CN103491928B - Dental materials, dental materials compositions, dental prosthetic material and solidfied material - Google Patents

Abstract

It is an object of the invention to provide a kind of especially polymerization shrinkage dental materials, dental materials compositions and dental prosthetic material little, that the most also can manufacture when solidification with cheap price.The dental materials of the present invention is characterised by, specific carbamate (methyl) acrylic compounds represented containing following formula (1).

Description

Dental materials, dental materials compositions, dental prosthetic material and solidfied material

Technical field

The present invention relates to a kind of novel dental materials, dental materials compositions, dental prosthetic material and make this dentistry material The solidfied material of material solidification.In detail, the present invention relates to a kind of containing novel carbamate (methyl) acrylic compounds The dental materials of compound, comprise the dental materials compositions of this dental materials.

Background technology

In the past, its characteristic such as good curable and the transparency was utilized, with (methyl) acrylate free radical as representative Polymerizable monomer is widely used in the various fields such as coating, plate making, optical material and dental materials.

Wherein, in dental materials field, the tooth used in the dental caries that is widely used in natural teeth, the reparation fractureed etc. The dental prosthetic materials such as section's composite resin, for making dental composite resin and the bonding various dental adhesives of tooth, And artificial tooth, dental plate material etc..

Dental composite resin is typically made up of polymerizable monomer, polymerization initiator and filler, as polymerizable monomer, from From the viewpoint of safety, the mechanical strength of solidfied material, mar proof and aesthetic property etc. in organism, use radical polymerization Multifunctional (methyl) acrylate of property.As multifunctional (methyl) acrylate, use 2, double (4-(the 3-methacryl of 2- Epoxide-2-hydroxy propyloxy group) phenyl propane (being commonly referred to as Bis-GMA), dimethacrylate 2,2,4-tri-methyl hexamethylene is double (2-carbamoyloxy ethyl) ester (being commonly referred to as UDMA), particularly Bis-GMA was proposed at tooth by Bowen first since 1962 Since application in section's material, the most still the polymerizable monomer as almost all of dental composite resin uses.

But, for dental composite resin, point out from clinical sites, the bending strength of solidfied material, elastic modelling quantity and The minimizing of the polymerization shrinkage when minimizing of the raising of mar proof, water suction and color-shifting colorant, solidification is as natural teeth The improvement leeway of the aspects such as the transparency and aesthetic property is big.Particularly polymerization shrinkage can cause because dental composite resin is from bonding plane The generation of shrinkage joint peeled off and generate, becomes recurrent caries, plup stimulus, coloring, restoration come off etc. reason, the most strongly Wish to be reduced as far as.It addition, in order to meet the high request to aesthetic property, and give x-ray imaging, multiple at dental The filler of commonly used high index of refraction in resin, it is therefore desirable to give the transparency close with natural teeth, it is desirable to used The refractive index of polymerizable monomer is high.And then, from from the viewpoint of intraoral durability (resistance to impact and broken resistance), uncommon Prestige has high bending strength.

Minimizing for polymerization shrinkage, it is proposed that use the open loop that polymerization shrinkage is generally less than acrylic compounds to gather The epoxide of conjunction property, oxetane compound (patent documentation 1 and patent documentation 2).By using these compounds, have The tendency of polymerization shrinkage can be reduced, but because curing system is different, so needing the problems such as special priming paint (primer) the most very Many.It addition, it is problematic from the viewpoint of aesthetic property and operability.

The loading of filler is improved to reduce polymerization shrinkage (patent documentation 3 and patent documentation 4) it addition, it is also proposed.So And, because the shrinkage factor of monomer used is big, so its effect is limited.

Also proposed the low-shrinkage material (patent documentation 5) using siliceous (methyl) acrylate.But, this material Synthesize loaded down with trivial details, leave problem at industry manufacture view.It addition, it is problematic from the viewpoint of the mechanical strength of solidfied material.

Accordingly, it would be desirable to have a kind of polymerization shrinkage when can be used for dental prosthetic material, solidification little, the most also can be with The polymerizable monomer that cheap price manufactures.

Patent documentation 1: Japanese Unexamined Patent Publication 2007-15946 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2005-187385 publication

Patent documentation 3: Japanese Unexamined Patent Application Publication 2007-526270 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2005-89312 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2009-179596 publication

Summary of the invention

It is an object of the invention to provide a kind of especially solidification time polymerization shrinkage little, have appropriateness viscosity, in work Also can be with the cheap dental materials of price manufacture, dental materials compositions, dental prosthetic material and make this dental materials in industry The solidfied material of solidification.

The present inventor has carried out conscientiously studying, it was found that intramolecular has at least one fat to solve above-mentioned problem Novel carbamate (methyl) acrylic compounds of ring structure or aromatic ring structure can solve above-mentioned problem, thus completes The present invention.

The dental materials of the present invention is characterised by, the compound represented containing following formula (1).

The dental materials compositions of the present invention is characterised by, comprise the dental materials of the present invention, (B) polymerization initiator and (C) filler.

The dental prosthetic material of the present invention is characterised by, comprise the dental materials of the present invention, (B) Photoepolymerizationinitiater initiater and (C) filler.

The solidfied material of the present invention is characterised by, is that the dental materials making the present invention solidifies.

The dental materials containing carbamate (methyl) acrylic compounds of the present invention is except the machinery of solidfied material Beyond intensity, mar proof, aesthetic property, operability, safety, the especially polymerization shrinkage when polymerizing curable is little, in system There is during standby dental prosthetic material the viscosity of preferably appropriateness.Therefore, it is suitable for dental prosthetic material etc., is particularly suitable for The filling reparation composite resin for the treatment of dental caries cavity.The dental prosthetic such as the composite resin comprising the dental materials of the present invention Material, because polymerization shrinkage when solidifying is little, so being not likely to produce shrinkage joint between itself and the bonding plane of tooth, can reduce and continuing Send out dental caries, plup stimulus, such worry that comes off of restoration.

It addition, the refractive index of the dental materials of the present invention is higher, have and the dental filler with x-ray imaging The refractive index that refractive index is roughly the same.Therefore, the solidfied material of the dental materials comprising the present invention can ensure that the transparency, attractive in appearance Property excellent.

Accompanying drawing explanation

[Fig. 1] Fig. 1 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 1 The FT-IR spectrum of material.

[Fig. 2] Fig. 2 represents the dentistry comprising carbamate (methyl) acrylic compounds obtained in manufacture example 2 The FT-IR spectrum of material.

[Fig. 3] Fig. 3 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 3 The FT-IR spectrum of material.

[Fig. 4] Fig. 4 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 4 The FT-IR spectrum of material.

[Fig. 5] Fig. 5 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 5 The FT-IR spectrum of material.

[Fig. 6] Fig. 6 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 6 The FT-IR spectrum of material.

[Fig. 7] Fig. 7 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 7 The FT-IR spectrum of material.

[Fig. 8] Fig. 8 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 8 The FT-IR spectrum of material.

[Fig. 9] Fig. 9 represents the dentistry material comprising carbamate (methyl) acrylic compounds obtained in manufacture example 9 The FT-IR spectrum of material.

[Figure 10] Figure 10 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 10 The FT-IR spectrum of section's material.

[Figure 11] Figure 11 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 11 The FT-IR spectrum of section's material.

[Figure 12] Figure 12 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 12 The FT-IR spectrum of section's material.

[Figure 13] Figure 13 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 13 The FT-IR spectrum of section's material.

[Figure 14] Figure 14 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 14 The FT-IR spectrum of section's material.

[Figure 15] Figure 15 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 15 The FT-IR spectrum of section's material.

[Figure 16] Figure 16 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 16 The FT-IR spectrum of section's material.

[Figure 17] Figure 17 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 17 The FT-IR spectrum of section's material.

[Figure 18] Figure 18 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 18 The FT-IR spectrum of section's material.

[Figure 19] Figure 19 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 19 The FT-IR spectrum of section's material.

[Figure 20] Figure 20 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 20 The FT-IR spectrum of section's material.

[Figure 21] Figure 21 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 21 The FT-IR spectrum of section's material.

[Figure 22] Figure 22 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 22 The FT-IR spectrum of section's material.

[Figure 23] Figure 23 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 23 The FT-IR spectrum of section's material.

[Figure 24] Figure 24 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 24 The FT-IR spectrum of section's material.

[Figure 25] Figure 25 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 25 The FT-IR spectrum of section's material.

[Figure 26] Figure 26 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 26 The FT-IR spectrum of section's material.

[Figure 27] Figure 27 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 27 The FT-IR spectrum of section's material.

