CN101595138B

CN101595138B - Polymerizable monomer-containing composition

Info

Publication number: CN101595138B
Application number: CN2008800024564A
Authority: CN
Inventors: 石野博重; 关口卓宏; 冈田浩一
Original assignee: Kuraray Noritake Dental Inc
Current assignee: Kuraray Noritake Dental Inc
Priority date: 2007-01-17
Filing date: 2008-01-16
Publication date: 2012-08-22
Anticipated expiration: 2028-01-16
Also published as: CN101595139A; CN101589070B; CN101595138A; CN101595139B; CN101636420A; CN101589070A

Abstract

本发明提供适于牙科用组合物的组合物。本发明的组合物含有聚合性单体(A)和水(B)而成，所述聚合性单体(A)具有4个以上的碳连续键合的非共轭碳链、2个以上的聚合性基团以及2个以上的羟基，所述组合物相对于聚合性单体成分的总量100重量份，含有水(B)6～2000重量份而成。该组合物通过含有适当的成分，可以适合用于底料、粘接材料、复合树脂以及粘固剂等的牙科用材料。The present invention provides compositions suitable for dental compositions. The composition of the present invention contains a polymerizable monomer (A) and water (B), and the polymerizable monomer (A) has a non-conjugated carbon chain in which four or more carbons are continuously bonded, two or more The polymerizable group and two or more hydroxyl groups are formed by containing 6 to 2000 parts by weight of water (B) relative to 100 parts by weight of the total amount of the polymerizable monomer component. The composition can be suitably used for dental materials such as primers, adhesive materials, composite resins, and cements by containing appropriate components.

Description

The compsn that contains polymerizable monomer

Technical field

The present invention relates to contain the difunctionality polymerizable monomer with polymerizable group and hydroxyl, the compsn that He Shui forms.

Background technology

Fill or when coating restoration, usually, use the dental adhesives at damaged of tooth.As the dental adhesives, the known dental adhesives that has cooperation to have the polymerizable monomer of polymerizable group and hydroxyl.

For example; In the International Publication WO2004/047773 pph; Put down in writing the dental adhesive composition; It is characterized in that containing: the polyvalent alcohol of carbonatoms 3～6 and a plurality of (methyl) acrylic acid ester cpds and have the multifunctional polymerization property monomer of 1～2 hydroxyl, simple function (methyl) propenoate that intramolecularly does not have hydroxyl, the polymerizable monomer that intramolecularly contains acidic-group form as the organoboron compound and the packing material of solidifying agent.Thus, through the above-mentioned multifunctional polymerization property monomer of a small amount of interpolation in compsn, adhesiveproperties, cured body rerum natura, almost not influence of operable time to compsn can significantly improve curing speed.But, may not be good to the impregnability of Dentinal collagen layer, the possibility that has bonding strength to reduce, expectation improves.

At this; For dentine; Make such dental adhesives do the time spent; The monomer component that has the decalcification of acidic component dissolving dentin surface, penetrant action that monomer component is impregnated into Dentinal collagen layer and soak into solidify and with solidification that collagen forms mixolimnion (below, be called " resin impregnation layer ") be important.

Till now; Carried out use-pattern with the dental adhesives by three components, the 3 step type of sequentially using above-mentioned decalcification, above-mentioned penetrant action and above-mentioned solidification; To with above-mentioned decalcification and unified 2 step of the two-pack type of above-mentioned penetrant action, and then to all self-criticism of 1 step of single component simpleization of type of integrated above-mentioned decalcifications, above-mentioned penetrant action and above-mentioned solidification.In arbitrary use-pattern, all requirement can be as the compsn of dental adhesives use excellent in adhesion.

Summary of the invention

The present invention accomplishes in order to solve above-mentioned problem, and its purpose is, provide be applicable to dental composition, contain the compsn that difunctionality polymerizable monomer with polymerizable group and hydroxyl and water form.

The present invention relates to compsn; It is to contain the compsn that polymerizable monomer (A) and water (B) form; Said polymerizable monomer (A) has non-conjugated carbochain, the polymerizable group more than 2 and the hydroxyl more than 2 of the continuous bonding of carbon more than 4; With respect to total amount 100 weight parts of polymerizable monomer composition, contain water (B) 6～2000 weight parts and form.

Among the present invention, polymerizable monomer (A) preferably has the group of formula (1) expression,

[Chemical formula 1]

(in the formula, G is hydroxyl or polymerizable group, and * representes associative key.)。

In addition, the group of the preferred following formula of polymerizable group (2), following formula (3) or following formula (4) expression.

[Chemical formula 2]

[chemical formula 3]

[chemical formula 4]

(in the formula, R ¹, R ², and R ³Represent the aliphatic alkyl of Wasserstoffatoms or carbonatoms 1～10 respectively, * representes associative key.)

The compound of above-mentioned polymerizable monomer (A) preferred formula (5) expression.

[chemical formula 5]

(in the formula, G is hydroxyl or polymerizable group, and n is the integer more than 2, and at least 2 is hydroxyl among the G, and among the G at least 2 be polymerizable group.)。As an example of preferred polymerizable monomer (A), can enumerate the compound of formula (6) expression.

[chemical formula 6]

(in the formula, R ¹The aliphatic alkyl of expression Wasserstoffatoms or carbonatoms 1～10, m representes the integer more than 2, and k representes the integer more than 1, and the unit with m ester group is arbitrarily with unitary the putting in order with k hydroxyl.) at this, m is preferred 2～5, and k preferred 1～5.

As the other example of preferred polymerizable monomer (A), can enumerate the compound of formula (7) expression.

[chemical formula 7]

(in the formula, R ¹The aliphatic alkyl of expression Wasserstoffatoms or carbonatoms 1～10, p representes the integer more than 2.) at this, p preferred 2～4.

In above-mentioned, R ¹Preferred Wasserstoffatoms or methyl.

Compsn of the present invention preferably contains polymerizable monomer (A) 1～99 weight part and forms in total amount 100 weight parts of polymerizable monomer composition.In addition, in total amount 100 weight parts of polymerizable monomer composition, and then preferably contain polymerizable monomer (C) 1～90 weight part and form with acidic-group.In addition, in total amount 100 weight parts of polymerizable monomer composition, and then preferably contain bridging property polymerizable monomer (D) 1～90 weight part and form.

Compsn of the present invention with respect to total amount 100 weight parts of polymerizable monomer composition, preferably contains organic solvent (E) 1～2000 weight part and forms.Organic solvent (E) preferably water solubleness organic solvent.In addition, with respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain polymerization starter (F) 0.001～30 weight part and form.In addition, with respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain polymerization promotor (G) 0.001～30 weight part and form.In addition, with respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain filler (H) 1～2000 weight part and form.

Compsn of the present invention contains polymerizable monomer (A) and the water (B) with a plurality of polymerizable groups and a plurality of hydroxyls, therefore with headed by the dental use, in various uses, becomes the compsn of performance excellent in curing property and cementability.Particularly, therefore compsn of the present invention can be suitable for using as dental composition to the impregnability of Dentinal collagen layer and high with the bonding strength and the adhesion durability of dentine (particularly dentine).

Another aspect of the present invention is in addition, the bed material, adhesives, compound resin and the cement that use above-mentioned dental composition to obtain.The bonding strength and the adhesion durability of the excellence of these dental materials demonstrations and dentine (particularly dentine).

Embodiment

Compsn of the present invention contains difunctionality polymerizable monomer (A) and water (B) with polymerizable group and hydroxyl and forms, and is useful as dental composition.Among the present invention, use the term of " simple function property ", " difunctionality " and " trifunctional property ", " simple function property ", " difunctionality " and " trifunctional property " represent to have in 1 molecule 1,2 and 3 polymerizable groups respectively.

Polymerizable monomer (A) aggregates into non-conjugated carbochain, the polymerizable group more than 2 and the hydroxyl more than 2 that monomer (A) has the continuous bonding of carbon more than 4.As aggregating into monomer (A), can be with the independent use of the polymerizable monomer that satisfies this definition or with also using more than 2 kinds.

Polymerizable monomer (A) has the polymerizable group more than 2.When compsn of the present invention was used for dental use, this polymerizable group solidified compsn through polymerization, can be used as the dental material performance function of bed material, adhesives, compound resin and cement etc.In addition, the quantity of polymerizable group is more than 2, so polymerizable monomer (A) has bridging property.Thereby the solidified nature of compsn and the physical strength of cured article are high.

About polymerizable monomer (A), polymerizable group is meant the group of the functional group that contains free redical polymerization, for example, can enumerate the group that contains vinyl.Particularly,, consider that the group of preferred following formula (2), formula (3) or formula (4) expression among them, is considered from the viewpoint that imports easy property to polymerizable monomer (A), most preferably the group of formula (2) expression from the viewpoint of polymerisation reactivity as polymerizable group.

[chemical formula 8]

[chemical formula 9]

[Chemical formula 1 0]

At this, R ¹, R ², and R ³Be respectively the aliphatic alkyl of Wasserstoffatoms or carbonatoms 1～10, * representes associative key.As the example of the aliphatic alkyl of carbonatoms 1～10, can enumerate the alkyl of carbonatoms 1～10, the thiazolinyl of carbonatoms 2～10, the alkynyl of carbonatoms 2～10 etc.

The alkyl of carbonatoms 1～10 can be straight chain shape, branched and cyclic any one; As an example, can enumerate methyl, ethyl, n-propyl, sec.-propyl, cyclopropyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, cyclobutyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, 2-ethylhexyl, ring octyl group, n-nonyl, ring nonyl, positive decyl etc.

The thiazolinyl of carbonatoms 2～10 can be straight chain shape, branched and cyclic any one; As an example, can enumerate vinyl, allyl group, methyl ethylene, propenyl, crotonyl, pentenyl, hexenyl, cyclopropenyl radical, cyclobutene base, cyclopentenyl, cyclohexenyl etc.

The alkynyl of carbonatoms 2～10 can be straight chain shape, branched and cyclic any one; As an example, can enumerate ethynyl, 1-proyl, 2-propynyl, ethyl acetylene base, 1-methyl-2-propynyl, 2-butyne base, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, valerylene base, 3-pentynyl, 1-methyl-2-butyne base, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexyn, 2-hexyn, 1-ethyl-2-butyne base, 3-hexyn, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 4-methyl-1-pentene alkynyl, 3-methyl-1-pentene alkynyl, 5-hexyn, 1-ethyl-3-butynyl etc.

When polymerizable monomer (A) is used for dental use etc., carry out radical polymerization.Thereby, consider R from the viewpoint of the Raolical polymerizable property of end product ¹, R ², and R ³Preferred Wasserstoffatoms of difference or methyl.In addition, when using as dental composition, because hydrolysis etc., polymerizable group has the possibility that breaks away from from polymerizable monomer (A).The polymerizable group that consider to break away from is when giving birth to the pungency of body, and polymerizable group preferably contains methacryloxy.Therefore, R ¹, R ², and R ³More preferably methyl.

Polymerizable monomer (A) has the polymerizable group more than 2, and the polymerizable group more than 2 can be the same or different.

Polymerizable monomer (A) has the hydroxyl more than 2.Through this hydroxyl, polymerizable monomer (A) is endowed high wetting ability, and is good to the impregnability of Dentinal collagen layer, and compsn is good to the cementability of dentine thus.

Polymerizable monomer (A) has the non-conjugated carbochain of the continuous bonding of carbon more than 4.This carbochain constitutes all or part of of polymerizable monomer (A) skeleton, on this carbochain, and preferred above-mentioned polymerizable group of bonding and hydroxyl.

Example as polymerizable monomer (A); The a part of hydroxyl that can enumerate the alkylol cpd more than 4 valencys of the non-conjugated carbochain with the continuous bonding of carbon more than 4 is replaced into the compound that polymerizable group obtains, so that hydroxyl and polymerizable group are respectively more than 2.As the example of the alkylol cpd more than 4 valencys of the non-conjugated carbochain with the continuous bonding of carbon more than 4, not special the qualification has sugar alcohol, monose, disaccharides and three carbohydrates etc. of carbonatoms 4～20 as preferred example.As sugar alcohol, preferably using carbonatoms is the tetrahydroxybutane of 4 sugar alcohol; Carbonatoms is Xylitol, ribitol, the arabitol of 5 sugar alcohol; Or carbonatoms is mannitol, Sorbitol Powder and the iditol of 6 sugar alcohol; Or carbonatoms is maltose alcohol of 12 sugar alcohol etc.In addition, the also preferred glycosamine that contains amino sugar alcohol that uses.As monose, preferably using carbonatoms is wood sugar, ribose, pectinose, the lyxose of 5 monose; Or carbonatoms is glucose, seminose, semi-lactosi, sorbose and the fructose etc. of 6 monose.In addition, contain amino with and the glucosamine of the monose of verivate, mannosamine, GalN, N-acetylamino glucose, N-ethanoyl mannosamine, N-ethanoyl GalN etc. also preferably use.As disaccharides, preferably use trehalose, sucrose, SANMALT-S, lactose, cellobiose etc.As three carbohydrates, preferably use カ Star プリ Application グシユガ one (registered trademark), lactulose (ラ Network トス Network ロ one ス), trisaccharide maltose, Isomaltotriose etc.Compsn of the present invention preferably uses as dental composition, more preferably uses as the dental adhesive composition.From considering that with the viewpoint of the cementability of dentine (particularly dentine) preferably the impregnability to dentine (particularly dentine) is high.Consider from this viewpoint, as the carbonatoms of above-mentioned alkylol cpd, more preferably 4～15, and then preferred 4～9, preferred especially 4～7.In addition, consider that the quantity of the hydroxyl of above-mentioned alkylol cpd is preferred 4～15, more preferably 4～9, preferred especially 4～7 from same viewpoint.Preferred concrete alkylol cpd as sugar alcohol, can be enumerated tetrahydroxybutane, mannitol, Sorbitol Powder, maltose alcohol; As monose, can enumerate glucose, glucosamine; As disaccharides, can enumerate trehalose, SANMALT-S; As three carbohydrates, can enumerate trisaccharide maltose.Among them, and then preferred tetrahydroxybutane, mannitol, glucose, trehalose, preferred especially tetrahydroxybutane, mannitol.

