adhering to the annular tip surface 333h dripping is also suppressed. Furthermore, the presence of the tapered portion 333c allows the viscous material discharged through the peripheral wall 333e, the peripheral wall 333d, and the annular tip surface 333h to pass smoothly without being caught by the edge of the discharge port. Therefore, when the discharge of the viscous material is stopped, when the plunger 330 returns to its original position and the paste is drawn back, the viscous material does not remain on the annular tip surface 333h and is drawn back into the nozzle, thereby reducing the dripping of the viscous material. Furthermore, the viscous material is smoothly drawn back into the nozzle, which allows the viscous material to be cut off smoothly.

[0205] Furthermore, in the nozzle portion 333 of this embodiment, the cross-sectional area gradually increases toward the discharge port 333b at the tapered portion 333c continuing from the discharge port 333b, increasing the internal volume of the nozzle portion. Therefore, even if the plunger 330 is pulled back, the paste volume inside the nozzle increases, and the air sucked in from the tip portion remains at the nozzle tip, thereby reducing the inclusion of air bubbles.

[0206] The tapered flow path 333c in this embodiment has a truncated cone shape. Therefore, in a cross section including the virtual center line of the flow path 333a, the peripheral wall 333d of the tapered flow path 333c has a straight line shape. By making the peripheral wall 333d of the tapered flow path 333c have a straight line shape in this way in a cross section including the virtual center line of the flow path 333a, it is possible to improve the cutting of the viscous material.

[0207] In the nozzle portion 333 of this embodiment, in a cross section of the flow path 333a including the imaginary center line ICL of the flow path 333a, the angle between the extending direction of the peripheral wall 333e of the flow path 333a at the end portion on the discharge port 333b side and the extending direction of the peripheral wall 333d of the tapered flow path 333c is preferably 5° to 85°, and more preferably 10° to 60°. By setting it to 5° to 85°, it is possible to prevent adhesion of the viscous material to the outer wall portion 333f of the nozzle portion 333. In this embodiment, the angle between the extending direction of the peripheral wall 333e of the flow path 333a at the end portion on the discharge port 333b side and the extending direction of the peripheral wall 333d of the tapered flow path 333c is 45°.

[0208] In the nozzle portion 333 of this embodiment, the tapered flow path 333c and the outer circumferential wall portion 333g of the nozzle portion 333 are connected by an annular tip surface 333h. In particular, in this embodiment, the annular tip surface 333h has a flat circular ring shape, which can improve the cutting of the viscous material.

[0209] Fig. 31 is a side view of a cap 336 of a compule according to one embodiment, and Fig. 32 is a cross-sectional view of the compule, cap, and piston according to one embodiment with the cap 336 attached. The compule 301 of this embodiment is configured such that, by attaching the cap 326 from the nozzle side during storage or when not in use, the light-shielding properties of the nozzle are improved to improve storage stability and prevent unintended dripping of the viscous material.

[0210] In the above embodiment of the Compule, the nozzle portion, the cylindrical portion, and the engagement portion are integrally molded from a resin material. This eliminates the need to press the nozzle in during manufacturing, making manufacturing easier. In addition, since the nozzle portion, the cylindrical portion, and the engagement portion are made only from a resin material, separation of metals is not required when disposing of the product, making disposal easier.

[0211] In the compule of the above embodiment, the nozzle portion, the cylindrical portion and the engagement portion are molded as a single unit, but the nozzle portion, the cylindrical portion and the engagement portion can be molded individually as separate parts, as in the compule of other embodiments shown in Figures 33 to 36.

[0212] As shown in FIG. 37, the piston 334 of this embodiment has a substantially cylindrical shape.

[0213] Although in the above embodiment the compule has a symmetrical shape, the compule may have an asymmetrical shape.

[0214] Although the Compule in the above embodiment is configured such that the extension direction of the nozzle portion is bent from the extension direction of the cylindrical portion, the nozzle portion and the cylindrical portion can be configured to be linear.

[0215] In the above embodiment of the Compule, the flow passage of the nozzle portion is formed linearly, but the flow passage of the nozzle portion can be formed in a curved shape.

[0216] In the Compule of the above embodiment, the cross-sectional size of the nozzle portion is formed to be constant toward the discharge port, but the cross-sectional size of the nozzle portion can be formed to become smaller toward the discharge port.