[Figure 28] Figure 28 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 28 The FT-IR spectrum of section's material.

[Figure 29] Figure 29 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 29 The FT-IR spectrum of section's material.

[Figure 30] Figure 30 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 30 The FT-IR spectrum of section's material.

[Figure 31] Figure 31 represents the tooth comprising carbamate (methyl) acrylic compounds obtained in manufacture example 31 The FT-IR spectrum of section's material.

Detailed description of the invention

[dental materials]

(carbamate (methyl) acrylic compounds)

Novel carbamate (methyl) acrylic compounds of the present invention is that intramolecular has at least one alicyclic ring Carbamate (methyl) acrylic compounds of structure or aromatic ring structure, represents with formula (1).This specific amino first The polymerization shrinkage of acid esters (methyl) acrylic compounds is little, when being applied to the dental prosthetic materials such as composite resin, in preparation There is during dental prosthetic material the viscosity of preferably appropriateness.It addition, the dental materials of the present invention can comprise one or both Above this carbamate (methyl) acrylic compounds uses.

In formula (1), R₁And R₂Separately representing hydrogen atom or methyl, A represents that the divalent in following a～h is organic Group, X₁And X₂Represent divalent organic group, X₁And X₂In either one represent the divalent organic group in following i～m Group.It should be noted that in following a～m, binding site represents with " * ".

Here, in the organic group of above-mentioned a～m, R₃Expression can have aryl or the cycloalkyl of substituent group, R₄、R₅、R₆ And R₇Separately represent hydrogen atom or methyl, R₈Represent the alkyl that carbon number is 4～20.

Here, formula (1) not including, A is c or d and X₁And X₂It is R simultaneously₃Be the compound of the i of phenyl and A be a and R₁And R₂It is methyl and X simultaneously₁And X₂It is R simultaneously₃It it is the compound of the i of phenyl.

In formula (1), A, X₁And X₂In, from the viewpoint of reducing polymerization shrinkage, preferably there is the ring structure of more than 2, More preferably there is the ring structure of more than 3.

In formula (1), from the viewpoint of obtaining less polymerization shrinkage, A be preferably selected from above-mentioned a, b, c, d, e and Divalent organic group in h.

In formula (1), because there being the tendency of not easy coloring when making solidfied material, A is preferably selected from above-mentioned a, c, e, f, g And the divalent organic group in h.

In formula (1), because there is the viscosity of preferably appropriateness when preparing dental prosthetic material, so A is preferably selected from Divalent organic group in above-mentioned a, d, e, f, g and h.

In formula (1), because less polymerization shrinkage can be obtained, and have when preparing dental prosthetic material preferably The viscosity of appropriateness, so the A more preferably divalent organic group in above-mentioned a, d, e and h.

In formula (1), because less polymerization shrinkage can be obtained, and there is the tendency of not easy coloring when making solidfied material, So the A more preferably divalent organic group in above-mentioned a, c, e and h, and then, because having when preparing dental prosthetic material There is the viscosity of preferably appropriateness, so A is preferably selected from the divalent organic group in above-mentioned a, e and h.

It addition, in formula (1), from the viewpoint of aesthetic property in addition to there is the effect above also excellence, the most above-mentioned a of A.

It addition, in formula (1), because have the viscosity of preferably appropriateness when preparing dental prosthetic material, it is advantageous to X₁ And X₂In either one be the divalent organic group in above-mentioned i, j, 1 and m.

In formula (1), because refractive index is higher, the dental materials compositions containing this dental materials and filler composition is made It is easy to ensure that the transparency during solidfied material, aesthetic property is excellent, it is advantageous to X₁And X₂In either one be in above-mentioned i, j, k and m Divalent organic group, and then, because have the viscosity of preferably appropriateness when preparing dental prosthetic material, so more preferably X₁ And X₂In either one be the divalent organic group in above-mentioned i, j and m.

It addition, in formula (1), because there being the tendency that can obtain less polymerization shrinkage, so R₁And R₂It is hydrogen the most simultaneously Atom.

In formula (1), because less polymerization shrinkage can be obtained, it is advantageous to A is any one in above-mentioned a, b, c or e, X₁And X₂It is above-mentioned i, R simultaneously₁And R₂It it is hydrogen atom simultaneously.

In formula (1), because less polymerization shrinkage can be obtained, it is advantageous to A is above-mentioned d, X₁And X₂It is above-mentioned i simultaneously, R₁And R₂It it is methyl simultaneously.

It should be noted that in formula (1), if X₁And X₂In either one be the carbon number such as methylene, ethylidene be 1 ～the alkylidene of 4, then there is the tendency that polymerization shrinkage during solidification is higher, undesirable.

Carbamate (methyl) acrylic compounds represented as formula (1), does not just have as long as meeting formula (1) It is particularly limited to, such as compound number 1-1 shown in table 1～9～9-6 can be enumerated.It addition, the compound described in formula includes institute Some isomers.It should be noted that the C in formula₉Represent the nonyl including isomer.

[table 1]

Table 1

[table 2]

Table 2

[table 3]

Table 3

[table 4]

Table 4

[table 5]

Table 5

[table 6]

Table 6

[table 7]

Table 7

[table 8]

Table 8

[table 9]

Table 9

As carbamate (methyl) acrylic compounds of the present invention, from can obtain less polymerization shrinkage, Aesthetic property is excellent, have the viscosity of preferably appropriateness when preparing dental prosthetic material, have when making solidfied material not easy coloring Tendency and refractive index higher thus from the viewpoint of can ensure that the transparency when making solidfied material, most preferably at dental materials In comprise at least one compound in following formula (2)～(5).

(manufacture method of carbamate (methyl) acrylic compounds)

The manufacture method of carbamate (methyl) acrylic compounds of the present invention is not particularly limited, under generally passing through The additive reaction of (methyl) acrylic compounds stating the diisocyanate cpd shown in reaction process Fig. 1 and hydroxyl comes Manufacture.

Here, A, the R during A, R and the X in reaction process Fig. 1 is respectively equivalent to formula (1)₁Or R₂, and X₁Or X₂。

In reaction process Fig. 1, it is possible to use (methyl) acrylic compounds of the hydroxyl that structure is different manufactures X in formula (1)₁And X₂Different compounds.Owing to being generally difficult to only manufacture X₁And X₂Different compounds, therefore with formula (1) in, only there is X₁The compound of structure, formula (1) only has X₂The compound of structure and formula (1) in tool There is X₁And X₂The form of mixture of compound of structure obtain.Mixture also comprises isomer.

Such as, R in formula (1)₁And R₂It is a, X for hydrogen atom, A₁For j, X₂For raw material diisocyanate cpd during m, The acrylic compounds of hydroxyl and mixture (a part of) enumerate in table 10.

[table 10]

Table 10

((methyl) acrylic compounds of hydroxyl)

(methyl) acrylic compounds of the hydroxyl of the present invention also has the most obtainable a lot of compound, but Can also be obtained by epoxide and (methyl) acrylic acid esterification by ring opening.

The reaction of esterification by ring opening both can be carried out in the absence of a solvent, or can also carry out in a solvent.As This solvent, as long as the solvent inert to reaction, can use known solvent, can enumerate such as normal hexane, benzene, toluene And the hydrocarbon system solvent such as dimethylbenzene,

The ketone series solvents such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK),

The ester series solvent such as ethyl acetate and butyl acetate,

The ether series solvents such as ether, oxolane and dioxane,

Dichloromethane, chloroform, carbon tetrachloride, 1, the halogen series solvent such as 2-dichloroethanes and perchloroethylene,

DMF, N,N-dimethylacetamide, N, N-methylimidazole alkanone, dimethyl sulfoxide and ring fourth Sulfone polar solvent.

These solvents can one be used alone or two or more and use.

It addition, this reaction can also use catalyst as required.Catalyst can use known catalyst, can enumerate The organic phosphine compounds such as such as triphenylphosphine,

The tertiary amines such as triethylamine and triethanolamine,

The quaternary ammonium salt such as trimethyl ammonium chloride and triethyl benzyl ammonia chloride,

The imidazoles such as the organophosphor salt such as tetrabutyl phosphonium bromide, tetraphenylphosphonibromide bromide and 2-methylimidazole,

The organo-metallic compound classes such as octenoic acid cobalt.

The addition of catalyst is usually 0.01～10.0 weight % relative to gross weight 100 weight % of reactant, excellent Elect 0.01～5.0 weight % as.If the addition of catalyst is within the above range, then can obtain enough reaction speed during reaction Degree, the most preferably.

