CN100463925C - Curable composition - Google Patents

Abstract

A curable composition comprising: (A) 100 parts by mass of a monomer component which comprises a radically polymerizable monomer and has a water absorbing capacity of not larger than 20% by weight; (B) 0.5 to 10 parts by mass of water; (C) 0.1 to 20 parts by mass of a surfactant; and (D) an effective amount of a radical polymerization initiator. The curable composition is cured by polymerization in a state where a water layer is formed on the surfaces of the cured body that is being formed, effectively suppressing the hindrance of polymerization caused by oxygen and decreasing the formation of unpolymerized product on the surfaces of the cured body. The curable composition is particularly useful as a dental restorative.

Description

Solidification compound

Technical field

The present invention relates to a kind of solidification compound, more particularly, the present invention relates to a kind of the grade oxygen barrier layer is set, just reduce the novel curable composition of the influence of oxygen when solidifying by the coating oxygen barrier material by radical polymerization formation cured article.

Background technology

Solidification compound as basal component, is the material that contains polymerisable monomer and polymerization starter.Solidification compound if carry out polymerization process in air, is exposed on the surface of airborne cured article and produces not polymeric layer when forming cured article by radical polymerization.This is that airborne oxygen combines with the polymerisable monomer of free radicalization and forms peroxide radical, thereby polymerization is stopped owing to being exposed on the surface of airborne solidification compound.

In the past, there is not the not cured article of polymeric layer from the teeth outwards in order to provide, carried out under nitrogen environment or in the water, solidifying, use oxygen barrier material that oxygen barrier layer etc. is set, cut off with the contacting of air in make solidification compound carry out the method for radical polymerization (for example, referring to patent documentation 1,2).

Patent documentation 1: the spy opens clear 2000-128723 communique

Patent documentation 2: the spy opens the 2004-284969 communique

Make (methyl) esters of acrylic acid polymerisable monomer solidified method by radical polymerization, be widely used for dental field, as the material that uses such method, can enumerate the finishing of dental cement, dental jointing material (matrix material), compound resin, the material of giving the resin dental material surface lubrication, tooth etc.In a single day these dental restorations have not polymeric layer on the cured article surface, just cause that surface hardness and tint permanence reduce.In addition since have not polymeric layer on the surface and when the polishing grinding that is cured thing not polymeric layer be wound on the polishing rod, cause its polishability to reduce.

Use as mentioned above the dental treatment great majority of dental repair materials directly solidify use in the oral cavity, since be in water or nitrogen environment under polymkeric substance is not reduced by curing method, therefore need earlier solidification compound to be taken out in the oral cavity, the shape that forms in the oral cavity so just has been out of shape.In addition, great majority are the trouble examples that be difficult to form oxygen barrier layer, and can not utilize oxygen barrier material on low material such as the viscosity of matrix material etc.

As mentioned above, the method for record is not suitable for the purposes of dental repair materials etc. in patent documentation 1,2, the technology that the influence of oxygen when solidifying is reduced.

On the other hand, reported by in the monomer of free redical polymerization, adding tensio-active agent, obtained the time as the binding agent of sclerous tissueses such as tooth, little and to the stimulation of dental pulp to the little solidification compound of soaking into of dentine (referring to patent documentation 3).

Patent documentation 3: the spy opens flat 7-316391 communique

But patent documentation 3 discloses as the further mixing water of diluting solvent, this diluting solvent can use when using tensio-active agent as bed material, for example, the bed material (monomer that contains free redical polymerization sometimes) that will contain water and tensio-active agent is applied on tooth etc., drying, coating contains the monomer of free redical polymerization and the composition of polymerization starter carries out polymerizing curable then.Therefore, do not have water in the patent documentation 3 when solidifying, water does not exert an influence to the formation of polymkeric substance not.

Summary of the invention

The purpose of this invention is to provide a kind ofly when under the environment of aerobic, being cured,, just suppress the not solidification compound of the formation of polymeric layer of surface effectively without oxygen barrier material by radical polymerization.

Other purpose of the present invention provides a kind of solidification compound that is applicable to effectively as the purposes of dental repair materials.

The inventor furthers investigate and has realized above-mentioned purpose.Found that, under the monomeric situation of using specific free redical polymerization,, can reduce the polymerization retardation effect of oxygen effectively, finished the present invention based on this new discovery by with less water and tensio-active agent and usefulness.

The invention provides a kind of solidification compound, comprising:

(A) form by the monomer of free redical polymerization and absorption of water is 20wt% or lower monomer component 100 mass parts;

(B) water 0.5～10 mass parts;

(C) tensio-active agent 0.1～20 mass parts; With

(D) radical polymerization initiator of significant quantity.

In the solidification compound of the present invention, preferred

(1) aforementioned monomer composition (A) is that absorption of water is that 5wt% or lower strong-hydrophobicity polymerisable monomer (a-1) and absorption of water are the mixture of 100wt% or higher strongly hydrophilic polymerisable monomer (a-2),

(2) aforementioned surfactants (C) is made up of anionic surfactant (c-1) and nonionic surfactant (c-2),

(3) the aforementioned monomer composition (A) of relative 100 mass parts contains the aforementioned anionic surfactant (c-1) of 0.1～10 mass parts and the aforementioned nonionic surfactant (c-2) of 0.1～10 mass parts,

(4) the aforementioned monomer composition (A) of relative 100 mass parts also contains the water-soluble polymers (E) of 0.00001～10 mass parts.

And in the present invention, the absorption of water of monomer component is to be calculated by the value substitution following formula of measuring the water content of the monomer component that the monomer by free redical polymerization of saturated suction forms by Karl Fischer method under 23 ℃.

The weight (g) * 100 of absorption of water=water content (g)/monomer component (A)

Contain above-mentioned (A)～(D) composition or further contain the solidification compound of the present invention of (E) composition, even when under the environment of aerobic, carrying out polymerizing curable, do not use special means such as oxygen barrier material, also can obtain with surface that oxygen contacts on the cured article that is inhibited effectively of the formation of polymeric layer not.This cured article, because the formation of polymeric layer is not inhibited, so excellents such as physical strength and weather resistance.For example, surperficial at least a portion of this solidification compound is under the situation that the environment that contains aerobic is opened, even when forming cured article by radical polymerization, on the cured article surface not the formation of polymeric layer suppressed effectively, the gained cured article, particularly resemble the excellent of the sort of dental repair materials of polishability requirement, this solidification compound is particularly exceedingly useful as the purposes of dental repair materials.

Embodiment

Solidification compound of the present invention, contain monomer component (A) and the polymerization starter (D) formed by the monomer of free redical polymerization, yet the feature of particularly important is optionally to use the monomer of specific free redical polymerization by absorption of water mode of (20wt% or lower) below certain value of monomer component (A), and with the monomer component of adjusting absorption of water in this way (A) combination, and water (composition B) and tensio-active agent (composition C).

Promptly, in this solidification compound, effect by polymerization starter makes monomer component (A) polymerization of being made up of the monomer of free redical polymerization form cured article, yet because polymerization is to carry out under the situation that water and tensio-active agent are arranged, form the layer of tensio-active agent and water on the surface at cured article when the monomer of free redical polymerization solidifies, the layer that this tensio-active agent and water form has stoped oxygen to the inner intrusion of cured article, and the result has reduced the not formation of polymkeric substance on the cured article surface.Therefore, on the cured article surface of following polymerization to produce, need have water and tensio-active agent with certain quality of balance, for example, under the too much situation of water or tensio-active agent, cured article intensity reduces, or can not solidify fully sometimes.Therefore, the present invention is adjusted to the absorption of water of monomer component (A) in the certain limit, and the amount of the water (composition B) of monomer component (A) and tensio-active agent (composition C) also must be set within the specific limits relatively.Each composition is described in detail in detail below.

＜monomer component (A) 〉

In the present invention,, can use the monomer of free redical polymerization as monomer component (A), however this monomer component (A), and the absorption of water of measuring by preceding method is necessary for 20wt% or lower.And, as monomer component (A), absorption of water is that the monomer of 20wt% or lower free redical polymerization can a kind uses separately, perhaps can be the monomer and the usefulness of monomer and the absorption of water of 20wt% or the lower free redical polymerization free redical polymerization bigger with absorption of water, and absorption of water is adjusted to 20wt% or lower mixture uses as monomer component (A) than 20wt%.And, this monomer of the wetting ability free redical polymerization of absorption of water height (absorption of water is 100wt% or higher) when independent of weevil base Hydroxyethyl Acrylate also can be that the form of 20wt% or lower mixture is used as monomer component (A) with the combination of monomers of the low hydrophobicity free redical polymerization of absorption of water with the absorption of water.