[0217] In the above embodiment of the compule, the flow path is formed so that the cross-sectional size is constant toward the discharge port, but the cross-sectional size of the flow path can be formed so that it becomes smaller toward the discharge port. Fig. 38 is a schematic diagram showing the configuration of a double-syringe type injector 401 having a discharge structure according to one embodiment of the present invention, and Fig. 39 is a schematic diagram showing an exploded state of injector 401. Injector 401 of this embodiment includes a double syringe 420 and a mixing tip 430 attached to a tip portion 422 of double syringe 420. In this embodiment, a viscous material is stored inside double syringe 420. In this embodiment, injector 401 constitutes a set of the present invention.

[0218] 40 is a cross-sectional view of the mixing tip taken along line XXXIII-XXXIII in FIG. 39, and FIG. 41 is a cross-sectional view of the double syringe taken along line XXXIV-XXXIV in FIG.

[0219] The double syringe 420 is made of, for example, a resin material or a glass material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the double syringe 420 is made of polypropylene.

[0220] The double syringe 420 of this embodiment includes a push rod 440. The double syringe 420 of this embodiment includes two syringe portions 421 each containing a different material. Each of the two syringe portions 421 includes a tip portion 422 having a discharge port 422a at one end, a rear end portion 423 having an insertion port 423a at the other end into which a push rod 440, which will be described later, is inserted, and a main body portion 424 located between the tip portion 421 and the rear end portion 422. When the push rod 440 is pushed into the syringe portion 421 from the insertion port 423a, the viscous material contained therein is pushed out from the discharge port 422a.

[0221] A hollow portion 425 for storing a viscous material is formed inside main body 424 over the entire longitudinal direction centered on the central axis. At tip 422, hollow portion 425 has a tapered portion whose cross-sectional size decreases toward discharge port 422a, and a cylindrical portion whose cross-sectional size is constant.

[0222] In main body 424, hollow portion 425 is formed to have a cylindrical shape with a constant cross-sectional size. In rear end 423, hollow portion 425 is formed to have a cylindrical shape with a constant cross-sectional size.

[0223] The double syringe 420 is connected to the mixing tip 430 and the mixing element 450 by inserting the discharge port 422a of the syringe part 421 into a syringe receiver 452 of the mixing element 450 described later. When the push rod 440 is pressed while the mixing tip 430 and the mixing element 450 are connected to the double syringe 420, the viscous material contained in the hollow part 421 of the main body part 424 is pushed out from the discharge port 422a to the mixing tip 430.

[0224] 42 is a schematic cross-sectional view of a mixing element 450 according to this embodiment. Mixing element 450 can have a mixing portion 451, two syringe receivers 452, and a connecting portion 453 that connects the two syringe receivers 452.

[0225] Mixing section 451 has an axis member extending in a direction away from connecting section 453, and a plurality of blade members provided along this axis member. Syringe receiver 452 has a cylindrical shape with an inner diameter approximately equal to the outer diameter of discharge port 422a of syringe part 421, and has opening 454 at the end on the mixing section 451 side and insertion port 455 at the end opposite to mixing section 451.

[0226] The mixing tip 430 of this embodiment has a connecting cover 431 connected to the outlet 422a of the double syringe 420, a cylindrical portion 432 extending from the connecting cover 431, and a nozzle portion 433. The mixing tip 430 is fixed to the double syringe 420 by a locking member 404 with the connecting cover 431 connected to the outlet 422a of the double syringe 420.

[0227] The mixing tip 430 mixes two kinds of materials pushed out from the outlet 422 a of the double syringe 420 by the push rod 440 in the mixing element 450 and discharges the mixture from the outlet 433 b provided at one end of the nozzle portion 433 .

[0228] Specifically, the mixing element 450 is press-fitted into the mixing tip 430 such that the mixing portion 451 is inserted into the nozzle portion 433 of the mixing tip 430 and the syringe receiver 452 and the connecting portion 453 are covered by the connecting cover 431 of the mixing tip 430 .

[0229] The mixing tip 430 and the mixing element 450 are connected to the double syringe 420 by inserting the discharge port 422 a of the syringe portion 421 into the syringe receiver 452 of the mixing element 450 .

[0230] When the push rod 440 is pressed while the mixing tip 430 and the mixing element 450 are connected to the double syringe 420, the material extruded from the syringe portion 421 is injected into the mixing tip 430 through the discharge port 422a and the opening 454 of the syringe receiver 452.