Polymerizable monomer (A) preferably has the group of following formula (1) expression.This group is the feature structure in the above-mentioned illustrative compound.

[Chemical formula 1 1]

At this, G is hydroxyl or polymerizable group, and * representes associative key.

For the structure of polymerizable monomer (A), particularly, the compound of polymerizable monomer (A) preferred formula (5) expression.

[Chemical formula 1 2]

At this, G is hydroxyl or polymerizable group, and n is the integer more than 2, and at least 2 is hydroxyl among the G, and among the G at least 2 be polymerizable group.

Bonding polymerizable group or hydroxyl on each carbon atom of carbochain in this structure, polymerizable group and hydroxyl are intensive with high density.Therefore, when the compsn that will contain this polymerizable monomer (A) is applied to dental material, show excellent in curing property and cementability.In addition, also has the advantage of using sugar alcohol to make easily.

Consider the integer of n preferred 2～18, more preferably 2～9 integer, most preferably 2～4 integer from the solidified nature of compsn and with the cementability of dentine and the viewpoint that obtains the easy property of raw material.

When paying attention to the cementability of compsn and dentine, the compound of the preferred following formula of polymerizable monomer (A) (6) expression.

[Chemical formula 1 3]

At this, R ¹With above-mentioned synonym, m representes the integer more than 2, and k representes the integer more than 1, and the unit with m ester group is arbitrarily with unitary the putting in order with k hydroxyl.

From the solidified nature of compsn, consider to the impregnability of Dentinal collagen layer and with the cementability of dentine and the viewpoint that obtains the easy property of raw material, m is preferred 2～5, and more preferably 2～4, most preferably 2.K is preferred 1～5, and more preferably 2～4, most preferably 2.M and k sum are preferred 3～18, and more preferably 3～9, and then preferred 4～8, most preferably 4.

The compound of formula (6) expression has the hydroxyl more than 3, and wherein 2 is primary hydroxyl.This primary hydroxyl is very favorable when interacting with dentine (particularly dentine), when the compound compositions that therefore will contain formula (6) expression is applied to dental use, becomes the extra high compsn of cementability with dentine (particularly dentine).In addition, as polymerizable group, have 2 groups, so solidified nature is also good with following formula (2) expression.

And then, in the compound of formula (6) expression, consider the compound of preferred formula (8) and formula (9) expression from the solidified nature of compsn and with the viewpoint of the cementability of dentine.

[Chemical formula 1 4]

[Chemical formula 1 5]

On the other hand, when paying attention to the solidified nature of compsn, the compound of the preferred following formula of polymerizable monomer (A) (7) expression.

[Chemical formula 1 6]

At this R ¹With above-mentioned synonym, p representes the integer more than 2.

The compound of formula (7) expression has the polymerizable group of formula (2) expression at two ends of the non-conjugated carbochain of the continuous bonding of carbon more than 4, considers that from three-dimensional key element polymerization is high especially.Thereby, when the compound compositions that contains formula (7) expression is applied to dental use, become the extra high compsn of solidified nature.In addition, owing to have a plurality of hydroxyls, therefore good to the impregnability of Dentinal collagen layer, also good with the cementability of dentine.

When generating resolvent owing to the effect of hydrolysis in the oral cavity etc., resolvent is safe compounds such as tetrahydroxybutane, Xylitol, Sorbitol Powder or mannitol, and p preferred 2～4.As p is 2～4 compound, for example, can enumerate tetrahydroxybutane two (methyl) propenoate, Xylitol two (methyl) propenoate, Sorbitol Powder two (methyl) propenoate.And then more preferably p is 2 tetrahydroxybutane two (methyl) propenoate, considers above-mentioned polymerizability in the lump and to giving birth to irritating viewpoint of body, most preferably the tetrahydroxybutane dimethacrylate of formula (10) expression.

[Chemical formula 1 7]

Polymerizable monomer (A) can obtain through the known method manufacturing.Particularly for example; Make according to conventional methods have polymerizable group carboxylic acid (for example; The carboxylic acid that the hydrogen bonding atom obtains on the associative key of the group of formula (2) expression) or derivatives thereof, carry out esterification with the above alkylol cpd of 4 valencys of non-conjugated carbochain, through refining the getting final product of separation means of chromatography etc. with the continuous bonding of carbon more than 4.In order to improve yield, carry out esterification after also can above-mentioned carboxylic acid with polymerizable group being transformed to the verivate of carboxylic acid halides etc.

Particularly polymerizable monomer (A) is the compound of formula (6) expression; When wherein being the compound of formula (8) or formula (9) expression; Use compound that the primary hydroxyl of above-mentioned alkylol cpd is protected in advance as raw material; Preferred this compound and the carboxylic acid with polymerizable group (at this, the carboxylic acid of hydrogen bonding atom on the associative key of the group of formula (2) expression) or derivatives thereof implemented carries out the operation (a) of esterification and the operation (b) of the protection base deprotection of the primary hydroxyl of the ester cpds that obtains made.As above-mentioned verivate with carboxylic acid of polymerizable group, not special the qualification preferably used carboxylic acid halides or acid anhydrides.When considering, more preferably use carboxylic acid halides with above-mentioned alkylol cpd reactive.In addition, when considering to obtain compound or storage stability easily, in the above-mentioned carboxylic acid halides, especially preferably use acyl chlorides.The method of manufacture that comprises this operation can obtain polymerizable monomer with high yield, is preferred on industrial production.

The compound that the primary hydroxyl of above-mentioned alkylol cpd is protected in advance, for example, 1,2:5; 6-two-O-isopropylidene-D-mannitol (1,2:5,6-Di-O-isopropylidene-D-mannitol); 1,3:4,6-two-O-tolylene-D-mannitol (1; 3:4 6-Di-O-benzylidene-D-mannitol) etc., can obtain as commercially available article.In addition, also can implement to protect above-mentioned alkylol cpd primary hydroxyl operation and make.In the compound that the primary hydroxyl of above-mentioned alkylol cpd is protected in advance, in the time of the preferred residual a plurality of hydroxyl of the hydroxyl beyond the primary hydroxyl, a part is protected.Obtain having the structure of 3 above hydroxyls like this, easily.

Protect the operation of the primary hydroxyl of above-mentioned alkylol cpd to implement through the reaction that imports known protection base.

As the protection base of the primary hydroxyl of above-mentioned alkylol cpd, can select preferentially to import to the group of primary hydroxyl.In addition, protection base is difficult to cause deprotection reaction when esterification, during this external this deprotection reaction, can select ester bond to be difficult to break off.Consider from such viewpoint, as preferred ether system protection base, silyl ether system protection base and the acetal system protection base of using of protection base.As ether system protection base, more preferably use 1-ethoxyethyl group ether and trityl group ether.More preferably use triisopropyl silyl ether, t-butyldimethylsilyl ether and t-butyldiphenylsilyl ether as silyl ether system protection base.These protection bases all can preferentially import to primary hydroxyl, and, owing to can therefore have and need not break off the just advantage of ability deprotection of ester bond at deprotection under the solutions of weak acidity.On the other hand, as acetal system protection base more preferably use isopropylidene, encircle inferior heptyl, tolylene and to the methoxyl group tolylene.When using acetal system protection base, for primary hydroxyl, not only can preferentially import, and can once protect the hydroxyl more than 2 that comprises primary hydroxyl, be very to be fit in polymerizable monomer (A) synthetic therefore.Therefore, ether system protection base, silyl ether system protect in base and the acetal system protection base and then preferably use the protection of acetal system basic.And then, particularly can be at deprotection under the solutions of weak acidity, the viewpoint that the purified by product is removed easily during from deprotection is considered, is especially preferably used isopropylidene.

The compound that the primary hydroxyl of above-mentioned alkylol cpd is protected in advance can carry out according to known method with the operation that the carboxylic acid or derivatives thereof with polymerizable group carries out esterification; In the esterification; Consider the kind of protection base; The appropriate reaction conditions (particularly, the kind of temperature condition and catalyzer) of selecting deprotection reaction to be difficult to take place is important.In addition; After the esterification; Form a plurality of ester bonds in 1 molecule; In addition for hydroxyl and the unreacted hydroxyl that makes protection adds up to more than 3, selective reaction condition (particularly, the compound that is protected in advance of the primary hydroxyl of above-mentioned alkylol cpd with have the usage quantity of the carboxylic acid or derivatives thereof of polymerizable group) is important.

The operation of the protection base of the primary hydroxyl of the ester cpds that deprotection obtains, the kind basic according to protection gets final product according to known method.At this moment, the reaction conditions (particularly, the kind of temperature condition and catalyzer) of selecting to be difficult to break off ester bond is important.As above-mentioned, when the ether system protection base that preferably uses as the protection base of primary hydroxyl, silyl ether system protection base and acetal system protection base, all can not break off ester bond and just can carry out deprotection at deprotection under the solutions of weak acidity.In addition, through using TBAF (tetrabutyl ammonium fluoride) fluorochemicals of etc.ing, silyl ether system protection base can high optionally deprotection, the availability height.Under acidic conditions during deprotection, preferably use mineral acids such as hydrochloric acid, sulfuric acid with and the aqueous solution; Organic acids such as formic acid, acetate, trifluoroacetic acid with and the aqueous solution; Zeo-karb etc.In them, consider that acid degree suppresses the deprotection of the disconnection of ester bond suitably, effectively, more preferably organic acids such as formic acid, acetate, trifluoroacetic acid with and the aqueous solution, and then preferable formic acid, acetate with and the aqueous solution.

Polymerizable monomer (A) has a plurality of polymerizable groups and a plurality of hydroxyl, so crosslinking reaction property is excellent, and is strong with the interaction of the compound of possess hydrophilic property group.Thereby, this polymerizable monomer and suitable composition are mixed and made into compsn, in the various uses headed by the dental use, become the compsn of excellent solidified nature of performance and cementability.Consider the compound that also to represent with above-mentioned formula (6) and above-mentioned formula (7) from the viewpoint of taking into account with cementability dentine and solidified nature balance compsn.

As the use level of polymerizable monomer (A), according to the purposes of compsn suitably decision get final product, common, in total amount 100 weight parts of polymerizable monomer composition (see after state for other polymerizable monomer compositions), preferably contain polymerizable monomer (A) 1～99 weight part.The use level of using polymerizable monomer (A) during as dental composition, has the advantage good, that bonding strength is high of soaking into to Dentinal collagen layer at the compsn of scope like this.The use level of polymerizable monomer (A) has the possibility that bonding strength reduces has adhesion durability to reduce simultaneously, more preferably more than 2 weight parts, and then more than preferred 5 weight parts during less than 1 weight part.On the other hand, when the use level of polymerizable monomer (A) surpasses 99 weight parts, the possibility that decalcification is insufficient, can not obtain sufficient adhesion strength is arranged, more preferably below 98 weight parts, and then below preferred 95 weight parts.

Water (B) compsn of the present invention is characterised in that, with respect to total amount 100 weight parts of polymerizable monomer composition, contains water (B) 6～2000 weight parts and forms.Through the water (B) that contains such use level, when compsn of the present invention is used as dental composition, when showing excellent bonding strength, show excellent adhesion durability.The use level of water (B) is during less than 6 weight parts, and is insufficient to the monomeric impregnability of collagen layer, and bonding strength reduces.More than preferred 7 weight parts of the use level of water (B), more preferably more than 8 weight parts, and then more than preferred 10 weight parts.On the other hand, when the use level of water (B) surpassed 2000 weight parts, monomeric polymerizability reduced, and when bonding strength reduced, adhesion durability reduced.Therefore, the use level of water (B) is below 2000 weight parts, below preferred 1500 weight parts.In fact; By after embodiment 1 and 2, the contrast of comparative example 1 among the embodiment that states can know that the use level of water (B) can not obtain sufficient adhesion strength during less than 6 weight parts; Use level through making water (B) is in specific scope, and affirmation can be brought into play effect of the present invention.In addition,, preferably do not contain and bring dysgenic impurity, preferred zero(ppm) water or ion exchanged water as water (B).Above-mentioned water (B) can use separately, also can be used as water (B) with after the mixed solvent of the organic solvent (E) stated use.

Then, any composition to compsn of the present invention describes.Compsn of the present invention according to the purposes of compsn, can contain polymerizable monomer (A) and water (B) composition in addition.For example, compsn of the present invention as polymerizable monomer (A) polymerizable monomer composition in addition, also can contain the polymerizable monomer composition of polymerizable monomer (C) with acidic-group, bridging property polymerizable monomer (D) etc.Polymerizable group that these polymerizable monomers have preferably with the group of the polymerizable group free redical copolymerization of polymerizable monomer (A).

In addition, compsn of the present invention can also contain organic solvent (E), polymerization starter (F), polymerization promotor (G) and filler (H).

Among the present invention, " total amount of polymerizable monomer composition " is meant the meaning of the total amount of polymerizable monomer (A), polymerizable monomer (C) and polymerizable monomer (D).