That is, in the present invention, when the absorption of water of monomer component (A) is bigger than 20wt%, worry can not form water layer on the cured article surface that forms when carrying out polymerizing curable, the result can not reduce the not formation of polymkeric substance on the cured article surface.

In solidification compound of the present invention, suppress effect in order to improve on the cured article surface the not formation of polymkeric substance, obtain the more excellent cured article of mechanical characteristics, the absorption of water of above-mentioned monomer component (A) is more preferably 0.1～15wt%, most preferably in the scope of 0.5～5wt%.

As mentioned above, as long as absorption of water is adjusted in the above-mentioned scope, the monomer that can use various free redical polymerizations is as monomer component (A), however particularly from the polymerizability excellence, near room temperature also solidified angle easily, preferred (methyl) acrylic acid or the like polymerisable monomer that uses.(methyl) acrylic acid or the like polymerisable monomer like this according to its absorption of water, makes the absorption of water of monomer component (A) in above-mentioned scope, and they can use separately or two or more mix and use.

And, the absorption of water of monomer component (A) can obtain by Karl Fischer method as mentioned above, yet as simple target, the polymerisable monomer of 100 mass parts can be mixed with the water of 20 mass parts, can judge evenly whether absorption of water is 20wt% or lower according to whether becoming.That is, if become evenly, if absorption of water inhomogeneous, can judge that absorption of water is 20wt% or lower greater than 20wt% so.

Absorption of water is 20wt% or lower hydrophobicity (methyl) acrylic acid or the like polymerisable monomer when independent, can be listed below compound.Value in the bracket is an absorption of water, and, band ^*The value of absorption of water be the value of inferring by molecular structure.

The mean number of ethylene oxide group be 6 polyethoxylated trimethylolpropane trimethacrylate ( ^*5～10wt%)

The mean number of ethylene oxide group be 10 ethoxylation bisphenol a dimethacrylate ( ^*5～10wt%)

The mean number of ethylene oxide group be 13 ethoxylation bisphenol a dimethacrylate ( ^*10～20wt%)

The mean number of ethylene oxide group be 9 polyethoxylated trimethylolpropane trimethacrylate ( ^*10～20wt%)

Methacrylic acid hydroxyl pentyl ester ( ^*10～20wt%)

Methacrylic acid hydroxyl butyl ester ( ^*10～20wt%)

The glycerine dimethacrylate ( ^*10～20wt%)

Methyl methacrylate (1.5wt%)

Jia Jibingxisuanyizhi (1.0wt% or lower)

Butyl methacrylate (1.0wt% or lower)

Isopropyl methacrylate (1.0wt% or lower)

Acetoacetoxyethyl methacrylate (1.8wt%)

2,2-two (methacryloxy phenyl) propane (1.0wt% or lower)

2,2-two [4-(3-methacryloxy)-2-hydroxyl propoxy-phenyl] propane (2.2wt%)

2,2-two (4-methacryloxy phenyl) propane (0.5wt% or lower)

2,2-two (4-methacryloxy polyethoxye phenyl) propane (0.5wt%)

2,2-two (4-methacryloxy diethoxy phenyl) propane (1.0% or lower)

2,2-two (4-methacryloxy tetraethoxy phenyl) propane ( ^*1～5%)

2,2-two (4-methacryloxy five ethoxyl phenenyls) propane ( ^*1～5%)

2,2-two (4-methacryloxy dipropoxy phenyl) propane ( ^*1～5%)

2 (4-methacryloxy diethoxy phenyl)-2 (4-methacryloxy diethoxy phenyl) propane ( ^*1～5%)

2 (4-methacryloxy diethoxy phenyl)-2 (4-methacryloxy two triethoxy phenyl) propane ( ^*1～5%)

2 (4-methacryloxy dipropoxy phenyl)-2-(4-methacryloxy triethoxy phenyl) propane ( ^*1～5%)

2,2-two (4-methacryloxy propoxy-phenyl) propane ( ^*1～5%)

2,2-two (4-methacryloxy isopropyl phenyl) propane ( ^*1～5%)

Monoethylene glycol dimethacrylate (1.0% or lower)

Diethylene glycol dimethacrylate ( ^*1～5%)

Triethylene glycol dimethacrylate (1.7%)

Tetraethylene glycol dimethacrylate ( ^*1～5%)

1,3 butylene glycol dimethacrylate (0.5% or lower)

1,4-butylene glycol dimethacrylate (0.5% or lower)

1,6-hexanediol dimethacrylate (0.1%)

1,9-nonanediol dimethacrylate (0.1%)

Trimethylolpropane trimethacrylate ( ^*1～5%)

The trimethylolethane trimethacrylate methacrylic ester ( ^*1～5%)

Pentaerythritol acrylate trimethyl ( ^*1～5%)

The Pehanorm trimethacrylate ( ^*1～5%)

Tetramethylolmethane tetramethyl-acrylate ( ^*1～5%) etc.

In the present invention, especially preferably use absorption of water to be 5wt% or lower strong-hydrophobicity (methyl) acrylic acid or the like polymerisable monomer (a-1) in the above-claimed cpd, that is, and following polymerisable monomer.

Strong-hydrophobicity (methyl) acrylic acid or the like polymerisable monomer (a-1):

2,2-two (methacryloxy phenyl) propane (0.5wt%)

2,2-two [4-(3-methacryloxy)-2-hydroxyl propoxy-phenyl] propane (2.2wt%)

2,2-two (4-methacryloxy phenyl) propane (1.0wt% or lower)

2,2-two (4-methacryloxy polyethoxye phenyl) propane (0.5%)

2,2-two (4-methacryloxy diethoxy phenyl) propane (1.0wt% or lower)

2,2-two (4-methacryloxy tetraethoxy phenyl) propane ( ^*1～5%)

2,2-two (4-methacryloxy five ethoxyl phenenyls) propane ( ^*1～5wt%)

2,2-two (4-methacryloxy dipropoxy phenyl) propane ( ^*1～5wt%)

2 (4-methacryloxy diethoxy phenyl)-2 (4-methacryloxy diethoxy phenyl) propane ( ^*1～5wt%)

2 (4-methacryloxy diethoxy phenyl)-2 (4-methacryloxy two triethoxy phenyl) propane ( ^*1～5wt%)

2 (4-methacryloxy dipropoxy phenyl)-2-(4-methacryloxy triethoxy phenyl) propane ( ^*1～5wt%)

2,2-two (4-methacryloxy propoxy-phenyl) propane ( ^*1～5wt%)

2,2-two (4-methacryloxy isopropyl phenyl) propane ( ^*1～5wt%)

1,3 butylene glycol dimethacrylate (0.5wt% or lower)

1,4-butylene glycol dimethacrylate (0.5wt% or lower)

1,6-hexanediol dimethacrylate (0.1wt%)

1,9-nonanediol dimethacrylate (0.1wt%)

Monoethylene glycol dimethacrylate (1.0wt% or lower)

Diethylene glycol dimethacrylate ( ^*1～5wt%)

Triethylene glycol dimethacrylate (1.7wt%)

Tetraethylene glycol dimethacrylate ( ^*1～5wt%).

And, (methyl) acrylic acid or the like polymerisable monomer that absorption of water is bigger than 20wt% can be various materials, yet in the present invention, selecting absorption of water especially is 100wt% or higher strongly hydrophilic (methyl) acrylic acid or the like polymerisable monomer (a-2), with itself and aforesaid absorption of water is 20wt% or lower hydrophobicity (methyl) acrylic acid or the like polymerisable monomer, particularly absorption of water is 5wt% or lower strong-hydrophobicity (methyl) acrylic acid or the like polymerisable monomer (a-1) combination, make that absorption of water is 20wt% or lower (preferred 0.1～15wt%, most preferably 0.5～5wt%), it is suitable using with the form of this mixture.The mode that the combination of monomers of the monomer of this hydrophobicity free redical polymerization and wetting ability free redical polymerization is used, make on the cured article surface that the inhibition effect of the formation of polymkeric substance does not improve, particularly strong-hydrophobicity (methyl) acrylic acid or the like polymerisable monomer and strongly hydrophilic (methyl) acrylic acid or the like polymerisable monomer combination, as shown in the embodiment of back, can significantly reduce the not formation of polymkeric substance.As this absorption of water is 100wt% or higher strongly hydrophilic (methyl) acrylic acid or the like polymerisable monomer (a-2), can enumerate following material.Below listed compound, all have strongly hydrophilic, can any amount soluble in water, absorption of water surpasses 100%.