[0231] The two types of materials pushed out from the two syringe portions 421 and guided to the nozzle portion 433 of the mixing tip 430 are mixed by the mixing portion 451 while passing through the nozzle portion 433 and are discharged from the discharge port of the mixing tip 430.

[0232] The connecting cover part 431 can be formed of, for example, a resin material. Examples of the resin material that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenol resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, etc. In this embodiment, the connecting cover part 431 is made of polypropylene.

[0233] The tubular portion 432 of this embodiment is a cylindrical member centered on the imaginary center line IC, and has a hollow portion 432a centered on the imaginary center line IC. Specifically, the tubular portion 432 of this embodiment has a cylindrical main body portion 432b with a hollow portion 432a formed therein. The outer diameter of the tubular portion 432 can be, for example, 2 mm to 15 mm, and the dimension of the tubular portion 432 in the longitudinal direction can be, for example, 5 mm to 120 mm. The tip of the hollow portion 432a in the discharge direction of this embodiment is continuous with the flow path of the viscous material formed inside the nozzle portion 433. The main body portion 432b of this embodiment is formed so that the size of the cross section is constant. Moreover, the hollow portion 432a of this embodiment is formed so that the size of the cross section is constant.

[0234] The cylindrical portion 432 can be formed of, for example, a resin material. Examples of the resin material that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenol resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylic styrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the cylindrical portion 432 is made of polypropylene.

[0235] Nozzle portion 433 discharges the viscous material. Specifically, nozzle portion 433 of this embodiment has a flow path for the viscous material formed therein, and one end of the flow path is connected to discharge port 433b. Nozzle portion 433 may have a dimension in the direction in which the flow path extends of 5 mm or more, and may have a dimension in the direction in which the flow path extends of 8 mm or more. By setting the dimension of the nozzle portion in the direction in which the flow path extends to such a length, for example, it is possible to easily fill the viscous material into the molar tooth at the back of the oral cavity. The viscous material may have the same composition as that of the syringe tip.

[0236] The nozzle portion 433 of this embodiment is formed so that the size of the cross section decreases toward the discharge port 433b. Moreover, the flow path of this embodiment is formed in a cylindrical shape so that the size of the cross section is constant toward the discharge port 433b.

[0237] The nozzle portion 433 is made of, for example, a resin material or a metal material. Examples of resin materials that can be used include polyethylene, polyacetal, polypropylene, polyamide, vinyl chloride resin, nylon, phenolic resin, polyurethane, saturated polyester resin, melamine resin, polyvinylidene chloride, unsaturated polyester resin, polybutadiene, polystyrene, EVA (ethylene-vinyl acetate copolymer) resin, styrene resin, polymethylpentene, methacrylstyrene, ABS (acrylonitrile, butadiene, styrene) resin, polycarbonate, and the like. In this embodiment, the nozzle portion 433 is made of polypropylene.

[0238] The flow path in this embodiment is formed around a virtual center line, and a tapered flow path whose cross-sectional area gradually increases toward the discharge port 433b is formed between the flow path and the discharge port 433b. In this embodiment, the flow path and the tapered flow path are formed in the nozzle portion 433, and therefore, in this embodiment, the discharge structure is configured in the nozzle portion 433.

[0239] The tapered flow passage of this embodiment has a truncated cone shape. Therefore, in a cross section including the imaginary center line of the flow passage, the peripheral wall of the tapered flow passage has a straight line shape. By making the peripheral wall of the tapered flow passage straight line in this manner in a cross section including the imaginary center line of the flow passage, it is possible to improve the cutting of the viscous material.

[0240] In the nozzle portion 433 of this embodiment, in a cross section of the flow path including the virtual center line of the flow path, the angle between the extension direction of the peripheral wall of the flow path at the end portion on the discharge port 433b side and the extension direction of the peripheral wall of the tapered flow path is preferably 5° to 85°, and more preferably 10° to 60°. By setting the angle to 5° to 85°, it is possible to prevent adhesion of the viscous material to the outer wall portion of the nozzle portion 433. In this embodiment, the angle between the extension direction of the peripheral wall of the flow path at the end portion on the discharge port 433b side and the extension direction of the peripheral wall of the tapered flow path is 45°.