Polymerizable monomer (C) compsn of the present invention with acidic-group in total amount 100 weight parts of polymerizable monomer composition, preferably contains polymerizable monomer (C) 1～90 weight part with acidic-group and forms.The use level of polymerizable monomer (C) that will have acidic-group is when the compsn of this scope uses as dental composition; Therefore polymerizable monomer (C) with acidic-group self has acid etching effect or bed material treatment effect, has the advantage of the pre-treatment that do not need acid etching processing or bed material processing etc. etc.Thereby, have the polymerizable monomer (C) of acidic-group through combination, can provide easy and bonding strength is high, and good adhesives, the preferred especially one-pack type adhesives of adhesion durability.The use level of polymerizable monomer (C) with acidic-group has the possibility that can not obtain acid etching effect or bed material treatment effect, more preferably more than 2 weight parts, and then more than preferred 5 weight parts during less than 1 weight part.On the other hand, when the use level with polymerizable monomer (C) of acidic-group surpasses 90 weight parts, the possibility of the reduction that can not obtain sufficient solidified nature, adhesiveproperties is arranged, more preferably below 80 weight parts, and then below preferred 70 weight parts.

Polymerizable monomer (C) with acidic-group can use separately or appropriate combination is used more than 2 kinds.As the polymerizable monomer with acidic-group (C); Not special the qualification, can enumerate intramolecularly have 1 carboxyl or its anhydride group simple function property polymerizable monomer, have the simple function property polymerizable monomer of a plurality of carboxyls or its anhydride group at intramolecularly, have the simple function property polymerizable monomer (being sometimes referred to as simple function free love base polymerizable phosphate ester) of phosphinyl oxygen base (ホス Off イニ Le オキシ yl) or phosphono oxygen base (ホスホノオキシ yl) etc. at intramolecularly.

Example as the simple function property polymerizable monomer that has 1 carboxyl or its anhydride group at intramolecularly; Can enumerate (methyl) vinylformic acid, N-(methyl) acryl glycocoll, N-(methyl) acryl aspartic acid, N-(methyl) acryl-5-aminosalicylic acid, 2-(methyl) acryl oxygen base ethyl hydrogen succinate ester, 2-(methyl) acryl oxygen base ethyl hydrogen phthalic acid, 2-(methyl) acryl oxygen base ethyl hydrogen maleic acid ester, 6-(methyl) acryl oxygen base ethyl naphthalene-1; 2,6-tricarboxylic ester, O-(methyl) acryl tyrosine, N-(methyl) acryl tyrosine, N-(methyl) acryl phenylalanine(Phe), N-(methyl) acryl-para-amino benzoic acid, N-(methyl) acryl-o-benzaminic acid, to vinyl benzoic acid, 2-(methyl) acryl aminobenzoic acid, 3-(methyl) acryl aminobenzoic acid, 4-(methyl) acryl aminobenzoic acid, N-(methyl) acryl-5-aminosalicylic acid, N-(methyl) acryl-4-aminosallcylic acid etc. and compound that the carboxylic acid baseization of these compounds is obtained.

Example as the simple function property polymerizable monomer that has a plurality of carboxyls or its anhydride group at intramolecularly; Can enumerate 11-(methyl) acryl oxygen base undecane-1; 1-dicarboxylicacid, 10-(methyl) acryl oxygen base decane-1; 1-dicarboxylicacid, 12-(methyl) acryl oxygen base dodecyl-1; 1-dicarboxylicacid, 6-(methyl) acryl oxygen base hexane-1; 1-dicarboxylicacid, 2-(methyl) acryl oxygen base ethyl-3 '-methacryloyl oxygen base-2 '-(3,4-dicarboxyl benzoyl-oxygen base) propyl group succinate, 4-(2-(methyl) acryl oxygen base ethyl) trimellitic acid 1,2-anhydride ester, 4-(2-(methyl) acryl oxygen base ethyl) trimellitate, 4-(methyl) acryl oxygen base ethyl trimellitate, 4-(methyl) acryl oxygen Ji Dingji trimellitate, 4-(methyl) acryl oxygen base hexyl trimellitate, 4-(methyl) acryl oxygen base decyl trimellitate, 4-(methyl) acryl oxygen Ji Dingji trimellitate, 6-(methyl) acryl oxygen base ethyl naphthalene-1,2; 6-tricarboxylic acid anhydride, 6-(methyl) acryl oxygen base ethyl naphthalene-2; 3,6-tricarboxylic acid anhydride, 4-(methyl) acryl oxygen base ethyl carbonyl propionyl-1,8-naphthalic anhydride, 4-(methyl) acryl oxygen base ethyl naphthalene-1; 8-tricarboxylic acid anhydride, 9-(methyl) acryl oxygen base nonane-1; 1-dicarboxylicacid, 13-(methyl) acryl oxygen base tridecane-1,1-dicarboxylicacid, 11-(methyl) acrylic amide undecane-1,1-dicarboxylicacid etc.

As the example of the simple function property polymerizable monomer that has phosphinyl oxygen base or phosphono oxygen base at intramolecularly (being sometimes referred to as simple function free love base polymerizable phosphate ester), can enumerate 2-(methyl) acryl oxygen base ethyl dihydrogen phosphoric acid ester, 2-(methyl) acryl oxygen base ethylphenyl hydrogen-phosphonate, 10-(methyl) acryl oxygen base decyl dihydrogen phosphoric acid ester, 6-(methyl) acryl oxygen base hexyl dihydrogen phosphoric acid ester, 2-(methyl) acryl oxygen base ethyl-2-bromotrifluoromethane hydrogen-phosphonate, 2-(methyl) acrylic amide ethyl dihydrogen phosphoric acid ester etc.

As other simple function property polymerizable monomers, can enumerate simple function property polymerizable monomer that has sulfo group at intramolecularly of 2-(methyl) acrylic amide-2-methyl propane sulfonic acid, 10-sulfo group decyl (methyl) propenoate etc. etc. with acidic-group.

Bridging property polymerizable monomer (D) compsn of the present invention in total amount 100 weight parts of polymerizable monomer composition, preferably contains bridging property polymerizable monomer (D) 1～90 weight part and forms.The use level of bridging property polymerizable monomer (D) when the compsn of this scope uses as dental composition, had the advantage of bonding strength and then raising etc.The use level of bridging property polymerizable monomer (D) has the possibility that can not obtain sufficient adhesion strength, more preferably more than 2 weight parts, and then more than preferred 5 weight parts during less than 1 weight part.On the other hand, insufficient when the use level of bridging property polymerizable monomer (D) surpasses 90 weight parts to soaking into of Dentinal collagen layer, the possibility that can not obtain high bonding strength is arranged, more preferably below 85 weight parts, and then below preferred 80 weight parts.

Bridging property polymerizable monomer (D) can use separately or appropriate combination is used more than 2 kinds.As bridging property polymerizable monomer (D), there be not special the qualification, can enumerate the difunctionality polymerizable monomer of aromatics system, the difunctionality polymerizable monomer of fatty compounds system, the polymerizable monomer more than the trifunctional property etc.

Example as the difunctionality polymerizable monomer of aromatics system; Can enumerate 2; Two ((methyl) acryl oxygen base phenyl) propane, 2 of 2-; Two (4-(3-(methyl) acryl oxygen base)-2-hydroxyl propoxy-phenyl) propane of 2-(common name " Bis-GMA "), 2; Two (4-(methyl) the acryl oxygen base oxethyl phenyl) propane, 2 of 2-; Two (4-(methyl) the acryl oxygen Quito ethoxyl phenenyl) propane, 2 of 2-; Two (4-(methyl) the acryl oxygen base diethoxy phenyl) propane of 2-), 2; Two (4-(methyl) the acryl oxygen base triethoxy phenyl) propane of 2-), 2, two (4-(methyl) the acryl oxygen base tetraethoxy phenyl) propane, 2 of 2-, two (4-(methyl) the acryl oxygen base five ethoxyl phenenyls) propane, 2 of 2-; Two (4-(methyl) the acryl oxygen base dipropoxy phenyl) propane of 2-, 2-(4-(methyl) acryl oxygen base diethoxy phenyl)-2-(4-(methyl) acryl oxygen base oxethyl phenyl) propane, 2-(4-(methyl) acryl oxygen base diethoxy phenyl)-2-(4-(methyl) acryl oxygen base triethoxy phenyl) propane, 2-(4-(methyl) acryl oxygen base dipropoxy phenyl)-2-(4-(methyl) acryl oxygen base triethoxy phenyl) propane, 2; Two (4-(methyl) the acryl oxygen base propoxy-phenyl) propane, 2 of 2-, two (4-(methyl) the acryl oxygen base isopropyl phenyl) propane, 1 of 2-, two (2-(methyl) acryl oxygen base ethyl) pyromellitic esters of 4-etc.

Example as the difunctionality polymerizable monomer of fatty compounds system; Can enumerate ethylene glycol bisthioglycolate (methyl) propenoate, glycol ether two (methyl) propenoate, triglycol two (methyl) propenoate, Ucar 35 two (methyl) propenoate, butyleneglycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, 1; 3-butyleneglycol two (methyl) propenoate, 1; 5-pentanediol two (methyl) propenoate, 1; 6-pinakon two (methyl) propenoate, decamethylene-glycol two (methyl) propenoate, 1, two (the 3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane and 2 of 2-; 2, two (2-formamyl oxygen base ethyl) dimethacrylates of 4-trimethylammonium hexylidene (common name " UDMA ") etc.

Example as the polymerizable monomer more than the trifunctional property; Can enumerate trimethylolpropane tris (methyl) propenoate, trimethylolethane trimethacrylate (methyl) propenoate, Pehanorm three (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol three (methyl) propenoate, Dipentaerythritol four (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, N; N-(2; 2,4-trimethylammonium hexylidene) two (2-(amino carboxyl) propane-1,3-glycol) tetramethyl-propenoate and 1; 7-two acryl oxygen bases-2; 2,6,6-tetrapropylene acyloxy methyl-4-oxygen base heptane etc.

Compsn of the present invention can also contain above-mentioned (A), (C) and (D) in addition polymerizable monomer as required.

Organic solvent (E) compsn of the present invention preferably contains organic solvent (E) according to the difference of concrete embodiment.Organic solvent (E) can use separately or appropriate combination is used more than 2 kinds.As organic solvent (E), can enumerate methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-methyl-2-propyl alcohol, acetone, methyl ethyl ketone, THF, ether, Di Iso Propyl Ether, hexane, toluene, chloroform, acetate ethyl ester, acetate butyl ester etc.Among them, consider that organic solvent (E) preferably water solubleness organic solvent particularly, preferably uses ethanol, 2-propyl alcohol, 2-methyl-2-propyl alcohol, acetone and THF to the security of giving birth to body with based on volatile when removing this two aspect of easy property.The use level of above-mentioned organic solvent (E) is not special to be limited, and according to the difference of embodiment, the situation of mismatching above-mentioned organic solvent (E) is arranged also.Use in the embodiment of above-mentioned organic solvent (E),, preferably contain organic solvent (E) 1～2000 weight part and form with respect to total amount 100 weight parts of polymerizable monomer composition.The preferred use level of above-mentioned organic solvent (E) has a great difference according to the difference of the embodiment that uses, with after the embodiment of the compsn of the present invention stated explain in the lump, will show preferably use level of the corresponding above-mentioned organic solvent of each embodiment (E).

The polymerization starter (F) that uses among polymerization starter (F) the present invention can select to use the polymerization starter that uses in the general industry field, wherein preferably uses the polymerization starter that uses in the dental use.Particularly, the polymerization starter of photopolymerization and chemical polymerization is used separately or appropriate combination more than 2 kinds is used.

As Photoepolymerizationinitiater initiater, can enumerate quaternary ammonium salt, ketal class, α-two ketone, coumarins, anthraquinone class, benzoin alkylether compounds, alpha-amino group ketone based compound of (two) acylphosphine oxide class, water-soluble acylphosphine oxide class, thioxanthene ketone or thioxanthene ketone etc.

Among (two) acylphosphine oxide class as above-mentioned Photoepolymerizationinitiater initiater use,, can enumerate 2 as the acylphosphine oxide class; 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 p-methoxy-phenyl phosphine oxide, 2; 4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide, 2,3; 5,6-tetramethyl-benzene formyl radical diphenyl phosphine oxide, benzoyl-two-(2, the 6-3,5-dimethylphenyl) phosphonic acid ester etc.As two acylphosphine oxide classes, can enumerate two-(2,6-dichloro-benzoyl base) phenyl phosphine oxide, 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 oxide, 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 oxide, (2,5; The 6-trimethylbenzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.

The water-soluble acylphosphine oxide class of using as above-mentioned Photoepolymerizationinitiater initiater preferably has alkalimetal ion, alkaline earth metal ion, pyridinium ion or ammonium ion at the acylphosphine oxide intramolecularly.For example, can to open in the clear 57-197289 communique disclosed method through No. 0009348 specification sheets of Europe patent or spy synthetic for water-soluble acylphosphine oxide class.