Reaction temperature is not particularly limited, generally in the range of 0～200 DEG C, preferably in the range of 0～150 DEG C.

Response time depends on the conditions such as reaction temperature, is therefore not particularly limited, usually several minutes～tens of hours.Separately Outward, it is also possible to confirmed anti-by known analysis method (such as liquid chromatography, thin layer chromatography, infrared spectrometry etc.) Should rate, with arbitrary response rate stopped reaction.

(diisocyanate cpd)

The diisocyanate cpd of the present invention also has the most obtainable a lot of compound, and they can directly make With, but such as can also carry out being synthesized into by the reaction of corresponding diamine compound and phosgene.

(operation)

Carbamate (methyl) acrylic compounds such as by include following (B) operation, preferably include following (A), the method for the operation of (B) and (C) manufactures.It addition, the carbamate of gained (methyl) acrylic compounds has Time also can be mixed into the foreign body of trace, the most further preferably include the operation that this foreign body is filtered to remove.

(A) operation at 20～90 DEG C, (methyl) acrylic compounds of hydroxyl being dehydrated；

(B) (methyl) acrylic compounds of the hydroxyl after dehydration procedure or (methyl) of hydroxyl that be not dehydrated Acrylic compounds puts into diisocyanate cpd by dropping, carries out the operation of urethane reaction；With And

(C) at 20～90 DEG C, carry out the operation of deodorize.

<operation A>

Operation (A) is to mix inhibition as required in hydroxyl (methyl) acrylic compounds in the presence of oxygen Agent, urethanation catalyst etc., carry out the operation being dehydrated at a temperature of 20～90 DEG C.If (methyl) third of hydroxyl Containing moisture in olefin(e) acid compounds, then when the urethane of subsequent handling (B) reacts, it is possible to can lead because of moisture Cause diisocyanate cpd decomposes, and the most preferably carries out operation A.

Operation (A) preferably adds polymerization inhibitor.The present invention can use known polymerization inhibitor, be not particularly limited, can example Citing such as hydroquinone (HQ), hydroquinone monomethyl ether (MQ), 2,6-di-tert-butyl hydroxy toluene (BHT) and phenothiazine (PTZ).BHT and its Its phenolic polymerization inhibitor is compared, and situation about being consumed by reacting with NCO is less, can see in amine system polymerization inhibitor Coloring as arriving is few, the most preferably.The consumption of polymerization inhibitor is relative to (methyl) acrylic compounds and two of hydroxyl Gross weight 100 weight % of isocyanate compound is preferably 0.001～0.5 weight %.As the interpolation period of polymerization inhibitor, can Medium to be pre-mixed (methyl) acrylic compounds at hydroxyl, as long as before dropping diisocyanate cpd just Can add in any period, but before dehydration, add the loss that can alleviate the polymerizable group caused by thermal history, the most excellent Choosing.

Operation (A) preferably adds urethanation catalyst.The present invention can use known carbamate Change catalyst, be not particularly limited, can enumerate such as:

Dibutyl tin laurate, two octanoic acid the organo-tin compounds such as dibutyl tin and tin octoate,

Beyond the stannum such as copper naphthenate, cobalt naphthenate, zinc naphthenate, acetylacetone,2,4-pentanedione zirconium, ferric acetyl acetonade and acetylacetone,2,4-pentanedione germanium Other organo-metallic compound,

Triethylamine, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane, 2,6,7-trimethyls-1-diazabicyclo [2.2.2] are pungent Alkane, 1,8-diazabicyclo [5.4.0] hendecene, N, N-dimethyl cyclohexyl amine, pyridine, N-methylmorpholine, N, N, N ', N '-four Methyl ethylenediamine, N, N, N ', N '-tetramethyl-1,3-butanediamine, N, N, N ', N '-five methyl diethylentriamine, N, N, N ', N '-four (3-dimethylamino-propyl)-methane diamidogen, N, N '-lupetazin and 1, the amines such as 2-methylimidazole and it Salt,

The trialkyl phosphine compounds such as tri-n-butyl phosphine, three n-hexyl phosphines, tricyclohexyl phosphine and tri-n-octyl phosphine.

Wherein, be preferably used can carry out on a small quantity reacting, the tin dilaurate high to the selectivity of diisocyanate cpd Dibutyl tin and tin octoate.When using urethanation catalyst, relative to (methyl) acrylic compounds of hydroxyl With gross weight 100 weight % of diisocyanate cpd, preferably add 0.001～0.1 weight %.If fewer than 0.001 weight Amount %, then the effect of catalyst is little, and the response time is long, if more than 0.1 weight %, then catalyst effect is big, produces substantial amounts of Reaction heat, is difficult to temperature control sometimes.As the interpolation period of urethanation catalyst, can be pre-mixed and contain (methyl) acrylic compounds of hydroxyl is medium, as long as can be just any before dripping diisocyanate cpd Phase.

(methyl) acrylic compounds as hydroxyl of oxygen, carbamate (methyl) acrylic compounds of the present invention The polymerization inhibitor of compound is effective.As oxygen, use dry air or oxygen, dry air is preferably used, from the bottom of reaction vessel Supply with air bubble-shaped.As dry air, the air being preferably dried with freeze type air drier etc..If being dried insufficient, Reaction system is then mixed into moisture, causes diisocyanate cpd and the reaction of water, gained carbamate may be caused The increase of the viscosity of (methyl) acrylic compounds.It addition, the quantity delivered of dry air depends on the size of reaction vessel, nothing It is particularly limited to, such as, when reaction vessel is 1L, is 1～500ml/ minute, preferably 1～300ml/ minute.If fewer than 1ml/ Minute, then cannot supply enough amounts, it is possible to do not have the effect of polymerization inhibitor, if more than 500ml/ minute, then in reaction Time can increase the volatilization of diisocyanate cpd, the solidification of carbamate (methyl) acrylic compounds may be reduced After physical property.

Temperature during dehydration is the temperature that polymerizable group does not occur thermal polymerization, generally in the range of 20～90 DEG C, excellent It is selected in the range of 30～80 DEG C.If less than 20 DEG C, then it is dehydrated insufficient, causes the anti-of diisocyanate cpd and water Should, the viscosity of carbamate (methyl) acrylic compounds may increase.On the other hand, if above 90 DEG C, then may be used Polyreaction, carbamate (methyl) acrylic compounds can be occurred to colour.

Pressure during dehydration is not particularly limited, generally in the range of 0.133～13.3kPa (1～100mmHg), preferably In the range of 0.133～6.67kPa (1～50mmHg).If less than 0.133kPa, then energy consumption increases, and causes environment negative Load, the most undesirable.On the other hand, if above 13.3kPa, then it is dehydrated insufficient, causes diisocyanate cpd and water Reaction, the viscosity of carbamate (methyl) acrylic compounds may increase.

Dewatering time is not particularly limited, the moisture in suitable mensuration system, by (methyl) acrylic acid relative to hydroxyl Gross weight 100 weight % of compounds, polymerization inhibitor and urethanation catalyst reaches below 0.15 weight %, preferably Moment below 0.10 weight % is as terminal.Determination of water can use moisture content determining device to enter on the basis of JIS K0068 OK, the volumetric precipitation method such as using the automatic titration device using karr Karl Fischer reagent can be enumerated.Specifically, Ke Yi After being dehydrated under vacuum, recover to normal pressure, gather (methyl) acrylic compounds, polymerization inhibitor and the carbamic acid of hydroxyl The mixture of esterification catalyst is measured.

<process B>

Operation (B) is (methyl) acrylic compounds of the hydroxyl after dehydration procedure or the hydroxyl not being dehydrated (methyl) acrylic compounds puts into diisocyanate cpd by dropping, carries out the work of urethane reaction Sequence.

In the present invention, as (methyl) acrylic compounds and the use ratio of diisocyanate cpd of hydroxyl Example, relative to NCO 1.0 equivalent of diisocyanate cpd, the hydroxyl of (methyl) acrylic compounds of hydroxyl Base is 1.0～1.3 equivalents, preferably 1.0～1.1 equivalents.The amount of the hydroxyl of (methyl) acrylic compounds of hydroxyl is such as Fruit less than 1.0 equivalents, then NCO unreacted and left behind, the most likely can cause solids precipitation, The increase of viscosity.On the other hand, if more than 1.3 equivalents, (methyl) acrylic compounds of the most unreacted hydroxyl increases Many, it is thus possible to the physical property after solidification to be caused and decline.