[0241] In the nozzle portion 433 of this embodiment, the tapered flow path and the outer circumferential wall portion of the nozzle portion 433 are connected by an annular tip surface. In particular, in this embodiment, the annular tip surface has a flat circular ring shape, which can improve the cutting of the viscous material. EXAMPLES

[0242] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0243] <Preparation of Syringe Tip> Syringe chips with container numbers 1 to 45 shown in Table 1 were produced. In all of the produced syringe chips, the cross-sectional size of the nozzle portion is constant toward the discharge port, and the cross-sectional size of the flow path is constant toward the discharge port. In addition, the tapered flow path has a truncated cone shape. In Table 1, A indicates the angle between the extending direction of the peripheral wall of the flow passage at the end on the discharge port side and the extending direction of the peripheral wall of the tapered portion in a cross section including the imaginary center line of the flow passage. In Table 1, C indicates the distance between the end of the tapered flow path on the discharge port side and the end of the flow path on the discharge port side in the direction perpendicular to the imaginary center line of the flow path. In Table 1, D indicates the distance between the end of the tapered flow passage on the discharge port side and the end of the flow passage on the discharge port side in a cross section including the imaginary center line of the flow passage. In Table 1, F indicates the distance between the end of the tapered flow passage on the discharge port side and the end of the flow passage on the discharge port side in the direction parallel to the imaginary center line of the flow passage.

[0244] [Table 1]

[0245] The following viscous materials were prepared. The materials used in the preparation of the viscous materials and their abbreviations are shown below. [Polymerizable monomer] Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 3G: Triethylene glycol dimethacrylate D-2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane having an average molar number of ethoxy groups of 2.6. E-B5: Di(methacryloxyethyl)trimethylhexamethylenediurethane

[0246] [Polymerization initiator] CQ: Camphorquinone DM: 2-(N,N-dimethylamino)ethyl methacrylate DMBE: Ethyl 4-(dimethylamino)benzoate DPI: Diphenyliodonium hexafluorophosphate

[0247] [Filler] Filler A: GM27884 (manufactured by Schott) with a volume median particle size of 0.18 μm was treated with 13 wt % of 3-methacryloyloxypropyltrimethoxysilane to obtain filler A. Filler B: GM32087 (manufactured by Schott) with a volume median particle size of 0.4 μm was treated with 9.4 wt % of 3-methacryloyloxypropyltrimethoxysilane to obtain filler C. Filler C: GM32087 (manufactured by Schott) with a volume median particle size of 0.4 μm was treated with 12 wt % 8-methacryloyloxyoctyltrimethoxysilane to obtain filler D.

[0248] [Preparation of viscous material] ·Viscous material A A resin material was prepared by adding 40g of 3G to 60g of Bis-GMA, and then dissolving 0.1g of CQ, 2.0g of DM, and 0.5g of DPI. 70g of filler A was dispersed in 15g of this resin material to obtain viscous material A. ·Viscous material B 30g of E-B5 and 20g of 3G were added to 50g of D-2.6E, and then 0.3g of CQ and 1.0g of DMBE were dissolved to prepare a resin material. 58g of filler C was dispersed in 15g of this resin material to obtain viscous material B. ·Viscous material C A resin material was prepared by adding 40g of 3G to 60g of Bis-GMA, and then dissolving 0.3g of CQ and 1.0g of DMBE. 35g of filler B was dispersed in 15g of this resin material to obtain viscous material C. ·Viscous material D A resin material was prepared by adding 10 g of 3G to 90 g of Bis-GMA, and then dissolving 0.3 g of CQ and 1.0 g of DMBE. This resin material was named viscous material D. ·Viscous material F A resin material was prepared by adding 30g of E-B5 and 20g of 3G to 50g of D-2.6E, and then dissolving 0.1g of CQ, 2.0g of DM, and 0.5g of DPI. 15g of filler B was dispersed in 15g of this resin material to obtain viscous material F. ·Viscous material G A resin material was prepared by adding 40g of 3G to 60g of Bis-GMA, and then dissolving 0.3g of CQ and 1.0g of DMBE. A viscous material G was obtained by dispersing 10g of filler C in 15g of this resin material.

[0249] [Flow value measurement] The flow values ​​were measured for the prepared viscous materials A to G. The flow values ​​were measured by the following steps 1 to 4.