Strongly hydrophilic (methyl) acrylic acid or the like polymerisable monomer (a-2):

Vinylformic acid

Methacrylic acid

(methyl) vinylformic acid 2-hydroxy methacrylate

(methyl) vinylformic acid 2-hydroxy propyl ester

(methyl) vinylformic acid 3-hydroxy propyl ester

(methyl) vinylformic acid 1,3-dihydroxyl propyl ester

(methyl) vinylformic acid 2,3-dihydroxyl propyl ester

(methyl) acrylamide

2-hydroxyethyl (methyl) acrylamide

Molecular-weight average is 400 or the dimethacrylate of bigger polyoxyethylene glycol

Molecular-weight average is 400 or the methacrylic ester of bigger polyoxyethylene glycol

Biphosphate 2-methacryloxy ethyl ester

The mean number of ethylene oxide group is 25 or bigger ethoxylation bisphenol a dimethacrylate.

And, in the present invention, in the monomer and the time spent of the monomer and the wetting ability free redical polymerization of this hydrophobicity free redical polymerization, although the reason of the reduction effect of the formation of polymkeric substance raising is also not indeterminate on the surface, but by containing the monomer of wetting ability free redical polymerization, relative solidification compound, the dispersiveness of water improves, and can predict it whether is because the homogeneity raising of the layer that the tensio-active agent that forms from the teeth outwards when this solidification compound is solidified and water constitute thus.

And, as mentioned above, with the monomeric mixture of two or more free redical polymerizations during as monomer component (A), the absorption of water of this mixture itself can be calculated by arithmetical mean by the monomeric absorption of water of each free redical polymerization, and it is just passable therefore according to their ratio of mixture of target adjusting the absorption of water of monomer component (A) to be adjusted in the aforementioned range.For example, the monomeric mixture that uses the monomer of strong-hydrophobicity free redical polymerization and strongly hydrophilic free redical polymerization for absorption of water is adjusted in the aforementioned range, can use the monomer of strong-hydrophobicity free redical polymerization during as monomer component (A) in a large number.

And, in the present invention, as long as (promptly with the absorption of water of monomer component (A), the absorption of water of the monomer integral body of used free redical polymerization) is adjusted in the aforementioned range, can with the monomer of various free redical polymerizations separately or two or more mix and use, particularly, by a large amount of use two senses or the monomer more than the trifunctional, can make mechanical properties such as the intensity of cured article of final gained and weather resistance all good.

In addition, in solidification compound of the present invention, except aforementioned (methyl) acrylic acid or the like polymerisable monomer, for easily polymerization, regulate viscosity or regulate other rerum natura, also can mix the monomer that uses other free redical polymerization except that above-mentioned (methyl) acrylic acid or the like polymerisable monomer.In either case, the absorption of water of the monomer component of free redical polymerization is necessary for 20wt% or lower.The monomeric example of these other free redical polymerization can have been enumerated vinylbenzene or alpha-methyl styrene derivatives such as fumaric acid esters, vinylbenzene, Vinylstyrene, alpha-methyl styrene such as monomethyl fumarate, DEF, fumaric acid diphenyl ester; Allylic cpds such as diallyl p phthalate, Phthalic acid, diallyl ester, diallyl diglycol carbonates etc.The monomer of these other free redical polymerizations can use separately, and perhaps two or more are also used.

＜water (composition B) 〉

In solidification compound of the present invention, comprise in the matrix of aforementioned monomer composition (A) and be dispersed with water, under the state that is dispersed with water thus, be cured by radical polymerization, form cured article.Promptly, because water is carrying out radical polymerization under tensio-active agent dispersive state described later, therefore carrying out the polymeric suitable water layer (containing tensio-active agent) of formation on the cured article surface of formation simultaneously, this water layer suppresses oxygen invades in cured article, and the result can suppress to form on the cured article surface not polymkeric substance.

The aforementioned monomer composition (A) of relative 100 mass parts, the combined amount of this water are in 0.5～10 mass parts, and preferred 0.5～5 mass parts is most preferably in the scope of 1～3 mass parts.That is, the combined amount of water is many more, can reduce the not formation of polymkeric substance more, but the mechanical properties of cured articles such as opposite intensity and hardness has also reduced.And, when mixing water not and when in water, carrying out polymerizing curable, no problem from the angle that reduces the not formation of polymkeric substance, but the mechanical characteristics of cured article significantly reduces, or solidify not enough, solidification compound must be impregnated in the water, so the purposes of solidification compound obviously is restricted, for example can not be applicable to for example purposes such as dental repair materials.And, the present invention can aforesaid amount with water-dispersion in solidification compound.

＜tensio-active agent (composition C) 〉

In solidification compound of the present invention, tensio-active agent and water are mixed together.That is, by using tensio-active agent, carry out polymeric simultaneously can be on the surface of the cured article that forms the branch water distribution layer, thereby can reduce the not formation of polymkeric substance on the cured article surface effectively.

The aforementioned monomer composition (A) of relative 100 mass parts, this tensio-active agent uses with the amount of 0.1～20 mass parts.That is, same with water, the combined amount of tensio-active agent is many more, can reduce the not formation of polymkeric substance on the surface more, but the mechanical characteristics of cured article has reduced but.Therefore, the combined amount of tensio-active agent is in above-mentioned scope.

And, as tensio-active agent, can use in anionic property, cationic, amphoteric plasma type tensio-active agent and the nonionic surfactant any one.The specific examples of such tensio-active agent has no particular limits, and can be following material:

The anionic surfactant:

Alkyl-sulphate such as sodium decyl sulfate, sodium lauryl sulphate;

Alkylsulfonates such as hexane sodium sulfonate, decyl sodium sulfonate;

Alkylbenzene sulfonates such as decyl benzene sulfonic acid sodium salt, Sodium dodecylbenzene sulfonate;

Aliphatic carboxylic acid metallic salts such as sodium laurate, sodium stearate, sodium oleate;

The affixture of lauryl alcohol and ethylene oxide is through the metallic salt of senior alkyl ether sulphate such as Sulfated lauryl ether sodium sulfovinate;

Sulfosuccinic acid diesters classes such as sodium sulfosuccinate;

The phosphates of higher alcohols ethylene oxide adduct;

Cationic surfactant:

Alkylamine salts such as dodecyl chlorination ammonium;

Quaternary ammonium salts such as trimethyldodecane base brometo de amonio;

Zwitterionics:

Alkyl dimethyl amine oxide classes such as dimethyl dodecyl amine oxide;

Alkyl carboxyl betaines such as dodecyl carboxybetaine;

Alkyl sultaine classes such as dodecyl sultaine;

Amido amino acid saltss such as lauroyl amido propyl group amine oxide;

Nonionic surfactant:

Voranol EP 2001 classes such as polyoxyethylene lauryl ether;

Polyoxyethylene alkyl phenyl ether classes such as polyoxyethylene lauryl phenyl ether;

Polyoxyethylene carboxylate classes such as aliphatic acid polyethenoxy Lauryl Ester;

Sorbitan ethoxylate classes such as polyethenoxy sorbitan Lauryl Ester.

In the present invention, above-mentioned tensio-active agent, separately can a kind or two or more mix and use, but especially preferably anionic surfactant (c-1) can be mixed use with nonionic surfactant (c-2).That is, can know clearly that when by described 2 kinds of tensio-active agents and time spent being compared when using separately with tensio-active agent, the formation inhibition effect at the lip-deep not polymkeric substance of cured article during polymerizing curable significantly improves from aftermentioned embodiment.