It addition, dropping refers to the diisocyanate cpd of regulation is added the dropping container being connected with reaction vessel, logical Overregulate flow, through the method that a certain amount of diisocyanate cpd is added reaction vessel by the regular hour.In contrast, By in the baiting method in the lump of the diisocyanate cpd of regulation all blankings at short notice, according to (methyl) of hydroxyl Acrylic compounds, the structure of diisocyanate cpd, molecular weight, the structure of reaction vessel, the shape of stirring vane, stir Mixing the difference of speed etc., temperature can significantly raise, it is possible to is difficult to temperature control, and the crosslinking of diisocyanate cpd is anti- Should be promoted, the increase of the viscosity of gained carbamate (methyl) acrylic compounds may be caused, according to circumstances May cause the polymerization of polymerizable group, thus gelation.

(methyl) acrylic compounds of hydroxyl can also be dropped in diisocyanate cpd.Now, because of For in most cases using (methyl) acrylic compounds of the hydroxyl of more amount compared with diisocyanate cpd, So compared with the situation of dropping diisocyanate cpd, time for adding extends, and to carbamate (methyl) propylene Acid compounds applies unnecessary thermal history, causes the polymerization of polymerizable group, and production efficiency is deteriorated sometimes.

Temperature in reaction system depends on the size of reaction vessel, structure etc., is not particularly limited, usually 20～120 DEG C, preferably 30～100 DEG C.If above 120 DEG C, then it may happen that polyreaction, possibly cannot obtain having desired Carbamate (methyl) acrylic compounds of effect.If less than 20 DEG C, then the response time extends, and production efficiency may Can be deteriorated.

Temperature when dropping starts is not particularly limited, usually 20～90 DEG C, preferably 30～80 DEG C.If less than 20 DEG C, then reaction needs a lot of times, may cause the decline of production efficiency.On the other hand, if above 90 DEG C, then have and send out The probability of raw polyreaction, reaction (dropping) temperature may raise, and reaction becomes uncontrollable.

As long as rate of addition maintains the speed of the temperature in above-mentioned reaction system.

As long as time for adding meets the time of said temperature, usually 0.1～30 hour, preferably 0.1～5 is little Time.If being shorter than 0.1 hour, then temperature may significantly raise, it is difficult to carries out temperature control.If it addition, be longer than 5 hours, Then there is the tendency that the production efficiency of carbamate (methyl) acrylic compounds is deteriorated.

In operation (B), react in above-mentioned time for adding unclosed in the case of, can be as required after completion of dropwise addition Continue reaction.This response time depends on reaction temperature, the size of reaction vessel, structure, time for adding etc., therefore without limit especially Fixed, it is usually 1～30 hour with the summation of time for adding, preferably 1～20 hour.If being shorter than 1 hour, then react likely It is not fully complete, if being longer than 30 hours, then carbamate (methyl) acrylic compounds may be applied unnecessary heat and go through History, causes the polymerization of polymerizable group, may result in production efficiency variation, product price rising.

As long as the reaction temperature polymerizable group after completion of dropwise addition does not occur the temperature of thermal polymerization, indefinite, lead to Often in the range of 20～120 DEG C, preferably in the range of 30～100 DEG C.If less than 20 DEG C, then the response time may prolong Long, the decline of production efficiency may be caused.It addition, if above 120 DEG C, then it may happen that polyreaction, carbamic acid Ester (methyl) acrylic compounds may colour.

As the confirmation method of the terminal of reaction, can enumerate and be surveyed by the assay method on the basis of JIS K15565.5 Determine the method for the content of the diisocyanate cpd in reaction product, use the analysis etc. of HPLC (high performance liquid chromatography). Specifically, following method can be enumerated: taken out from reaction vessel by reaction product so that it is react with di-n-butylamine, use salt Acid titrates unreacted amine, thus measures the content of the diisocyanate cpd in reaction product.Calculated by the method Go out the content of diisocyanate cpd, by the content of diisocyanate cpd relative to weight 100 weight of reaction product Amount % reaches the moment of below below 0.5 weight %, preferably 0.1 weight % as terminal.

<operation C>

After above-mentioned operation (B) terminates, there is operation (C) the most as required that carry out deodorize.By deodorize, can obtain Good carbamate (methyl) acrylic compounds.

There is not the temperature of thermal polymerization in the temperature preferred polymeric group of operation (C), generally the scope of 20～120 DEG C In, preferably in the range of 30～100 DEG C.If less than 20 DEG C, then deodorize is insufficient, may obtain foul smell and strongly and preserve Carbamate (methyl) acrylic compounds of poor stability.It addition, if above 120 DEG C, then it may happen that be polymerized Reaction, carbamate (methyl) acrylic compounds may colour.

The pressure of operation (C) is not particularly limited, generally in the range of 0.133～13.3kPa (1～100mmHg), preferably In the range of 0.133～6.67kPa (1～50mmHg).If less than 0.133kPa, being the most industrially difficult to, causing Cost raises, the most undesirable.It addition, if above 13.3kPa, then deodorize is insufficient, foul smell may be obtained and strongly and protect Deposit carbamate (methyl) acrylic compounds of poor stability.

Deodorization time depends on the size of reaction vessel, structure, is not particularly limited, usually 1～10 hour, preferably 1 ～5 hours.If being shorter than 1 hour, then deodorize is insufficient, may obtain the carbamic acid that foul smell is strong and storage stability is poor Ester (methyl) acrylic compounds.If it addition, be longer than 10 hours, then may be to carbamate (methyl) acrylic compounds Compound applies unnecessary thermal history, causes the polymerization of polymerizable group, may result in production efficiency variation, product price liter High.

(other)

In the dental materials of the present invention, can not damage coordinate as required in the range of the purpose of the present invention heat-resisting surely Determine agent, antilubricant, crystallization auxiliary, nucleator, pigment, dyestuff, plasticizer, antiaging agent, antioxidant, impact improving agent, friendship The various additives such as connection agent, co-crosslinker, crosslinking coagent, binding agent, softening agent, processing aid.

[solidfied material]

Make the solidification that the dental materials containing carbamate (methyl) acrylic compounds of the present invention solidifies Thing in addition to mechanical strength, mar proof, aesthetic property, operability, safety, the especially polymerization shrinkage when polymerizing curable Rate is little.Therefore, this solidfied material is suitable for dental materials purposes.

Curing is not particularly limited, and can enumerate such as normal temperature cure, be heating and curing, by visible ray, the photograph of ultraviolet Inject row photocuring etc..

[dental materials compositions and dental prosthetic material]

The dental materials of the present invention can be preferably used as the composition of dental materials compositions.

As dental materials compositions, (abutment builds with multiple can to enumerate such as dental prosthetic material, dental composite resin Resin, corona composite resin, fill reparation composite resin), dental plate resin, dental plate gasket material, die Material, bonding material (resinoid bond, resin addition type glass ionomer cement), dental adhesive material, denture are rectified Just with adhesives, pit and fissure sealant, CAD/CAM resin mass, temporary crown, artificial teeth material etc..

Particularly comprise the dental materials of the present invention, following polymerization initiator (B) and the dental materials compositions of filler (C) Being preferably to use one of form, this dental materials compositions is such as suitable as dental composite resin.

It addition, the dental materials compositions comprising the dental materials of the present invention, Photoepolymerizationinitiater initiater (B) and filler (C) is fitted Cooperation is dental prosthetic material.This dental prosthetic material has photo-curable, is suitable as dental composite resin, is particularly suitable for As filling reparation composite resin.

It addition, the dental materials compositionss such as dental prosthetic material can be applied in combination the amino first of the present invention as required Known polymerizable monomer (D) beyond acid esters (methyl) acrylic compounds.If being applied in combination polymerizable monomer (D), Then can adjust the viscosity of said composition, refractive index according to purpose, the most preferably.

It should be noted that dental prosthetic material is typically to comprise the pastel of filler (C).This thickener typically at least incite somebody to action this Carbamate (methyl) acrylic compounds, this polymerizable monomer (D) and the Photoepolymerizationinitiater initiater (B) of invention and filler (C) it is obtained by mixing.If comprising this carbamate (methyl) acrylic compounds and the combination of this polymerizable monomer (D) The viscosity of thing (I) is too high, then difficult with the mixing of filler (C), it is difficult to improve loading.If it addition, viscosity is too low, then with The mixing of filler (C) is difficult to become pasty state.The viscosity of said composition (I) is usually 50～50000 (mpa s, 30 DEG C), excellent Elect 100～20000 as (mpa s, 30 DEG C), more preferably 100～10000 (mpa s, 30 DEG C).The dental materials of the present invention Compositions has two kinds of reverse effects, i.e. have suitable viscosity when preparing dental prosthetic material, but in said composition Polymerization shrinkage during polymerizing curable is the lowest.