As the concrete example of above-mentioned water-soluble acylphosphine oxide class, can enumerate monomethyl ethanoyl phosphonic acid ester sodium, monomethyl (1-oxopropyl) phosphonic acid ester sodium, monomethyl benzoyl-phosphonic acid ester sodium, monomethyl (1-oxo butyl) phosphonic acid ester sodium, monomethyl (2-methyl isophthalic acid-oxopropyl) phosphonic acid ester sodium, ethanoyl phosphonic acid ester sodium, monomethyl ethanoyl phosphonic acid ester sodium, ethanoyl methylphosphonate sodium, methyl 4-(hydroxyl methoxyl group phosphinyl)-4-ketobutyric acid ester sodium salt, methyl-4-oxo phosphonic acids butyric ester list sodium salt, acetylphenyl phosphonic acid ester sodium salt, (1-oxopropyl) amyl group phosphonic acid ester sodium, methyl-4-(hydroxyl amyl group phosphinyl)-4-ketobutyric acid ester sodium salt, ethanoyl amyl group phosphonic acid ester sodium, ethanoyl ethyl phosphonate sodium, methyl (1, the 1-dimethyl-) methylphosphonate sodium, (1; 1-diethoxy ethyl) methylphosphonate sodium, (1,1-diethoxy ethyl) methylphosphonate sodium, methyl-4-(hydroxy-methyl-phosphinyl)-4-oxobutanoic acid esters lithium salts, 4-(hydroxy-methyl-phosphinyl)-4-ketobutyric acid dilithium salt, methyl (2-methyl isophthalic acid, 3-dioxolane-2-yl) phosphonic acid ester sodium salt, methyl (2-methyl isophthalic acid; 3-thiazoline-2-yl) phosphinate sodium salt, (2-methyl perhydro--carotene 1; 3-diazine-2-yl) phosphinate sodium salt, ethanoyl phosphonic acid ester sodium salt, (1,1-diethoxy ethyl) phosphinate sodium salt, (1,1-diethoxy ethyl) methyl phosphinate sodium salt, methyl (2-methyl oxygen Thiophane (オキサチオラ Application)-2-yl) phosphonic acid ester sodium salt, methyl (2; 4; 5-trimethylammonium-1,3-dioxolane-2-yl) phosphonic acid ester sodium salt, methyl (1,1-propoxy-ethyl) phosphonic acid ester sodium salt, (1-methoxy-ethylene base) methyl-phosphorous acid ester sodium salt, (1-ethylenebis dithiocarbamate vinyl) methyl-phosphorous acid ester sodium salt, methyl (2-methyl perhydro--carotene 1; 3-diazine-2-yl) phosphonic acid ester sodium salt, methyl (2-methyl perhydro--carotene 1; 3-thiazine-2-yl) phosphonic acid ester sodium salt, methyl (2-methyl isophthalic acid, 3-two azo alkane (ジアゾリジ Application)-2-yl) phosphonic acid ester sodium salt, methyl (2-methyl isophthalic acid, the phosphonic acid ester sodium salt, (2 of 3-thiazolidine-2-yl); 2-dicyano-1-methylacetylenyl) phosphonic acid ester sodium salt, ethanoyl methyl-phosphorous acid lactazone sodium salt, ethanoyl methylphosphonate-O-benzyl oxime sodium salt, 1-[(N-ethoxy imino) ethyl] methyl-phosphorous acid ester sodium salt, methyl (1-phenylimino ethyl) phosphonic acid ester sodium salt, methyl (1-phenyl hydrazones ethyl) phosphonic acid ester sodium salt, [1-(2; 4-dinitrophenyl hydrazono-) ethyl] methyl-phosphorous acid ester sodium salt, ethanoyl methylphosphonate semicarbazone sodium salt, (1-cyanic acid-1-hydroxyethyl) methyl-phosphorous acid ester sodium salt, (dimethoxy-methyl) methyl-phosphorous acid ester sodium salt, formyl radical methyl-phosphorous acid ester sodium salt, (1,1-dimethoxy propyl group) methyl-phosphorous acid ester sodium salt, methyl (1-oxopropyl) phosphonic acid ester sodium salt, (1,1-dimethoxy propyl group) methylphosphonate dodecyl guanidinesalt, (1; 1-dimethoxy propyl group) methylphosphonate sec.-propyl amine salt, ethanoyl methylphosphonate thiosemicarbazone sodium salt, 1; 3,5-tributyl-4-methylamino-1,2; 4-triazole (トリアゾリウ system) (1; The 1-dimethoxy-ethyl)-and methylphosphonate, 1-butyl-4-butyl amino methyl amino-3,5-dipropyl-1,2; 4-triazole (1; The 1-dimethoxy-ethyl)-and methylphosphonate, 2,4,6-trimethylbenzoyl phenyl phosphine oxide sodium salt, 2; 4; 6-trimethylbenzoyl phenyl phosphine oxide sylvite, 2,4, the ammonium salt of 6-trimethylbenzoyl phenyl phosphine oxide etc.And then can also enumerate the spy and open the compound of putting down in writing in the 2000-159621 communique.

In these (two) acylphosphine oxide classes and the water-soluble acylphosphine oxide class, preferred especially 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyl p-methoxy-phenyl phosphine oxide, two (2; 4; The 6-trimethylbenzoyl) phenyl phosphine oxide and 2,4,6-trimethylbenzoyl phenyl phosphine oxide sodium salt.

As the thioxanthene ketone of above-mentioned Photoepolymerizationinitiater initiater use or the quaternary ammonium salt of thioxanthene ketone, for example can use thioxanthone, 2-diuril ton-9-ketone, 2-hydroxyl-3-(9-oxygen base-9H-thioxanthene-4-base oxygen base)-N, N; N-trimethylammonium-propane ammonium chloride, 2-hydroxyl-3-(1-methyl-9-oxygen base-9H-thioxanthene-4-base oxygen base)-N, N, N-trimethylammonium-propane ammonium chloride, 2-hydroxyl-3-(9-oxo-9H-thioxanthene-2-base oxygen base)-N; N, N-trimethylammonium-propane ammonium chloride, 2-hydroxyl-3-(3,4-dimethyl--9-oxo-9H-thioxanthene-2-base oxygen base)-N; N, N-trimethylammonium-1-propane ammonium chloride, 2-hydroxyl-3-(3,4-dimethyl--9H-thioxanthene-2-base oxygen base)-N; N, N-trimethylammonium-1-propane ammonium chloride, 2-hydroxyl-3-(1,3; 4-trimethylammonium-9-oxo-9H-thioxanthene-2-base oxygen base)-and N, N, N-trimethylammonium-1-propane ammonium chloride etc.

In the quaternary ammonium salt of these thioxanthene ketones or thioxanthene ketone; Preferred especially thioxanthene ketone is 2-diuril ton-9-ketone, and the quaternary ammonium salt of preferred especially thioxanthene ketone is 2-hydroxyl-3-(3,4-dimethyl--9H-thioxanthene-2-base oxygen base)-N; N, N-trimethylammonium-1-propane ammonium chloride.

The example of the ketal class of using as above-mentioned Photoepolymerizationinitiater initiater can be enumerated benzyldimethylketal, the benzyl two acetaldehyde methyl phenyl ketone etc. that contracts.

As α-two ketone that above-mentioned Photoepolymerizationinitiater initiater uses, for example can enumerate dimethyl diketone, dibenzoyl, camphorquinone, 2,3-diacetylmethane, 2,3-acetyl caproyl, 9,10-phenanthrenequione, 4,4 '-oxygen base dibenzoyl, acenaphthene quinone etc.Wherein, the viewpoint that has maximum absorption wavelength from the visible region is considered, preferred especially camphorquinone.

The example of the coumarin compound that uses as above-mentioned Photoepolymerizationinitiater initiater; Can enumerate 3; Two (7-diethylamino) tonka bean camphors of 3 '-carbonyl, 3-(4-anisoyl) tonka bean camphor, 3-thienyl tonka bean camphor, 3-benzoyl--5; 7-escoparone, 3-benzoyl--ayapanin, 3-benzoyl--6-methoxy coumarin, 3-benzoyl--8-methoxy coumarin, 3-benzoyl-tonka bean camphor, 7-methoxyl group-3-(p-nitrophenyl formyl radical) tonka bean camphor, 3-(p-nitrophenyl formyl radical) tonka bean camphor, 3-benzoyl--8-methoxy coumarin, 3; 5-carbonyl two (ayapanin), 3-benzoyl-s-6-bromine tonka bean camphor, 3,3 '-carbonyl temparin, 3-benzoyl--7-dimethylamino tonka bean camphor, 3-benzoyl-benzo [f] tonka bean camphor, 3-carboxyl tonka bean camphor, 3-carboxyl-ayapanin, 3-ethoxy carbonyl-6-methoxy coumarin, 3-ethoxy carbonyl-8-methoxy coumarin, 3-ethanoyl benzo [f] tonka bean camphor, 7-methoxyl group-3-(p-nitrophenyl formyl radical) tonka bean camphor, 3-(p-nitrophenyl formyl radical) tonka bean camphor, 3-benzoyl--8-methoxy coumarin, 3-benzoyl--6-nitro tonka bean camphor, 3-benzoyl--7-diethyl amino coumarin, 7-dimethylamino-3-(4-anisoyl) tonka bean camphor, 7-diethylamino-3-(4-anisoyl) tonka bean camphor, 7-diethylamino-3-(4-diethylamino) tonka bean camphor, 7-methoxyl group-3-(4-anisoyl) tonka bean camphor, 3-(4-nitro benzoyl) benzo [f] tonka bean camphor, 3-(4-oxyethyl group cinnamoyl)-ayapanin, 3-(4-dimethylamino cinnamoyl) tonka bean camphor, 3-(4-diphenyl amino cinnamoyl) tonka bean camphor, 3-[(3-dimethyl-benzothiazole-2-subunit) ethanoyl] tonka bean camphor, 3-[(1-methyl naphtho-[1,2-d] thiazole-2-ylides) ethanoyl] tonka bean camphor, 3; 3 '-carbonyl two (6-methoxy coumarin), 3; 3 '-carbonyl two (7-acetoxyl group tonka bean camphor), 3,3 '-carbonyl two (7-dimethylamino tonka bean camphor), 3-(2-[4-morpholinodithio base)-7-(diethylamino) tonka bean camphor, 3-(2-[4-morpholinodithio base)-7-(dibutylamino) tonka bean camphor, 3-(2-benzimidazolyl-)-7-(diethylamino) tonka bean camphor, 3-(2-[4-morpholinodithio base)-7-(dioctyl is amino) tonka bean camphor, 3-ethanoyl-7-(dimethylamino) tonka bean camphor, 3,3 '-carbonyl two (7-dibutylamino tonka bean camphor), 3; 3 '-carbonyl-7-diethyl amino coumarin-7 '-two (butoxyethyl group) aminocoumarin, 10-[3-[4-(dimethylamino) phenyl]-1-oxo-2-propenyl]-2; 3,6,7-1; 1; 7,7-tetramethyl-1H, 5H; 11H-[1] chromene also [6; 7,8-ij] quinolizine-11-ketone, 10-(2-[4-morpholinodithio base)-2; 3; 6,7-tetrahydrochysene-1,1; 7; 7-tetramethyl-1H, 5H, 11H-[1] chromene also [6; 7,8-ij] spy of quinolizine-11-ketone etc. opens flat 9-3109 communique, the spy opens the compound of putting down in writing in the flat 10-245525 communique.

In the above-mentioned coumarin compound, preferred especially 3,3 '-carbonyl two (7-diethyl amino coumarin) and 3,3 '-carbonyl two (7-dibutylamino tonka bean camphor).

The example of the anthraquinone class of using as above-mentioned Photoepolymerizationinitiater initiater can be enumerated anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromo anthraquinone, 1,2-benzo anthraquinone, 1-methylanthracene quinone, 2-ethyl-anthraquinone, 1-hydroxyanthraquinone etc.

The example of the benzoin alkylether class of using as above-mentioned Photoepolymerizationinitiater initiater can be enumerated benzoin methyl ether, bitter almond oil camphor ethyl ether, bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether etc.

The example of the alpha-amino group ketone that uses as above-mentioned Photoepolymerizationinitiater initiater can be enumerated 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone etc.

In these Photoepolymerizationinitiater initiaters, preferred use be selected from (two) acylphosphine oxide class with and salt, α-two ketone and coumarin compound at least a kind.Thus, excellent at the light solidified of visible light and near ultraviolet region, even use arbitrary light source of halogen lamp, photodiode (LED), xenon lamp, also obtain showing the compsn of sufficient light solidified.

Among the polymerization starter that uses among the present invention (F),, preferably use organo-peroxide as chemical polymerisation initiator.The organo-peroxide that uses in the above-mentioned chemical polymerisation initiator is not special to be limited, and can use known.As the organo-peroxide of representative, can enumerate ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxy ketal, peroxyester, peroxy dicarbonate etc.

As the ketone peroxide that above-mentioned chemical polymerisation initiator is used, can enumerate methyl-ethyl-ketone peroxide, methyl-isobutyl ketone peroxide, methyl cyclohexanone peroxide and pimelinketone superoxide etc.

As the hydroperoxide that above-mentioned chemical polymerisation initiator is used, can enumerate 2,5-dimethylhexane-2; 5-dihydro-peroxidase, diisopropyl benzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and 1; 1,3,3-tetramethyl butyl hydroperoxide etc.

Diacyl peroxide as above-mentioned chemical polymerisation initiator use; Can enumerate acetyl peroxide, isobutyryl superoxide, benzoyl peroxide, caprinoyl superoxide, 3; 5; 5-trimethyl acetyl superoxide, DCBP 2,4 dichlorobenzoyl peroxide and lauroyl peroxide etc.

Dialkyl peroxide as above-mentioned chemical polymerisation initiator use; Can enumerate ditertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, 2; 5-2,1, two (t-butylperoxy sec.-propyl) benzene and 2 of 3-; 5-dimethyl--2,5-two (t-butylperoxy)-3-hexin etc.

As the peroxy ketal that above-mentioned chemical polymerisation initiator is used, can enumerate 1,1-bis(t-butylperoxy)-3; 3; 5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy) cyclohexane, 2,2-bis(t-butylperoxy) butane, 2; 2-bis(t-butylperoxy) octane and 4,4-bis(t-butylperoxy) valeric acid-n-butyl etc.

Peroxyester as above-mentioned chemical polymerisation initiator use; Can enumerate peroxide neodecanoic acid α-cumyl ester, the peroxide neodecanoic acid tert-butyl ester, t-butylperoxy pivarate, 2; 2; 4-tri-methyl-amyl peroxy-2-ethylhexanoate, tert-pentyl peroxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, peroxide m-phthalic acid di-t-butyl ester, peroxide six hydrogen terephthalic acid di-t-butyl esters, t-butylperoxy-3; 3,5-tri-methyl hexanoic acid ester, tert-butyl peroxy acetate, t-butyl per(oxy)benzoate and the peroxy maleic acid tert-butyl ester etc.