And, mixed anionic surfactant's solidification compound, there is the low problem of package stability under the so-called low temperature.That is, the monomer of free redical polymerization and polymerization starter blended solidification compound have carried out polymerizing curable sometimes at lay up period, and therefore, (for example 0～10 ℃) is stored in refrigeration in advance, gets back to room temperature during use and carries out polymerizing curable.In this case, if the mixed anion surfacant, they are just separated out, and the result not formation of polymkeric substance suppresses the effect reduction.Yet, when as above-mentioned anionic surfactant (c-1) is mixed when use with nonionic surfactant (c-2), anionic surfactant in the time of can preventing from effectively to refrigerate storage separates out, and therefore can improve the preservation stability of solidification compound.

In anionic surfactant (c-1) and nonionic surfactant (c-2) and time spent, as the anionic surfactant (c-1) who uses, in aforementioned listed compound, the preferred HLB of the angle of the formation of polymkeric substance (hydrophilic-lipophilic balance) is 20～50 from suppressing on the surface not, particularly 30～50 compound most preferably uses alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate (wherein the carbonatoms of alkyl is 6～16).And as nonionic surfactant (c-2), in aforementioned listed compound, preferred HLB is 3 or higher, particularly 6～18 compound.And, with these tensio-active agents and time spent, the aforementioned monomer composition (A) of relative 100 mass parts, from the angle preferred anionic surfacant (c-1) of the formation that suppresses polymkeric substance not and package stability with 0.1～10 mass parts, particularly the amount of 0.3～3 mass parts is used, nonionic surfactant (c-2) is in 0.1～10 mass parts, particularly in the scope of 0.3～3 mass parts.

＜polymerization starter (components D) 〉

Solidification compound of the present invention is mixed with the polymerization starter that is used for polymerization aforementioned monomer composition (A).As this polymerization starter, as long as monomer polymerization, the curing of the free redical polymerization that uses as monomer component (A) can be able to be used known polymerization starter without any restrictedly using.For example, polymerization starter as the dental field use, chemical polymerisation initiator (normal temperature oxidation reduction initiator), Photoepolymerizationinitiater initiater, thermal polymerization etc. are arranged, yet consider and in the oral cavity, solidify, preferred chemical polymerisation initiator and/or Photoepolymerizationinitiater initiater.Describe at various polymerization starters below.

-chemical polymerisation initiator-

Chemical polymerisation initiator is grouped into by two or more one-tenth, is before being about to use whole compositions to be mixed, and produces the polymerization starter of polymerization activity kind near room temperature.As such chemical polymerisation initiator, representational have amine compound/organic peroxide systems.

The example of the amine compound that uses as such chemical polymerisation initiator can have been enumerated N, N-dimethyl-para-totuidine, N, accelerine, N, aromatic amines compounds such as N-di-alcohol-para-totuidine.

And; the representative substances of the organo-peroxide that uses as chemical polymerisation initiator has ketone peroxide, peroxy ketal, hydroperoxide, diaryl superoxide, peroxy esters, diacyl peroxide, peroxy dicarbonate etc.; specifically, can enumerate following material.

Ketone peroxide:

Methyl-ethyl-ketone peroxide, pimelinketone superoxide, methyl cyclohexanone peroxide, methyl acetoacetate superoxide, acetylacetone peroxide etc.

Peroxy ketal:

1,1-two (uncle's hexyl peroxide) 3,3, the 5-trimethyl-cyclohexane,

1,1-two (uncle's hexyl peroxide) hexanaphthene,

1,1-two (t-butyl peroxy) 3,3, the 5-trimethylcyclohexanone,

1,1-two (t-butyl peroxy) hexanaphthene,

1,1-two (t-butyl peroxy) cyclodecane,

2,2-two (t-butyl peroxy) butane,

4,4-two (t-butyl peroxy) n-butyl pentanoate,

2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane etc.

Hydroperoxide:

P-methane hydroperoxide,

The diisopropyl benzene superoxide,

1,1,3,3-tetramethyl butyl hydroperoxide,

Cumene hydroperoxide,

Uncle's hexyl hydroperoxide,

Tert-butyl hydroperoxide etc.

Dialkyl peroxide:

α, α-two (t-butyl peroxy) two different interior basic benzene,

Dicumyl peroxide,

2,5-dimethyl-2,5-two (t-butyl peroxy) hexane,

Tertiary butyl cumyl peroxide,

Ditertiary butyl peroxide,

2,5-dimethyl-2,5-two (t-butyl peroxy) hexane-3 etc.

Diacyl peroxide:

The isobutyryl superoxide,

2,4 dichloro benzene formyl radical superoxide,

3,5,5-trimethyl acetyl base superoxide,

Sim peroxides,

The lauroyl superoxide,

The stearyl-superoxide,

Succinic acid peroxide,

Toluoyl base benzoyl peroxide,

Benzoyl peroxide etc.

Peroxycarbonates:

Di n propyl peroxy dicarbonate,

Diisopropyl peroxydicarbonate,

Two (4-tert-butylcyclohexyl) peroxide, two carbonic ethers,

Two-2-ethoxyethyl group peroxide, two carbonic ethers,

Two-2-ethylhexyl peroxide, two carbonic ethers,

Two-2-methoxyl group butyl peroxy, two carbonic ethers,

Two (3-methyl-3-methoxyl group butyl) peroxide two carbonic ethers etc.

Peroxy esters:

α, α-two (new decanoyl peroxide) diisopropyl benzene,

Cumyl peroxide neodecanoic acid ester,

1,1,3,3-tetramethyl butyl peroxide neodecanoic acid ester,

1-cyclohexyl-1-methylethyl peroxide neodecanoic acid ester,

Uncle's hexyl peroxide neodecanoic acid ester,

T-butyl peroxy neodecanoic acid ester,

Uncle's hexyl peroxide pivalate,

The t-butyl peroxy pivalate,

1,1,3,3-tetramethyl butyl peroxide-2-ethylhexanoate,

2,5-dimethyl-2,5-two (2-ethyl hexanoyl base peroxide) hexane,

1-cyclohexyl-1-methylethyl peroxide-2-ethylhexanoate,

Uncle's hexyl peroxide-2-ethylhexanoate,

T-butyl peroxy-2-ethylhexanoate,

The t-butyl peroxy isobutyrate,

Uncle's hexyl peroxy isopropyl base monocarbonate,

The t-butyl peroxy toxilic acid,

T-butyl peroxy-3,5,5 Trimethylhexanoic acid ester,

The t-butyl peroxy laurate,

2,5-dimethyl-2,5-two (toluoyl base peroxide) hexane,

T-butyl peroxy sec.-propyl monocarbonate,

T-butyl peroxy-2-ethylhexyl monocarbonate,

Uncle's hexyl peroxy benzoate,

2,5-dimethyl-2,5-two (benzoyl peroxide) hexane,

The t-butyl peroxy acetic ester,

T-butyl peroxy toluoyl yl benzoic acid ester,

The t-butyl peroxy benzoic ether,

Two (t-butyl peroxy) isophthalic acid ester etc.

Other organo-peroxide:

Tertiary butyl trimethyl silyl superoxide,

3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone etc.

Used organo-peroxide can suitably be selected to use, and independent or two or more mixing are used all without any restriction, yet from the preferred especially hydroperoxide of the angle of polymerization activity, ketone peroxide, peroxy esters and diacyl peroxide.The angle of the package stability from as solidification compound the time, more preferably using 10 hours half life temperatures is 60 ℃ or higher organo-peroxide.

In the chemical polymerisation initiator that such organo-peroxide and amine compound are formed, can mix with benzene sulfinic acid or to barbital acids initiators such as-sulfinic acid such as toluenesulfinic acid and salt thereof or 5-butyl malonylureas further and use, without any problem.

And, utilize the aryl boric acid salt compound to decompose and produce free radical through acid, also can use the chemical polymerisation initiator of aryl boric acid salt compound/acidic cpd system.

The aryl boric acid salt compound, have no particular limits, so long as have the compound of at least one boron-aryl key in the molecule, can use known compound, wherein, consider package stability, preferably use the aryl boric acid salt compound that 3 or 4 boron-aryl keys are arranged in 1 molecule, from operating, synthesize, obtain the aryl boric acid salt compound that easy angle more preferably contains 4 boron-aryl key.As this aryl boric acid salt compound, can enumerate following material.