(polymerization initiator or Photoepolymerizationinitiater initiater (B))

Known (light) polymerization initiator that (light) polymerization initiator uses in can using dental field, it is generally considered that Polymerism and the polymerizing condition of polymerizable monomer select.

When being polymerized at normal temperatures, the polymerization of the redox system the most preferably oxidant and reducing agent combined Initiator.When using the polymerization initiator of redox system, need to use the form packed respectively by Oxidizing and Reducing Agents, Just before use both are mixed.

It is not particularly limited as oxidant, such as diacyl peroxide class, peroxyesters, dialkyl group peroxide can be enumerated The organic peroxides such as compound class, peroxy ketal class, ketone peroxide class and hydroperoxide type.Specifically can enumerate benzoyl peroxide Formyl, 2, the diacyl peroxide class such as 4-dichlorobenzoperoxide and m-toluyl peroxide,

Peroxidized t-butyl perbenzoate, peroxidating M-phthalic acid di tert butyl carbonate, 2,5-dimethyl-2, the double (peroxidating of 5- Benzoyl) hexane, the peroxyesters such as peroxide-2-ethyl hexanoic acid tert-butyl and tert-butylperoxy isopropyl carbonate,

The dialkyl peroxide classes such as dicumyl peroxide, di-t-butyl peroxide and lauroyl peroxide,

1,1-bis(t-butylperoxy)-3, the peroxy ketal class such as 3,5-trimethyl-cyclohexanes,

The ketone peroxide classes such as methyl-ethyl-ketone peroxide,

The hydroperoxide type such as tert-butyl hydroperoxide.

It addition, be not particularly limited as reducing agent, generally use tertiary amine, such as DMA, N, N-can be enumerated Dimethyl-p-toluidine, N, N-dimethyl meta-aminotoluene, N, N-diethyl-p-tlouidine, N, N-dimethyl-3,5-dimethyl benzene Amine, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-MEA, N, N-dimethyl-4-isopropyl aniline, N, N-dimethyl-4-tert-butyl group aniline, N, N-dimethyl-3,5-di-tert-butyl aniline, N, double (2-hydroxyethyl) para-totuidine of N-, Double (the 2-hydroxyethyl)-3 of N, N-, 5-dimethylaniline, N, double (the 2-hydroxyethyl)-3 of N-, 4-dimethylaniline, N, the double (2-of N- Hydroxyethyl)-4-MEA, double (2-the hydroxyethyl)-4-isopropyl aniline of N, N-, double (2-the hydroxyethyl)-4-uncle of N, N- Butylaniline, N, N-bis-(2-hydroxyethyl)-3,5-diisopropyl aniline, N, N-bis-(2-hydroxyethyl)-3,5-di-t-butyl Aniline, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid n-butoxy ethyl ester, 4-dimethylaminobenzoic acid (2-first Base acryloxy) ethyl ester, trimethylamine, triethylamine, N methyldiethanol amine, N-ethyldiethanolamine, N-normal-butyl diethanol Amine, N-Lauryl Diethanolamine, triethanolamine, methacrylic acid (2-dimethylamino) ethyl ester, the double (methacryloxy of N, N- Ethyl)-N-methylamine, double (the methacryloxyethyl)-N-ethamine of N, N-, double (2-the hydroxyethyl)-N-metering system of N, N- Acyloxy ethamine, N, N-double (methacryloxyethyl)-N-(2-hydroxyethyl) amine, three (methacryloxyethyl) Amine etc..

In addition to these organic peroxides/amine system, it is also possible to use cumene hydroperoxide/thiourea system, ascorbic acid/ Cu²⁺Salt system, organic peroxide/amine/sulfinic acid (or its salt) such as are at the redox system polymerization initiator.

It addition, as polymerization initiator, it is also preferred that use tri-n-butylbo-rane, organic sulfinic acid etc..

When carrying out photopolymerization by radiation of visible light, preferably α-diketone/tertiary amine, α-diketone/aldehyde, α-diketone/mercaptan etc. Oxidoreduction series initiators.

It is not particularly limited as Photoepolymerizationinitiater initiater, such as α-diketone/reducing agent, ketal/reducing agent, thioxanthene can be enumerated Ketone/reducing agent etc..As α-diketone, camphorquinone, benzil and 2,3-pentanedione etc. can be enumerated.As ketal, benzene can be enumerated even Acyl dimethyl ketal and benzil diethyl ketal etc..As thiaxanthone, CTX and 2,4-diethyl thioxanthene can be enumerated Ketone etc..As reducing agent, can enumerate Michler's keton etc.,

Methacrylic acid-2-(dimethylamino) ethyl ester, N, N-double ((methyl) acryloyl-oxyethyl)-N-methylamine, N, N- Dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid butoxyethyl, N-methyl diethyl Hydramine, 4-dimethylamino benzopheone, double (2-hydroxyethyl) tertiary amine such as para-totuidine and dimethylamino phenanthrol of N, N-,

The aldehydes such as citronellal, lauryl aldehyde, o-phthalaldehyde(OPA), dimethylaminobenzaldehyde and terephthalaldehyde,

2-mercaptobenzooxazole, decyl mercaptan, 3-mercaptopropyi trimethoxy silane, 4-sulfydryl 1-Phenylethanone., thiosalicylic acid And thiobenzoate etc. has the compound etc. of mercapto.

It is also preferred that use the α-diketone/organic peroxy adding organic peroxide in these redox systems and obtain The system of compound/reducing agent.

Irradiated when carrying out photopolymerization by ultraviolet, preferably benzoin alkylether and benzil dimethyl ketal etc..Separately Outward, it is also preferred that use the Photoepolymerizationinitiater initiater of (double) acylphosphine oxide class.

(double) acylphosphine oxide apoplexy due to endogenous wind, as acylphosphine oxide class, can enumerate such as 2,4,6-trimethylbenzoyls two Phenyl phosphine oxide, 2,6-Dimethoxybenzoyl diphenyl phosphine oxide, 2,6-dichloro-benzoyl base diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl methoxyphenyl phosphine oxide, 2,4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxides, 2,3,5, 6-durol formoxyl diphenyl phosphine oxide and benzoyl two (2,6-3,5-dimethylphenyl) phosphonate ester etc..

As double acylphosphine oxide classes, can enumerate the most double (2,6-dichloro-benzoyl base) phenyl phosphine oxide, double (2,6-bis- Chlorobenzene formacyl)-2,5-3,5-dimethylphenyl phosphine oxide, double (2,6-dichloro-benzoyl base)-4-propylphenylphosphine oxide, double (2, 6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, double (2,6-Dimethoxybenzoyl) phenyl phosphine oxide, double (2,6-dimethoxies Base benzoyl)-2,4,4-trimethylpentylphosphine oxide, double (2,6-Dimethoxybenzoyl)-2,5-3,5-dimethylphenyl oxygen Change phosphine, double (2,4,6-trimethylbenzoyl) phenyl phosphine oxide and (2,5,6-trimethylbenzoyl)-2,4,4-trimethyls Amyl group phosphine oxide etc..

The Photoepolymerizationinitiater initiater of these (double) acylphosphine oxide classes can be used alone or can also be with various amines, aldehyde The reducing agents such as class, thio-alcohol and sulfinate are also used.

Can also preferably with the Photoepolymerizationinitiater initiater of above-mentioned visible ray using.

Above-mentioned polymerization initiator or Photoepolymerizationinitiater initiater can be used alone or two or more appropriately combined use, coordinating Measure and be usually 0.01～20 weight % relative to dental materials compositions 100 weight %, be preferably the scope of 0.1～5 weight % Interior use.

(filler (C))

Filler can use the known filler used in dental field, is generally roughly divided into organic filler and inorganic fills out Material.

As organic filler, can enumerate polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate- Ethyl methacrylate copolymers, cross-linking type polymethyl methacrylate, cross-linking type polyethyl methacrylate, ethylene-acetate Vinyl ester copolymers and SB etc..

As inorganic filler, can enumerate various category of glass (with silicon dioxide as main constituent, as required contain heavy metal, The oxide of boron and aluminum etc.), various ceramic-like, kieselguhr, Kaolin, clay mineral (montmorillonite etc.), active hargil, synthesis boiling Stone, Muscovitum, calcium fluoride, fluorination ytterbium, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite etc..

Alternatively, it is also possible to use makes it be polymerized after adding polymerizable monomer in advance in these inorganic fillers, making pasty state Solidification, pulverized and the organo-mineral complexing filler that obtains.