As the peroxy dicarbonate that above-mentioned chemical polymerisation initiator is used, can enumerate two-3-methoxyl group peroxy dicarbonate, two-2-ethylhexyl peroxy dicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, diisopropyl peroxydicarbonate, two-n-propyl peroxy dicarbonate, two-2-ethoxyethyl group peroxy dicarbonate and diallyl peroxy dicarbonate etc.

In these organo-peroxides, consider, preferably use diacyl peroxide, wherein especially preferably use benzoyl peroxide from the overall equilbrium of security, storage stability and radical generative capacity.

The use level of the polymerization starter that uses among the present invention (F) is not special to be limited; Consider from the viewpoint of the solidified nature of the compsn that obtains etc.; With respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain polymerization starter (F) 0.001～30 weight part and form.The use level of polymerization starter (F) is during less than 0.001 weight part, and the possibility that has polymerization can not fully carry out, cause bonding force to reduce is more preferably more than 0.05 weight part.On the other hand, when the use level of polymerization starter (F) surpasses 30 weight parts, when the polymerization of polymerization starter self hangs down, the possibility that can not obtain sufficient adhesion strength is arranged, and then the possibility of separating out from compsn is arranged, more preferably below 20 weight parts.

Polymerization promotor (G) preferred embodiment in, use polymerization promotor (G).As the polymerization promotor that uses among the present invention (G), can enumerate amine,-sulfinic acid and salt thereof, boron cpd, barbituric acid derivatives, triaizine compounds, copper compound, tin compound, vanadium compound, halogen compounds, aldehydes, mercaptan compound, sulphite, hydrosulphite, thiourea compound etc.

The amine that uses as polymerization promotor (G) is divided into fatty amine and aromatic amine.As fatty amine, for example, can enumerate the armeen of n-butylamine, n-hexyl amine, n-octylamine etc.; The secondary aliphatic amine of diisopropylamine, dibutylamine, N-Mono Methyl Ethanol Amine etc.; The aliphatic tertiary amine of N methyldiethanol amine, N-ethyldiethanolamine, N-normal-butyl diethylolamine, N-lauryl diethylolamine, 2-(dimethylamino) ethyl-methyl propenoate, N methyldiethanol amine dimethacrylate, N-ethyldiethanolamine dimethacrylate, trolamine monomethacrylates, trolamine dimethacrylate, trolamine trimethacrylate, trolamine, Trimethylamine, triethylamine, TBuA etc. etc.Among them, consider that from the solidified nature of compsn and the viewpoint of storage stability the aliphatic tertiary amine wherein more preferably uses N methyldiethanol amine and trolamine.

In addition, as aromatic amine, for example, can enumerate N; Two (the 2-hydroxyethyls)-3 of N-, 5-xylidine, N, N-two (2-hydroxyethyl)-para-totuidine, N, two (the 2-hydroxyethyls)-3 of N-; 4-xylidine, N, two (2-the hydroxyethyl)-4-MEAs of N-, N, two (2-the hydroxyethyl)-4-isopropyl anilines of N-, N, two (2-the hydroxyethyl)-4-tertiary butyl aniline of N-, N; Two (the 2-hydroxyethyls)-3 of N-, 5-two-isopropyl aniline, N, two (the 2-hydroxyethyls)-3 of N-, 5-di-tert-butyl aniline, N; Accelerine, N, N-dimethyl--para-totuidine, N, N-dimethyl--meta-aminotoluene, N, N-diethylammonium-para-totuidine, N; N-dimethyl--3,5-xylidine, N, N-dimethyl--3,4-xylidine, N; N-dimethyl--4-MEA, N, N-dimethyl--4-isopropyl aniline, N, N-dimethyl--4-tertiary butyl aniline, N, N-dimethyl--3; 5-di-tert-butyl aniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N; N-dimethylaminobenzoic acid n-butoxy ethyl ester, 4-N, N-dimethylaminobenzoic acid 2-(methacryloyl oxygen base) ethyl ester, 4-N, N-dimethylamino UVNUL MS-40,4-dimethylaminobenzoic acid butyl ester etc.Among them; Consider from the viewpoint that can give compsn excellent in curing property; The preferred use is selected from N, N-two (2-hydroxyethyl)-para-totuidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N; N-dimethylaminobenzoic acid n-butoxy ethyl ester and 4-N, at least a kind of N-dimethylamino UVNUL MS-40.

The-sulfinic acid and the salt thereof that use as polymerization promotor (G) for example, can be enumerated to toluenesulfinic acid, SPTS, to toluenesulfinic acid potassium, to the toluenesulfinic acid lithium, to toluenesulfinic acid calcium, benzene sulfinic acid, benzene sulfinic acid sodium salt, benzene sulfinic acid potassium, benzene sulfinic acid lithium, benzene sulfinic acid calcium, 2,4 6-Three methyl Benzene-sulfinic acid, 2; 4,6-trimethylammonium benzene sulfinic acid sodium salt, 2,4,6-Three methyl Benzene-sulfinic acid potassium, 2,4; 6-Three methyl Benzene-sulfinic acid lithium, 2,4,6-Three methyl Benzene-sulfinic acid calcium, 2,4,6-triethylbenzene-sulfinic acid, 2; 4,6-triethyl benzene sulfinic acid sodium salt, 2,4,6-triethylbenzene-sulfinic acid potassium, 2,4; 6-triethylbenzene-sulfinic acid lithium, 2,4,6-triethylbenzene-sulfinic acid calcium, 2,4; 6-triisopropyl benzene sulfinic acid, 2,4,6-triisopropyl benzene sulfinic acid sodium, 2,4; 6-triisopropyl benzene sulfinic acid potassium, 2,4,6-triisopropyl benzene sulfinic acid lithium, 2,4; 6-triisopropyl benzene sulfinic acid calcium etc., preferred especially benzene sulfinic acid sodium salt, SPTS, 2,4,6-triisopropyl benzene sulfinic acid sodium.

As the boron cpd that polymerization promotor (G) uses, preferred aryl groups boron cpd.The object lesson of the preferred aryl boron cpd that uses; As the boron cpd that has 1 aryl in 1 molecule; Can enumerate trialkyl phenyl boron, trialkyl (rubigan) boron, trialkyl (to fluorophenyl) boron, trialkyl (3; 5-two (trifluoromethyl)) phenyl boron, trialkyl [3; 5-two (1; 1,1,3; 3,3-hexafluoro-2-methoxyl group-2-propyl group) phenyl] sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium, butyl quinolinium etc. of boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitro base) boron, trialkyl (to butyl phenyl) boron, trialkyl (butyl phenyl) boron, trialkyl (to butyl oxygen base phenyl) boron, trialkyl (a butyl oxygen base phenyl) boron, trialkyl (to octyl group oxygen base phenyl) boron and trialkyl (an octyl group oxygen base phenyl) boron (alkyl is selected from normal-butyl, n-octyl and dodecyl etc. at least a kind).

In addition; As the boron cpd that has 2 aryl in 1 molecule; Can enumerate dialkyl group phenylbenzene boron, dialkyl group two (rubigan) boron, dialkyl group two (to fluorophenyl) boron, dialkyl group two (3; 5-two (trifluoromethyl)) phenyl boron, dialkyl group two [3; 5-two (1; 1,1,3; 3,3-hexafluoro-2-methoxyl group-2-propyl group) phenyl] sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium, butyl quinolinium etc. of boron, dialkyl group two (p-nitrophenyl) boron, dialkyl group two (m-nitro base) boron, dialkyl group two (to butyl phenyl) boron, dialkyl group two (butyl phenyl) boron, dialkyl group two (to butyl oxygen base phenyl) boron, dialkyl group two (a butyl oxygen base phenyl) boron, dialkyl group two (to octyl group oxygen base phenyl) boron and dialkyl group two (an octyl group oxygen base phenyl) boron (alkyl is selected from normal-butyl, n-octyl and dodecyl etc. at least a kind).

And then; As the boron cpd that has 3 aryl in 1 molecule; Can enumerate monoalkyl triphenyl-boron, monoalkyl three (rubigan) boron, monoalkyl three (to 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] sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium, butyl quinolinium etc. of boron, monoalkyl three (p-nitrophenyl) boron, monoalkyl three (m-nitro base) boron, monoalkyl three (to butyl phenyl) boron, monoalkyl three (butyl phenyl) boron, monoalkyl three (to butyl oxygen base phenyl) boron, monoalkyl three (a butyl oxygen base phenyl) boron, monoalkyl three (to octyl group oxygen base phenyl) boron and monoalkyl three (an octyl group oxygen base phenyl) boron (alkyl is selected from normal-butyl, n-octyl or dodecyl etc. a kind).

And then as the boron cpd that has 4 aryl in 1 molecule; Can enumerate tetraphenyl boron, four (rubigan) boron, four (to 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] sodium salt, lithium salts, sylvite, magnesium salts, 4-butyl ammonium, tetramethyl ammonium, tetraethyl-ammonium salt, picoline salt, ethylpyridine salt, butyl-pyridinium salt, toluquinoline salt, ethyl quinolinium, butyl quinolinium etc. of boron, four (p-nitrophenyl) boron, four (m-nitro base) boron, four (to butyl phenyl) boron, four (butyl phenyl) boron, four (to butyl oxygen base phenyl) boron, four (a butyl oxygen base phenyl) boron, four (to octyl group oxygen base phenyl) boron, four (an octyl group oxygen base phenyl) boron, (to fluorophenyl) triphenyl-boron, (3,5-two (trifluoromethyl)) phenyl triphenyl-boron, (p-nitrophenyl) triphenyl-boron, (a butyl oxygen base phenyl) triphenyl-boron, (to butyl oxygen base phenyl) triphenyl-boron, (an octyl group oxygen base phenyl) triphenyl-boron and (to octyl group oxygen base phenyl) triphenyl-boron.

In these aryl boron cpds, consider, more preferably use the boron cpd that has 3 or 4 aryl in 1 molecule from the viewpoint of storage stability.In addition, also can mix these aryl boron cpds of use more than a kind or 2 kinds.

Barbituric acid derivatives as polymerization promotor (G) use; Can enumerate barbituric acid, 1,3-dimethyl barbituric acid, 1,3-phenylbenzene barbituric acid, 1; 5-dimethyl barbituric acid, the acid of 5-soneryl, 5-ethyl barbituric acid, 5-sec.-propyl barbituric acid, 5-cyclohexyl barbituric acid, 1; 3,5-trimethylammonium barbituric acid, 1,3-dimethyl--5-ethyl barbituric acid, 1; 3-dimethyl--normal-butyl barbituric acid, 1; 3-dimethyl--5-isobutyl-barbituric acid, 1,3-dimethyl barbituric acid, 1,3-dimethyl--5-cyclopentyl barbituric acid, 1; 3-dimethyl--5-cyclohexyl barbituric acid, 1; 3-dimethyl--5-phenyl barbituric acid, 1-cyclohexyl-1-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methylbarbituric acid, 5-propyl group barbituric acid, 1,5-diethyl barbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutyl-barbituric acid, 1,3-diethylammonium-5-soneryl acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethyl barbituric acid, 1-cyclohexyl-5-octyl group barbituric acid, 1-cyclohexyl-5-hexethal acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and thiobarbituricacid class and their salt (special preferred as alkali or earth alkali metal class); Salt as these veronal acids; 5-soneryl acid sodium, 1,3 is for example arranged, 5-trimethylammonium barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric acid sodium etc.

Special as preferred especially barbituric acid derivatives, can enumerate 5-soneryl acid, 1,3, the sodium salt of 5-trimethylammonium barbituric acid, 1-cyclohexyl-5-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and these veronal acids.

Triaizine compounds as polymerization promotor (G) uses for example has 2,4; 6-three (trichloromethyl)-s-triazine, 2,4,6-three (trisbromomethyl)-s-triazine, 2-methyl-4; Two (the trichloromethyl)-s-triazines of 6-, 2-methyl-4, two (the trisbromomethyl)-s-triazines of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-(to the methylthio group phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(rubigan)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(2; The 4-dichlorophenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(to bromophenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methylphenyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-n-propyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(α, α; β-three chloroethyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(p-methoxyphenyl) vinyl]-4; Two (the trichloromethyl)-s-triazines of 6-, 2-[2-(o-p-methoxy-phenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(to butoxy phenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, [2-(3 for 2-; The 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, [2-(3,4 for 2-; The 5-trimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-(1-naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-xenyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-[2-{N, two (2-hydroxyethyl) amino of N-} oxyethyl group]-4, and two (the trichloromethyl)-s-triazines of 6-, 2-[2-{N-hydroxyethyl-N-ethylamino } oxyethyl group]-4; Two (the trichloromethyl)-s-triazines of 6-, 2-[2-{N-hydroxyethyl-N-methylamino } oxyethyl group]-4; Two (the trichloromethyl)-s-triazines of 6-, 2-[2-{N, the N-diallyl is amino } oxyethyl group]-4, two (the trichloromethyl)-s-triazines of 6-etc.

Among the above-mentioned illustrative triaizine compounds, consider preferred especially 2 from the polymerization activity aspect; 4,6-three (trichloromethyl)-s-triazine considers from the storage stability aspect in addition; Preferred especially 2-phenyl-4; Two (the trichloromethyl)-s-triazines of 6-, 2-(rubigan)-4, two (trichloromethyl)-s-triazines of 6-and 2-(4-xenyl)-4, two (the trichloromethyl)-s-triazines of 6-.Can mix and use above-mentioned triaizine compounds more than a kind or 2 kinds.

Copper compound as polymerization promotor (G) uses for example preferably uses Acetyl Acetone copper, venus crystals, cupric oleate, cupric chloride, cupric bromide etc.

As the tin compound that polymerization promotor (G) uses, for example, can enumerate two toxilic acid di-n-butyl tin, two toxilic acids, two-n-octyl tin, two LAURIC ACID 99 MIN, two-n-octyl tin, two LAURIC ACID 99 MIN di-n-butyl tin etc.Preferred especially tin compound is two LAURIC ACID 99 MIN, two-n-octyl tin and two LAURIC ACID 99 MIN di-n-butyl tin.