The borate compound that contains 3 boron-aryl key in 1 molecule:

As this aryl boric acid salt compound, can enumerate sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, tributyl amine salt, triethanolamine salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium or the butyl quinolinium etc. of following boron compound.

The monoalkyl triphenyl-boron,

Monoalkyl three (right-chloro-phenyl-) boron,

Monoalkyl three (right-fluorophenyl) boron,

Monoalkyl three (3,5-two (trifluoromethyl)) phenyl boron,

Monoalkyl three [3,5-two (1,1,1,3,3,3-hexafluoro-2-methoxyl group-2-propyl group) phenyl] boron,

Monoalkyl three (right-nitrophenyl) boron,

Monoalkyl three (-nitrophenyl) boron,

Monoalkyl three (right-butyl phenyl) boron,

Monoalkyl three (-butyl phenyl) boron,

Monoalkyl three (right-butoxy phenyl) boron,

Monoalkyl three (-butoxy phenyl) boron,

Monoalkyl three (right-octyloxyphenyl) boron,

Monoalkyl three (-octyloxyphenyl) boron etc.

Wherein, in each compound in alkyl represent normal-butyl, n-octyl or the dodecyl any one.

The borate compound that contains 4 boron-aryl key in 1 molecule:

As this aryl boric acid salt compound, can enumerate sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, tributyl amine salt, triethanolamine salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium or the butyl quinolinium etc. of following boron compound.

Tetraphenyl boron,

Four (right-chloro-phenyl-) boron,

Four (right-fluorophenyl) boron,

Four (3,5-two (trifluoromethyl)) phenyl boron,

Four [3,5-two (1,1,1,3,3,3-hexafluoro-2-methoxyl group-2-propyl group) phenyl] boron,

Four (right-nitrophenyl) boron,

Four (-nitrophenyl) boron,

Four (right-butyl phenyl) boron,

Four (-butyl phenyl) boron,

Four (right-butoxy phenyl) boron,

Four (-butoxy phenyl) boron,

Four (right-octyloxyphenyl) boron,

Four (-octyloxyphenyl) boron etc.

Wherein, in each compound in alkyl represent normal-butyl, n-octyl or the dodecyl any one.

Above-named various aryl boric acid salt compound also can two or more mix use.

And, as with the acidic cpd of above-mentioned aryl boric acid salt compound and usefulness, preferably can use the monomer of the free redical polymerization that contains acidic-group.The monomer of the free redical polymerization that uses as this acidic cpd contains in 1 molecule in free-radical polymerised unsaturated group and the acidic-group separately that at least one is just passable.This acidic-group works the monomeric aqueous solution or the aqeous suspension that make free redical polymerization and is the tart effect, can enumerate carboxyl (COOH), sulfo group (SO ₃H), phosphinico-{=P (=O) OH}, phosphono { P (=O) (OH) ₂Etc..And this acidic-group also can be present in the molecule with the form of 2 acidic-groups through the acid anhydride structure of dehydrating condensation, and the hydroxyl that perhaps also can be used as acidic-group is present in the molecule by the acyl halide group that halogen replaces.

As the monomer of the free redical polymerization that contains acidic-group as mentioned above, the monomer of the free redical polymerization of (methyl) acrylic acid or the like that preferred monomers composition (A) item is enumerated.

And, when the monomer of this free redical polymerization that contains acidic-group and aromatic yl acid salt compound are used as polymerization starter, this monomer that contains the free redical polymerization of acidic-group, owing to be included in the monomer component (A), therefore under the monomeric form that comprises this free redical polymerization that contains acidic-group, the absorption of water of monomer component (A) must be adjusted in the aforementioned range.

The polymerization starter of above-mentioned aryl boric acid salt compound/acidic cpd system can also be used in combination organo-peroxide and/or transistion metal compound.This organo-peroxide as previously mentioned.And, as transistion metal compound, preferred+IV valency or+vanadium compound of V valency.Specific examples as this vanadium compound, can enumerate vanadium tetraoxide (IV), etheric acid vanadium oxide (IV), vanadium oxalate (IV), Vanadosulfuric acid (IV), oxygenate two (1-phenyl-1,3-butanone acid group closes) vanadium (IV), two (voitol closes) vanadium oxide (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium meta-vanadate (V) etc.

-Photoepolymerizationinitiater initiater-

As Photoepolymerizationinitiater initiater, can use following material separately, perhaps two or more are mixed and use.

The acylphosphine oxide derivative:

2,4,6-trimethylbenzoyl diphenyl phosphine oxide,

2,6-dimethoxy benzoyl diphenyl phosphine oxide,

2,6-dichloro-benzoyl base diphenyl phosphine oxide,

2,4,6-trimethylbenzoyl phenyl-phosphonic acid methyl esters,

2-methyl benzoyl diphenyl phosphine oxide,

Valeryl phenyl-phosphonic acid isopropyl ester,

Two-(2,6-dichloro-benzoyl base) phenyl phosphine oxides,

Two-(2,6-dichloro-benzoyl base)-2,5-3,5-dimethylphenyl phosphine oxide,

Two-(2,6-dichloro-benzoyl base)-4-propyl group phenyl phosphine oxide,

Two-(2,6-dichloro-benzoyl base)-1-naphthyl phosphine oxide,

Two-(2,6-dimethoxy benzoyl) phenyl phosphine oxides,

Two-(2,6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide,

Two-(2,6-dimethoxy benzoyl)-2,5-3,5-dimethylphenyl phosphine oxide,

Two-(2,4, the 6-trimethylbenzoyl) phenyl phosphine oxides,

Two-(2,5, the 6-trimethylbenzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.

α-diketone:

Dimethyl diketone,

Methylphenyl diketone,

Benzil,

2, the 3-diacetylmethane,

2, the 3-acetyl caproyl,

4,4 '-the dimethoxy benzil,

4,4 '-the hydroxyl benzil,

Camphanone,

9, the 10-phenanthrenequione,

Acenaphthene quinone etc.

Benzoin alkylether:

Benzoin methylether,

Ethoxybenzoin,

Bitter almond oil camphor propyl ether etc.

Thioxanthone derivates:

2,4-diethoxy thioxanthone,

The 2-clopenthixal ketone,

Methyl thioxanthone etc.

Benzophenone derivates:

Benzophenone,

P, p '-dimethylamino benzophenone,

P, p '-methoxy benzophenone etc.

In the above-mentioned Photoepolymerizationinitiater initiater, good from polymerization activity, to the little equal angles of the harm of organism preferred α-two ketone.And under the situation of using α-diketone, preferably mix use with tertiary amine compound.Can mix the tertiary amine compound that uses with α-diketone can be the material of enumerating below.

Tertiary amine compound:

N, accelerine,

N, the N-Diethyl Aniline,

N, N-di-n-butyl aniline,

N, the N-dibenzyl aniline,

N, N-dimethyl-para-totuidine,

N, N-diethyl-para-totuidine,

N, N-dimethyl-meta-aminotoluene,

Right-bromo-N, accelerine,

Between-chloro-N, accelerine,

Right-the dimethylamino benzaldehyde,

Right-the dimethylamino benzoylformaldoxime,

Right-the dimethylamino M-nitro benzoic acid,

Right-the dimethylamino ethyl benzoate,

Right-dimethylamino M-nitro benzoic acid pentyl ester,

N, N-dimethyl methyl o-aminobenzoate,

N, N-dihydroxy ethyl aniline,

N, N-dihydroxy ethyl-para-totuidine,

Right-the dimethylamino phenylethyl alcohol,

Right-the dimethylamino Stilbene,

N, N-dimethyl-3, the 5-xylidine,

4-dimethylaminopyridine,

N, the N-dimethyl-,

N, N-dimethyl-beta-naphthylamine,

Tributylamine,

Tripropylamine,

Triethylamine,

N methyldiethanol amine,

The N-ethyldiethanolamine,

N, the N-dimethylhexylamine,

N, N-dimethyl lauryl amine,

N, N-dimethyl stearylamine,

Methacrylic acid N, the N-dimethylamino ethyl ester,

Methacrylic acid N, N-diethylamino ethyl ester,

2,2 '-(normal-butyl imino-) di-alcohol etc.

Above-mentioned various polymerization starter not only can use separately separately, and can multiple mixing use as required.