These fillers suitably one can be used alone or be used in combination.

Consider that the operability (viscosity) of thickener, mechanical strength suitably determine the use level of filler, relative to tooth All the components 100 weight portion beyond filler contained in section's material compositions, usually 10～2000 weight portion, preferably 50 ～1000 weight portions, more preferably 100～600 weight portions.

In the present invention, if coordinate refractive index in this inorganic filler be 1.5～1.6 there is the inorganic of x-ray imaging Filler, then become the dental composite resin useful as dental prosthetic material.Desired heavy as dental composite resin The physical property wanted, has the transparency as natural teeth and x-ray imaging.The transparency is by making inorganic filler and polymerism list Refractive index after the solidification of body the most unanimously realizes.In order to give x-ray imaging, as inorganic filler, increasingly How to use the inorganic oxide with heavy metal elements such as zirconium, barium, titanium and lanthanums.Such inorganic filler containing heavy metal element Refractive index generally the highest, in the range of 1.5～1.6.Carbamate (methyl) acrylic compounds of the present invention because of There is for intramolecular the ring structure of more than 1, so the refractive index after Gu Hua is higher, there is the refractive index of more than 1.50 more.Cause This, if combined with the inorganic filler of this high index of refraction, then can reduce refractivity, is therefore readily obtained high the consolidating of the transparency Compound.

As this inorganic filler, can enumerate such as barium borosilicate glass (Kimble Raysorb T3000, Schott8235, Schott GM27884 and Schott GM39923 etc.), strontium Boroalumino silicate glasses (Raysorb T4000, Schott G018-093 and Schott GM32087 etc.), lanthanum glass (Schott GM31684 etc.), aluminum fluoride glass (Schott G018-091 and Schott G018-117 etc.), Boroalumino silicate glasses (Schott G018-containing zirconium and/or caesium 307, G018-308 and G018-310 etc.).

It addition, in dental materials compositions, the compositions being combined with micro-filler that particle diameter is below 0.1 μm is that dental is multiple One of preferred configuration of resin.

As the material of the little filler of this particle diameter, preferably silicon dioxide (such as trade name AEROSIL), aluminium oxide, oxidation Zirconium, titanium oxide etc..

The cooperation of the inorganic filler that such particle diameter is little has in terms of obtaining the grinding lubricity of solidfied material of composite resin Profit.

For these fillers, implement surface with silane coupler etc. sometimes according to purpose and process.Process as this surface Agent, can use known silane coupler, such as γ-methacryloxyalkyl trimethoxy silane (methacryloxypropyl Carbon number between base and silicon atom is: 3～12), γ-methacryloxyalkyl triethoxysilane (metering system Carbon number between acyloxy and silicon atom is: 3～12), vinyltrimethoxy silane, VTES and The organo-silicon compound such as vinyltriacetoxy silane.The concentration of surface conditioning agent is usual relative to filler 100 weight % It is 0.1～20 weight %, is preferably use in the range of 1～5 weight %.

(polymerizable monomer (D))

Polymerizable monomer be beyond carbamate (methyl) acrylic compounds of the present invention in dental field Conventional monomer, is not particularly limited, can enumerate such as alpha-cyanoacrylate, (methyl) acrylic acid, alpha-halogen acrylic acid, bar The carboxylate in bean acid, cinnamic acid, sorbic acid, maleic acid and itaconic acid etc., (methyl) acrylamide, (methyl) acrylamide are derivative Thing, vinyl ester, vinyl ethers, list-N-ethenyl derivatives and styrene derivative etc..(methyl) is wherein preferably used Acrylate.The example of this polymerizable monomer is as follows.It should be noted that in the present invention, will have an alkene double The monomer of key is denoted as monofunctional monomer.Similarly, the monomer that alkene double bond is two is denoted as bifunctional monomer, by alkene Double bond is that the monomer of three is denoted as trifunctional monomer.

It addition, these polymerizable monomers one can be used alone or be used in combination.

(I) as monofunctional monomer, (methyl) acrylic acid methyl ester., (methyl) Isobutyl 2-propenoate, (methyl) third can be enumerated Olefin(e) acid benzyl ester, (methyl) lauryl acrylate, (methyl) acrylic acid 2-(N, N-dimethylamino) ethyl ester, (methyl) acrylic acid 2,3- Dibromo propyl ester, 3-methacryloxypropyl trimethoxy silane, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid The own ester of 6-hydroxyl, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, propylene glycol list (methyl) acrylate, glycerol list (methyl) acrylic acid Ester, erithritol list (methyl) acrylate, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N, N-(dihydroxy ethyl) (methyl) acrylamide, (methyl) acryloxy dodecylpyridinium bromide, (methyl) acryloyl Epoxide cetylpyridinium chloride and (methyl) acryloxy hexadecylpyridinium chloride etc..

(II) as bifunctional monomer, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) propylene can be enumerated Acid esters, propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylic acid Ester, decamethylene-glycol two (methyl) acrylate, bisphenol-A methacrylic acid 2-glycidyl ester (2,2-double (4-(3-methyl-prop Alkene acyloxy-2-hydroxy propyloxy group) phenyl propane；Common name BisGMA), 2, double (4-(methyl) the acryloyloxyethoxy benzene of 2- Base) propane, 2, double (4-(methyl) acryloyl-oxy Quito ethoxyl phenenyl) propane of 2-, 2, the double (4-(3-acryloxy-2-of 2- Hydroxy propyloxy group) phenyl propane, 1,2-double (3-(methyl) acryloxy-2-hydroxy propyloxy group) ethane, tetramethylolmethane two (methyl) acrylate and double (the 2-carbamoyloxy ethyl) ester (common name of dimethacrylate 2,2,4-tri-methyl hexamethylene And the compound etc. that represents of following formula (6) UDMA).

It should be noted that in formula (6), R separately represents hydrogen atom or methyl, m and n be respectively 0～10 whole Number, and m+n=0～10.

It addition, for formula (6), can refer to Japanese Laid-Open Patent Publication 56-26809 publication, its manufacture method is not particularly limited, Such as in the case of m+n is not equal to 0, can be as shown in following reacting flow chart 2, in adding of diatomic alcohol compounds and oxirane After becoming reaction, manufactured by this reactant and (methyl) acrylic acid reaction.

(III) as monomer more than trifunctional, trimethylolpropane tris (methyl) acrylate, trihydroxy methyl can be enumerated Ethane three (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, N, N '-(2,2,4-tri-methyl hexamethylene) double (2-(amino carboxyl) propane-1,3-glycol) tetramethyl acrylate, 1,7-dipropyl Alkene acyloxy-2,2,6,6-tetrapropylene pivaloyloxymethyl-4-oxygen heptane etc..

In the present invention, because shrinkage factor and viscosity are relatively low, so as polymerizable monomer (D), the most above-mentioned formula (6) represents Compound, the R in the most above-mentioned formula (6) is integer and the change of m+n=2～6 that hydrogen atom, m and n are respectively 0～6 Compound.

During it addition, above-mentioned dental composition is used as dental adhesive material, as the monomer of copolymerization, preferably further Various adhesive monomer, particularly intramolecular is coordinated to have the monomer of acidic-group.The monomer with acidic-group refers to same There is in a part the compound of acidic-group and polymerizable group, can enumerate and there is such as phosphate moiety, pyrophosphoric acid residue, sulfur For phosphate moiety, carboxylic acid residues or sulfonic acid moieties etc. as acidic-group, there is such as acryloyl group, methylacryloyl, second Thiazolinyl, styryl etc. are as the compound of polymerizable group.

As having the polymerizable monomer of phosphate moiety, such as biphosphate 2-(methyl) acryloxy second can be enumerated Ester, biphosphate 9-(methyl) acryloxy nonyl ester, biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems, biphosphate 11- (methyl) acryloxy undecyl ester, biphosphate 20-(methyl) acryloxy eicosyl ester, 2-biphosphate 1, 3-bis-(methyl) acryloxy propyl ester, 2-(methyl) acryloyl-oxyethyl phosphenylic acid, 2-(methyl) acryloxy second Base 2 '-bromoethyl phosphoric acid, (methyl) acryloyl-oxyethyl phenyl phosphonic acid esters etc. or their acyl chlorides compound.

As having the polymerizable monomer of pyrophosphoric acid residue, such as pyrophosphoric acid two (2-(methyl) acryloxy can be enumerated Ethyl ester) etc. or their acyl chlorides compound.