[0250] Step 1: A cellophane sheet (disc-shaped) is inserted into a cylindrical glass tube (inner diameter 7.5 mm).

[0251] Step 2: Fill the sample into the sample filling section (volume 309 mm3) at the top of the cylindrical glass tube (inner diameter 7.5 mm) without trapping any air bubbles, and use a plastic spatula to flatten the top surface of the filled sample to fit the cylindrical glass tube.

[0252] Step 3: After removing the cylindrical glass tube, a glass rod is inserted from the side opposite the filled section, and the viscous material is gently extruded onto a 50 x 50 x 1 mm glass plate.

[0253] Step 4: Transfer this glass plate to a loader, place a glass plate of the same size on the sample, and at the same time gently add the weight (385gf) of the loader and leave for 3 minutes. After 3 minutes, remove the weight and use graph paper to select any point on the sample spread between the glass plates and determine the tangent. Determine a tangent parallel to that tangent and measure the dimension between the parallel tangents (see Figure 11). Measure the dimension between parallel tangents perpendicular to that parallel tangent. These two points are designated as Amm and Bmm, and the pressure flow rate (flow value) is calculated using the following formula. Pressure flow rate (mm)=(A+B) / 2 Note that the value is valid only when |AB|≦1 mm, and if |AB|>1 mm, the measurement is to be repeated. This procedure was carried out twice for each sample, and the average value was taken as the flow value. The flow values ​​of each viscous material are shown in Table 2.

[0254] [Table 2]

[0255] Next, in the combinations shown in Table 3, syringe tips with container numbers 1 to 45 were filled with any of the viscous materials A to G, and a test was performed to check whether the ejected viscous material adhered to the outer wall of the nozzle and the position it reached. [Test to confirm the location where the discharged viscous material reaches] 1. Test Method The syringe used in the Beauty Fill Flow Plus XF00A3 (Matsukaze) was filled with viscous materials A to H. A syringe tip was attached to the syringe filled with each viscous material, and the viscous material was discharged. Evaluation was performed by using the line extending from the virtual center line of the nozzle toward the discharge port as the axis, and evaluating the angle at which the discharged material reached according to the evaluation criteria. 2. Evaluation criteria A: No adhesion of the viscous material to the outer wall was confirmed, and the reach of the viscous material was less than 10°. B: No adhesion of the viscous material to the outer wall was confirmed, and the position at which the viscous material reached was less than 30°. C: The position at which the viscous material reached was greater than 30°, but no adhesion of the viscous material to the outer wall was confirmed. D: Viscous material adhered to the outer wall, but the amount was reduced compared to the comparative example.

[0256] The evaluation results of each of the examples and comparative examples are shown in the table.

[0257] [Table 3] [Industrial Applicability]

[0258] According to the present invention, it is possible to provide a set comprising a viscous material and a dispensing container or dispensing device having a dispensing structure that can apply a desired amount of viscous material to a desired location by reducing the amount of viscous material adhering to the outer wall portion, and preferably preventing adhesion of the viscous material to the outer wall portion, thereby increasing the efficiency of use of the viscous material. [Explanation of symbols]