In the present invention, the combined amount of these polymerization starters, so long as can be with the amount of monomer component (A) polymerizing curable formed by the monomer of aforementioned free redical polymerization, this is had no particular limits, according to the kind of used polymerization starter and the composition of monomer component (A), suitably select known combined amount just passable.In general, the monomer component of relative 100 mass parts (A), this amount is 0.01～30 mass parts, particularly 0.1～5 mass parts.But, as the aforementioned monomer that contains the free redical polymerization of acidic-group, under the situation of free-radical polymerised compound as a kind of composition use of polymerization starter, because monomer component (A) comprises this compound, therefore make the amount of the polymerization starter composition except that this compound in above-mentioned scope.

＜water-soluble polymers (composition E) 〉

And, in the present invention, except above-mentioned (A)～(D) composition, can the mixing water soluble polymer, can reduce the not formation of polymkeric substance on the cured article surface thus greatly.That is, water-soluble polymers, water-soluble, with tensio-active agent, be distributed in the water layer that on the cured article surface, forms.Therefore, think the oxygen barrier performance that can improve water layer, the formation of polymkeric substance suppresses effect and does not significantly improve.

And the water-soluble polymers among the present invention is meant that the solubleness to water is 1g/l or higher polymkeric substance under 23 ℃.

As the example of this water-soluble polymers, can enumerate multipolymer, vinyl-acetic ester-acrylic copolymer, vinyl-acetic ester-ethylene copolymer, vinylformic acid-styrol copolymer, ammonia esters resin vinylidene resin of polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyoxyethylene, derivatived cellulose, polyacrylic acid, polymethyl acrylic acid, sodium polyacrylate, sodium polymethacrylate, gelatin, alkyl vinyl ether and maleic anhydride etc.Wherein, the angle of the influence of oxygen is especially preferably used polyvinyl alcohol, polyacrylic acid etc. when further reduction is solidified.These water-soluble polymerss can use separately, perhaps can two or more also use.

And, above-mentioned water-soluble polymers, as long as to the solubleness of water in above-mentioned scope, this polymkeric substance is had no particular limits, yet if molecular weight is too big, it is too high that the viscosity of solidification compound becomes, this moment, operability reduced.Therefore, be preferably 1000～10,000,000, particularly 3000～500,000 with the weight-average molecular weight of polystyrene conversion.

In the present invention, the monomer component of relative 100 mass parts (A), the combined amount of above-mentioned water-soluble polymers can be in the scope of 0.00001～10 mass parts, preferred especially 0.0001～1 mass parts, most preferably 0.0005～0.5 mass parts.Combined amount is big more, can reduce the not formation of polymeric layer of surface, but combined amount is hour also little to the influence of rerum natura on the other hand.

＜other mixing element 〉

Solidification compound of the present invention, itself can be as dental repair materials such as the surface lubrication material of giving purpose uses such as the surface lubrication of various resene dental material, tooth finishing and the reparation of variable color tooth and matrix materials, but by with filler combination, can be used for purposes widely.For example, with the situation of organic filler combination under, be suitable as artificial tooth repair materials, backing layer with being filled into interim closed material and interim artificial corona and bridge making material etc. the cavity in several days of begin treatment again from the patient back of going home in material, the therapeutic process.And, with the situation of mineral filler combination under, can suitably be used as dental repair materials such as compound resin, hard resin, inlay, onlay, artificial corona.

As can suitably used representational organic filler and mineral filler, can enumerate following material, they can any one independent use, also can two or more mix and use.

Organic filler:

Polymethylmethacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymers, cross-linking type polymethylmethacrylate, cross-linking type polyethyl methacrylate, vinyl-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitritrile-styrene resin, acrylonitrile-styrene butadienecopolymer etc.

Mineral filler:

Quartz, silicon-dioxide, aluminum oxide, silicon oxide titanium, silicon oxide zirconium, lanthanum glass, barium glass, strontium glass etc.

And, in mineral filler, except above-mentioned enumerate, also have positively charged ion stripping property materials such as oxide compound such as oxyhydroxide, zinc oxide, silicate glass, aluminum fluoride glass such as calcium hydroxide, strontium hydroxide, these materials also can one or more mix and use.In addition, also have polymerisable monomer is added in the above-mentioned mineral filler in advance, behind the one-tenth pasty state,, pulverize the granular organic and inorganic compounded mix that obtains, also can use this organic and inorganic compounded mix through polymerization.

The particle diameter of above-mentioned various fillers has no particular limits, but the preferred scope of using as the median size (0.01 μ m～100 μ m) of the general filler that uses of dental material.And the specific refractory power of filler has no particular limits, 1.4～1.7 the scope that can use ad lib that the filler of general dental has.

Therefore in addition, cooperated in the above-mentioned filler the particularly solidification compound of spherical mineral filler, owing to the surface lubrication raising of gained cured article can become excellent dental repair materials.

And, above-mentioned mineral filler, through being that the surface treatment agent of representative is handled with the silane coupling agent,, physical strength good with the avidity of polymerisable monomer and water tolerance improve, and are preferred therefore.The surface-treated method can known method be carried out, and for example can carry out surface treatment by silane coupling agents such as methyltrimethoxy silane, Union carbide A-162, METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane, vinyl trichloro silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, γ-glycidoxypropyltrime,hoxysilane, hexamethyldisilazanes.

The combined amount of above-mentioned various fillers, can be according to application target, the mechanical properties of viscosity (operability) when consideration mixes with polymerisable monomer and the cured article that obtains suitably determines, in general, the monomer component of relative 100 mass parts (A), preferred 50～1500 mass parts are particularly in the scope of 70～1000 mass parts.

Solidification compound of the present invention, except above-mentioned filler, for example for consistent with the tone of tooth and gum, also can hybrid pigment, painted material such as high-visibility pigment, or add and be used to prevent ultraviolet ray relatively and the UV light absorber of variable color.And, in order to improve package stability, can mix stopper.

＜solidification compound 〉

Solidification compound of the present invention, be with above-mentioned various composition uniform mixing, by with (B)～(D) composition and blended composition (E) water-soluble polymers and other any composition as required, be distributed to preparation in the monomer component (A), type according to the polymerization starter (D) that uses suitably heats, perhaps, form cured article through polymerizing curable by rayed.

And, consider the stability when storing, refrigeration is stored under the temperature about 0～10 ℃, can return to room temperature during use and carry out polymerizing curable.Particularly as tensio-active agent (C), solidification compound with anionic surfactant (c-1) and nonionic surfactant (c-2) combined hybrid, as mentioned above, because it is good that property is stored in refrigeration, therefore can avoid effectively waiting the performance reduction that causes because of the anionic surfactant separates out.

In addition, can be before be about to using with solidification compound with two or more composition separate storage, when storing, be not cured like this, all the components is mixed carry out polymerizing curable in use.

And, because polymerizing curable is to carry out under the state that aforementioned composition (B) water is arranged, even at least a portion surface is when carrying out polymerizing curable under atmosphere (oxygen atmosphere) opened state, therefore can suppress the not formation of polymkeric substance on the cured article surface effectively, can avoid effectively that polymkeric substance reduces hardness and intensity because of forming not.Therefore, solidification compound of the present invention, very useful aspect the purposes of dental repair materials, be not limited to dental use, and can be used for general industry.

Embodiment

Enumerate embodiment below and specifically describe the present invention, but in any case the present invention is not limited to these embodiment.

And, show the evaluation method of the solidification compound of the compound that uses in embodiment and the Comparative Examples and abbreviation and preparation below.