As having the polymerizable monomer of thiophosphate residue, such as phosphordithiic acid dihydro 2-(methyl) propylene can be enumerated Acyloxy ethyl ester and D2EHDTPA dihydro 10-(methyl) acryloxy ester in the last of the ten Heavenly stems etc. or their acyl chlorides compound.

As having the polymerizable monomer of carboxylic acid residues, such as 4-(methyl) acryloyloxyethoxy carbonyl can be enumerated adjacent Phthalic acid, 5-(methyl) Acryloyl amino pentylformic acid and 11-(methyl) acryloxy-1,1-undecane etc. Or their acyl chlorides compound, anhydride etc..

As having the polymerizable monomer of sulfonic acid moieties, such as 2-(methyl) acrylamido-2-methyl-prop sulphur can be enumerated Acid, styrene sulfonic acid and (methyl) acrylic acid 2-Sulfoethyl esters etc..

These polymerizable monomers with acidic-group one can be used alone or be used in combination.

The use level of these polymerizable monomers is not particularly limited, at carbamate (methyl) propylene relative to the present invention Total amount 100 weight portion of acid compounds is typically not greater than in the range of 100 weight portions and uses.

(other)

In the dental materials compositions of the present invention, can contain as required in the range of the purpose of the present invention not damaging The additives such as polymerization inhibitor, UV absorbent, fluorescent agent, pigment.

As polymerization inhibitor, such as 2 can be enumerated, 6-dibenzylatiooluene, hydroquinone, dibutyl hydroquinone, dibutyl hydroquinone list Methyl ether, hydroquinone monomethyl ether, 2,6-DI-tert-butylphenol compounds etc., they can use one or more.

Embodiment

By embodiment, the present invention will be described in more detail, but the present invention is not limited to the examples.

[manufacturing example 1]

Acrylic acid 3-phenoxy group-2-hydroxyl is added in the 300 milliliters of four-necked bottles possessing stirring vane, thermometer and return duct Base propyl ester 111.1g (0.5 mole) and dibutyl tin laurate 0.11g ((methyl) acrylic compounds chemical combination relative to hydroxyl The weight of thing is 1000ppm), it is warming up to 60 DEG C.Then, (the hydrogenation of diisocyanate butylcyclohexyl methane was dripped through 0.5 hour MDI) 65.6g (0.25 mole), bearing reaction temperature rises to 80 DEG C.All after dropping, reaction temperature is maintained at 80～90 DEG C, Carry out the reaction of 10 hours.Weight % of the hydrogenation MDI in mensuration reaction product, result is 0.00 weight %.

From reactor, discharge product, thus obtain comprising carbamate (methyl) acrylic compounds represented with following formula The dental materials 170g of compound.

[manufacturing example 2～14]

(methyl) acrylic compounds and the diisocyanate that use the hydroxyl shown in table 11 replace manufacturing in example 1 The acrylic acid 3-phenoxy group-2-hydroxy propyl ester recorded and hydrogenation MDI, carry out the synthetic operation as manufacturing example 1, thus obtain Comprise the dental materials of various carbamate (methyl) acrylic compounds.

[table 11]

Table 11

[manufacturing example 15]

(0.2 rubs to add acrylic acid 14.4g in the 300 milliliters of four-necked bottles possessing stirring vane, thermometer and return duct You) and as tetrabutyl ammonium bromide 0.5g (1.7 mMs) of catalyst, it is warming up to 60 DEG C.Then, 4-was dripped through 0.7 hour Nonyl phenyl glycidyl glycerin ether 55.3g (0.2 mole), bearing reaction temperature rises to 65 DEG C.All after dropping, reaction temperature is protected Hold at 90～100 DEG C, carry out the reaction of 12 hours.After reaction terminates, reactant liquor is cooled to room temperature, adds toluene 200 milliliters. The toluene solution of gained is moved to the separatory funnel of 500 milliliters, washes with distilled water, until the pH of water layer reaches neutral.Washing After, from toluene layer, toluene is distilled off with vaporizer, obtains acrylic acid 2-hydroxyl-3-(4-Nonylphenoxy) propyl ester 60.6g (yield 87%).

The acrylic acid 2-previously obtained is added in the 300 milliliters of four-necked bottles possessing stirring vane, thermometer and return duct Hydroxyl-3-(4-Nonylphenoxy) propyl ester 52.3g (0.15 mole) and dibutyl tin laurate 0.05g is (relative to hydroxyl The weight of (methyl) acrylic compounds be 1000ppm), be warming up to 60 DEG C.Then, two Carbimide .s were dripped through 0.5 hour Ester group cyclohexyl-methane (hydrogenation MDI) 32.8g (0.125 mole), bearing reaction temperature rises to 80 DEG C.All after dropping, will be anti- Answer temperature to be maintained at 80～85 DEG C, carry out the reaction of 12 hours.Weight % of the hydrogenation MDI in mensuration reaction product, result It is 0.00 weight %.

From reactor, discharge product, thus obtain comprising carbamate (methyl) acrylic compounds represented with following formula The dental materials 81g of compound.

[manufacturing example 16～25]

Epoxide shown in use table 12 and acrylic or methacrylic acid replace manufacturing the 4-described in example 15 Nonyl phenyl glycidyl glycerin ether and acrylic acid, manufacture (methyl) acrylic compounds of hydroxyl, and then use shown in table 12 Diisocyanate replace HMDI, the synthetic operation carrying out with manufacturing as example 15, thus obtain comprising various carbamic acid The dental materials of ester (methyl) acrylic compounds.

[table 12]

Table 12

[manufacturing example 26]

(0.2 rubs to add acrylic acid 14.4g in the 300 milliliters of four-necked bottles possessing stirring vane, thermometer and return duct You) and as tetrabutyl ammonium bromide 0.5g (1.7 mMs) of catalyst, it is warming up to 60 DEG C.Then, 4-was dripped through 0.7 hour Nonyl phenyl glycidyl glycerin ether 55.3g (0.2 mole), bearing reaction temperature rises to 65 DEG C.All after dropping, reaction temperature is protected Hold at 90～100 DEG C, carry out the reaction of 12 hours.After reaction terminates, reactant liquor is cooled to room temperature, adds toluene 200 milliliters. The toluene solution of gained is moved to the separatory funnel of 500 milliliters, washes with distilled water, until the pH of water layer reaches neutral.Washing After, from toluene layer, toluene is distilled off with vaporizer, obtains acrylic acid 2-hydroxyl-3-(4-Nonylphenoxy) propyl ester 60.6g (yield 87%).

The acrylic acid 2-previously obtained is added in the 300 milliliters of four-necked bottles possessing stirring vane, thermometer and return duct Hydroxyl-3-(4-Nonylphenoxy) propyl ester 34.8g (0.1 mole), (0.1 rubs 1,4-CHDM mono acrylic ester 19.8g You) and dibutyl tin laurate 0.05g (relative to the weight of (methyl) acrylic compounds of hydroxyl be 1000ppm), 60 DEG C it are warming up to.Then, through dropping isophorone diisocyanate (IPDI) 22.2g (0.1 mole) in 0.5 hour, Bearing reaction temperature rises to 75 DEG C.All after dropping, reaction temperature is maintained at 80～90 DEG C, carries out the reaction of 12 hours.Survey Determining weight % of IPDI in reaction product, result is 0.00 weight %.

From reactor, discharge product, thus obtain comprising carbamate (methyl) acrylic compounds represented with following formula The dental materials 72g of compound.

[manufacturing example 27～31]

(methyl) acrylic compounds and the diisocyanate that use two shown in table 13 kind hydroxyl replace manufacturing Acrylic acid 2-hydroxyl-3-(4-Nonylphenoxy) propyl ester described in example 26 and 1,4-CHDM mono acrylic ester and IPDI, carries out the synthetic operation as manufacturing example 26, thus obtains comprising various carbamate (methyl) acrylic compounds The dental materials of compound.

[table 13]

Table 13

[FT-IR of dental materials measures]

Use infrared spectrophotometer (Biorad company FTS-6000), carry out manufacture example 1～31 in obtain comprise The FT-IR of the dental materials of carbamate (methyl) acrylic compounds measures.

Measurement result is shown in Fig. 1～31.

[embodiment 1～31: the mensuration of polymerization shrinkage]

Dental materials 70 weight comprising carbamate (methyl) acrylic compounds obtained in manufacturing example 1～31 Amount part mixes TEGDMA (the Xin Zhong village chemical industry strain formula of the diluting monomer adjusted as viscosity Commercial firm NK Ester3G) 30 weight portions, it is prepared as monomer composition, and then adds relative to this monomer composition 100 weight portion Add camphorquinone (with Guang Chun medicine Co., Ltd. system) 0.3 weight portion, N, N-dimethyl ethyl aminobenzoate (with Guang Chun medicine Co., Ltd. System) 0.3 weight portion so that it is dissolve, be prepared as light-cured type monomer composition (dental materials compositions).