As the vanadium compound that polymerization promotor (G) uses, the vanadium compound class of preferred IV valency and/or V valency.Vanadium compound class as IV valency and/or V valency; The spy that for example, can enumerate vanadium tetraoxide (IV), Acetyl Acetone vanadium oxide (IV), oxalic acid vanadyl (IV), vanadylic sulfate (IV), two (1-phenyl-1, the 3-dimethyl diketone) vanadium (IV) of oxo, two (voitol (マ Le トラ one ト)) oxo vanadium (IV), Vanadium Pentoxide in FLAKES (V), sodium metavanadate (V), ammonium meta-vanadate (V) etc. opens the compound of 2003-96122 communique record.

Halogen compounds as polymerization promotor (G) use; For example, preferably use dilauryl alkyl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl chloride ammonium, dilauryl dimethyl-brometo de amonio etc.

As the aldehydes that polymerization promotor (G) uses, for example, can enumerate terephthalic aldehyde or benzaldehyde derivative etc.As benzaldehyde derivative, can enumerate the dimethylamino benzaldehyde, to methyl oxygen benzaldehyde, to ethyl oxygen benzaldehyde, to n-octyl oxygen benzaldehyde etc.Among them, consider, preferably use n-octyl oxygen benzaldehyde from the viewpoint of solidified nature.

As the mercaptan compound that polymerization promotor (G) uses, for example, can enumerate 3-sulfydryl propyl trimethoxy silicane, 2-mercaptobenzoxazole, decyl mercaptan, thiobenzoic acid etc.

As the sulphite that polymerization promotor (G) uses, for example, can enumerate S-WAT, potassium sulfite, calcium sulfite, ammonium sulphite etc.

As the hydrosulphite that polymerization promotor (G) uses, for example, can enumerate sodium sulfite anhy 96, Potassium hydrogen sulfite etc.

Thiourea compound as polymerization promotor (G) use; Can enumerate 1-(2-pyridyl)-2-thiocarbamide, thiocarbamide, methyl-thiourea, ethyl thiourea, N; N '-diformazan thiocarbamide, N; N '-diethyl thiourea, N, N '-two-n-propyl thiocarbamide, N, N '-dicyclohexyl thiourea, three methyl-thioureas, triethyl thiocarbamide, three-n-propyl thiocarbamide, thricyclohexyl thiocarbamide, tetramethyl thiocarbamide, tetraethyl-thiocarbamide, four-n-propyl thiocarbamide, Fourth Ring hexyl thiocarbamide etc.

The use level of the polymerization promotor that uses among the present invention (G) is not special to be limited; Consider from the viewpoint of the solidified nature of the compsn that obtains etc.; With respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain polymerization promotor (G) 0.001～30 weight part and form.The use level of polymerization promotor (G) is during less than 0.001 weight part, have cause polymerization insufficiently to be carried out, possibility that bonding force reduces, more preferably more than 0.05 weight part.On the other hand, when the use level of polymerization promotor (G) surpasses 30 weight parts, when the polymerization of polymerization starter self hang down, possibility that can not obtain sufficient adhesion strength arranged, so have cause from compsn separate out possible, so more preferably below 20 weight parts.

In filler (H) compsn of the present invention,, and then preferably cooperate filler (H) according to the difference of embodiment.Such filler roughly is divided into organic filler, mineral filler and organic and inorganic compounded mix usually.Raw material as organic filler; For example can enumerate polymethylmethacrylate, polyethyl methacrylate, TEB 3K-ethyl methacrylate copolymers, cross-linking type polymethylmethacrylate, cross-linking type polyethyl methacrylate, polymeric amide, SE, PS, neoprene, paracril, vinyl-vinyl-acetic ester multipolymer, styrene-butadiene copolymer, acrylonitritrile-styrene resin, acrylonitrile-styrene-butadienecopolymer etc., they can use separately or use as the mixture more than 2 kinds.The shape of organic filler is not special to be limited, and can suitably select the particle diameter of filler and uses.The viewpoint of the operability of the compsn that obtains and physical strength etc. is considered, the median size of above-mentioned organic filler, preferred 0.001～50 μ m, more preferably 0.001～10 μ m.

As the raw material of mineral filler, can enumerate quartz, silicon-dioxide, aluminum oxide, silicon-dioxide-titanium oxide, silicon-dioxide-titanium oxide-barium oxide, silicon-dioxide-zirconium white, silica-alumina, lanthanum glass, pyrex, soda glass, barium glass, strontium glass, glass-ceramic, sillico aluminate glass, barium boroalumino silicate glasses, strontium boroalumino silicate glasses, fluorine silicon aluminum silicate glass, calcium fluorine silicon aluminum silicate glass, strontium fluorine silicon aluminum silicate glass, barium fluorine silicon aluminum silicate glass, strontium calcium fluorine silicon aluminum silicate glass etc.They can also use separately or use mixing more than 2 kinds.The shape of mineral filler is not special to be limited, and can suitably select the particle diameter of filler and uses.Consider preferred 0.001～50 μ m of the median size of above-mentioned mineral filler, more preferably 0.001～10 μ m from the viewpoint of the operability of the compsn that obtains and physical strength etc.

As the shape of mineral filler, can enumerate amorphous filler and ball filler.Consider from the viewpoint of the physical strength that improves compsn, preferably use ball filler as above-mentioned mineral filler.And then, when using above-mentioned ball filler, when compsn of the present invention is used as the dental compound resin, the advantage that obtains the excellent compound resin of surface lubrication property is arranged.At this; Ball filler is meant, takes the photo of filler with scanning electron microscope (below, abbreviate SEM as); The particle of in this unit visual field, observing is circular, and using maximum diameter is the filler more than 0.6 except that the average uniformity coefficient that the particle diameter with the vertical direction of this maximum diameter obtains.Preferred 0.1～5 μ m of the median size of above-mentioned ball filler.Median size is during less than 0.1 μ m, has the filling ratio of the ball filler in the compsn to reduce, the possibility of physical strength step-down.On the other hand, when median size surpasses 5 μ m, there is the surface-area of above-mentioned ball filler to reduce, can not obtains having the possibility of the cured body of high mechanical strength.

In order to adjust the flowability of compsn, above-mentioned mineral filler can be carried out using after the surface treatment in advance with known surface treatment agents such as silane coupling agents as required.As this surface treatment agent; For example, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloyl oxygen base propyl trimethoxy silicane, 11-methacryloyl oxygen base undecyl Trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan etc.

The organic and inorganic compounded mix that uses among the present invention is in above-mentioned mineral filler, to add monomeric compound in advance, carries out polymerization after processing the thickener shape, obtains through pulverizing.As above-mentioned organic and inorganic compounded mix, for example, can use TMPT filler (after mixing TriMethylolPropane(TMP) methacrylic ester and silica filler and polymerization, pulverizing obtains) etc.The shape of above-mentioned organic and inorganic compounded mix is not special to be limited, and can suitably select the particle diameter of filler and uses.Consider the median size of above-mentioned organic and inorganic compounded mix, preferred 0.001～50 μ m, more preferably 0.001～10 μ m from the viewpoint of the operability of the compsn that obtains and physical strength etc.

The use level of the filler that uses among the present invention (H) is not special to be limited, with respect to total amount 100 weight parts of polymerizable monomer composition, and preferred 1～2000 weight part of filler (H).The preferred use level of filler (H) has a great difference according to the embodiment that uses, will with after state compsn of the present invention concrete embodiment explanation in the lump, show preferred use level according to the filler (H) of each embodiment.

In addition, in the compsn of the present invention, in the scope that does not influence effect of the present invention, can cooperate pH regulator agent, stopper, UV light absorber, tackifier, tinting material, antiseptic-germicide, spices etc.

Compsn of the present invention contains polymerizable monomer (A) and the water (B) with a plurality of polymerizable groups and a plurality of hydroxyls; Therefore can mix suitable composition as required; Headed by dental use, in various uses, become the compsn of performance excellent in curing property and cementability.Particularly, therefore compsn of the present invention can preferably use as dental composition the impregnability of Dentinal collagen layer and high with the bonding strength and the adhesion durability of dentine (particularly dentine).This dental composition can be used for bed material, adhesives, compound resin, cement (resin-bonded agent, glass ionomer (グラスアイオノマ one) cement, resin enhancement type glass ionomer cement), little recessed crackle filling material, the dental plate dental material with resin etc., preferably uses as bed material, adhesives, compound resin or cement.At this moment, can be used as composition with compsn is divided into two parts two and becomes somatotypes and use.Below, carry out detailed explanation to dividing other embodiment.

As above-mentioned, damaged of tooth is filled or when coating restoration, use the dental adhesives usually.Typically, above-mentioned dental adhesives works to dentine.At this; For dentine; Make such dental adhesives do the time spent; Have with dentin surface be impregnated into the penetrant action of Dentinal collagen layer with acidic component dissolved decalcification, monomer component and the monomer component that soaks into to solidify the solidification that forms with the mixolimnion of collagen (below, be sometimes referred to as " resin impregnation layer ") be important.The bonding system of carrying out three operations of these " decalcifications ", " soaking into " and " curing " respectively is commonly referred to " bonding system of 3 steps ".Basically soaking into the goods that use in the operation is bed materials, and the goods that use in the curing process are adhesivess.

In recent years, because the simplification of flow chart, exploitation merges above-mentioned decalcification operation and above-mentionedly soaks into operation and goods that a step carries out, and practicability, and said products is called " self etching bed material ".Use the bonding system of self etching bed material and adhesives to be commonly referred to " bonding system of 2 steps ".The polymerizable monomer that uses among the present invention (A) has 2 above hydroxyls, and wetting ability is high, and Dentinal collagen layer is soaked into easily.Therefore, the compsn of the present invention that contains polymerizable monomer (A) can be used as the dental bed material and uses, and also can be used as dental self etching bed material and uses.

Use the bed material of compsn of the present invention preferably to contain polymerizable monomer (A), water (B), have the compsn of polymerizable monomer (C), organic solvent (E), polymerization starter (F) and the polymerization promotor (G) of acidic-group, such compsn and then more preferably contain polymerizable monomer (D) with bridging property.Use level as each composition; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～95 weight part, (C) 1～90 weight part and (D) 0～80 weight part, more preferably contain (A) 10～85 weight parts, (C) 10～85 weight parts and (D) 5～60 weight parts.In addition; Total amount 100 weight parts with respect to the polymerizable monomer composition; Preferably contain (B) 6～2000 weight parts, (E) 1～2000 weight part, (F) 0.001～30 weight part and (G) 0.001～30 weight part, more preferably contain (B) 8～1500 weight parts, (E) 5～1000 weight parts, (F) 0.05～20 weight part and (G) 0.05～20 weight part.

Use in the bed material of compsn of the present invention, polymerizable monomer (A) has the hydroxyl more than 2 at intramolecularly, and compsn wetting ability therefore of the present invention is high, and the impregnability of Dentinal collagen layer is improved.Therefore, as polymerization promotor (G), preferred amine, organic solvent (E) are preferably to use with the form of the mixed solvent of water (B).The content of the water in the above-mentioned mixed solvent (B) is not special to be limited, more than the preferred 10 weight %, more preferably more than the 30 weight %, and then more than the preferred 50 weight %.In addition, according to the difference of embodiment, the situation that need not cooperate above-mentioned organic solvent (E) is arranged.

Compsn of the present invention preferably uses as adhesives.Adhesives as in above-mentioned " bonding system of 2 steps " preferably contains above-mentioned (A), (B), (F), (G) and compsn (H), such compsn and then more preferably contain (C) and/or (D).Use level as each composition; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～80 weight part, (C) 0～80 weight part and (D) 0～80 weight part, more preferably contain (A) 3～80 weight parts, (C) 3～80 weight parts and (D) 3～80 weight parts.Above-mentioned (A) that kind of using among the present invention has the compound of 2 polymerizable groups through use, can improve the physical strength of cured article.Consider that from this viewpoint above-mentioned (D) more preferably contains the polymerizable monomer of 2 above polymerizable groups.In addition; Total amount 100 weight parts with respect to the polymerizable monomer composition; Preferably contain (B) 6～100 weight parts, (E) 1～100 weight part, (F) 0.001～30 weight part, (G) 0.001～30 weight part and (H) 1～30 weight part, more preferably contain (B) 6～50 weight parts, (E) 2～50 weight parts, (F) 0.05～20 weight part, (G) 0.05～20 weight part and (H) 2～20 weight parts.

In addition, further require the simplification of operation in recent years, develop three operations that merge " decalcification ", " soaking into " and " curing " and the goods that a step carries out, be called " bonding system of 1 step ".The adhesives that uses in bonding system as this 1 step, the goods of representative have the two-pack that is divided into A liquid and B liquid are mixed before use and used adhesives and two kinds of the adhesives of the bonding system of 1 step of so-called one-pack type that provides with the shape of single component at first.Wherein, one-pack type one side's operation is oversimplified more, and the advantage of therefore using is big.When compsn of the present invention was used as the adhesives of bonding system of 1 step of above-mentioned one-pack type, above-mentioned compsn preferably contained (A), (B), (C), (E), (F), (G) and compsn (H), such compsn and then more preferably contain (D).Use level as each composition; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～80 weight part, (C) 1～90 weight part and (D) 0～80 weight part, more preferably contain (A) 5～70 weight parts, (C) 3～75 weight parts and (D) 2～80 weight parts.In the bonding system of one-pack type 1 step, " soaking into " and " curings " carries out simultaneously, and as above-mentioned (A), use has the hydroxyl more than 2 and contain the meaning of polymerizable monomer of 2 polymerizable groups big.In addition; Total amount 100 weight parts with respect to the polymerizable monomer composition; Preferably contain (B) 6～2000 weight parts, (E) 1～2000 weight part, (F) 0.001～30 weight part, (G) 0.001～30 weight part and (H) 1～30 weight part, more preferably contain (B) 8～1500 weight parts, (E) 5～1500 weight parts, (F) 0.05～20 weight part, (G) 0.05～20 weight part and (H) 2～20 weight parts.