[monomer of free redical polymerization]

AAEM：

Acetoacetoxy groups ethyl-methyl acrylate (absorption of water: 1.4wt%)

HD：

1,6-hexanediol dimethacrylate (absorption of water: 0.1wt%)

bis-GMA：

2,2-two (4-(2-hydroxy-3-methyl acryloxy propoxy-) phenyl) propane (absorption of water: 2.2wt%)

3G：

Triethylene glycol dimethacrylate (absorption of water: 1.7wt%)

D2.6E：

2,2-two (4-methacryloxy polyethoxye phenyl) propane (absorption of water: 0.3wt%)

HEMA：

Methacrylic acid hydroxyl ethyl ester (absorption of water〉100wt%)

14G：

Molecular weight is the dimethacrylate (absorption of water〉100wt%) of 600 polyoxyethylene glycol

MAC-10：

11-methacryloxy-1,1-11 carbon dicarboxylic acid (absorptions of water: 0.6wt%)

PM：

The mixture of biphosphate 2-methacryloxy ethyl ester and phosphoric acid hydrogen two (2-methacryloxyethyl) ester (absorption of water〉100wt%)

[anionic surfactant]

SLS：

Sodium lauryl sulphate (HLB:40)

SDS：

Sodium decyl sulfate (HLB:41)

SOS：

Hot sodium sulfonate

LBS：

Sodium dodecylbenzene sulfonate

[cationic surfactant]

LDAGCI：

DAG (HLB:30)

LTMACI：

Dodecyl trimethyl ammonium chloride (HLB:11)

[nonionic surfactant]

POEL：

Polyoxyethylene (10) lauryl ether (HLB:14)

POEL4：

Polyoxyethylene (4) lauryl ether (HLB:10)

POEO2：

Polyoxyethylene (2) oleyl ether (HLB:8)

POEO7：

Polyoxyethylene (7) oleyl ether (HLB:11)

POEO15：

Polyoxyethylene (15) oleyl ether (HLB:16)

[polymerization starter]

(organo-peroxide)

BPO：

Benzoyl peroxide

パ—オクH：

1,1,3,3-tetramethyl butyl hydroperoxide

(amine compound)

DEPT：

N, N-di-alcohol-para-totuidine

DMPT：

N, N-dimethyl-para-totuidine

PEAT：

N, N-diethyl-para-totuidine

DMBE：

The dimethyl ethyl benzoate

(α-diketone)

CQ: camphorquinone

(aryl boric acid salt compound)

PhBTEOA：

Tetraphenyl boron triethanolamine salt

(vanadium compound)

VOAA：

The ethanoyl acetate moiety closes vanadium oxide (IV)

[water-soluble polymers]

PVA1000：

Polyvinyl alcohol

(fully saponified thing, mean polymerisation degree 1000, molecular-weight average 50000)

[filler]

3Si-Zr：

Soft silica-zirconium white, γ-methacryloxypropyl trimethoxy silane surface treatment thing (median size: 3 μ m)

0.3Si-Ti：

The γ of spherical silicon dioxide-titanium oxide-methacryloxypropyl trimethoxy silane surface treatment thing (median size: 0.3 μ m)

PEMA：

Polyethyl methacrylate (median size: 30 μ m)

[absorption of water measuring method]

Monomer (or its mixture) with free redical polymerization under 23 ℃ mixes with water, measures this monomeric water content of saturated suction, obtains absorption of water according to following formula by カ-Le Off イ Star シ ヤ-(CA-02 type, Mitsubishi Chemical society makes).

The weight (g) * 100 of absorption of water (%)=water content (g)/monomer (or its mixture)

[surface is the polymerization amount measuring method not]

In the model that the polyacetal in the hole with diameter 50mm, thick 1mm is made, fill the solidification compound for preparing in each embodiment or the Comparative Examples, under 37 ℃, wet condition, in thermostat container, place and be cured in 15 minutes.But embodiment 19～23 and Comparative Examples 16～20 are by being cured for 30 seconds with visible rays irradiator (ト Network ヤ マ society makes, パ ワ-ラ イ ト) rayed.

Afterwards, with ethanol surperficial the cleaning of gained cured article removed not polymeric layer.By the weight of the solidification compound of filling in the model, deduct and remove value that the weight of the cured article of polymeric layer not obtains as polymerization amount not, be expressed as the weight of per surface area.

[measuring method of flexural strength]

In the model that the polyacetal of the slot with wide 4mm, thick 2mm, long 40mm is made, fill solidification compound, to be cured in the same manner with the mensuration of polymerization amount not.

To the gained cured article, with strength testing machine (society of Shimadzu Seisakusho Ltd. makes, オ-ト グ ラ Off), under the condition of pinblock speed 1mm/ branch, span 15mm, carry out 3 pliability tests, obtain flexural strength.

And, according to the surface hardness of ADAS No.17 (Denture Base Temporary Relining Resins) mensuration cured article.

[evaluation of polishing grindability]

In the model that the polyacetal of the square hole with wide 10mm, thick 2mm is made, fill solidification compound, to be cured in the same manner with the mensuration of polymerization amount not.

Go up the installation skilled worker with カ-バ イ ト バ-(ト Network ヤ マ society makes, Ha-デ イ ア-ロ イ バ-DD6), estimate the polishing grindability on gained cured article surface the skilled worker with motor (モ リ society makes, micromotor ANS3000).Judgement criteria is as follows.

O: at the カ-バ イ ト バ-not polymeric layer of upward not reeling

X: カ-バ イ ト バ-on be wound with not polymeric layer

[storage stability test]

Solidification compound stored for 1 week in 4 ℃ refrigerator after, separating out of look-up table surface-active agent estimated with two following standards.

Zero: do not have tensio-active agent to separate out

*: there is tensio-active agent to separate out

＜embodiment 1 〉

Use absorption of water as the 3G of 1.7wt% as polymerisable monomer, according to following formulation first liquid and second liquid.

The prescription of first liquid:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (anionic surfactant): 1.5 mass parts

BPO (organo-peroxide): 3 mass parts

The prescription of second liquid:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (anionic surfactant): 1.5 mass parts

DMPT (amine compound): 1.5 mass parts

First liquid and second liquid that will have aforesaid composition mix, and prepare the solidification compound of following composition.

The composition of solidification compound:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (tensio-active agent): 1.5 mass parts

BPO (organo-peroxide): 1.5 mass parts

DMPT (amine compound): 0.75 mass parts

Estimate the various characteristics of this solidification compound according to foregoing method.Consequently the surface not polymerization amount be 6 μ g/mm ², the flexural strength of cured article is 80MPa.

＜embodiment 2～5 〉

Except the variation of the type of the tensio-active agent that uses such as table 1 record, prepare solidification compound in the same manner with embodiment 1, carry out the not evaluation of polymerization amount of surface.Show the result in table 1 with embodiment 1.

＜Comparative Examples 1 〉

Except water, tensio-active agent do not use, prepare the solidification compound of forming shown in the table 1 with embodiment 1 identically.Consequently the surface not polymerization amount be 730 μ g/mm ², and the flexural strength of cured article is 83MPa.

＜Comparative Examples 2,3 〉

Prepare the solidification compound of forming shown in the table 1 in the same manner with embodiment 1, measure not polymerization amount of surface, it the results are shown in table 1.

[table 1]

^*: the absorption of water of 3G is 1.7wt%

＜embodiment 6 〉

Except use absorption of water be the HD of 0.1wt% as the polymerisable monomer, prepare the solidification compound of forming shown in the table 2 in the same manner with embodiment 1, measure not polymerization amount of surface.Consequently the surface not polymerization amount be 7 μ g/mm ²(the surface not measurement result of polymerization amount is presented at table 2 together.)

＜Comparative Examples 4 〉

Except not mixing water and tensio-active agent, prepare the solidification compound of forming shown in the table 2 in the same manner with embodiment 6, carry out the not mensuration of polymerization amount of surface.Consequently the surface not polymerization amount be 512 μ g/mm ²(the surface not measurement result of polymerization amount is presented at table 2 together.)

＜embodiment 7 〉

Except use absorption of water be the AAEM of 1.4wt% as the polymerisable monomer, prepare solidification compound in the same manner with embodiment 1, carry out the not mensuration of polymerization amount of surface.Consequently the surface not polymerization amount be 32 μ g/mm ²(the surface not measurement result of polymerization amount is presented at table 2 together.)

＜embodiment 8 〉

The mixture of HEMA for preparing the AAEM of 95 mass parts and 5 mass parts is as polymerisable monomer.The absorption of water of measuring this polymerizable monomer mixture is 2.9wt%.

Except using said mixture to replace preparing solidification compound in the same manner with embodiment 1 3G, carry out the not mensuration of polymerization amount of surface.

Consequently the surface not polymerization amount be 6 μ g/mm ²(the surface not measurement result of polymerization amount is presented at table 2 together.)

＜Comparative Examples 5 〉

Except not mixing water and tensio-active agent, with embodiment 7 in the same manner, use AAEM to prepare the solidification compound of forming shown in the table 2 as polymerisable monomer, carry out the not mensuration of polymerization amount of surface.Consequently the surface not polymerization amount be 652 μ g/mm ²(the surface not measurement result of polymerization amount is presented at table 2 together.)