This photo-polymerization type monomer composition is filled in diameter 10mm, the aluminium-making mould of deep 2mm, with coverslip from upper and lower After clamping, being irradiated with dental visible light irradiation device ((strain) Song Feng company TWIN polymerizer), every one side is 3 points Clock, two sides amounts to 6 minutes, makes light-cured type monomer composition solidify.

The light-cured type list before and after solidification is measured with dry type densimeter (company of (strain) Shimadzu Seisakusho Ltd. Accupyc1330) The density of body compositions, obtains polymerization shrinkage by following formula (1).

Formula (1): polymerization shrinkage (%)=(density after (density before density-polymerization after polymerization)/polymerization) × 100

Then, the single polymerization shrinkage of TEGDMA is measured by operation similar to the above Rate.As a result of which it is, its polymerization shrinkage is 13.0%.

Then, the dental materials comprising carbamate (methyl) acrylic compounds and triethylene glycol dimethyl are used The polymerization shrinkage (S1) of the mix monomer compositions of acrylate and TEGDMA are individually polymerized receipts Shrinkage (S2,13.0%), by obtaining the dental materials that comprises carbamate (methyl) acrylic compounds with following formula (2) Polymerization shrinkage (S3).

Formula (2): (S3)=((S1)-((S2) × 0.3))/0.7

Result is shown in table 14～16.

[embodiment 1～24,26～31: the mensuration of viscosity]

The dentistry comprising carbamate (methyl) acrylic compounds obtained in manufacturing example 1～23,28 and 29 Material 60 weight portion mixes the TEGDMA (NK of the diluting monomer adjusted as viscosity Ester3G) 40 weight portion, is prepared as monomer composition.

It addition, obtain in manufacturing example 24,26,27,30 and 31 comprises carbamate (methyl) acrylic compounds chemical combination Dental materials 40 weight portion of thing mixes TEGDMA 60 weight portion, is prepared as monomer composition.

Then, use these monomer compositions, measure 30 DEG C with E type viscometer (Dong Ji industry companies TV-22 type) Viscosity.It should be noted that cone rotor uses No4.It addition, the viscosity of TEGDMA is 10 (mpa s、30℃)。

Result is shown in table 14～16.

[comparative example 1 and 2]

Replace above-described embodiment the dental materials comprising carbamate (methyl) acrylic compounds, as with Bis-GMA (chemical industry Co., Ltd. of Xin Zhong village system toward the methacrylate monomer being widely used in dental composite resin D-GMA) TEGDMA (NK is mixed or in UDMA (Negami Chemical Ind Co., Ltd. SH500S) 60 weight portions Ester3G) 40 weight portion, is prepared as monomer composition.

Then, in comparative example 1, measure the 30 of said composition in the same manner as above-described embodiment with E type viscometer (TV-22 type) DEG C viscosity.

Then, in the same manner as above-described embodiment, add camphorquinone relative to this monomer composition 100 weight portion (pure with light Medicine Co., Ltd. system) 0.3 weight portion, N, N-dimethyl ethyl aminobenzoate (with Guang Chun medicine Co., Ltd. system) 0.3 weight portion, make It dissolves, and is prepared as light-cured type monomer composition.Then, the poly-of this monomer composition is obtained by method similar to the above Close shrinkage factor (S4).

And then, use the polymerization shrinkage (S4) of this monomer composition and TEGDMA individually to gather Close shrinkage factor (S2,13.0%), by the single polymerization shrinkage (S5) obtaining Bis-GMA or UDMA with following formula (3).

Formula (3): (S5)=((S4)-((S2) × 0.4))/0.6

Result is shown in table 16.

[table 14]

Table 14

[table 15]

Table 15

[table 16]

Table 16

[embodiment 32～37: polymerization shrinkage and the mensuration of viscosity]

The dental materials comprising carbamate (methyl) acrylic compounds obtained in manufacturing example 3,12 and 16 40 weight portions mix DCP-4EO-A (R=hydrogen atom, the chemical combination of m+n=4 in formula (6) of the diluting monomer adjusted as viscosity Thing) or DCP-A (R=hydrogen atom, the compound of m+n=0 in formula (6)) 60 weight portions, it is prepared as monomer composition, with above-mentioned enforcement Example similarly measures the viscosity of 30 DEG C of said composition with E type viscometer (TV-22 type).

Then, in the same manner as above-described embodiment, add camphorquinone relative to this monomer composition 100 weight portion (pure with light Medicine Co., Ltd. system) 0.3 weight portion, N, N-dimethyl ethyl aminobenzoate (with Guang Chun medicine Co., Ltd. system) 0.3 weight portion, make It dissolves, and is prepared as light-cured type monomer composition (dental materials compositions).Then, by method similar to the above, use Formula (1) is obtained the polymerization shrinkage of this light-cured type monomer composition by the density of this light-cured type monomer composition before and after solidification Rate.

It addition, measure the single polymerization shrinkage of DCP-4EO-A and DCP-A and viscosity by method similar to the above, As a result of which it is, the polymerization shrinkage of DCP-4EO-A be 8.0%, viscosity be 130 (mpa s, 30 DEG C), the polymerization shrinkage of DCP-A Rate is 8.3%, viscosity be 110 (mpa s, 30 DEG C).

Result is shown in table 17.

[comparative example 3]

Except using the monomer group mixing DCP-4EO-A60 weight portion in Bis-GMA (D-GMA) 40 weight portion and obtain Beyond compound, obtain viscosity and polymerization shrinkage by the operation as embodiment 32～37.

Result is shown in table 17.

[table 17]

Table 17

[embodiment 100～112: the mensuration of the polymerization shrinkage of light-cured type thickener]

By light-cured type monomer composition 40 weight portion obtained in embodiment 1～31 with γ-methacryloxy Propyl trimethoxy silicane (Shin-Etsu Chemial Co., Ltd KBM503) 10 weight portions implement the average particle that surface processes Barium glass (NEC SCHOTT Components Co., Ltd. GM8235) the 60 weight portion mixing of footpath 1 μm, obtains uniform light Curing type thickener (dental materials compositions).

About this light-cured type thickener, measured poly-by the method as the light-cured type monomer composition of embodiment 1 Close shrinkage factor.

The results are shown in table 18～20.

[comparative example 10 and 11]

Use as methacrylate monomer Bis-GMA (chemical industry Co., Ltd. of Xin Zhong village D-GMA) or What UDMA (Negami Chemical Ind Co., Ltd. SH500S) replaced above-described embodiment comprises carbamate (methyl) acrylic compounds The dental materials of compound, is prepared as into light-cured type thickener with embodiment 100.

About this light-cured type thickener, measured poly-by the method as the light-cured type monomer composition of embodiment 1 Close shrinkage factor.

Result is shown in table 20.

[table 18]

Table 18

[table 19]

Table 19

[table 20]

Table 20

Claims (10)

1. dental materials, it is characterised in that containing the compound of following formula (4),

2. dental materials compositions, wherein comprises the dental materials described in claim 1, (B) polymerization initiator and (C) filler.

3. dental materials compositions as claimed in claim 2, the most also comprises (D) polymerizable monomer.

4. dental materials compositions as claimed in claim 3, wherein, described polymerizable monomer (D) is with following formula (6) table Show,

In formula (6), R separately represents hydrogen atom or methyl, m and n is respectively the integer of 0～10, and m+n=0～10.

5. dental materials compositions as claimed in claim 4, wherein, in above-mentioned formula (6), R represents hydrogen atom, m and n is respectively It is the integer of 0～6, and m+n=2～6.

6. dental prosthetic material, wherein comprises the dental materials described in claim 1, (B) Photoepolymerizationinitiater initiater and (C) filler.

7. dental prosthetic material as claimed in claim 6, the most also comprises (D) polymerizable monomer.

8. dental prosthetic material as claimed in claim 7, wherein, described polymerizable monomer (D) represents with following formula (6),

In formula (6), R separately represents hydrogen atom or methyl, m and n is respectively the integer of 0～10, and m+n=0～10.

9. dental prosthetic material as claimed in claim 8, wherein, in above-mentioned formula (6), R represents hydrogen atom, m and n is respectively The integer of 0～6, and m+n=2～6.

10. solidfied material, is to make the dental materials described in claim 1 solidify.