Compsn of the present invention preferably uses as compound resin.When compsn of the present invention was used as compound resin, above-mentioned compsn preferably contained (A), (B), (D), (F), (G) and compsn (H), such compsn and then can contain (C).With at cutting corrosion happening part form pothole after, use usually by the form that is filled in above-mentioned pothole for compound resin.Afterwards, the compound resin of filling solidifies through photopolymerization usually.Therefore, as above-mentioned (F), preferably use Photoepolymerizationinitiater initiater.In addition, as above-mentioned, fill.The solidified compound resin receives biting pressure in the oral cavity, therefore require excellent physical strength.Therefore, above-mentioned compsn with respect to total amount 100 weight parts of polymerizable monomer composition, preferably contains filler (H) 30～2000 weight parts, more preferably contains 50～1500 weight parts.The content of filler (H) is during less than 30 weight parts, the physical strength of cured article have inadequate maybe.On the other hand, when the content of filler (H) surpasses 2000 weight parts in the total amount of polymerizable monomer composition filler (H) be difficult to homogeneous and disperse, the possibility that becomes the inadequate compsn of physical strength and operability aspect is arranged.Use level as each composition; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～99 weight part, (C) 0～50 weight part and (D) 1～90 weight part, more preferably contain (A) 2～95 weight parts, (C) 0～30 weight part and (D) 2～85 weight parts.In addition; Total amount 100 weight parts with respect to the polymerizable monomer composition; Preferably contain (B) 6～10 weight parts, (F) 0.001～30 weight part, (G) 0.001～30 weight part and (H) 30～2000 weight parts, more preferably contain (B) 7～9 weight parts, (F) 0.05～20 weight part, (G) 0.05～20 weight part and (H) 50～1500 weight parts.

In addition, compsn of the present invention being used as cement for dental applications also is one of preferred embodiment.As above-mentioned cement, resin-bonded agent, glass ionomer cement, resin enhancement type glass ionomer cement etc. are arranged as preferred example.When compsn of the present invention was used as the resin-bonded agent, above-mentioned compsn preferably contained (A), (B), (D), (F), (G) and compsn (H), such compsn and then also can contain (C).Grafting material when cement for dental applications is for example preferably inlayed metal or the pottery system of (イ Application レ one) or hat (Network ラウ Application) as being called corona is fixed on the tooth with repair materials uses.As above-mentioned (A) that use among the present invention,, can improve physical strength, the tolerance biting pressure etc. of the cured article that obtains through having the polymerizable group more than 2.Consider this viewpoint, above-mentioned (D) more preferably contains the polymerizable monomer of the polymerizable group more than 2.In addition, in the situation of above-mentioned type of service, above-mentioned corona is the light impermeability with the great majority of repair materials, and therefore above-mentioned cement only is not easy to solidify through photopolymerization.Therefore, as above-mentioned (F), preferably use chemical polymerisation initiator.And, when using chemical polymerisation initiator to carry out polymerization,,, preferably use amine and/or-sulfinic acid and salt thereof as above-mentioned (G) in order to improve its reactivity, more preferably use amine and-sulfinic acid and salt thereof simultaneously.In addition, do not limit as the filler (H) that uses is special.

When hope is given the fluorine slow-releasing for above-mentioned cement; As above-mentioned filler (H); Preferred use is selected from fluorine silicon aluminum silicate glass, calcium fluorine silicon aluminum silicate glass, strontium fluorine silicon aluminum silicate glass, barium fluorine silicon aluminum silicate glass and strontium calcium fluorine silicon aluminum silicate glass at least a kind, more preferably uses fluorine silicon aluminum silicate glass and/or barium fluorine silicon aluminum silicate glass.On the other hand; When hope is given X line radiography property for above-mentioned cement; As above-mentioned filler (H); Preferred use is selected from barium glass, strontium glass, barium boroalumino silicate glasses, strontium boroalumino silicate glasses, strontium fluorine silicon aluminum silicate glass and barium fluorine silicon aluminum silicate glass at least a kind, more preferably uses barium glass and/or barium fluorine silicon aluminum silicate glass.

In addition, when using chemical polymerisation initiator, consider, preferably above-mentioned (F) and above-mentioned (G) is kept at respectively in the independent container from the viewpoint of storage stability.That is, in a preferred embodiment, above-mentioned resin-bonded agent is used with the form of two one-tenth somatotypes.In more preferably embodiment, above-mentioned resin-bonded agent is used with the form of two thickener types.Preferred thickener separately to be that isolated state is preserved between the thickener, uses before that these 2 kinds of thickeners are mixingly, carries out chemical polymerization and solidifies.Above-mentioned thickener is through with the aqueous composition of polymerizable monomer etc. and filler (H) (powder) mixing preparation.In addition, when using-sulfinic acid and salt thereof, consider, preferably above-mentioned (C) and above-mentioned (G) preserved in independent container from the viewpoint of storage stability as above-mentioned (G).When 2 kinds of above-mentioned thickeners are called A thickener and B thickener respectively, preferably especially use above-mentioned A thickener to contain (A), (B), (C), (F) and (H), above-mentioned B thickener contains (G) and embodiment (H).

When compsn of the present invention is used as cement for dental applications; Do not limit as the use level of each composition is special; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～98 weight part, (C) 1～80 weight part and (D) 1～90 weight part, more preferably contain (A) 2～96 weight parts, (C) 2～80 weight parts and (D) 2～80 weight parts.In addition; Use level as above-mentioned (B), above-mentioned (F) and above-mentioned (G); When considering to obtain suitable set time; With respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain (B) 6～1000 weight parts, (F) 0.001～30 weight part and (G) 0.001～30 weight part, more preferably contain (B) 10～500 weight parts, (F) 0.05～20 weight part and (G) 0.05～20 weight part.

And then total amount 100 weight parts with respect to the polymerizable monomer composition preferably contain (H) 30～2000 weight parts, more preferably contain (H) 50～1500 weight parts.The content of filler (H) is during less than 30 weight parts, the physical strength of cured article have inadequate maybe.On the other hand; When the content of filler (H) surpasses 2000 weight parts, with above-mentioned resin-bonded agent during as the cement use of two thickener types of its preferred implementation, the illiquidity of above-mentioned thickener; Be difficult to mix fully, therefore the possibility of the intensity reduction of cured article is arranged.

In addition, compsn of the present invention preferably uses as glass ionomer cement, more preferably uses as resin enhancement type glass ionomer cement.Glass ionomer cement is typically to carry out acid-alkali through the mineral filler that the fluorine silicon aluminum silicate glass is the such polyolefin acid such with ROHM (Port リア Le ケ Application is sour) to react and solidify and obtain.And, think to interact the performance binding function through the calcium in the Win 40350 of above-mentioned ROHM and formation dentine.Compsn of the present invention is as glass ionomer cement; When especially preferably using as resin enhancement type glass ionomer cement; Above-mentioned compsn preferably contains the compsn of (A), (B), (D), (E), (F), (G), (H) and polyolefin acid, such compsn and then also can contain (C).

Above-mentioned polyolefin acid is meant the polymkeric substance of unsaturated monocarboxylic or unsaturated dicarboxylic acid.As the concrete illustration of above-mentioned polyolefin acid, but can enumerate homopolymer or the multipolymer of these unsaturated carboxylic acids or the monomeric multipolymer of these unsaturated carboxylic acids and copolymerization of vinylformic acid, methylacrylic acid, 2-chloracrylic acid, 2-alpha-cyanoacrylate, equisetic acid, methylfumaric acid, toxilic acid, methylene-succinic acid, fumaric acid, propene dicarboxylic acid, citraconic acid, the acid of ウトラコ Application etc.The situation of multipolymer, the unitary ratio of unsaturated carboxylic acid, with respect to full structural unit, preferred 50 moles more than the %.As copolymerisable monomer; The preferred unsaturated polymerization property monomer of ethylenic; For example can enumerate vinylbenzene, acrylic amide, vinyl cyanide, TEB 3K, vinylformic acid salt, vinylchlorid, chlorallylene, vinyl-acetic ester, 1,1,6-trimethylammonium hexylidene dimethacrylate etc.In these polyolefin acids, the homopolymer or the multipolymer of preferred vinylformic acid or toxilic acid.The weight average molecular weight of these polyolefin acids had the intensity step-down of the cured article of cement for dental applications compsn, the situation of weather resistance variation less than 5,000 o'clock.On the other hand, weight average molecular weight surpasses at 40,000 o'clock, the situation that the denseness hardening when having the cement for dental applications compsn to mediate, operability reduce.Thereby the weight average molecular weight of preferred polyolefin acid is 5,000～40,000.

As the filler (H) that uses; The viewpoint of the solidified nature from the acid-alkali reaction and the fluorine slow-releasing of compsn is considered; Preferred use is selected from fluorine silicon aluminum silicate glass, calcium fluorine silicon aluminum silicate glass, strontium fluorine silicon aluminum silicate glass, barium fluorine silicon aluminum silicate glass and strontium calcium fluorine silicon aluminum silicate glass at least a kind, more preferably uses fluorine silicon aluminum silicate glass and/or barium fluorine silicon aluminum silicate glass.

In addition, the use level of the organic solvent of use (E) is not special to be limited, and organic solvent (E) is preferably to use with the form of the mixed solvent of water (B).Through containing water (B), the acid-alkali reaction can be carried out smoothly like this.More than the preferred 50 weight % of the content of water in the above-mentioned mixed solvent (B), more preferably more than the 70 weight %, and then more than the preferred 90 weight %.

With compsn of the present invention as glass ionomer cement, when especially preferably using as resin enhancement type glass ionomer cement; Do not limit as the use level of each composition is special; In total amount 100 weight parts of polymerizable monomer composition; Preferably contain (A) 1～99 weight part, (C) 0～50 weight part and (D) 1～90 weight part, more preferably contain (A) 2～95 weight parts, (C) 0～30 weight part and (D) 2～85 weight parts.In addition; Use level as above-mentioned (F) and above-mentioned (G); When obtaining considering suitable set time; With respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain (B) 6～1000 weight parts, (F) 0.001～30 weight part and (G) 0.001～30 weight part, more preferably contain (B) 10～500 weight parts, (F) 0.05～20 weight part and (G) 0.05～20 weight part.And then total amount 100 weight parts with respect to the polymerizable monomer composition preferably contain (H) 30～2000 weight parts, more preferably contain (H) 50～1500 weight parts.The content of filler (H) is during less than 30 weight parts, the physical strength of cured article have inadequate maybe.On the other hand, when the content of filler (H) surpassed 2000 weight parts, the flowability of compsn thickener reduced, and was difficult to mix fully, therefore had the acid-alkali reaction can not carry out situation smoothly.Its result, the possibility that has the intensity of cured article to reduce.

In addition,, preferably contain organic solvent (E) 7～500 weight parts, more preferably contain 10～300 weight parts, and then preferably contain 20～100 weight parts with respect to total amount 100 weight parts of polymerizable monomer composition.Contain organic solvent (E) in this scope, the acid-alkali reaction can be carried out smoothly, and, the physical strength of the cured article that obtains and good to the cementability of dentine.

With respect to total amount 100 weight parts of polymerizable monomer composition, preferably contain above-mentioned polyolefin acid 1～200 weight part, more preferably contain 5～100 weight parts, and then preferably contain 10～50 weight parts.Contain polyolefin acid in this scope, carry out smoothly by the curing that acid-alkali reaction causes, and, can so that to cured article diminish in the disintegration that intraoral hydrolysis etc. causes.

As above-mentioned, in the glass ionomer cement, the carrying out that reacts through acid-alkali causes curing, considers from the viewpoint of storage stability, and filler (H) and polyolefin acid are packaged in respectively in the independent container, and mixing is used before preferred the use.As the form of goods, preferably use the goods form of so-called powder-liquid type, consider from the viewpoint that improves operability, more preferably contain the thickener of 2 kinds, the i.e. form of pair thickener type glass ionomer cement.During for the goods form of two thickener types, when 2 kinds of above-mentioned thickeners were called A thickener and B thickener respectively, preferred above-mentioned A thickener contained (A), (C), (G), (H), (E) and polyolefin acid, and above-mentioned B thickener contains (A), (B), (F) and embodiment (H).In addition, the above-mentioned A thickener of same preferred use contains (A), (C), (F), (H), (E) and polyolefin acid, and above-mentioned B thickener contains (A), (B), (G) and embodiment (H).In arbitrary embodiment; Contain polyolefin acid in the above-mentioned A thickener side; Therefore as the filler (H) that contains in the above-mentioned B thickener; Preferred use is selected from fluorine silicon aluminum silicate glass, calcium fluorine silicon aluminum silicate glass, strontium fluorine silicon aluminum silicate glass, barium fluorine silicon aluminum silicate glass and strontium calcium fluorine silicon aluminum silicate glass at least a kind, more preferably uses fluorine silicon aluminum silicate glass and/or barium fluorine silicon aluminum silicate glass.On the other hand, as the filler (H) that contains in the above-mentioned A thickener, preferred use does not show reactive for polyolefin acid, the preferred especially quartz that uses.

These dental materials can prepare and use according to conventional methods.These dental materials show bonding strength and the adhesion durability to the excellence of dentine (particularly dentine).

Below, enumerate embodiment and specify the present invention, but the present invention is not limited to these embodiment.

The preparation of application (one-pack type adhesives) (1) the one-pack type adhesives of embodiment 1 in bonding system of 1 step mixes each composition at normal temperatures, preparation one-pack type adhesives compsn.Its composition is shown in table 1.According to following sequential determination and the Dentinal bonding strength of baurodont.