＜embodiment 9～11, Comparative Examples 6～9 〉

Use the polymerizable monomer mixture of AAEM and HEMA, with embodiment 1 in the same manner, the solidification compound of forming shown in the preparation table 2 carries out the not mensuration of polymerization amount of surface.With the absorption of water of the polymerizable monomer mixture that uses and surface not the evaluation result of polymerization amount be shown in table 2 together.

＜embodiment 12～15, Comparative Examples 10～11 〉

Except the combined amount that changes water, tensio-active agent, with embodiment 1 in the same manner, the solidification compound of forming shown in the preparation table 3 carries out the not evaluation of polymerization amount and flexural strength of surface.The result is shown in table 3 with the result of the foregoing description 1.

[table 3]

^*: the absorption of water of 3G is 1.7wt%

＜embodiment 16～18, Comparative Examples 12～15 〉

Except using the monomer mixture of forming shown in the table 4, and change outside the combined amount of water, tensio-active agent, with embodiment 1 in the same manner, the solidification compound of forming shown in the preparation table 4 carries out the not mensuration of polymerization amount and flexural strength of surface.The result is shown in table 3 with the result of described embodiment 1.

Except in order to reach the composition shown in the table 4, and change outside the combined amount of water, tensio-active agent, with embodiment 1 in the same manner, the preparation cured article is also estimated.With the surface not the evaluation result of polymerization amount be shown in table 4 with the result of previous embodiment 1.And, the absorption of water of the monomer mixture that uses is shown in table 4.

＜embodiment 19～20, Comparative Examples 16～17 〉

Under the shading, the visible-light curing composition of forming shown in the preparation table 5 according to aforementioned evaluation method, with this solidification compound, solidifies the acquisition cured article by the rayed of using the radiation of visible light device, estimates surface not polymerization amount, hardness and polishing grindability.The result is shown in table 5 together.And, the absorption of water of the polymerizable monomer mixture that uses is shown in table 5.

＜embodiment 21～22, Comparative Examples 18～19 〉

Prepare two kinds of composition A, B of composition as shown in table 5 respectively, they are mixed with solidification compound.With embodiment 19 in the same manner, this solidification compound is cured by rayed, the surface of estimating this cured article is polymerization amount, hardness and polishing grindability not.It the results are shown in table 5.And, in table 5, shown the absorption of water of the polymerizable monomer mixture that uses when preparing two kinds of compositions together.

＜embodiment 23, Comparative Examples 20 〉

Prepare two kinds of composition A, B of composition as shown in table 6 respectively, they are mixed with solidification compound.With embodiment 19 in the same manner, this solidification compound is cured by rayed, the surface of estimating this cured article is polymerization amount, hardness and polishing grindability not.It the results are shown in table 6.In addition, according to the blending ratio of the polymerisable monomer in the solidification compound of record in the table 6, the preparation polymerizable monomer mixture is measured absorption of water.This result is shown in table 6 together.

＜embodiment 24 〉

Use absorption of water as the 3G of 1.7wt% as polymerisable monomer, according to following formulation first liquid and second liquid.

The prescription of first liquid:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (anionic surfactant): 1.5 mass parts

POEL4 (nonionic surfactant) 1.5 mass parts

BPO (organo-peroxide): 3 mass parts

The prescription of second liquid:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (anionic surfactant): 1.5 mass parts

POEL4 (nonionic surfactant) 1.5 mass parts

DMPT (amine compound): 1.5 mass parts

First liquid and second liquid that will have aforesaid composition mix, and prepare the solidification compound of following composition.

The composition of solidification compound:

3G (monomer component (A)): 100 mass parts

Water: 3 mass parts

SLS (anionic surfactant): 1.5 mass parts

POEL4 (nonionic surfactant) 1.5 mass parts

BPO (organo-peroxide): 1.5 mass parts

DMPT (amine compound): 0.75 mass parts

To this solidification compound, estimate surface not polymerization amount, flexural strength and package stability (whether having tensio-active agent to separate out).Consequently the surface not polymerization amount be 3 μ g/mm ², the flexural strength of cured article is 80MPa.And, in storage stability test, do not see that tensio-active agent separates out.The composition of solidification compound, surface not polymerization amount and package stability the results are shown in table 7.

＜embodiment 25～31 〉

Except the type of the tensio-active agent that uses such as table 7 record change, prepare solidification compound in the same manner with embodiment 24, the gained solidification compound is carried out the not evaluation of polymerization amount and package stability of surface.The results are shown in table 7.In addition, the result who in table 7, has shown embodiment 1 together.

＜embodiment 32 〉

Except using HD the monomer as free redical polymerization of absorption of water, prepare solidification compound in the same manner with embodiment 24 as 0.1wt%.The solidification compound that obtains is carried out the evaluation of surperficial not polymerization amount and package stability, the results are shown in table 8.In addition, the result who in table 8, has shown embodiment 6 together.

And surface not polymerization amount is 5 μ g/mm ², do not see that in storage stability test tensio-active agent separates out.

＜embodiment 33 〉

The mixture for preparing 70 mass parts AAEM and 30 mass parts HEMA is as polymerisable monomer.The absorption of water of measuring this polymerizable monomer mixture is 10.3wt%.

Except using said mixture to replace preparing solidification compound in the same manner with embodiment 24 3G.Carry out the mensuration of surperficial not polymerization amount and package stability, the results are shown in table 8.

And surface not polymerization amount is 8 μ g/mm ², do not see that in storage stability test tensio-active agent separates out.

＜embodiment 34～36 〉

Use the AAEM of composition as shown in table 8 and the polymerizable monomer mixture of HEMA, prepare solidification compound in the same manner, carry out the mensuration of surperficial not polymerization amount and package stability, the results are shown in table 8 with embodiment 24.

And, in table 8, shown the absorption of water of polymerizable monomer mixture together.

＜embodiment 37,38 〉

Except the combined amount that changes water, prepare the solidification compound of forming shown in the table 9 in the same manner with embodiment 24, carry out the not evaluation of polymerization amount, flexural strength and package stability of surface.Its result is shown in table 9 with the result of embodiment 24.

＜embodiment 39 〉

According to the composition shown in the table 10, polymerisable monomer, water, tensio-active agent, water-soluble polymers and polymerization starter are mixed the preparation solidification compound.This solidification compound is carried out the not mensuration of polymerization amount of surface, the results are shown in table 10.

＜Comparative Examples 21 〉

Except not using fully the tensio-active agent, prepare solidification compound in the same manner with embodiment 39, carry out the not mensuration of polymerization amount of surface, the results are shown in table 10.

＜embodiment 40～43 〉

Except the type that changes tensio-active agent, prepare solidification compound in the same manner with embodiment 39, carry out the not mensuration of polymerization amount of surface, the results are shown in table 10.

As shown in Table 10, by with water-soluble polymers and tensio-active agent and usefulness, can make the surface not polymerization amount reduce greatly.

Claims (6)

1. solidification compound comprises:

(A) form by the monomer of free redical polymerization and absorption of water is 20wt% or lower monomer component 100 mass parts;

(B) water 0.5～10 mass parts;

(C) tensio-active agent 0.1～20 mass parts; With

(D) radical polymerization initiator of significant quantity,

Wherein, under the state that keeps aforementioned water (B), be cured by radical polymerization.

2. the solidification compound of claim 1, aforementioned monomer composition (A) are that absorption of water is that 5wt% or lower strong-hydrophobicity polymerisable monomer (a-1) and absorption of water are the mixture of 100wt% or higher strongly hydrophilic polymerisable monomer (a-2).

3. the solidification compound of claim 1, aforementioned surfactants (C) is made up of anionic surfactant (c-1) and nonionic surfactant (c-2).

4. the solidification compound of claim 3, the aforementioned monomer composition (A) of relative 100 mass parts contains the aforementioned anionic surfactant (c-1) of 0.1～10 mass parts and the aforementioned nonionic surfactant (c-2) of 0.1～10 mass parts.

5. the solidification compound of claim 1, the aforementioned monomer composition (A) of relative 100 mass parts also contains the water-soluble polymers (E) of 0.00001～10 mass parts.

6. the application of the solidification compound of claim 1 in the dental repair materials.