[0259] 1 syringe 2 Syringes 21 Tip 21a Discharge port 21b Outer surface 21c end face 22 Rear end 22a Insertion port 22b Finger grip attachment part 22c Flange part 22d Flange part 22e Recess 23 Main body 23a Outer surface 24 Hollow part 24a First tapered portion 24b First cylindrical section 24c Second taper section 24d Second cylindrical section 24e Third taper 25 Syringe tip attachment part 25a Inner surface 25b Outer surface 3 Syringe Tip 31 Syringe engagement part 31a Syringe insertion part 31b Insertion port 31c Tapered section 31d Engagement piece 32 Cylindrical section 32a Hollow part 32b Main body 32c Connection 32d Connection Hollow Section 32e Contact surface 33 Nozzle section 33a Flow path 33b Discharge port 33c Tapered flow path 33d surrounding wall 33e Surrounding wall 33f External wall 33g outer peripheral wall 33h Tip surface 34 Wing 34a Reduced diameter part 4 Push Stick 41 Main body 42 Seal part 43 Finger rest 5 Finger Grip C1 center axis C2 center axis IC virtual center line 101 Two-component mixing container 103 Housing 105 Nozzle 106 Nozzle holding structure 107 Partition wall material 109 Second component housing member 111 Piston parts 113 Piston part 115 Operating rod part 117 Contact Part 119 Spring structure 121 Arm section 123 Space 131 First Opening 133 First cylindrical part 135 First bottom wall 137 Recess 139 Mixing Chamber 141 Outlet 151 Channel 152 Discharge port 171 Second Opening 173 Second cylindrical section 175 Second bottom wall 177 Bulkhead 179 Cylindrical part 181 Projecting piece 191 Third Opening 193 Third cylindrical section 194 Inner wall 195 Third bottom wall 196 Fitting groove 201 Second component storage chamber 301 Compule 310 Ejector holder 311 barrels 312 Inner hole 314 Rear end 316 front end 318 Plunger 320 Extension 322 Handle member 324 Operating Lever 326 Pivot pin 330 Button 331 Engagement part 331a Hollow part 331b Insertion port 332 Cylindrical part 332a Hollow part 332b Main body 333 Nozzle section 333a Channel 333b Discharge port 333c Tapered flow path 333d Peripheral wall 333g outer peripheral wall 333h Tip surface 334 Piston 335 Flange 401 Syringe 420 Double Syringe 421 Syringe part 422 Tip 422a Discharge port 423 Rear end 423a Insertion port 424 Main body 425 Hollow part 430 Mixing Tip 431 Connecting cover part 432 Cylindrical part 433 Nozzle part 433b Discharge port 440 Push Stick 450 Mixing Element 451 Mixing Department 452 Syringe holder 453 Connection section 454 Aperture 455 Insertion port

Claims

1. A set including a viscous material and a discharge container or a discharge tool having a discharge structure for discharging the viscous material from a discharge port, The viscous material comprises (a) a polymerizable monomer and (b) a polymerization initiator; The discharge structure is as follows: a flow path formed around a virtual center line and capable of moving a viscous material; a tapered flow path formed between the flow path and the discharge port, the cross-sectional area of ​​which gradually increases toward the discharge port; A set including a viscous material and a dispensing container or dispensing device.

2. The set according to claim 2, wherein in a cross section of the flow path including the imaginary center line, an angle between an extension direction of the peripheral wall of the flow path at an end portion on the discharge port side and an extension direction of the peripheral wall of the tapered flow path is 5° to 85°.

3. The set of claim 1 , wherein the tapered passage has a frusto-conical shape.

4. The set of claim 1 , wherein the tapered flow passage has a frusto-conical or cylindrical shape.

5. The set according to claim 1 , wherein the tapered flow passage and the outer peripheral wall of the discharge container or the discharge device are connected by an annular tip surface.

6. 6. The set of claim 5, wherein the annular tip surface has a torus shape.

7. The set according to claim 1, wherein the viscous material contains 0.01 to 10 parts by mass of a polymerization initiator per 100 parts by weight of the (a) polymerizable monomer.

8. The set of claim 1 , wherein the viscous material further comprises (c) a filler.

9. Viscous materials are (a) a polymerizable monomer and (c) a filler in a ratio of 10:90 to 99.9:0.1; The set according to claim 8, comprising 0.01 to 10 parts by mass of a polymerization initiator per 100 parts by weight in total of (a) the polymerizable monomer and (c) the filler.

10. The set of claim 1 , wherein the viscous material is free of (c) a filler.

11. 2. The set of claim 1, wherein the viscous material is a dental material.

12. The set according to claim 1 , wherein the flow value D mm of the viscous material satisfies the following relationship (1): D≧20 (1)

13. The set according to any one of claims 1 to 12, wherein the discharge container or the discharge device is a compule.

14. The set according to any one of claims 1 to 12, wherein the discharge container or the discharge device is a capsule.

15. The set according to any one of claims 1 to 12, wherein the discharge container or the discharge device is a syringe.

16. The discharge container or the discharge device is a syringe; The set according to any one of claims 1 to 12, further comprising a syringe tip attached to a tip of the syringe and having a discharge structure.

17. The discharge container or the discharge device is a syringe; The syringe further includes a syringe tip that is attached to the tip of the syringe and has a discharge structure; The syringe has a main body portion formed in a cylindrical shape and a tip portion provided at one end of the main body portion and to which a syringe tip is attached, The set according to any one of claims 1 to 12, wherein the tip portion has a shape capable of abutting against the nozzle portion inside the syringe tip.

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