[table 1]

(the use level unit of each composition is a weight part) EDMA: tetrahydroxybutane dimethacrylate (1; Two (the methacryloyl oxygen bases)-2 of 4-, the 3-butyleneglycol) XDMA: the Xylitol dimethacrylate (1, two (the methacryloyl oxygen bases)-2 of 5-; 3; 4-pentane triol) SDMA: the Sorbitol Powder dimethacrylate (1, two (the methacryloyl oxygen bases)-2,3 of 6-; 4; 5-hexane tetrol) MDMA: mannitol dimethacrylate (3,4-two-O-methacryloyl-D-mannitol) #801:1, two (3-methacryloyl oxygen base-2-hydroxyl propoxy-) ethane GDMA of 2-: glycerine dimethacrylate (polymerizable monomer of not using) ErMA: dimethyl pentaerythritol acrylate MDP:10-methacryloyl oxygen base decyl dihydrogen phosphoric acid ester Bis-GMA:2 for the comparative example of polymerizable monomer (A); Two (4-(3-methacryloyl oxygen base)-2-hydroxyl propoxy-phenyl) propane (the dihydroxyphenyl propane diglycidyl methacrylic ester) TMDPO:2 of 2-; 4,6-trimethylbenzoyl diphenyl phosphine oxide CQ: camphorquinone DBB:N, N-dimethylaminobenzoic acid n-butoxy ethyl ester mineral filler 1: Japanese アエロジ Le society's system " R972 "

MDMA is a new compound, and is synthetic through following method.Synthetic (i) 1 of reference example MDMA; 2:5,6-two-O-isopropylidene-3, the synthesizing in the split type flask of the 2L that cooling tube has been installed of 4-two-O-methacryloyl-D-N.F,USP MANNITOL add anhydrous pyridine 700mL after; In flask, slowly add 1; 2:5,6-two-O-isopropylidene-D-N.F,USP MANNITOL (with the pure medicine system of light) 65g dissolves it fully.Ice bath is set in reaction system reaction system is cooled to 0 ℃.Then, the temperature that keeps reaction system and the stirring reaction system time, uses separating funnel that methacrylic chloride (with the pure medicine system of light) 60g was added drop-wise in the reaction system with about 1 hour under nitrogen atmosphere near 0 ℃.Separating funnel is replaced with glass stopper, used oil bath that reaction system is heated to 70 ℃.These heating and continuous 8 hours.After heating finishes, after the disengaging oil bath reaction system is cooled to room temperature.Then, reaction system being injected the beaker that has added the 1L frozen water stops reaction.Behind the stopped reaction, use the 1500mL ether to carry out 5 times and extract.Afterwards, the organic layer that obtains is used the vaporizer concentrating under reduced pressure, obtain oily mater.Above-mentioned oily mater is used the refining (eluent system: hexane: ether=7: 3), after concentrating, add hexane and carry out recrystallization and obtain the purpose compound of silica dioxide gel column chromatography.The receipts amount is 36.3g, and yield is 37%. ¹H-NMR(400MHz，CDCl ₃，δ)1.31(s，6H)，1.36(s，6H)，1.96(s，6H)，3.85-3.96(m，4H)，4.21-4.27(m，2H)，5.43(dd，2H)，5.64(s，2H)，6.15(s，2H)(ppm) ¹³C-NMR(100MHz，CDCl ₃，δ)18.2，25.1，26.3，65.5，71.6，74.7，109.3，126.6，135.6，166.0(ppm)

(ii) synthesizing of MDMA (3,4-two-O-methacryloyl-D-N.F,USP MANNITOL) adds acetate 540mL and water 180mL in the 2L round-bottomed flask.In the time of acetic acid aqueous solution that stirring obtains, with above-mentioned synthetic 1,2:5,6-two-O-isopropylidene-3,4-two-O-methacryloyl-D-N.F,USP MANNITOL 18g slowly add dissolving fully.The temperature of the solution of preparation remains on 25 ℃ state like this, carries out stirring in 18 hours.After stirring end, use vaporizer that above-mentioned solution decompression is concentrated, obtain oily mater.Above-mentioned oily mater is used the refining (eluent system: acetate ethyl ester 100%), concentrate, separate out white crystals of silica dioxide gel column chromatography.Through NMR, confirm that this crystallization is the purpose compound.The receipts amount is 8.7g, and yield is 60%. ¹H-NMR(400MHz，CD ₃OD，δ)1.84(s，6H)，3.39(dd，2H)，3.51(dd，2H)，3.59-3.66(m，2H)，5.28(d，2H)，5.56(s，2H)，6.03(s，2H)(ppm) ¹³C-NMR(100MHz，CD ₃OD，δ)18.4，64.2，71.6，73.1，126.8，137.4，167.9(ppm)

(2) grind with #80 silicon carbide paper (paper Co., Ltd. system is ground by Japan) under flowing water with the labial surface of the Dentinal bonding evaluation method of baurodont, obtain the sample that Dentinal tabular surface exposes ox lower jaw labial teeth.With the sample that obtains under flowing water with #1000 silicon carbide paper (paper Co., Ltd. system is ground by Japan) and then grind.After grind finishing, the water on surface is passed through blow dried.On dried even surface, paste the sealing tape of the about 150 μ m of thickness of circular hole, the regulation bond area with diameter 3mm.

Use pen that the one-pack type adhesives of above-mentioned preparation is coated in the above-mentioned circular hole, place after 20 seconds, through using dental air gun his-and-hers watches top blast gas, dry do not have flowability until the one-pack type adhesives that makes coating.Then, utilize dental visible rays irradiator " JET ライト 3000 " (J.MoritaUSA system) rayed 10 seconds, the one-pack type adhesives of coating is solidified.

Fill dentistry on the surface of the cured article of the one-pack type adhesives that obtains and fill, coat with mould release film (polyester) with compound resin (Network ラレメデイカ Le Co., Ltd. system, trade(brand)name " Network リア Off イ Le AP-X " (registered trademark)).Then, upload at this mould release film and to put slide glass,, make the coated face of above-mentioned compound resin level and smooth through pushing.Then,, use above-mentioned irradiator " JET ライト 3000 " to carry out 20 seconds rayed, above-mentioned compound resin is solidified for above-mentioned compound resin through above-mentioned mould release film.

Fill surface for the dentistry that obtains with the cured article of compound resin; Use commercially available dental resin cement (Network ラレメデイカ Le Co., Ltd. system; Trade(brand)name " パ Na PVC ア 21 "); One side's of bonding stainless steel system cylindrical rod (diameter 5mm, length 1.5cm) end face (circular cross section).After bonding, this sample after leaving standstill under the room temperature in 30 minutes, impregnated in the zero(ppm) water.The sample in the zero(ppm) water of impregnated in that obtains is rested in the thermostatted that remains 37 ℃ 24 hours, prepare adhesive test thus and supply test agent.The preparation adhesive test supplies test agent to amount to 10, is statically placed in the thermostatted that remains on 37 ℃ 24 hours impregnated in whole samples in the zero(ppm) water.To 5 among 10 samples, in order to estimate the bonding force at bonding initial stage, measured bonding strength immediately after leaving standstill in 24 hours.For remaining 5, in order to estimate adhesion durability, and then after will 1 minute operation of mutual dipping is carried out 4000 circulations as 1 round-robin thermal cycling in the warm water of 4 ℃ cold water and 60 ℃, measure bonding strength.

(3) 5 above-mentioned adhesive tests of the mensuration of bonding strength supply test agents the stretching bonding strength with universal testing machine (Instron society system) mensuration, be 2mm/ minute with the pinblock speed setting, with MV as the stretching bonding strength.The result who obtains is shown in table 1 in the lump.

The application (two-component-type adhesives) (1) of embodiment 2 in bonding system of 2 steps uses the preparation of the bed material of the photopolymerizable composition that contains polymerizable monomer (A) that each composition is mixed at normal temperatures, the preparation primer composition.Its composition is shown in table 2.

[table 2]

(2) grind with #80 silicon carbide paper (paper society system is ground by Japan) under flowing water with the labial surface of the Dentinal bonding evaluation method of baurodont, obtain the sample that Dentinal tabular surface exposes ox lower jaw labial teeth.With the sample that obtains under flowing water with #1000 silicon carbide paper (paper society system is ground by Japan) and then grind.After grind finishing, the water on surface is passed through blow dried.On dried even surface, paste the sealing tape of the about 150 μ m of thickness of circular hole, the regulation bond area with diameter 3mm.

Use pen that the bed material of above-mentioned preparation is coated in the above-mentioned circular hole, place after 20 seconds, through his-and-hers watches top blast gas, dry do not have flowability until the bed material that makes coating.Then, with on the overlapping facing that is coated in coating and dry above-mentioned bed material and obtains of the adhesives of the composition of table 3.Then, utilize dental visible rays irradiator " JET ライト 3000 " (J.Morita USA system) rayed 10 seconds, the one-pack type adhesives of coating is solidified.

Fill dentistry on the surface of the cured article of the adhesives that obtains and fill, coat with mould release film (polyester) with compound resin (Network ラレメデイカ Le society system, trade(brand)name " Network リア Off イ Le AP-X " (registered trademark)).Then, upload at this mould release film and to put slide glass,, make the coated face of above-mentioned compound resin level and smooth through pushing.Then,, use above-mentioned irradiator " JET ライト 3000 " to carry out 20 seconds rayed, above-mentioned compound resin is solidified for above-mentioned compound resin through above-mentioned mould release film.

Fill surface for the dentistry that obtains with the cured article of compound resin; Use commercially available dental resin cement (Network ラレメデイカ Le society system; Trade(brand)name " パ Na PVC ア 21 "), a side's of bonding stainless steel system cylindrical rod (diameter 7mm, length 2.5cm) end face (circular cross section).After bonding, this sample after leaving standstill under the room temperature in 30 minutes, impregnated in the zero(ppm) water.The preparation adhesive test supplies test agent to amount to 10, is statically placed in the thermostatted that remains on 37 ℃ 24 hours impregnated in whole samples in the zero(ppm) water.To 5 among 10 samples, in order to estimate the bonding force at bonding initial stage, measured bonding strength immediately after leaving standstill in 24 hours.For remaining 5, in order to estimate adhesion durability, and then after will 1 minute operation of mutual dipping is carried out 4000 circulations as 1 round-robin thermal cycling in the warm water of 4 ℃ cold water and 60 ℃, measure bonding strength.

The composition of [table 3] adhesives

Composition	Use level (weight part)
		HEMA	40
Bis-GMA	40
		NPG	20
Light trigger (TMDPO)	3
		Mineral filler 1	5.5
Mineral filler 2	1.5

NPG: TD 1523 mineral filler 2: Japanese アエロジ Le society's system " Ar380 " (other abbreviations and above-mentioned same meaning)

(3) the above-mentioned adhesive test of bonding evaluation test (evaluation of bonding strength and adhesion durability) supplies the stretching bonding strength of test agent to measure with universal testing machine (society of Shimadzu Seisakusho Ltd. system); With the pinblock speed setting is 2mm/ minute, with MV as the stretching bonding strength.The result who obtains is shown in table 2 in the lump.

Result by embodiment 1 and embodiment 2 can know, when compsn of the present invention is applied to dental material, shows the cementability (bonding strength and adhesion durability) with the excellence of dentine.

Industrial applicability

Polymerizable monomer of the present invention (A) is owing to have a plurality of polymerizable groups and a hydroxyl, therefore in the purposes that requires solidified nature and require in the hydrophilic purposes useful.The photopolymerizable composition that contains this polymerizable monomer can be used for various uses with headed by the dental use.Particularly, said composition is suitable for the dental material of bed material, adhesives, compound resin and cement etc.

Claims

1. compsn; It is to contain polymerizable monomer (A) and water (B) forms compsn; Said polymerizable monomer (A) has non-conjugated carbochain, the polymerizable group more than 2 and the hydroxyl more than 2 of the continuous bonding of carbon more than 4; Said compsn contains water (B) 6～2000 weight parts and forms with respect to total amount 100 weight parts of polymerizable monomer composition

Above-mentioned polymerizable monomer (A) is the compound of formula (6) expression,

[chemical formula 6]

In the formula, R ¹Be Wasserstoffatoms or methyl, m is 2～5, and k is 1～5, and the unit with m ester group is arbitrarily with unitary the putting in order with k hydroxyl.

2. compsn according to claim 1 in total amount 100 weight parts of polymerizable monomer composition, contains polymerizable monomer (A) 1～99 weight part and forms.

3. compsn according to claim 1 in total amount 100 weight parts of polymerizable monomer composition, and then contains polymerizable monomer (C) 1～90 weight part with acidic-group and forms.

4. compsn according to claim 1 in total amount 100 weight parts of polymerizable monomer composition, and then contains bridging property polymerizable monomer (D) 1～90 weight part and forms.

5. compsn according to claim 1 with respect to total amount 100 weight parts of polymerizable monomer composition, contains organic solvent (E) 1～2000 weight part and forms.

6. compsn according to claim 5, organic solvent (E) is a water-miscible organic solvent.

7. compsn according to claim 1 with respect to total amount 100 weight parts of polymerizable monomer composition, contains polymerization starter (F) 0.001～30 weight part and forms.

8. compsn according to claim 1 with respect to total amount 100 weight parts of polymerizable monomer composition, contains polymerization promotor (G) 0.001～30 weight part and forms.

9. compsn according to claim 1 with respect to total amount 100 weight parts of polymerizable monomer composition, contains filler (H) 1～2000 weight part and forms.

10. compsn according to claim 1, it is a dental.

11. bed material, it uses compsn according to claim 10.

12. adhesives, it uses compsn according to claim 10.

13. compound resin, it uses compsn according to claim 10.

14. cement, it uses compsn according to claim 10.